Bisimide compound, acid generator and resist composition each containing the same, and method of for

专利摘要:
The present invention relates to a novel bisimidecompound useful as an acid generator for a chemically amplifiedresist composition used in manufacturing of semiconductorelement and the like or a raw material for synthesizing heatresistant polymers, an acid generator and a resist compositionusing said compound and a method for pattern formation usingsaid composition, and further relates to a synthetic nintermediate for a bisimide compound and a bis(N-hydroxy)phthalimide compound useful as an intermediate for afunctional compound such as a heat resistant polymer orphotosensitive material, and provides a bisimide compound shownby the general formula [1]:(wherein R and A1 are as defined in claim 1.)
公开号:EP1449833A1
申请号:EP20020785967
申请日:2002-11-28
公开日:2004-08-25
发明作者:Tsuneaki Maesawa；Fumiyoshi Urano；Masayuki Endo；Masaru Sasago
申请人:Wako Pure Chemical Industries Ltd；Panasonic Corp；
IPC主号:C07D209-00

专利说明:
TECHNICAL FIELD
The present invention relates to a novel bisimide compounduseful as an acid generator for a chemically amplified resistcomposition used in manufacturing of semiconductor element andthe like or a raw material for synthesizing heat resistantpolymers, an acid generator and a resist composition using saidcompound and a method for pattern formation using saidcomposition, and further relates to a synthetic intermediatefor a bisimide compound, and a bis(N-hydroxy)phthalimidecompound useful as, for example, an intermediate for a functionalcompound such as a heat resistant polymer or a photosensitivematerial. BACKGROUND OF THE INVENTION
In manufacturing of semiconductor elements as an example,with the recent trend of higher density integration insemiconductor devices, wavelengths of energy sources forirradiation instruments used in fine processing, particularlythose used in lithography, have become shorter and shorter, andnow deep UV (300 nm or less) and KrF excimer laser (248 nm) havealready been made into practical use, and ArF excimer laser (193nm) is close to practical use. Further studies for exposuretechnology using F₂ laser (157 nm), electron beams, extreme UV(EUV: 1 to 30 nm band) and the like has been promoted for thepurpose of ultrafine fabrication of 100 nm or less. In resistcompositions under development for these applications, variousknown acid generators are used, but use of these known acidgenerators causes various problems.
For example, when a diazodisulfone compound having analiphatic alkyl group, which is presently used, is used as an acid generator, the compound has such problems that strong acidcannot be generated or acid generation efficiency is poor,whereas, use of a diazodisulfone compound having an aromaticgroup as an acid generator, also has problems such as poorsolution stability. Further, when a sulfonium salt or an iodoniumsalt is used as an acid generator, there are also such problemsthat fine particles are easily formed due to poor solubility,storage for several weeks is difficult due to poor solutionstability, and when said salt has a counter anion derived fromtrifluoromethanesulfonic acid, easy variations in resistperformances are caused (e.g. variations in dimension,sensitivity, shape and the like) , and thus a practically suitableacid generator has not been found.
Further, as a resist composition using an imidesulfonatecompound as an acid generator, the following resist compositionshave been disclosed: use of a combination ofpoly(hydroxystyrene/styrene/tert-butyl acrylate) and N-trifluoromethylsulfonyloxy-bicyclo-[2.2.1]-hept-5-ene-2,3-dicarboxyimide(see JP-A-7-209868); use of a combination ofpoly(p-hydroxystyrene/tert-butyl acrylate) and N-camphorsulfonyloxynaphthalimideor N-trifluoromethylsulfonyloxy-bicyclo-[2.2.1]-hept-5-ene-2,3-dicarboxyimide[see H. Ito et al., ACS. Symp. Ser. , 1995, vol. 614(Microelectronics Technology), p21-34; H. Ito et al., J.Photopolym. Sci. Technol., 1996, vol.9 (No.4), p.557-572; andJP-A-6-266112]; use of N-pentafluorobenzenesulfonyloxy-bicyclo-[2.2.1]-hept-5-ene-2,3-dicarboxyimide (see JP-A-3-206458);use of a combination of poly(styrene/p-hydroxystyrene/p-tert-butoxycarbonylmethoxystyrene) and N-benzenesulfonyloxysuccinimide(see JP-A-6-214395); and use ofN-norbornanesulfonyloxy-bicyclo-[2.2.1]-hept-5-ene-2,3-dicarboxyimide(see JP-A-2001-199955). However, these N-imidesulfonatecompounds have such problems that the resistcomposition using these compounds is, due to asymmetricstructure and high reactivity thereof, labile to moisture andthe like, and thus gives a solution with poor solution stability, low acid generation efficiency and low sensitivity. In addition,a N-imidesulfonate compound having a counter anion derived fromtrifluoromethanesulfonic acid also has a problem such as easyvariation in resist performances, similar to the above.
As an analogous compound to a bisimide compound of thepresent invention, for example, 2,6-bis(methanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H, 6H) - tetrone [see Y. Imai et al. , J. Polym. Sci. Polym.Chem. Ed., 1975, vol.13 (No.10), p.2391-2396; DE-A-19540107 andthe like] has been reported. However, these compounds are usedas a raw material for a polyimide compound and not relates toan acid generator, and even if use of said compouds as an acidgenerator is intended, they cannot be used due to extremely poorsolubility in a resist solvent. Further, 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(butanesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H, 6H)-tetrone (see JP-A-11-258801) has alsobeen reported. However, this compound was used as a cross-linkingagent for a chemically amplified negative resist compositionand not relates to an acid generator, and even if use of saidcompound as an acid generator is intended, it cannot be useddue to low sensitivity, low resolution and poor profile.
Further, as other analogous compounds to a bisimidecompound of the present invention, for example, 5,5'-oxybis[2-trifluoromethanesulfonyloxy-1H-isoindole-1,3(2H)-dione]and 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-trifluoromethanesulfonyloxy-1H-isoindole-1,3(2H)-dione](seeJP-A-3-206458, JP-A-6-301200, JP-A-8-501890 and the like), and5,5'-oxybis[2-(4-toluenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione](see JP-A-11-167199) have been reported as an acidgenerator for chemically amplified resist materials. However,these compounds cannot be practically used as a resistcomposition due to no solubility in a resist solvent generallyused.
As described above, conventional acid generators practically used or studied have the following problems: an acidgenerated is weak; acid generation efficiency is insufficient;fine particles are easily formed due to poor solubility; useof said acid generator as a resist composition occursdecomposition during storage due to poor solution stabilityresulting in variation in sensitivity or poor pattern formation;and a resist composition itself cannot be prepared due to littlesolubility in a resist solvent. Thus, development of a usefulcompound which can solve these problems and generates an acidin response to radioactive ray, is now demanded. SUMMARY OF THE INVENTION
The present invention has been completed under suchcircumstances as mentioned above, and the theme of the inventionis to provide a novel compound efficiently generating an acidin response to radiation, an acid generator and a resistcomposition using said compound and a method for patternformation using said composition, along with an intermediatefor synthesizing an acid generating compound.
The present invention has an object to solve theabove-described problems, and provides the following. (1)A bisimide compound shown by the general formula [1]:
[wherein two Rs are each independently a hydrogen atom or a groupshown by the general formula [2]:-SO₂R¹ (wherein R¹ is an alkyl group having 1 to 12 carbon atoms, ahaloalkyl group having 1 to 12 carbon atoms, or an aryl group,an aralkyl group or an aromatic heterocyclic group, which mayhave a substituent selected from the group consisting of ahalogen atom, an alkyl group, a lower haloalkyl group, an alkoxygroup, a lower haloalkoxy group, a lower alkenyl group, a nitro group, an N,N-dimethylamino group and an acetamide group, acamphor group or a naphthoquinonediazide group); A₁ is atetra-valent alicyclic hydrocarbon group having 4 to 10 carbonatoms, a tetra-valent bridged alicyclic hydrocarbon grouphaving 7 to 8 carbon atoms, a tetra-valent aromatic hydrocarbongroup having 6 to 14 carbon atoms or a group shown by the generalformula [3]:
(wherein A₂ is a direct-linkage, an -O- group or a -C (CF₃) ₂- group) ,and provided that A₁ is a group shown by the general formula [3]when R is a hydrogen atom, an alkyl group shown by R¹ in the generalformula [2] is one having 6 to 12 carbon atoms when A₁ is atetra-valent bridged alicyclic hydrocarbon group having 7 to8 carbon atoms, and one having 3 to 12 carbon atoms when A₁ isa tetra-valent aromatic hydrocarbon group having 6 to 14 carbonatoms; and a haloalkyl group shown by R¹ is one having 3 to 12carbon atoms when A₁ is a group shown by the general formula [3] ;and further an alkyl group as a substituent of an aryl groupwhich may have a substituent, shown by R¹ is one having 2 to 12carbon atoms when A₂ in the general formula [3] is an -O- group] . (2) An acid generator for a chemically amplified resistcomprising said bisimide compound, wherein R is one shown bythe general formula [2]. (3) A positive resist composition comprising at least one ormore kinds of said bisimide compound, wherein R is one shownby the general formula [2]. (4) A negative resist composition comprising at least one ormore kinds of said bisimide compound, wherein R is one shownby the general formula [2]. (5) A method for pattern formation comprising: a process of forming a positive resist composition in thesaid (3) on a substrate as a resist film; a process of exposing an arbitrary pattern on the said resistfilm; and a process of forming a positive resist pattern by developing. (6) A method for pattern formation comprising: a process of forming a negative resist composition in thesaid (4) on a substrate as a resist film; a process of exposing an arbitrary pattern on the said resistfilm; and a process of forming a negative resist pattern by developing.

The present inventors have conducted extensive study inorder to realize the object mentioned above to arrive at thefinding that a bisimide compound, wherein R in the above-describedgeneral formula [1] is a group shown by the generalformula [2], can be an acid generator having excellent effectsof, for example, high acid generation efficiency and highsolubility in a resist solvent, and also a raw material and across-linking agent for a heat resistant resin such as polyimide,and furthermore, a bis (N-hydroxy) phthalimide compound, whereinR in the above-described general formula [1] is a hydrogen atom,can be a synthetic intermediate for a bisimide compound usefulas the said acid generator, a raw material and a cross-linkingagent for a heat resistant resin such as polyimide, and anintermediate of a functional compound such as photosensitivematerial, and finally the present invention has been completedon the basis of these findings. BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a cross-sectional view showing each process ofa method of pattern formation using a resist composition of thepresent invention (Example 67).Fig. 2 is a cross-sectional view showing each process ofa method of pattern formation using a resist composition of thepresent invention (Example 73).Fig. 3 is a cross-sectional view showing each process ofa method of pattern formation using a conventional resistcomposition (Comparative Example 8).Fig. 4 is a cross-sectional view showing each processesof a method of pattern formation using a conventional resist composition (Comparative Example 9).
BEST MODE FOR CARRYING OUT THE INVENTION
In the general formula [2], the alkyl group having 1 to12 carbon atoms shown by R¹ may be straight chained, branchedor cyclic, and includes one having preferably 1 to 10 carbonatoms and more preferably 6 to 8 carbon atoms, which isspecifically exemplified by, for example, a methyl group, anethyl group, a n-propyl group, an isopropyl group, a n-butylgroup, an isobutyl group, a sec-butyl group, a tert-butyl group,a n-pentyl group, an isopentyl group, a sec-pentyl group, atert-pentyl group, a neopentyl group, a 2-methylbutyl group,a 1-ethylpropyl group, a n-hexyl group, an isohexyl group, asec-hexyl group, a tert-hexyl group, a neohexyl group, a 2-methylpentylgroup, a 1,2-dimethylbutyl group, a 1-ethylbutylgroup, a n-heptyl group, an isoheptyl group, a sec-heptyl group,a tert-heptyl group, a neoheptyl group, a n-octyl group, anisooctyl group, a sec-octyl group, a tert-octyl group, a neooctylgroup, a n-nonyl group, an isononyl group, a sec-nonyl group,a tert-nonyl group, a neononyl group, a n-decyl group, anisodecyl group, a sec-decyl group, a tert-decyl group, a neodecylgroup, a n-undecyl group, an isoundecyl group, a sec-undecylgroup, a tert-undecyl group, a neoundecyl group, a n-dodecylgroup, an isododecyl group, a sec-dodecyl group, a tert-dodecylgroup, a neododecyl group, a cyclopropyl group, a cyclobutylgroup, a cyclopentyl group, a cyclohexyl group, acyclohexylmethyl group, a 2-cyclohexylethyl group, acycloheptyl group, a cyclooctyl group, a cyclononyl group, acyclodecyl group, a cycloundecyl group and a cyclododecyl group,and among others, a preferable one includes, for example, amethyl group, an ethyl group, a n-propyl group, an isopropylgroup, a n-butyl group, a sec-butyl group, a tert-butyl group,a n-pentyl group, a sec-pentyl group, a tert-pentyl group, an-hexyl group, a sec-hexyl group, a tert-hexyl group, a n-heptylgroup, a sec-heptyl group, a tert-heptyl group, a n-octyl group,a sec-octyl group, a tert-octyl group, a n-nonyl group, a sec-nonyl group, a tert-nonyl group, a n-decyl group, a sec-decylgroup, a tert-decyl group, a cyclopentyl group and a cyclohexylgroup, and a more preferable one includes, for example, a n-hexylgroup, n-heptyl group and n-octyl group.
The alkyl group having 6 to 12 carbon atoms shown by R¹in the general formula [2] , when A₁ in the general formula [1]is a tetra-valent bridged alicyclic hydrocarbon group having7 to 8 carbon atoms, may be straight chained, branched or cyclic,and includes one having preferably 6 to 8 carbon atoms, whichis specifically exemplified by the same as examples of one having6 to 12 carbon atoms among the alkyl groups having 1 to 12 carbonatoms, shown by R¹ in the above-described general formula [2] ,and among others, a preferable one includes, for example, an-hexyl group, a sec-hexyl group, a tert-hexyl group, a n-heptylgroup, a sec-heptyl group, a tert-heptyl group, a n-octyl group,a sec-octyl group, a tert-octyl group and a cyclohexyl group,and a more preferable one includes, for example, a n-hexyl group,a n-heptyl group and a n-octyl group.
The alkyl group having 3 to 12 carbon atoms shown by R¹in the general formula [2], when A₁ in the general formula [1]is a tetra-valent aromatic hydrocarbon group having 6 to 14carbon atoms, may be straight chained, branched or cyclic, andincludes one having preferably 6 to 8 carbon atoms, which isspecifically exemplified by the same as examples of one having3 to 12 carbon atoms among the alkyl groups having 1 to 12 carbonatoms, shown by R¹ in the above-described general formula [2],and among others, a preferable one includes, for example, an-hexyl group, a sec-hexyl group, a tert-hexyl group, a n-heptylgroup, a sec-heptyl group, a tert-heptyl group, a n-octyl group,a sec-octyl group, a tert-octyl group and a cyclohexyl group,and a more preferable one includes, for example, a n-hexyl group,a n-heptyl group and a n-octyl group.
The haloalkyl group having 1 to 12 carbon atoms shown byR¹ includes one, wherein a part of or all of the hydrogen atoms,preferably 1 to 17 hydrogen atoms and more preferably 7 to 17hydrogen atoms of the alkyl group having 1 to 12 carbon atoms, shown by R¹ in the above-described general formula [2] aresubstituted by a halogen atom (e.g. a fluorine atom, a chlorineatom, a bromine atom and an iodine atom) , and includes one havingpreferably 1 to 8 carbon atoms, more preferably 3 to 8 carbonatoms, which is specifically exemplified by, for example, afluoromethyl group, a chloromethyl group, a bromomethyl group,an iodomethyl group, a difluoromethyl group, a trifluoromethylgroup, a trichloromethyl group, a tribromomethyl group, atriiodomethyl group, a trifluoroethyl group, a trichloroethylgroup, a tribromoethyl group, a triiodoethyl group, apentafluoroethyl group, a pentachloroethyl group, apentabromoethyl group, a pentaiodoethyl group, atrifluoropropyl group, a heptafluoropropyl group, aheptachloropropyl group, a heptabromopropyl group, aheptaiodopropyl group, a trifluorobutyl group, anonafluorobutyl group, a nonachlorobutyl group, anonabromobutyl group, a nonaiodobutyl group, a trifluoropentylgroup, an undecafluoropentyl group, an undecachloropentyl group,an undecabromopentyl group, an undecaiodopentyl group, atrifluorohexyl group, a tridecafluorohexyl group, atridecachlorohexyl group, a tridecabromohexyl group, atridecaiodohexyl group, a trifluoroheptyl group, apentadecafluoroheptyl group, a pentadecachloroheptyl group, apentadecabromoheptyl group, a pentadecaiodoheptyl group, atrifluorooctyl group, a heptadecafluorooctyl group, aheptadecachlorooctyl group, a heptadecabromooctyl group, aheptadecaiodooctyl group, a trifluorononyl group, anonadecafluorononyl group, a nonadecachlorononyl group, anonadecabromononyl group, a nonadecaiodononyl group, atrifluorodecyl group, a perfluorodecyl group, a perchlorodecylgroup, a perbromodecyl group, a periododecyl group, aperfluoroundecyl group, a perchloroundecyl group, aperbromoundecyl group, a periodoundecyl group, aperfluorododecyl group, a perchlorododecyl group, aperbromododecyl group and a periodododecyl group, and amongothers, a preferable one includes, for example, a trifluoromethyl group, a nonafluorobutyl group and aheptadecafluorooctyl group, and a more preferable one is anonafluorobutyl group.
The haloalkyl group having 3 to 12 carbon atoms shown byR¹ in the general formula [2], when A₁ in the general formula[1] is a group shown by the general formula [3] , includes one,wherein a part of or all of the hydrogen atoms, preferably 1to 17 hydrogen atoms and more preferably 7 to 17 hydrogen atomsof the alkyl group having 3 to 12 carbon atoms among the alkylgroups having 1 to 12 carbon atoms, shown by R¹ in theabove-described general formula [2] are substituted by a halogenatom (e.g. a fluorine atom, a chlorine atom, a bromine atom andan iodine atom) , and includes one having preferably 3 to 8 carbonatoms, which is specifically exemplified by the same as examplesof one having 3 to 12 carbon atoms among the haloalkyl groupshaving 1 to 12 carbon atoms, shown by R¹ in the above-describedgeneral formula [2], and among others, a preferable one includes,for example, a nonafluorobutyl group and a heptadecafluorooctylgroup, and more preferable one is a nonafluorobutyl group.
The aryl group of the aryl group which may have asubstituent, shown by R¹ includes one having generally 6 to 16carbon atoms, preferably 6 to 10 carbon atoms, which isspecifically exemplified by, for example, a phenyl group, a1-naphthyl group, a 2-naphthyl group, an anthryl group and apyrenyl group, and among others, a phenyl group and a naphthylgroup are preferable, and a phenyl group is more preferable.
The aralkyl group of the aralkyl group which may have asubstituent, shown by R¹ includes one having generally 7 to 10carbon atoms, preferably 7 to 8 carbon atoms, which isspecifically exemplified by, for example, a benzyl group, aphenethyl group, a 1-phenylethyl group, a 2-phenylpropyl group,a 3-phenylpropyl group, a phenylbutyl group and a 1-methyl-3-phenylpropylgroup, and among others, a benzyl group ispreferable.
The aromatic heterocyclic group of the aromaticheterocyclic group which may have a substituent, shown by R¹ includes, for example, one having at least one hetero atom,preferably 1 to 3 hetero atoms, such as a nitrogen atom, a sulfuratom and an oxygen atom, and may be a monocyclic or bicyclicone, which is specifically exemplified by, for example, a2-thienyl group, a 8-quinolyl group, a 5-isoquinolyl group, a3-pyridyl group, a 2-thiazolyl group, a 2-furfuryl group anda 2-imidazolyl group, and among others, a 2-thienyl group ispreferable.
The substituent of an aryl group, an aralkyl group and anaromatic heterocyclic group, which may have a substituent, shownby R¹ includes, for example, a halogen atom, an alkyl group, alower haloalkyl group, an alkoxy group, a lower haloalkoxy group,a lower alkenyl group, a nitro group, a N, N-dimethylamino groupand an acetamide group.
The halogen atom as the substituent includes, for example,a fluorine atom, a chlorine atom, a bromine atom and an iodineatom, and among others, a fluorine atom and a chlorine atom arepreferable, and a fluorine atom is more preferable.
The alkyl group as the substituent may be straight chained,branched or cyclic, and includes one having generally 1 to 12carbon atoms, preferably 1 to 4 carbon atoms, which isspecifically exemplified by, for example, a methyl group, anethyl group, a n-propyl group, an isopropyl group, a n-butylgroup, an isobutyl group, a sec-butyl group, a tert-butyl group,a n-pentyl group, an isopentyl group, a sec-pentyl group, atert-pentyl group, a neopentyl group, a n-hexyl group, anisohexyl group, a sec-hexyl group, a tert-hexyl group, a neohexylgroup, a 2-methylpentyl group, an 1,2-dimethylbutyl group, an1-ethylbutyl group, a n-heptyl group, an isoheptyl group, asec-heptyl group, a tert-heptyl group, a neoheptyl group, an-octyl group, an isooctyl group, a sec-octyl group, a tert-octylgroup, a neooctyl group, a n-nonyl group, an isononyl group,a sec-nonyl group, a tert-nonyl group, a neononyl group, an-decyl group, an isodecyl group, a sec-decyl group, a tert-decylgroup, a neodecyl group, a n-undecyl group, an isoundecyl group,a sec-undecyl group, a tert-undecyl group, a neoundecyl group, a n-dodecyl group, an isododecyl group, a sec-dodecyl group,a tert-dodecyl group, a neododecyl group and a cyclohexyl group,and among others, a preferable one includes, for example, amethyl group, an ethyl group, a n-propyl group, an isopropylgroup, a n-butyl group, a sec-butyl group and a tert-butyl group,and a more preferable one includes, for example, a methyl group,an ethyl group, a n-propyl group, a n-butyl group and a tert-butylgroup.
The lower haloalkyl group as the substituent includes one,wherein a part of or all of hydrogen atoms of a lower alkyl grouphaving generally 1 to 4 carbon atoms, preferably 1 to 2 carbonatoms are substituted by a halogen atom (e.g. a fluorine atom,a chlorine atom, a bromine atom and an iodine atom), which isspecifically exemplified by, for example, a fluoromethyl group,a chloromethyl group, a trifluoromethyl group, atrichloromethyl group, a tribromomethyl group, a triiodomethylgroup, a trifluoroethyl group, a trichloroethyl group, apentafluoroethyl group, a pentachloroethyl group, apentabromoethyl group, a pentaiodoethyl group, atrifluoropropyl group, a trichloropropyl group, aheptafluoropropyl group, a heptachloropropyl group, aheptabromopropyl group, a heptaiodopropyl group, atrifluorobutyl group, a trichlorobutyl group, a nonafluorobutylgroup, a nonachlorobutyl group, a nonabromobutyl group and anonaiodobutyl group, and among others, a trifluoromethyl groupand a pentafluoroethyl group are preferable and atrifluoromethyl group is more preferable.
The alkoxy group as the substituent may be straight chained,branched or cyclic, and includes one having generally 1 to 12carbon atoms, preferably 1 to 4 carbon atoms, which isspecifically exemplified by, for example, a methoxy group, anethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxygroup, an isobutoxy group, a sec-butoxy group, a tert-butoxygroup, a n-pentyloxy group, an isopentyloxy group, a sec-pentyloxygroup, a tert-pentyloxy group, a neopentyloxy group,a n-hexyloxy group, an isohexyloxy group, a sec-hexyloxy group, a tert-hexyloxy group, a neohexyloxy group, a cyclohexyloxygroup, a n-heptyloxy group, an isoheptyloxy group, a sec-heptyloxy group, a tert-heptyloxy group, a neoheptyloxy group,a n-octyloxy group, an isooctyloxy group, a sec-octyloxy group,a tert-octyloxy group, a neooctyloxy group, a n-nonyloxy group,an isononyloxy group, a sec-nonyloxy group, a tert-nonyloxygroup, a neononyloxy group, a n-decyloxy group, an isodecyloxygroup, a sec-decyloxy group, a tert-decyloxy group, aneodecyloxy group, a n-undecyloxy group, an isoundecyloxy group,a sec-undecyloxy group, a tert-undecyloxy group, aneoundecyloxy group, a n-dodecyloxy group, an isododecyloxygroup, a sec-dodecyloxy group, a tert-dodecyloxy group and aneododecyloxy group, and among others, a methoxy group, an ethoxygroup, a n-propoxy group, an isopropoxy group, a n-butoxy group,a sec-butoxy group and a tert-butoxy group are preferable anda methoxy group is more preferable.
The lower haloalkoxy group as the substituent includes one,wherein a part of or all of the hydrogen atoms of an alkoxy grouphaving generally 1 to 4 carbon atoms, preferably 1 to 2 carbonatoms are substituted by a halogen atom (e.g. a fluorine atom,a chlorine atom, a bromine atom and an iodine atom), which isspecifically exemplified by, for example, afluoromethoxygroup,a chloromethoxy group, a trifluoromethoxy group, atrichloromethoxy group, a tribromomethoxy group, atriiodomethoxy group, a trifluoroethoxy group, apentafluoroethoxy group, a pentachloroethoxy group, apentabromoethoxy group, a pentaiodoethoxy group, atrifluoropropoxy group, a heptafluoropropoxy group, aheptachloropropoxy group, a heptabromopropoxy group, aheptaiodopropoxy group, a trifluorobutoxy group, anonafluorobutoxy group, a nonachlorobutoxy group, anonabromobutoxy group and a nonaiodobutoxy group, and amongothers, a trifluoromethoxy group is preferable.
The lower alkenyl group as the substituent may be straightchained, branched or cyclic, and includes one having generally2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, which is specificallyexemplifiedby, for example, a vinyl group, anallylgroup, a 1-propenyl group, an isopropenyl group, a 1-butenylgroup, a 2-butenyl group and a 2-methylallyl group, and amongothers, a vinyl group is preferable.
The alkyl group having 1 to 12 carbon atoms as thesubstituent of the aryl group which may have the substituent,shown by R¹ in the general formula [2], when A₁ in the generalformula [1] is a group shown by the general formula [3], andA₂ in the above-described general formula [3] is a direct-linkageor a -C(CF₃)₂- group, may be straight chained, branched or cyclic,and includes one having preferably 3 to 8 carbon atoms, whichis specifically exemplified by the same as examples of the alkylgroup having 1 to 12 carbon atoms shown by R¹ in the above-describedgeneral formula [2], and among others, a preferableone includes, for example, a n-propyl group, an isopropyl group,a n-butyl group, a sec-butyl group, a tert-butyl group, an-pentyl group, an isopentyl group, a sec-pentyl group, atert-pentyl group, a n-hexyl group, a sec-hexyl group, atert-hexyl group, a n-heptyl group, a sec-heptyl group, atert-heptyl group, a n-octyl group, a sec-octyl group, atert-octyl group and a cyclohexyl group, and more preferableone includes, for example, a n-propyl group, an isopropyl group,a n-butyl group, a sec-butyl group and a tert-butyl group.
The alkyl group having 2 to 12 carbon atoms as thesubstituent of the aryl group which may have a substituent, shownby R¹ in the general formula [2] , when A₁ in the general formula[1] is a group shown by the general formula [3], and A₂ in thegeneral formula [3] is an -O- group, may be straight chained,branched or cyclic, and includes one having preferably 3 to 12carbon atoms, more preferably 3 to 8 carbon atoms, which isspecifically exemplified by the same as examples of one having2 to 12 carbon atoms among the alkyl groups having 1 to 12 carbonatoms, shown by R¹ in the general formula [2] , and among others,a preferable one includes, for example, a n-propyl group, anisopropyl group, a n-butyl group, a sec-butyl group, a tert-butylgroup, a n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a n-hexyl group, a sec-hexyl group, atert-hexyl group, a n-heptyl group, a sec-heptyl group, atert-heptyl group, a n-octyl group, a sec-octyl group, atert-octyl group and a cyclohexyl group, and a more preferableone includes, for example, a n-propyl group, an isopropyl group,a n-butyl group, a sec-butyl group and a tert-butyl group.
The alkoxy group as the substituent of the aryl group whichhas a substituent, shown by R¹ in the general formula [2] , whenA₁ in the general formula [1] is a group shown by the generalformula [3], may be straight chained, branched or cyclic, andincludes one having generally 1 to 12 carbon atoms, preferably3 to 6 carbon atoms, which is specifically exemplified by thesame as examples one of the alkoxy group having 1 to 12 carbonatoms as the substituent of the aryl group, the aralkyl groupor the aromatic heterocyclic group, which may have a substituent,shown by R¹ in the above-described general formula [2] , and amongothers, a preferable one includes, for example, a n-propoxy group,an isopropoxy group, a n-butoxy group, an isobutoxy group, asec-butoxy group, a n-pentyloxy group, a sec-pentyloxy group,a tert-pentyloxy group, a n-hexyloxy group, a sec-hexyloxy group,a tert-hexyloxy group and a cyclohexyloxy group, and a morepreferable one includes, for example, a n-propoxy group, anisopropoxy group, a n-butoxy group, a sec-butoxy group and atert-butoxy group.
Among these substituents, electron-withdrawing groupssuch as a halogen atom, a trifluoromethyl group and a nitro groupis preferable.
The aryl group which may have a substituent, shown by R¹is preferably one having at least one electron-withdrawing groupatm-position, which is specifically exemplified by, for example,a m-trifluoromethylphenyl group, a 3,5-ditrifluoromethylphenylgroup and a pentafluorophenyl group.
Among these R¹s, a preferable one includes, for example,a haloalkyl group, an aryl group or an aromatic heterocyclicgroup, which may have a substituent and a camphor group, anda more preferable one includes a haloalkyl group, an aryl group which may have a substituent and a camphor group.
The two R¹s in the general formula [1] may be differenteach other, but preferably the same.
In the general formula [1], the tetra-valent alicyclichydrocarbon group having 4 to 10 carbon atoms, shown by A₂includes, for example, a group shown by the general formula [7] :
(wherein R⁵ and R⁶ are each independently a direct-linkage ora lower alkylene chain having 1 to 3 carbon atoms).
The lower alkylene chain having 1 to 3 carbon atoms, shownby R⁵ and R⁶ preferably includes a linear alkylene group having1 to 2 carbon atoms, which is specifically exemplified by, forexample, a methylene group, an ethylene group and a trimethylenegroup, and among others, a methylene group is preferable.
The combination of R⁵ and R⁶ includes specifically, forexample, one wherein both are direct-linkages (a 4-memberedring); one wherein one is a direct-linkage and the other is amethylene group (a 5-membered ring); and one wherein both aremethylene groups (a 6-membered ring).
The bridged alicyclic hydrocarbon group having 7 to 8carbon atoms, shown by A¹ includes, for example, a group shownby the general formula [16]:
(wherein R¹² is a methylene group, an ethylene group or a vinylenegroup) and among others, a preferable one includes a group shownby the formula [8]:
(corresponding to one wherein R¹¹ in the general formula [16]is a vinylene group).
The tetra-valent aromatic hydrocarbon group having 6 to 14 carbon atoms, shown by A¹ includes a monocyclic or a polycyclicgroup obtained by condensation of 2 to 3 rings, which isspecifically exemplified by, for example, a group shown by theformula [9],
a group shown by the formula [17],
and a group shown by the formula [18],
and among others, a preferable one is a group shown by theabove-described general formula [9].
The bisimide compound shown by the above-described generalformula [1] includes, for example, a bisimidesulfonate compoundshown by the general formula [4]:
(wherein R² is an alkyl group having 1 to 12 carbon atoms, ahaloalkyl group having 1 to 12 carbon atoms, or an aryl group,an aralkyl group or an aromatic heterocyclic group, which mayhave a substituent selected from the group consisting of ahalogen atom, an alkyl group, a lower haloalkyl group, an alkoxygroup, a lower haloalkoxy group, a lower alkenyl group, a nitrogroup, an N,N-dimethylamino group and an acetamide group, acamphor group or a naphthoquinonediazide group; A₃ is atetra-valent alicyclic hydrocarbon group having 4 to 10 carbonatoms, a tetra-valent bridged alicyclic hydrocarbon grouphaving 7 to 8 carbon atoms or a tetra-valent aromatic hydrocarbon group having 6 to 14 carbon atoms; and provided that an alkylgroup shown by R² is one having 6 to 12 carbon atoms when A₃ isa tetra-valent bridged alicyclic hydrocarbon group having 7 to8 carbon atoms, and one having 3 to 12 carbon atoms when A₃ isa tetra-valent aromatic hydrocarbon group having 6 to 14 carbonatoms); and a bisphthalimide compound shown by the generalformula [5]:
[wherein two R³s are each independently a hydrogen atom or a groupshown by the general formula [6]:-SO₂R⁴ (wherein R⁴ is an alkyl group having 1 to 12 carbon atoms, ahaloalkyl group having 3 to 12 carbon atoms, or an aryl group,an aralkyl group or an aromatic heterocyclic group, which mayhave a substituent selected from the group consisting of ahalogen atom, an alkyl group, a lower haloalkyl group, an alkoxygroup, a lower haloalkoxy group, a lower alkenyl group, a nitrogroup, an N,N-dimethylamino group and an acetamide group, acamphor group or a naphthoquinonediazide group;); A₂ is adirect-linkage, an -O- group or a -C (CF₃)₂- group; and providedthat an alkyl group as a substituent of an aryl group which mayhave a substituent, shown by R⁴ is one having 2 to 12 carbon atoms,when A₂ is an -O- group].
The alkyl group having 1 to 12 carbon atoms shown by R²,when A₃ in the general formula [4] is a tetra-valent alicyclichydrocarbon group having 4 to 10 carbon atoms, and an alkyl grouphaving 1 to 12 carbon atoms shown by R⁴, when R³ in the generalformula [5] is a group shown by the general formula [6], maybe straight chained, branched or cyclic, and includes one havingpreferably 1 to 10 carbon atoms, more preferably 6 to 8 carbonatoms, which is specifically exemplified by the same as examplesof the alkyl group having 1 to 12 carbon atoms, shown by R¹ inthe general formula [2], and among others, a preferable one includes, for example, a methyl group, an ethyl group, a n-propylgroup, an isopropyl group, a n-butyl group, a sec-butylgroup, a tert-butyl group, a n-pentyl group, a sec-pentyl group,a tert-pentyl group, a n-hexyl group, an isohexyl group, asec-hexyl group, a tert-hexyl group, a n-heptyl group, asec-heptyl group, a tert-heptyl group, a n-octyl group, asec-octyl group, a tert-octyl group, a n-nonyl group, a sec-nonylgroup, a tert-nonyl group, a n-decyl group, a sec-decyl group,a tert-decyl group, a cyclopentyl group and a cyclohexyl group,and a more preferable one includes, for example, a n-hexyl group,a n-heptyl group and a n-octyl group.
The alkyl group having 6 to 12 carbon atoms shown by R²,when A₃ in the general formula [4] is a tetra-valent bridgedalicyclic hydrocarbon group having 7 to 8 carbon atoms, may bestraight chained, branched or cyclic, and includes one havingpreferably 6 to 8 carbon atoms, which is specifically exemplifiedby the same as examples of one having 6 to 12 carbon atoms amongthe alkyl groups having 1 to 12 carbon atoms, shown by R¹ in theabove-described general formula [2], and among others, apreferable one includes, for example, a n-hexyl group, asec-hexyl group, a tert-hexyl group, a n-heptyl group, asec-heptyl group, a tert-heptyl group, a n-octyl group, asec-octyl group, a tert-octyl group and a cyclohexyl group, andamong others, a more preferable one is, for example, a n-hexylgroup, a n-heptyl group and a n-octyl group.
The alkyl group having 3 to 12 carbon atoms shown by R²,when A₃ in the general formula [4] is a tetra-valent aromatichydrocarbon group having 6 to 14 carbon atoms, may be straightchained, branched or cyclic, and includes one having preferably6 to 8 carbon atoms, which is specifically exemplified by thesame as examples of one having 3 to 12 carbon atoms among thealkyl groups having 1 to 12 carbon atoms, shown by R¹ in thegeneral formula [2], and among others, a preferable one includes,for example, a n-hexyl group, a sec-hexyl group, a tert-hexylgroup, a n-heptyl group, a sec-heptyl group, a tert-heptyl group,a n-octyl group, a sec-octyl group, a tert-octyl group and a cyclohexyl group, and a more preferable one includes, for example,a n-hexyl group, a n-heptyl group and a n-octyl group.
In the general formula [4], the haloalkyl group having 1to 12 carbon atoms shown by R² includes one, wherein a part ofor all of the hydrogen atoms, preferably 1 to 17 hydrogen atomsand more preferably 7 to 17 hydrogen atoms of the alkyl grouphaving 1 to 12 carbon atoms shown by R¹ in the above-describedgeneral formula [2] are substituted by a halogen atom (e.g. afluorine atom, a chlorine atom, a bromine atom and an iodineatom), includes one having preferably 1 to 8, more preferably3 to 8 carbon atoms, which is specifically exemplified by thesame as examples of the haloalkyl group having 1 to 12 carbonatoms, shown by R¹ in the above-described general formula [2],and among others, a preferable one includes, for example, atrifluoromethyl group, a nonafluorobutyl group and aheptadecafluorooctyl group, and a more preferable one is anonafluorobutyl group.
In the general formula [6], the haloalkyl group having 3to 12 carbon atoms shown by R⁴ includes one, wherein a part ofor all of the hydrogen atoms, preferably 1 to 17 hydrogen atomsand more preferably 7 to 17 hydrogen atoms of the alkyl grouphaving 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms,among the alkyl groups having 1 to 12 carbon atoms shown by R¹in the above-described general formula [2] are substituted bya halogen atom (e.g. a fluorine atom, a chlorine atom, a bromineatom and an iodine atom), which is specifically exemplified bythe same as examples of one having 3 to 12 carbon atoms amongthe haloalkyl groups having 1 to 12 carbon atoms, shown by R¹in the above-described general formula [2], and among others,a preferable one includes, for example, a nonafluorobutyl groupand a heptadecafluorooctyl group, and a more preferable one isa nonafluorobutyl group.
In the general formulae [4] and [6] , the aryl group of thearyl group which may have a substituent, shown by R² and R⁴includes one having generally 6 to 16 carbon atoms, preferably6 to 10 carbon atoms, which is specifically exemplified by the same as examples of the aryl group of the aryl group which mayhave a substituent, shown by R¹ in the general formula [2], andamong others, a preferable one includes, for example, a phenylgroup and a naphthyl group, and a more preferable one is a phenylgroup.
The aralkyl group of the aralkyl group which may have asubstituent, shown by R² and R⁴, includes one having generally7 to 10 carbon atoms, preferably 7 to 8 carbon atoms, which isspecifically exemplified by the same as examples of the aralkylgroup of the aralkyl group which may have a substituent, shownby R¹ in the above-described general formula [2] , and among others,a benzyl group is preferable.
The aromatic heterocyclic group of the aromaticheterocyclic group which may have a substituent, shown by R² andR⁴, includes one having at least 1 hetero atom, preferably 1 to3 hetero atoms such as a nitrogen atom, a sulfur atom and anoxygen atom, and may be a monocyclic or a bicyclic group, whichis specifically exemplified by the same as examples of thearomatic heterocyclic group of the aromatic heterocyclic groupwhich may have a substituent, shown by R¹ in the above-describedgeneral formula [2], and among others, a preferable one is a2-thienyl group.
The substituent of the aryl group, the aralkyl group orthe aromatic heterocyclic group, which may have a substituent,shown by R² and R⁴ includes, for example, a halogen atom, an alkylgroup, a lower haloalkyl group, an alkoxy group, a lowerhaloalkoxy group, a lower alkenyl group, a nitro group, aN,N-dimethylamino group and an acetamide group.
The halogen atom as the substituent includes, for example,a fluorine atom, a chlorine atom, a bromine atom and an iodineatom, and among others, a preferable one includes a fluorineatom and a chlorine atom, and a more preferable one is a fluorineatom.
The alkyl group as the substituent may be straight chained,branched or cyclic, and includes one having generally 1 to 12carbon atoms, preferably 1 to 4 carbon atoms, which is specifically exemplified by the same as examples of the alkylgroup having 1 to 12 carbon atoms, shown by R¹ in the above-describedgeneral formula [2], and among others, a preferableone includes, for example, a methyl group, an ethyl group, an-propyl group, an isopropyl group, a n-butyl group, a sec-butylgroup and a tert-butyl group, and a more preferable oneincludes, for example, a methyl group, an ethyl group, a n-propylgroup, a n-butyl group and a tert-butyl group.
The lower haloalkyl group as the substituent includes one,wherein a part of or all of hydrogen atoms of the lower alkylgroup having generally 1 to 4 carbon atoms, preferably 1 to 2carbon atoms are substituted by a halogen atom (e.g. a fluorineatom, a chlorine atom, a bromine atom and an iodine atom), whichis specifically exemplified by the same as examples of the lowerhaloalkyl group as the substituent of the aryl group, the aralkylgroup or the aromatic heterocyclic group, which may have asubstituent, shown by R¹ in the above-described general formula[2], and among others, a preferable one includes, for example,a trifluoromethyl group and a pentafluoroethyl group, and a morepreferable one is a trifluoromethyl group.
The alkoxy group as the substituent may be straight chained,branched or cyclic, and includes one having generally 1 to 12carbon atoms, preferably 1 to 4 carbon atoms, which isspecifically exemplified by the same as examples of the alkoxygroup as the substituent of the aryl group, the aralkyl groupor the aromatic heterocyclic group, which may have a substituent,shown by R¹ in the above-described general formula [2] , and amongothers, a preferable one includes, for example, a methoxy group,an ethoxy group, a n-propoxy group, an isopropoxy group, an-butoxy group, a sec-butoxy group and a tert-butoxy group, anda more preferable one is a methoxy group.
The lower haloalkoxy group as the substituent includes one,wherein a part of or all of the hydrogen atoms of an alkoxy grouphaving generally 1 to 4 carbon atoms, preferably 1 to 2 carbonatoms are substituted by a halogen atom (e.g. a fluorine atom,a chlorine atom, a bromine atom and an iodine atom), which is specifically exemplified by the same as examples of the lowerhaloalkoxy group as the substituent of the aryl group, thearalkyl group or the aromatic heterocyclic group, which may havea substituent, shown by R¹ in the above-described general formula[2], and among others, a trifluoromethoxy group is preferable.
The lower alkenyl group as the substituent may be straightchained, branched or cyclic, and includes one having generally2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, which isspecifically exemplified by the same as examples of the loweralkenyl group as the substituent of the aryl group, the aralkylgroup or the aromatic heterocyclic group, which may have asubstituent, shown by R¹ in the above-described general formula[2], and among others, a vinyl group is preferable.
The alkyl group having 1 to 12 carbon atoms, as thesubstituent of the aryl group which may have a substituent, shownby R⁴ in the general formula [6] , when R³ in the general formula[5] is a group shown by the general formula [6], and A₂ is adirect-linkage or a -C(CF₃)₂- group, may be straight chained,branched or cyclic, and includes one having preferably 3 to 8carbon atoms, which is specifically exemplified by the same asexamples of the alkyl group having 1 to 12 carbon atoms, shownby R¹ in the above-described general formula [2] , and among others,a preferable one includes, for example, a n-propyl group, anisopropyl group, a n-butyl group, a sec-butyl group, a tert-butylgroup, a n-pentyl group, an isopentyl group, a sec-pentyl group,a tert-pentyl group, a n-hexyl group, a sec-hexyl group, atert-hexyl group, a n-heptyl group, a sec-heptyl group, atert-heptyl group, a n-octyl group, a sec-octyl group, atert-octyl group and a cyclohexyl group, and a more preferableone includes, for example, a n-propyl group, an isopropyl group,a n-butyl group, a sec-butyl group and a tert-butyl group.
The alkyl group having 2 to 12 carbon atoms as thesubstituent of the aryl group which may have a substituent, shownby R⁴ in the general formula [6] , when R³ in the general formula[5] is a group shown by the general formula [6], and A₂ is an-O- group, may be straight chained, branched or cyclic, and includes one having preferably 3 to 12 carbon atoms, morepreferably 3 to 8 carbon atoms, which is specifically exemplifiedby the same as examples of the alkyl group having 1 to 12 carbonatoms, shown by R¹ in the above-described general formula [2] ,and among others, a preferable one includes, for example, an-propyl group, an isopropyl group, a n-butyl group, a sec-butylgroup, a tert-butyl group, a n-pentyl group, an isopentylgroup, a sec-pentyl group, a tert-pentyl group, a n-hexyl group,a sec-hexyl group, a tert-hexyl group, a n-heptyl group, asec-heptyl group, a tert-heptyl group, a n-octyl group, asec-octyl group, a tert-octyl group and a cyclohexyl group, anda more preferable one includes, for example, a n-propyl group,an isopropyl group, a n-butyl group, a sec-butyl group and atert-butyl group.
The alkoxy group as the substituent of the aryl group whichmay have a substituent, shown by R⁴ in the general formula [6],when R³ in the general formula [5] is a group shown by the generalformula [6], may be straight chained, branched or cyclic,includes one having generally 1 to 12 carbon atoms, preferably3 to 6 carbon atoms, which is specifically exemplified by thesame as examples of the alkoxy group having 1 to 12 carbon atomsas the substituent of the aryl group, the aralkyl group or thearomatic heterocyclic group, which may have a substituent, shownby R¹ in the above-described general formula [2] , and among others,a preferable one includes, for example, a n-propoxy group, anisopropoxy group, a n-butoxy group, an isobutoxy group, asec-butoxy group, a n-pentyloxy group, a sec-pentyloxy group,a tert-pentyloxy group, a n-hexyloxy group, a sec-hexyloxy group,a tert-hexyloxy group and a cyclohexyloxy group, and a morepreferable one includes, for example, a n-propoxy group, anisopropoxy group, a n-butoxy group, a sec-butoxy group and atert-butoxy group.
In the general formula [4], the tetra-valent alicyclichydrocarbon group having 4 to 10 carbon atoms, shown by A₃includes the same as examples of the tetra-valent alicyclichydrocarbon group having 4 to 10 carbon atoms, shown by A₁ in the above-described general formula [1].
The tetra-valent bridged alicyclic hydrocarbon grouphaving 7 to 8 carbon atoms, shown by A₃ includes the same asexamples of the tetra-valent bridged alicyclic hydrocarbongroup having 7 to 8 carbon atoms, shown by A₁ in the above-describedgeneral formula [1], and among others, the one shownby the above-described formula [8] is preferable.
The tetra-valent aromatic hydrocarbon group having 6 to14 carbon atoms, shown by A₃ includes the same as examples ofthe tetra-valent aromatic hydrocarbon group having 6 to 14 carbonatoms, shown by A₁ in the above-described general formula [1] ,and among others, the one shown by the above-described generalformula [9] is preferable.
The bisimidesulfonate compound shown by the above-describedgeneral formula [4], when A₁ is a tetra-valentalicyclic hydrocarbon group having 4 to 10 carbon atom, includespreferably one shown by the general formula [10]:
(wherein R⁷s are each independently an alkyl group having 1 to12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms,or an aryl group, an aralkyl group or an aromatic heterocyclicgroup, which may have a substituent selected from the groupconsisting of a halogen atom, an alkyl group, a lower haloalkylgroup, an alkoxy group, a lower haloalkoxy group, a lower alkenylgroup, a nitro group, an N, N-dimethylamino group and an acetamidegroup, a camphor group or a naphthoquinonediazide group; R⁵ andR⁶ are the same as described above) and the like, and when A₁is a tetra-valent bridged alicyclic hydrocarbon group having7 to 8 carbon atoms, includes preferably one shown by the generalformula [11]:
(wherein R⁸ is an alkyl group having 6 to 12 carbon atoms, ahaloalkyl group having 1 to 12 carbon atoms, or an aryl group,an aralkyl group or an aromatic heterocyclic group, which mayhave a substituent selected from the group consisting of ahalogen atom, an alkyl group, a lower haloalkyl group, an alkoxygroup, a lower haloalkoxy group, a lower alkenyl group, a nitrogroup, an N,N-dimethylamino group and an acetamide group, acamphor group or a naphthoquinonediazide group) and the like,and further when A₁ is a tetra-valent aromatic hydrocarbon group,includes preferably one shown by the general formula [12]:
(wherein R⁹ is an alkyl group having 3 to 12 carbon atoms, ahaloalkyl group having 1 to 12 carbon atoms, or an aryl group,an aralkyl group or an aromatic heterocyclic group, which mayhave a substituent selected from the group consisting of ahalogen atom, an alkyl group, a lower haloalkyl group, an alkoxygroup, a lower haloalkoxy group, a lower alkenyl group, a nitrogroup, an N,N-dimethylamino group and an acetamide group, acamphor group or a naphthoquinonediazide group) and the like.
In the general formula [10], the alkyl group having 1 to12 carbon atoms, shown by R⁷ may be straight chained, branchedor cyclic, and includes one having generally 1 to 10 carbon atoms,preferably 6 to 8 carbon atoms, which is specifically exemplifiedby the same as examples of the alkyl group having 1 to 12 carbonatoms, shown by R¹ in the above-described general formula [2],and among others, a preferable one includes, for example, amethyl group, an ethyl group, a n-propyl group, an isopropylgroup, a n-butyl group, a sec-butyl group, a tert-butyl group,a n-pentyl group, a sec-pentyl group, a tert-pentyl group, a n-hexyl group, a sec-hexyl group, a tert-hexyl group, a n-heptylgroup, a sec-heptyl group, a tert-heptyl group, a n-octyl group,a sec-octyl group, a tert-octyl group, a n-nonyl group, asec-nonyl group, a tert-nonyl group, a n-decyl group, a sec-decylgroup, a tert-decyl group, a cyclopentyl group and a cyclohexylgroup, and among others, a more preferable one includes, forexample, a n-hexyl group, a n-heptyl group and a n-octyl group.
In the general formula [11] , the alkyl group having 6 to12 carbon atoms, shown by R⁸ may be straight chained, branchedor cyclic, and includes one having preferably 6 to 8 carbon atoms,which is specifically exemplified by the same as examples ofone having 6 to 12 carbon atoms among the alkyl groups having1 to 12 carbon atoms, shown by R¹ in the above-described generalformula [2], and among others, a preferable one includes, forexample, a n-hexyl group, a sec-hexyl group, a tert-hexyl group,a n-heptyl group, a sec-heptyl group, a tert-heptyl group, an-octyl group, a sec-octyl group, a tert-octyl group and acyclohexyl group, and a more preferable one includes, for example,a n-hexyl group, a n-heptyl group and a n-octyl group.
In the general formula [12], the alkyl group having 3 to12 carbon atoms, shown by R⁹ may be straight chained, branchedor cyclic, and includes one having preferably 6 to 8 carbon atoms,which is specifically exemplified by the same as examples ofone having 3 to 12 carbon atoms among the alkyl groups having1 to 12 carbon atoms, shown by R¹ in the above-described generalformula [2], and among others, a preferable one includes, forexample, a n-hexyl group, a sec-hexyl group, a tert-hexyl group,a n-heptyl group, a sec-heptyl group, a tert-heptyl group, an-octyl group, a sec-octyl group, a tert-octyl group and acyclohexyl group, and a more preferable one includes, for example,a n-hexyl group, a n-heptyl group and a n-octyl group.
In the general formulae [10] to [12], the haloalkyl grouphaving 1 to 12 carbon atoms, shown by R¹ to R⁹ includes one, whereina part of or all of the hydrogen atoms, preferably 1 to 17 hydrogenatoms and more preferably 7 to 17 hydrogen atoms of the alkylgroup having 1 to 12 carbon atom, shown by R¹ in the above-described general formula [2] are substituted by a halogen atom(e.g. a fluorine atom, a chlorine atom, a bromine atom and aniodine atom), one having preferably 1 to 8 carbon atoms, morepreferably 3 to 8 carbon atoms, which is specifically exemplifiedby the same as examples of the haloalkyl group having 1 to 12carbon atoms, shown by R¹ in the above-described general formula[2], and among others, a preferable one includes, for example,a trifluoromethyl group, a nonafluorobutyl group and aheptadecafluorooctyl group, and a more preferable one is anonafluorobutyl group.
The aryl group of the aryl group which may have asubstituent, shown by R⁷ to R⁹, includes one having generally6 to 16 carbon atoms, preferably 6 to 10 carbon atoms, whichis specifically exemplified by the same as examples of the arylgroup of the aryl group which may have a substituent, shown byR¹ in the above-described general formula [2] , and among others,a preferable one includes, for example, a phenyl group and anaphthyl group, and a phenyl group is more preferable.
The aralkyl group of the aralkyl group which may have asubstituent, shown by R⁷ to R⁹, includes one having generally7 to 10 carbon atoms, preferably 7 to 8 carbon atoms, which isspecifically exemplified by the same as examples of the aralkylgroup of the aralkyl group which may have a substituent, shownby R¹ in the above-described general formula [2] , and among others,a benzyl group is preferable.
The aromatic heterocyclic group of the aromaticheterocyclic group which may have a substituent, shown by R⁷ toR⁹, includes one having at least 1 hetero atom, preferably 1 to3 hetero atoms such as a nitrogen atom, a sulfur atom and anoxygen atom, and may be a monocyclic or a bicyclic group, whichis specifically exemplified by the same as examples of thearomatic heterocyclic group of the aromatic heterocyclic groupwhich may have a substituent, shown by R¹ in the above-describedgeneral formula [2], and among others, a preferable one is a2-thienyl group.
The substituent of the aryl group, the aralkyl group or the aromatic heterocyclic group, which may have a substituent,shown by R⁷ to R⁹ includes, for example, a halogen atom, an alkylgroup, a lower haloalkyl group, an alkoxy group, a lowerhaloalkoxy group, a lower alkenyl group, a nitro group, aN,N-dimethylamino group and an acetamide group.
The halogen atom as the substituent includes, for example,a fluorine atom, a chlorine atom, a bromine atom and an iodineatom, and among others, a preferable one includes a fluorineatom and a chlorine atom, and a fluorine atom is more preferable.
The alkyl group as the substituent may be straight chained,branched or cyclic, and includes one having generally 1 to 12carbon atoms, preferably 1 to 4 carbon atoms, which isspecifically exemplified by the same as examples of the alkylgroup as the substituent of the aryl group, the aralkyl groupor the aromatic heterocyclic group, which may have a substituent,shown by R¹ in the above-described general formula [2], and amongothers, a preferable one includes, for example, a methyl group,an ethyl group, a n-propyl group, an isopropyl group, a n-butylgroup, a sec-butyl group and a tert-butyl group, and a morepreferable one includes, for example, a methyl group, an ethylgroup, a n-propyl group, a n-butyl group and a tert-butyl group.
The lower haloalkyl group as the substituent includes one,wherein a part of or all of hydrogen atoms of the lower alkylgroup having generally 1 to 4 carbon atoms, preferably 1 to 2carbon atoms are substituted by a halogen atom (e.g. a fluorineatom, a chlorine atom, a bromine atom and an iodine atom) , whichis specifically exemplified by the same as examples of the lowerhaloalkyl group as the substituent of the aryl group, the aralkylgroup or the aromatic heterocyclic group, which may have asubstituent, shown by R¹ in the general formula [2], and amongothers, a preferable one includes, for example, atrifluoromethyl group and a pentafluoroethyl group, and atrifluoromethyl group is more preferable.
The alkoxy group as the substituent maybe straight chained,branched or cyclic, and includes one having generally 1 to 12carbon atoms, preferably 1 to 4 carbon atoms, which is specifically exemplified by the same as examples of the alkoxygroup as the substituent of the aryl group, the aralkyl groupor the aromatic heterocyclic group, which may have a substituent,shown by R¹ in the above-described general formula [2] , and amongothers, a preferable one includes, for example, a methoxy group,an ethoxy group, a n-propoxy group, an isopropoxy group, an-butoxy group, a sec-butoxy group and a tert-butoxy group, anda methoxy group is more preferable.
The lower haloalkoxy group as the substituent includes one,wherein a part of or all of the hydrogen atoms of an alkoxy grouphaving generally 1 to 4 carbon atoms, preferably 1 to 2 carbonatoms are substituted by a halogen atom (e.g. a fluorine atom,a chlorine atom, a bromine atom and an iodine atom), which isspecifically exemplified by the same as examples of the lowerhaloalkoxy group as the substituent of the aryl group, thearalkyl group or the aromatic heterocyclic group, which may havea substituent, shown by R¹ in the above-described general formula[2] , and among others, a trifluoromethoxy group is preferable.
The lower alkenyl group as the substituent may be straightchained, branched or cyclic, and includes one having generally2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, which isspecifically exemplified by the same as examples of the loweralkenyl group as the substituent of the aryl group, the aralkylgroup or the aromatic heterocyclic group, which may have asubstituent, shown by R¹ in the above-described general formula[2], and among others, a vinyl group is preferable.
The two R⁷s to R⁹s in the general formulae [10] to [12]may be different, but are preferably the same.
Among these R⁷s to R⁹s, a preferable one includes, forexample, a haloalkyl group, an aryl group or an aromaticheterocyclic group which may have a substituent, and a camphorgroup, and a more preferable one includes a haloalkyl group,an aryl group which may have a substituent and a camphor group.
In the general formula [10] , the aliphatic ring comprisingR⁵ and R⁶ includes, for example, a cyclobutane ring, acyclopentane ring, a cyclohexane ring, a cycloheptane ring and a cyclooctane ring, and among others, a preferable one includesa cyclobutane ring and a cyclopentane ring.
The bisphthalimide compound shown by the above-describedgeneral formula [5] includes, when R³ is a hydrogen atom,preferably a bis(N-hydroxy) phthalimide compound shown by thegeneral formula [25]:
(wherein A₂ is the same as described above) and the like, andwhen R³ is a group shown by the general formula [6], preferablya bisphthalimidesulfonate compound, shown by the generalformula [26] :
(wherein definitions of R⁴, A₂ and others are the same as describedabove) and the like.
The bisphthalimidesulfonate compound shown by theabove-described general formula [26] includes, when A₂ is an -O- group, one shown by the general formula [13]:
(wherein R¹⁰s are each independently an alkyl group having 1 to12 carbon atoms, a haloalkyl group having 3 to 12 carbon atoms,an aryl group which may have a substituent selected from thegroup consisting of a halogen atom, an alkyl group having 2 to12 carbon atoms, a lower haloalkyl group, an alkoxy group, alower haloalkoxy group, a lower alkenyl group, a nitro group,an N,N-dimethylamino group and an acetamide group, an aralkylgroup or an aromatic heterocyclic group, which may have asubstituent selected from the group consisting of a halogen atom, an alkyl group, a lower haloalkyl group, an alkoxy group, a lowerhaloalkoxy group, a lower alkenyl group, a nitro group, anN,N-dimethylamino group and an acetamide group, a camphor groupor a naphthoquinonediazide group) , and when A₂ is a -C (CF₃) ₂- group,one shown by the general formula [14]:
(wherein R¹¹s are each independently an alkyl group having 1 to12 carbon atoms, a haloalkyl group having 3 to 12 carbon atoms,or an aryl group, an aralkyl group or an aromatic heterocyclicgroup, which may have a substituent selected from the groupconsisting of a halogen atom, an alkyl group, a lower haloalkylgroup, an alkoxy group, a lower halbalkoxy group, a lower alkenylgroup, a nitro group, an N, N-dimethylamino group and an acetamidegroup, a camphor group or a naphthoquinonediazide group), andfurther, when A₂ is a direct-linkage, one shown by the generalformula [15] :
(wherein R¹¹s are the same as described above).
In the general formulae [13] to [15], the alkyl grouphaving 1 to 12 carbon atoms, shown by R¹⁰ to R¹¹ may be straightchained, branched or cyclic, and includes one having preferably1 to 10 carbon atoms, more preferably 6 to 8 carbon atoms, whichis specifically exemplified by the same as examples of the alkylgroup having 1 to 12 carbon atoms, shown by R¹ in the generalformula [2], and among others, a preferable one includes, forexample, a methyl group, an ethyl group, a n-propyl group, anisopropyl group, a n-butyl group, a sec-butyl group, a tert-butylgroup, a n-pentyl group, a sec-pentyl group, a tert-pentyl group,a n-hexyl group, a sec-hexyl group, a tert-hexyl group, an-heptyl group, a sec-heptyl group, a tert-heptyl group, a n-octyl group, a sec-octyl group, a tert-octyl group, a n-nonylgroup, a sec-nonyl group, a tert-nonyl group, a n-decyl group,a sec-decyl group, a tert-decyl group, a cyclopentyl group anda cyclohexyl group, and a more preferable one includes, forexample, a n-hexyl group, a n-heptyl group and a n-octyl group.
In the general formulae [13] to [15], the haloalkyl grouphaving 3 to 12 carbon atoms, shown by R¹⁰ and R¹¹ includes one,wherein a part of or all of the hydrogen atoms, preferably 1to 17 hydrogen atoms and more preferably 7 to 17 hydrogen atomsof the alkyl group having 3 to 12 carbon atoms, preferably theone having 3 to 8 carbon atoms, among the alkyl groups having1 to 12 carbon atoms, shown by R¹ in the above-described generalformula [2], are substituted by a halogen atom (e.g. a fluorineatom, a chlorine atom, a bromine atom and an iodine atom) , whichis specifically exemplified by the same as examples of one having3 to 12 carbon atoms among the haloalkyl groups having 1 to 12carbon atoms, shown by R¹ in the general formula [2] , and amongothers, a preferable one includes, for example, anonafluorobutyl group and a heptadecafluorooctyl group, and amore preferable one is a nonafluorobutyl group.
The aryl group of the aryl group which may have asubstituent, shown by R¹⁰ and R¹¹ includes one having generally6 to 16 carbon atoms, preferably 6 to 10 carbon atoms, whichis specifically exemplified by the same as examples of the arylgroup of the aryl group which may have a substituent, shown byR¹ in the above-described general formula [2] , and among others,a preferable one includes, for example, a phenyl group and anaphthyl group, and a phenyl group is more preferable.
The aralkyl group of the aralkyl group which may have asubstituent, shown by R¹⁰ and R¹¹ includes one having generally7 to 10 carbon atoms, preferably 7 to 8 carbon atoms, which isspecifically exemplified by the same as examples of the aralkylgroup of the aralkyl group which may have a substituent, shownby R¹ in the above-described general formula [2] , and among others,a preferable one is a benzyl group.
The aromatic heterocyclic group of the aromatic heterocyclic group which may have a substituent, shown by R¹⁰and R¹¹ includes one having at least 1 hetero atom, preferably1 to 3 hetero atoms such as a nitrogen atom, a sulfur atom andan oxygen atom, and may be a monocyclic or a bicyclic group,which is specifically exemplified by the same as examples ofthe aromatic heterocyclic group of the aromatic heterocyclicgroup which may have a substituent, shown by R¹ in theabove-described general formula [2], and among others, apreferable one is a 2-thienyl group.
The substituent of the aryl group, the aralkyl group orthe aromatic heterocyclic group, which may have a substituent,shown by R¹⁰ and R¹¹ includes, for example, a halogen atom, analkyl group, a lower haloalkyl group, an alkoxy group, a lowerhaloalkoxy group, a lower alkenyl group, a nitro group, aN,N-dimethylamino group and an acetamide group.
The halogen atom as the substituent includes, for example,a fluorine atom, a chlorine atom, a bromine atom and an iodineatom, and among others, a preferable one includes, for example,a fluorine atom and a chlorine atom, and a fluorine atom is morepreferable.
The alkyl group having 2 to 12 carbon atoms as thesubstituent of the aryl group which may have a substituent; shownby R¹⁰, may be straight chained, branched or cyclic, and is notparticularly limited as long as it has high solubility in asolvent, and includes one having preferably 3 to 12 carbon atoms,more preferably 3 to 8 carbon atoms, which is specificallyexemplified by the same as examples of one having 2 to 12 carbonatoms, among the alkyl groups having 1 to 12 carbon atoms, shownby R¹ in the above-described general formula [2], and among others,a preferable one includes, for example, a n-propyl group, anisopropyl group, a n-butyl group, a sec-butyl group, a tert-butylgroup, a n-pentyl group, an isopentyl group, a sec-pentyl group,a tert-pentyl group, a n-hexyl group, a sec-hexyl group, atert-hexyl group, a n-heptyl group, a sec-heptyl group, atert-heptyl group, a n-octyl group, a sec-octyl group, atert-octyl group and a cyclohexyl group, and a more preferable one includes, for example, a n-propyl group, an isopropyl group,a n-butyl group, a sec-butyl group and a tert-butyl group.
The alkyl group as the substituent of an aryl group whichmay have a substituent, shown by R¹¹, and the aralkyl group orthe aromatic heterocyclic group, which may have a substituentshown by R¹⁰ and R¹¹, may be straight chained, branched or cyclic,and includes one having generally 1 to 12 carbon atoms,preferably 3 to 8 carbon atoms, which is specifically exemplifiedby the same as examples of the alkyl group having 1 to 12 carbonatoms, shown by R¹ in the above-described general formula [2],and among others, a preferable one includes, for example, an-propyl group, an isopropyl group, a n-butyl group, a sec-butylgroup, a tert-butyl group, a n-pentyl group, an isopentylgroup, a sec-pentyl group, a tert-pentyl group, a n-hexyl group,a sec-hexyl group, a tert-hexyl group, a cyclohexyl group, an-heptyl group, a sec-heptyl group, a tert-heptyl group, an-octyl group, a sec-octyl group and a tert-octyl group, anda more preferable one includes, for example, a n-propyl group,an isopropyl group, a n-butyl group, a sec-butyl group and atert-butyl group.
The lower haloalkyl group as the substituent of the arylgroup, the aralkyl group or the aromatic heterocyclic group,which may have a substituent, shown by R¹⁰ and R¹¹ includes one,wherein a part of or all of the hydrogen atoms of the lower alkylgroup having generally 1 to 4 carbon atoms, preferably 1 to 2carbon atoms are substituted by a halogen atom (e.g. a fluorineatom, a chlorine atom, a bromine atom and an iodine atom) , whichis specifically exemplified by the same as examples of the lowerhaloalkyl group as the substituent of the aryl group which mayhave a substituent, shown by R¹ in the above-described generalformula [2], and among others, a preferable one is atrifluoromethyl group.
The alkoxy group as the substituent of the aryl group, thearalkyl group or the aromatic heterocyclic group, which may havea substituent, shown by R¹⁰ and R¹¹ may be straight chained,branched or cyclic, and includes one having generally 1 to 12 carbon atoms, preferably 3 to 6 carbon atoms, which isspecifically exemplified by the same as examples of the alkoxygroup as the substituent of the aryl group which may have asubstituent, shown by R¹ in the above-described general formula[2], and among others, a preferable one includes, for example,a n-propoxy group, an isopropoxy group, a n-butoxy group, asec-butoxy group and a tert-butoxy group.
The lower haloalkoxy group as the substituent of the arylgroup, the aralkyl group or the aromatic heterocyclic group whichmay have a substituent, shown by R¹⁰ and R¹¹ includes one, whereina part of or all of the hydrogen atoms of the alkoxy group havinggenerally 1 to 4 carbon atoms, preferably 1 to 2 carbon atomsare substituted by a halogen atom (e.g. a fluorine atom, achlorine atom, a bromine atom and an iodine atom), which isspecifically exemplified by the same as examples of the lowerhaloalkoxy group as the substituent of the aryl group which mayhave a substituent, shown by R¹ in the above-described generalformula [2], and among others, a trifluoromethoxy group ispreferable.
The lower alkenyl group as the substituent of the arylgroup, the aralkyl group or the aromatic heterocyclic group,which may have a substituent, shown by R¹⁰ and R¹¹ may be straightchained, branched or cyclic, and includes one having generally2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, which isspecifically exemplified by the same as examples of the loweralkenyl group as the substituent of the aryl group which mayhave a substituent, shown by R¹ in the above-described generalformula [2], and among others, a vinyl group is preferable.
Among these substituents, an electron-withdrawing groupsuch as a halogen atom, a trifluoromethyl group and a nitro atomis preferable.
The aryl group which may have a substituent, shown by R¹⁰and R¹¹ is preferably one having at least one electron-withdrawinggroup at m-position or p-position, and among others,one having an electron-withdrawing group at m-position is morepreferable, which is specifically exemprified by, for example, a m-trifluoromethylphenyl group, a p-trifluoromethylphenylgroup, a 3,5-ditrifluoromethylphenyl group and apentafluorophenyl group.
Among these R¹⁰ and R¹¹, a preferable one includes, forexample, a haloalkyl group, an aryl group which may have asubstituent, an aromatic heterocyclic group which may have asubstituent and a camphor group, and among others, a morepreferable one includes, a haloalkyl group, an aryl group whichmay have a substituent and a camphor group.
The two R¹⁰ and R¹¹ in the general formulae [13] to [15]are may be different, but preferably the same.
The specific examples among the compounds shown by thegeneral formula [10], wherein an aliphatic ring is a cyclobutanering, include, for example, tetrahydro-2,5-bis(methanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(ethanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(n-propanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(isopropanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(n-butanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(n-octanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(cyclohexylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(decanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(trichloromethanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(trifluoromethanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(2,2,2-trifluoroethanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(nonafluorobutanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone, tetrahydro-2,5-bis(heptadecafluorooctanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6 (2H,5H)-tetrone, tetrahydro-2,5-bis(10-camphorsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(2-thiophenesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(benzylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(phenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(4-methylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(4-ethylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(2,5-dimethylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(2,4,6-trimethylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone, tetrahydro-2,5-bis(4-ethenylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(4-methoxyphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(4-dodecylbenzenesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(3,4-dimethoxyphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone, tetrahydro-2,5-bis(2,4,6-trimethoxyphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(4-trifluoromethoxyphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-2,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(4-trifluoromethylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(3-trifluoromethylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(2-trifluoromethylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone, tetrahydro-2,5-bis(3,5-di-trifluoromethylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(4-chlorophenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(4-bromophenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(4-iodophenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(4-fluorophenylsulfonyloxy)cyclobutaEl,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(2,5-dichlorophenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(2,4,5-trichlorophenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(pentafluorobenzenesulfonyloxy)cyclobuta(1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(4-nitrophenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(4-acetamidephenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(1-naphthalenesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(2-naphthalenephenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(2,1-naphthoquinonediazide-4-sulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(2,1-naphthoquinonediazide-5-sulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(4-N,N-dimethylaminonaphthalene-5-sulfonyloxy)cyclobuta-[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetroneandtetrahydro-2,5-bis(quinoline-8-sulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-l,3,4,6(2H,5H)-tetrone,and among others,a preferable one includes, for example, tetrahydro-2,5-bis(nonafluorobutanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone, tetrahydro-2,5-bis(heptadecafluorooctanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(10-camphorsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(4-trifluoromethylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(3-trifluoromethylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,tetrahydro-2,5-bis(3,5-di-trifluoromethylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetroneand tetrahydro-2,5-bis(pentafluorobenzenesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone.
The specific examples among the compounds shown by thegeneral formula [10] , wherein an aliphatic ring is a cyclopentanering include, for example, hexahydro-2,6-bis(methanesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(ethanesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(isopropylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(n-butanesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(n-octanesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(cyclohexylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(decanesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(trichloromethanesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(trifluoromethanesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(2,2,2-trifluoroethanesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, hexahydro-2,6-bis(nonafluorobutanesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, hexahydro-2,6-bis(heptadecafluorooctanesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(10-camphorsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, hexahydro-2,6-bis(2-thiophenesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(benzylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(phenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(4-methylphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(4-ethylphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(2,5-dimethylphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(2,4,6-trimethylphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(4-ethenylphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(4-methoxyphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(4-dodecylbenzenesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(3,4-dimethoxyphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(2,4,6-trimethoxyphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(4-trifluoromethoxyphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-l,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(4-trifluoromethylphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(3-trifluoromethylphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(2-trifluoromethylphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, hexahydro-2,6-bis(3,5-di-trifluoromethylphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, hexahydro-2,6-bis(4-chlorophenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(4-bromophenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(4-iodophenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(4-fluorophenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(2,5-dichlorophenylsulfonyloxy)cyclopenta(1,2-c:4,5-c'Jdipyrrole-1,3,5,7(2H.6H)-tetrone,hexahydro-2,6-bis(2,4,5-trichlorophenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(pentafluorobenzenesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(4-nitrophenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(4-acetamidephenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(1-naphthalenesulfonyloxy)cyclopenta[1,2-c:4,5-c'Jdipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(2-naphthalenelsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(2,1-naphthoquinonediazide-4-sulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(2,1-naphthoquinonediazide-5-sulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(4-N,N-dimethylaminonaphthalene-5-sulfonyloxy)cyclopenta-[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetroneand hexahydro-2,6-bis(quinoline-8-sulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,and among others, apreferable one includes, for example, hexahydro-2,6-bis(nonafluorobutanesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, hexahydro-2,6-bis(heptadecafluorooctanesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(10-camphorsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(4-trifluoromethylphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(3-trifluoromethylphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,hexahydro-2,6-bis(3,5-di-trifluoromethylphenylsulfonyloxy)cyclopenta[1,.2-c:4,5-c']dipyxrole-1,3,5,7(2H,6H)-tetroneand hexahydro-2,6-bis(pentafluorobenzenesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone.
The specific examples among the compounds shown by thegeneral formula [10] , wherein an aliphatic ring is a cyclohexanering include, for example, octahydro-2,6-bis(methanesulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(ethanesulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(isopropylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(n-butanesulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(n-octanesulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(cyclohexylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, octahydro-2,6-bis(decanesulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(trichloromethanesulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(trifluoromethanesulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, octahydro-2,6-bis(2,2,2-trifluoroethanesulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(nonafluorobutanesulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H, 6H)-tetrone, octahydro-2,6-bis(heptadecafluorooctanesulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, octahydro-2,6-bis(10-camphorsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(2-thiophenesulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(benzylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(phenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(4-methylphenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(4-ethylphenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(2,5-dimethylphenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(2,4,6-trimethylphenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(4-ethenylphenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(4-methoxyphenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(4-dodecylbenzenesulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(3,4-dimethoxyphenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(2,4,6-trimethoxyphenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(4-trifluoromethoxyphenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(4-trifluoromethylphenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3.5,7(2H,6H)-tetrone,octahydro-2,6-bis(3-trifluoromethylphenylsulfonyloxy)cyclohexa[2,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(2-trifluoromethylphenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, octahydro-2,6-bis(3,5-di-trifluoromethylphenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(4-chlorophenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(4-bromophenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(4-iodophenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(4-fluorophenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(2,5-dichlorophenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(2,4,5-trichlorophenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(pentafluorobenzenesulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(4-nitrophenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(4-acetamidephenylsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(1-naphthalenesulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(2-naphthalenelsulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(2,1-naphthoquinonediazide-4-sulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(2,1-naphthoquinonediazide-5-sulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,octahydro-2,6-bis(4-N,N-dimethylaminonaphthalene-5-sulfonyloxy)cyclohexa-[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetroneand octahydro-2,6-bis(quinoline-8-sulfonyloxy)cyclohexa[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone.
The specific examples of the compounds shown by the generalformula [11] include, for example, 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(n-hexanesulfonyloxy)-4,8-ethenobenzo[1,2-c:4.5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(n-octanesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(cyclohexylsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(decanesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(trichloromethanesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrane,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(trifluoromethanesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-2,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(2,2,2-trifluoroethanesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(nonafluorobutanesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c')dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(heptadecafluorooctanesulfonyloxy)-4,8-ethenobenzo(1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(10-camphorsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(2-thiophenesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(benzylsulfonyloxy)-4,8-ethenobenzo(1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(phenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-methylphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-ethylphenysulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(2,5-dimethylphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(2,4,6-trimethylphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-ethenylphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-methoxyphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-dodecylbenzenesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(3,4-dimethoxyphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c')dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(2,4,6-trimethoxyphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5.7(2H,6H)-tetrone,a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-trifluoromethoxyphenylsulfonyloxy)-4,8-ethenobenzo(1,2-c:3,4-c')dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-trifluoromethylphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(3-trifluoromethylphenylsulfonyloxy)-4,8-ethenobenzo(1,2-c:3,4-c')dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(2-trifluoromethylphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(3,5-di-trifluoromethylphenylsulfonyloxy)-4,8-ethenobenzo(1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-chlorophenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone;3a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-bromophenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-iodolphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-fluorophenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(2,5-dichlorophenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(2,4,5-trichlorophenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(pentafluorobenzenesulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-nitrolphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-acetamidephenylsulfonyloxy)-4,8-ethenobenzo(1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(1-naphthalenesulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(2-naphthalenesulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(2,1-naphthoquinonediazide-4-sulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(2,1-naphthoquinonediazide-5-sulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-N,N-dimethylaminonaphthalenesulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetroneand3a,4,4a,7a,8,8a-hexahydro-2,6-bis(quinoline-8-sulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,and among others, a preferable one includes, for example,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(nonafluorobutanesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(heptadecafluorooctanesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(10-camphorsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-trifluoromethylphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(3-trifluoromethylphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,3a,4,4a,7a,8,8a-hexahydro-2,6-bis(3,5-di-trifluoromethylphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetroneand3a,4,4a,7a,8,8a-hexahydro-2,6-bis(pentafluorobenzenesulfonyloxy)-4,8-ethenobenzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone.
The specific examples of the compounds shown by thegeneral formula [12] include, for example, 2,6-bis(isopropylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(n-butanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(n-octanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(cyclohexylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(decanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(trichloromethanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(trifluoromethanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(2,2,2-trifluoroethanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H) - tetrone, 2,6-bis(nonafluorobutansulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(heptadecafluorooctanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-,3,5,7(2H,6H)-tetrone,2,6-bis(10-camphorsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5-,7(2H,6H)-tetrone, 2,6-bis(2-thiophenesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3, 5, 7 (2H,6H)-tetrone, 2, 6-bis(benzylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(phenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(4-methylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(4-ethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(2,5-dimethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(2,4,6-trimethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(4-ethenylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrxole-1,3,5,7(2H,6H)-tetrone,2,6-bis(4-methoxyphenylsulfonyloxy)benzo[l,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(4-dodecylbenzenesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(3,4-dimethoxyphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(2,4,6-trimethoxyphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(4-trifluoromethoxyphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(4-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(3-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(2-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(3,5-di-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(4-chlorophenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, 2,6-bis(4-bromophenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(4-iodophenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(4-fluorophenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, 2,6-bis(2,5-dichlorophenylsulfonyloxy)benzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(2,4,5-trichlorophenylsulfonyloxy)benzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(pentafluorobenzenesulfonyloxy)benzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(4-nitrophenylsulfonyloxy)benzo[1.2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(4-acetamidephenylsulfonyloxy)benzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(1-naphthalenesulfonyloxy)benzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(2-naphthalenesulfonyloxy)benzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(2,1-naphthoquinonediazide-4-sulfonyloxy)benzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(2,1-naphthoquinonediazide-5-sulfonyloxy)benzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, 2,6-bis(4-N,N-dimethylaminonaphthalene-5-sulfonyloxy)benzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetroneand 2,6-bis(quinoline-8-sulfonyloxy)benzo[1,2-c:3,4-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,and among others,a preferable one includes, for example, 2,6-bis(nonafluorobutansulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone;2,6-bis(heptadecafluorooctanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tet:rone,2,6-bis(10-camphorsulfonyloxy)benzo[2,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(4-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, 2,6-bis(3-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,2,6-bis(3,5-di-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetroneand 2,6-bis(pentafluorobenzenesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone.
The specific example of the compound shown by the generalformula [25] includes, for example, 5,5'-oxybis[2-hydroxy-1H-isoindole-1,3(2H)-dione].
The specific examples of the compounds shown by the generalformula [13] includes, for example, 5,5'-oxybis[2-methanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-ethanesulfonyloxy-1H-isoindole-1,3(2H)-dione),5,5'-oxybis[2-n-propanesulfonyloxy-2H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-isopropylsulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-n-butanesulfonyloxy-1H-isoindole-2,3(2H)-dione], 5,5'-oxybis[2-n-hexanesulfonyloxy-1H-isoindole-1,3(2H)-dione], 5,5'-oxybis[2-n-octanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-cyclohexylsulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-decanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-nonafluorobutanesulfonyloxy-1H-isoindole-1,3(2H)-dione),5,5'-oxybis[2-heptadecafluorooctanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(10-camphor)sulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis(2-benzylsulfanyloxy-1H-isoindole-1,3(2H)-dione), 5,5'-oxybis[2-phenylsulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(4-ethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(2,5-dimethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(2,4,6-trimethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(4-ethenylphenylsulfony)oxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(4-methoxyphenylsulfony)oxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(4-dodecylbenzenesulfonyl)oxy-1H-isoindale-1,3(2H)-dione], 5,5'-oxybis[2-(3,4-dimethoxyphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-oxybis[2-(2,4,6-trimethoxyphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(4-trifluoromethoxyphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-oxybis[2-(4-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione),5,5'-oxybis[2-(2-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3f(2H)-dione],5,5'-oxybis[2-(3,5-di-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(4-chlorophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-oxybis[2-(4-bromophenylsulfonyl)oxy-1H-isoiridole-1,3(2H)-dione],5,5'-oxybis[2-(4-iodophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(4-fluorophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-oxybis[2-(2,5-dichlorophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(2,4,5-trichlorophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-oxybis[2-(pentafluorobenzenesulfonyl)oxy-2H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(4-nitrophenylsulfonyl)oxy-lH-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(4-acetamidephenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(1-naphthalenesulfonyl)oxy-1H-isoindole-1,3(ZH)-dione],5,5'-oxybis[2-(2-naphthalenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(2-thienylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(2,1-naphthoquinonediazide-4-sulfonyl)oxy-1H-isoindole-1,3(2H)-dione), 5,5'-oxybis[2-(2,1-naphthoquinonediazide-5-sulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(4-N,N-dimethylaminonaphthalene-5-sulfonyl)oxy-1H-isoindole-1,3(2H)-dione]and 5,5'-oxybis[2-(quinoline-8-sulfonyl)oxy-1H-isoindole-1,3(2H)-dione],andamong others, a preferable one includes, for example, 5,5'-oxybis[2-nonafluorobutanesulfonyloxy-1H-isoindole-1,3(2H)-dione], 5,5'-oxybis[2-heptadecafluorooctanesulfonyloxy-1H-isoindole-1,3(2H)-dione], 5,5'-oxybis[2-(10-camphor)sulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis[2-(4-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-oxybis(2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5.5'-oxybis[2-(3,5-di-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione]and 5,5'-oxybis[2-(pentafluorobenzenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione].
The specific examples of the compounds shown by the generalformula [14] include, for example, 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-methanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-ethanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-n-prpanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-isopropylsulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis(2-n-butanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-n-hexanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-n-octanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-cyclohexylsulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-decanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-nonafluorobutanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis(2-heptadecafluorooctanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(10-camphorsulfonyl)oxy-1H-isoindole-2,3(2H)-dione], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-benzylsulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-phenylsulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-t:rifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-toluenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-ethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(2,5-dimethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(2,4,6-trimethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-ethenylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-dodecylbenzenelsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-methoxyphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(3,4-dimethoxyphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(2,4,6-trimethoxyphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-trifluoromethoxyphenylsulfonyl)oxy-1H-isoindole-2,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(2-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(3,5-di-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-chlorophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-bromophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-iodophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-fluorophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(2,5-dichlorophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(2,4,5-trichlorophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(pentafluorobenzenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl) ethylidene]bis[2-(4-nitrophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-2-(trifluoromethyl)ethylidene]bis[2-(4-acetamidephenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(1-naphthalenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(2-naphthalenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(2-thienylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(2,1-naphthoquinonediazide-4-sulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(2,1-naphthoquinonediazide-5-sulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-N,N-dimethylaminonaphthalene-5-sulfonyl)oxy-1H-isoindole-1,3(2H)-dione] and 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(quinoline-8-sulfonyl)oxy-1H-isoindole-1,3(2H)-dione], and among others, apreferable one includes, for example, 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-nonafluorobutanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-heptadecafluorooctanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(10-camphorsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(3,5-di-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione]and 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(pentafluorobenzenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione].
The specific examples of the compounds shown by the generalformula [15] include, for example, 5,5'-bis[2-methanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-ethanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-n-propanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-isopropylsulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-n-butanesulfonyloxy-2H-isoindole-1,3(2H)-dione],5,5'-bis[2-n-hexanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-n-octanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-cyclohexylsulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-decanesulfonyloxy-1H-isoindole-1,3(2H)-dione], 5,5'-bis[2-nonafluorobutanesulfonyloxy-1H-isoindole-1,3(2H)-dione], 5,5'-bis[2-heptadecafluorooctanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(10-camphorsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-benzylsulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-phenylsulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(4-toluenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-bis[2-(4-ethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(2,5-dimethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(2,4,6-trimethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-bis[2-(4-ethenylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(4-methoxyphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(4-dodecylbenzenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(3,4-dimethoxyphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(2,4,6-trimethoxyphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-bis[2-(4-trifluoromethoxyphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(4-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-bis[2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(2-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-bis[2-(3,5-di-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(4-chlorolphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-bis[2-(4-bromophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(4-iodophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(4-fluorophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(2,5-dichlorophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(2,4,5-trichlorophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(pentafluorobenzenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(4-nitrophenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-bis[2-(4-acetamidephenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(1-naphthalenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(2-naphthalenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(2-thienylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-bis[2-(2,1-naphthoquinoediazide-4-sulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(2,1-naphthoquinoediazide-5-sulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(4-N,N-dimethylaminonaphthalene-5-sulfonyl)oxy-1H-isoindole-1,3(2H)-dione]and 5,5'-bis[2-(quinoline-8-sulfonyl)oxy-1H-isoindole-1,3(2H)-dione], and among others, a preferable oneincludes, for example, 5,5'-bis[2-nonafluorobutanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-heptadecafluorooctanesulfonyloxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(10-camphorsulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-bis[2-(4-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione],5,5'-bis[2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione], 5,5'-bis[2-(3,5-di-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione]and 5,5'-bis[2-(pentafluorobenzenesulfonyl)oxy-1H-isoindole-1,3 2H)-dione].
The bisimidesulfonate compound of the present invention,shown by the general formula [4] is useful as an acid generatorfor a resist composition, and in particular, the compounds shownby the general formulae [11] and [12] are preferable, becausehigh sensitivity is expected due to high acid generationefficiency responsive to radiation, when they are used as anacid generator for a resist composition.
The bisphthalimidesulfonate compound of the presentinvention, shown by the general formula [26] is also useful asan acid generator for a resist composition, and in particular,the compounds shown by the general formulae [13] and [14] arepreferable, because high sensitivity is expected due to highacid generation efficiency responsive to radiation as well as high solubility in a solvent, when they are used as an acidgenerator for a resist composition.
The bisimidesulfonate compound, shown by the generalformula [4] can be synthesized, for example, by the followingmethods [A], [B] , [C] , [D] and the like.
Namely, in the method [A], 1 mole of an acid anhydrideshown by the following general formula [16]:
(wherein A₃ is the same as described above) and 1 to 5 mole partsof a hydroxylamine or a salt thereof (e.g. a hydrochloride saltand a sulfate salt) are dissolved in a solvent such as toluene,acetone, N,N-dimethylformamide and N,N-dimethylacetamide, inthe presence of a basic compound such as pyridine, triethylamineand tributylamine, followed by reacting at 0 to 100 °C for 0.5to 10 hours with stirring and post-treatment in accordance witha conventional method to obtain a bis(N-hydroxyimide) compoundshown by the following general formula [17]:
(wherein A₃ is the same as described above) . Then, 1 mole of theobtained bis (N-hydroxyimide) compound and 1 to 5 mole parts ofa sulfonylhalide compound shown by the following general formula[18]:R²-SO₂X₁ [wherein X₁ is a halogen atom (e.g. a fluorine atom, a chlorineatom, a bromine atom and an iodine atom); and R² is the same asdescribed above] are dissolved in a suitable solvent (e.g.hydrocarbons such as cyclohexane; halogenated hydrocarbons suchas methylene chloride, chloroform and dichloroethane; aromatic hydrocarbons such as benzene and toluene: ketones such as acetone,methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone;ethers such as ethyl ether, dimethoxy ethane and 1,4-dioxane;and amides such as N,N-dimethylformamide and N,N-dimethylacetamide)in the presence of a basic compound such aspyridine, triethylamine, tripropylamine, tributylamine,trioctylamine, and 4-N,N-dimethylaminopyridine, followed byreacting at -10 to 120 °C for 0.5 to 10 hours with stirring andpost-treatment in accordance with a conventional method toobtain the compound shown by the general formula [4].
In the method [B], 1 mole of an acid anhydride shown bythe above-described general formula [16] and 2 to 6 mole partsof ammonia (aqueous ammonia) are mixed in a solvent such as water,methanol and ethanol, followed by reacting at 50 to 150 °C for0.5 to 10 hours with stirring and-post-treatment in accordancewith a conventional method, to obtain a bisimide compound shownby the following general formula [19]:
(wherein A₃ is the same as described above) . Then, 1 mole partof the obtained bisimide compound and 2 to 5 mole parts of ahalogenizing agent (e.g. halogens such as chlorine, bromine andiodine, and imides such as N-chlorosuccinimide, N-bromosuccinimideand N-iodosuccinimide) are mixed in a suitablesolvent (e.g. halogenated hydrocarbons such as methylenechloride, chloroform and dichloroethane; ethers such asdimethoxy ethane and ethyl ether; and esters such as ethylacetate), followed by reacting at -10 to 75 °C for 0.5 to 10 hourswith stirring and post-treatment in accordance with aconventional method to obtain a bishaloimide compound shown bythe following general formula [20].
[wherein Y is a halogen atom (e.g. a fluorine atom, a chlorineatom, a bromine atom and an iodine atom); A₃ is the same asdescribed above] . Further, 1 mole of the obtained bishaloimidecompound and 1 to 5 mole parts of a sulfonate shown by thefollowing general formula [21] :(R²-SO₃)nM₁ [wherein M is a metal atom (e.g. a sodium atom, a potassium atom,a lithium atom, a calcium atom, a barium atom, a magnesium atom,a copper atom, a silver atom and a zinc atom) ; n is an integerof 1 to 2; and R² is the same as described above] are mixed ina suitable solvent (e.g. alcohols such as methanol and ethanol;halogenated hydrocarbons such as methylene chloride andchloroform; aromatic hydrocarbons such as benzene and toluene;acetone, ethyl acetate, cyclohexane and water), followed byreacting at 0 to 100 °C for 0.5 to 10 hours with stirring andpost-treatment in accordance with a conventional method toobtain the compound shown by the general formula [4].
In the method [C], 1 mole of the bis(N-hydroxyimide)compound shown by the general formula [17] obtained by theabove-described method [A] , 1 to 5 mole parts of a sulfonic acidshown by the following general formula [22]:R²-SO₃H(wherein R² is the same as described above) and 1 to 5 mole partsof dicyclohexylcarbodiimide (DCC) are mixed in a suitablesolvent (e.g. halogenated hydrocarbons such as methylenechloride and chloroform; esters such as ethyl acetate, methylacetate and butyl acetate; ethers such as ethyl ether, isopropylether, dimethoxy ethane and propylenglycol dimethyl ether; andketones such as acetone, methyl isobutyl ketone andcyclohexanone), followed by reacting at 0 to 100 °C for 0.5 to10 hours with stirring and post-treatment in accordance with a conventional method to obtain the compound shown by the generalformula [4].
In the method [D], 1 mole of the bis(N-hydroxyimide)compound shown by the general formula [17] obtained by theabove-described method [A] and 1 to 5 mole parts of a sulfonylfluoride compound shown by the following general formula [23] :R²-SO₂F(wherein R² is the same as described above) or a sulfonicanhydride shown by the following general formula [24]:(R²-SO₂)₂O(wherein R² is the same as described above) are reacted at -10 to 100 °C for 0.5 to 10 hours with stirring in a suitable solvent(e.g. hydrocarbons such as cyclohexane; aromatic hydrocarbonssuch as benzene and toluene; and ethers such as ethyl ether and1,2-dimethoxy ethane) in the presence of 1 to 10 mole parts ofa basic compound (e.g. metal alkoxides such as sodium methoxideand potassium tert-butoxide; metal hydrides such as sodiumhydride; amines such as triethylamine, tri-n-butylamine andtri-n-octylamine; and pyridine and 2,6-lutidine), followed bypost-treatment in accordance with a conventional method toobtain the compound shown by the general formula [4].
The bisphthalimidesulfonate compound shown by the generalformula [26] can be obtained by the following [E], [F], [G],[H] methods and the like.
Namely, in the method [E] , 1 mole of acid anhydride shownby the following general formula [27]:
(wherein A₂ is the same as described above) and 1 to 5 mole partsof hydroxylamine or a salt thereof (e.g. a hydrochloride saltand a sulfate salt) are dissolved in a solvent such as toluene,acetone, N,N-dimethylformamide and N,N-dimethylacetamide, inthe presence of a basic compound such as pyridine, triethylamineand tributylamine, followed by reacting at 0 to 100 °C for 0.5 to 10 hours with stirring and post-treatment in accordance witha conventional method to obtain a bis(N-hydroxy)phthalimidecompound shown by the following general formula (25]:
(wherein A₂ is the same as described above). The above-describedreaction can also be carried out in a basic compound as a solvent.Then, 1 mole of the obtained bis (N-hydroxy) phthalimide compoundand 1 to 5 mole parts of a sulfonylhalide compound shown by thefollowing general formula [28]:R⁴-SO₂X₁ (wherein R⁴ and X₁ are the same as described above) are dissolvedin a suitable solvent (e.g. hydrocarbons such as cyclohexane;halogenated hydrocarbons such as methylene chloride, chloroformand dichloroethane; aromatic hydrocarbons such as benzene andtoluene; ketones such as acetone, methyl ethyl ketone, methylisobutyl ketone and cyclohexanone; ethers such as ethyl ether,dimethoxy ethane and 1,4-dioxane; and amides such as N,N-dimethylformamideand N,N-dimethylacetamide) in the presenceof a basic compound such as pyridine, triethylamine,tripropylamine, tributylamine, trioctylamine and 4-N,N-dimethylaminopyridine,followed by reacting at -10 to 120°C for0.5 to 10 hours with stirring and post-treatment in accordancewith a conventional method to obtain a compound shown by thegeneral formula [26].
In the method [F], 1 mole of an acid anhydride shown bythe above-described general formula [27] or 1 mole part of atetracarboxylic acid shown by the following general formula[29] :
(wherein A₂ is the same as described above) [it can be obtainedfrom o-xylene in accordance with a method disclosed in J.Am.Chem.Soc., 80, 1196 (1958) and the like.] and 2 to 6 moleparts of ammonia (aqueous ammonia) are mixed in a solvent suchas water, methanol and ethanol, and reacted at 50 to 300 °C for0.5 to 10 hours with stirring, or 1 mole part of an acid anhydrideshown by the above-described general formula [27] and 2 to 20mole parts of a formamide are reacted at 50 to 150 °C for 0.5to 10 hours with stirring without solvent or in a hydrocarbonsolvent such as toluene and xylene, followed by post-treatmentin accordance with a conventional method to obtain abisphthalimide compound shown by the general formula [30]:
(wherein A₂ is the same as described above) . Then, 1 mole of theobtained bisphthalimide compound and 2 to 5 mole parts of ahalogenizing agent (e.g. halogens such as chlorine, bromine andiodine; and imides such as N-chloroscuccinimide, N-bromoscuccinimideand N-iodoscuccinimide) are mixed in asuitable solvent (e.g. halogenated hydrocarbons such asmethylene chloride, dichloroethane, chloroform and carbontetrachloride; ethers such as dimethoxyethane and ethyl ether;esters such as ethyl acetate; and water) and in a basic compound(e.g. sodium hydroxide, potassium hydroxide, triethylamine,diethylamine, 2,6-lutidine and p-N,N-dimethylaniline), ifnecessary, followed by reacting at -10 to 75 °C for 0.01 to 10hours with stirring and post-treatment in accordance with aconventional method to obtain a bishalophthalimide compoundshown by the following general formula [31] :
[wherein X₂ is a halogen atom (e.g. a fluorine atom, a chlorineatom, a bromine atom and an iodine atom); and A₂ is the same as described above] . Furthermore, 1 mole of the bishalophthalimidecompound obtained and 1 to 5 mole parts of a sulfonateshown bythe following general formula [32]:(R⁴-SO₃)nM₁ (wherein R⁴, M₁ and n are the same as described above) are mixedin a suitable solvent (e.g. alcohols such as methanol andethanol; halogenated hydrocarbons such as methylene chlorideand chloroform; aromatic hydrocarbons such as benzene andtoluene; and acetone, ethyl acetate, cyclohexane and water),followed by reacting at 0 to 100 °C for 0.5 to 10 hours withstirring and post-treatment in accordance with a conventionalmethod to obtain the compound shown by the general formula [26] .
In the method [G] , 1 mole of the bis (N-hydroxy) phthalimidecompound shown by the general formula [25] obtained by theabove-described method [E] and 1 to 5 mole parts of a sulfonicacid shown by the following general formula [33] :R⁴-SO₃H(wherein R⁴ is the same as described above) and 1 to 5 mole partsof dicyclohexylcarbodiimide (DCC) are mixed in a suitablesolvent (e.g. halogenated hydrocarbons such as methylenechloride and chloroform; esters such as ethyl acetate, methylacetate and butyl acetate; ethers such as ethyl ether, isopropylether, dimethoxy ethane and propylene glycol dimethyl ether;ketones such as acetone, methyl isobutyl ketone andcyclohexanone), followed by reacting at 0 to 100 °C for 0.5 to10 hours with stirring and post-treatment in accordance witha conventional method to obtain the compound shown by the generalformula [26] .
In the method [H] , 1 mole of the bis (N-hydroxy) phthalimidecompound shown by the general formula [25] obtained by theabove-described method [E] and 1 to 5 mole parts of asulfonylfluororide compound shown by the following generalformula [34] :R⁴-SO₂F(wherein R⁴ is the same as described above) or a sulfonicanhydride shown by the following general formula [35] : (R⁴-SO₂)₂O(wherein R⁴ is the same as described above) are reacted at -10 to 100 °C for 0.5 to 15 hours with stirring in a suitable solvent(e.g. hydrocarbons such as pentane and cyclohexane; aromatichydrocarbons such as benzene and toluene; ethers such as ethylether and 1,2-dimethoxyethane) in the presence of 1 to 10 moleparts of a basic compound (e.g. metal alkoxides such as sodiummethoxide, sodium ethoxide and potassium tert-butoxide; metalhydrides such as sodium hydide; alkyl metals such as n-butyllithiumand sec-butyllithium; amines such as triethylamine,tri-n-butylamine and tri-n-octylamine; and pyridine and2,6-lutidine), followed by post-treatment in accordance witha conventional method to obtain the compound shown by the generalformula [26] .
The bisimide compound of the present invention, shown bythe general formula [1] , that is, a bisimidesulfonate compoundshown by the general formula [4] and a bisphthalimidesulfonatecompound shown by the general formula [26] is not only usefulas a raw material of a polyimide compound or a cross-linkingagent but also provides an excellent effect as an acid generatorfor a chemically amplified resist composition.
A chemically amplified resist composition using thebisimide compound of the present invention as an acid generatoris roughly classified into, for example, (1) a positive resistcomposition comprising, as main solid components, at least onekind of alkali-soluble resin, at least one kind ofdissolution-inhibiting resin or dissolution inhibitor, whichturn alkali-soluble through a chemical change in the presenceof an acid, and an acid generator, (2) a positive resistcomposition comprising, as main solid components, at least onekind of resin which turns alkali-soluble through a chemicalchange in the presence of an acid and an acid generator, and(3) a negative resist composition comprising, as main solidcomponents, at least one kind of alkali-soluble resin, at leastone kind of cross-linkable compound which makes said resin hardlyalkali-soluble through a chemical change by heating in the presence of an acid and an acid generator.
An amount of the bisimide compound shown by the generalformula [1] to be used is generally 1 to 20 wt%, preferably 3to 20 wt%, relative to a base polymer such as thesaidalkali-soluble resin and dissolution-inhibiting resin whichturns alkali-soluble through chemical change in the presenceof an acid.
The alkali-soluble resin includes, for example, one shownby the following general formula [36]:
(wherein R¹³s are each independently a hydrogen atom or a methylgroup; R¹⁴ is an alkyl group; R¹⁵ is an acid labile group; l, mand p are each 0 or a natural number; k is a natural number,and provided that 1≧k≧0.8, 0.2≧1≧0, 0.2≧m≧0, 0.2≧p≧0, andk+l+m+p=1), and one shown by the following general formula[37]:
(wherein m' is 0 or a natural number; k' and 1' are each a naturalnumber, and provided that 0. 9≧k' ≧0.1, 0.9≧1' ≧0.1, 0.9≧m'≧0, and k'+1'+m'=1; R¹³ is the same as described above).
In the general formula [36], the alkyl group shown by R¹⁴may be straight chained, branched or cyclic, preferably straightchained or branched, and includes one having generally 1 to 6carbon atoms, which is specifically exemplified by, for example,a methyl group, an ethyl group, a n-propyl group, an isopropylgroup, a n-butyl group, an isobutyl group, a sec-butyl group,a tert-butyl group, a n-pentyl group, an isopentyl group, asec-pentyl group, a tert-pentyl group, a neopentyl group, a n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexylgroup, a neohexyl group, a cyclopropyl group, a cyclobutyl group,a cyclopentyl group and a cyclohexyl group.
The acid labile group shown by R¹⁵ includes, for example,a tert-butyl group, a 1-methylcyclohexyl group, a 1-ethoxyethylgroup, a 1-cyclohexyloxyethyl group, a tert-butoxycarbonylgroup, a tetrahydropyranyl group, a trimethylsilyl group anda tert-butoxycarbonylmethy group.
The specific examples of the resin shown by the generalformula [36] include, for example, poly(p-hydroxystyrene),poly(p-hydroxystyrene/styrene), poly(p-hydroxystyrene/styrene/acrylic acid), poly(p-hydroxystyrene/styrene/methacrylic acid), poly(p-hydroxystyrene/acrylic acid), poly(p-hydroxystyrene/methacrylic acid), poly(p-tert-butoxystyrene/p-hydroxystyrene) [composition ratio: 20↓/80↑] ,poly(p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene)[composition ratio: 20↓/80↑], poly(p-tetrahydropyranyloxystyrene/p-hydroxystyrene) [compositionratio: 20↓/80↑], poly(p-trimethylsilyloxystyrene/p-hydroxystyrene) [composition ratio: 20↓/80↑], poly(p-tert-butoxycarbonylmethoxystyrene/p-hydroxystyrene) [compositionratio: 20↓/80↑], poly(p-isopropoxystyrene/p-hydroxystyrene)[composition ratio: 20↓/80↑] and poly (p-1-ethoxyethoxystyrene/p-hydroxystyrene)[composition ratio:20↓/80↑] .
The specific examples of the resin shown by the generalformula [37] include, for example, poly(5-norbornene-2-carboxylicacid/maleic anhydride/acrylic acid) and poly(5-norbornene-2-carboxylicacid/maleic anhydride/methacrylicacid) .
A weight-average molecular weight (Mw) of the alkali-solubleresin is generally 2,000 to 50,000, preferably 2,000to 25,000, and molecular weight distribution (Mw/Mn) thereofis generally 1.0 to 3.0, preferably 1.0 to 2.0.
The dissolution-inhibiting resin which turns alkali-soluble through a chemical change in the presence of an acidincludes, for example, one shown by the following general formula[38] :
(wherein R¹⁶ is an acid labile group; k", 1' ' , m" and p" areeach 0 or a natural number, and provided that 0.8≧k' ' ≧0, 0.5≧1"≧0, 1≧m' ' ≧0, 1≧p" ≧0, and k" +l' ' +m' ' +p' '=1; and R¹³;R¹⁴ and R¹⁵ are the same as described above), one shown by thefollowing general formula [39]:
[wherein R¹⁷ and R¹⁸ are each independently a hydrogen atom oran alkyl group (except the case when both R¹⁷ and R¹⁸ are hydrogenatoms); R¹⁹ is an alkyl group, a haloalkyl group, or an aralkylgroup; R²⁰ is an acid labile group; k' ' ' and m' ' ' are each 0 ora natural number, and l''' is a natural number, and providedthat 0.8≧k"' ≧0, 1≧1''' ≧0.2, 0.5≧m''' ≧0.01, and k'''+l'''+m'''=1; and R¹³ is the same as described above], one shown bythe general formula [40]:
(wherein R²¹ is a hydrogen atom or an alkoxycarbonyl group; k' ' ' ' , 1'''' and p'''' are each 0 or a natural number and m"" is anatural number, and provided that 0.9≧k''''≧0, 0.9≧1''''≧0, 0.9≧m''''≧0.1, 0.9≧p''''≧0, and k''''+l''''+m''''+p'''' =1; and R¹³ and R¹⁶ are the same as described above), andpoly[-1-ethoxyethoxystyrene/p-hydroxystyrene/p-1-oxyethoxystyrene(cross-linked with an alkylene chain, acycloalkane or an aromatic ring)] {specifically including, forexample, one shown by the general formula [41]:
[wherein R²² is a group shown by the following formulae;
R²³ is a group derived from a polymer having a group shown by the following formula [42]:
(wherein the oxygen atom is bonded to R²²); q, r and s are eacha natural number, and provided that 0.4≧q>0, 0.9≧r≧0.4 and0.6≧s>0]}.
In the general formulae [38] and [40], the acid labilegroup shown by R¹⁶ includes, for example, a tert-butyl group,a 1-methylcyclohexyl group, a 2-methyl-2-adamantyl group, amevalonic lactonyl group and a 1-adamantyl group.
In the general formula [39], the alkyl group shown by R¹⁷and R¹⁸ may be straight chained, branched or cyclic, and includesone having generally 1 to 6 carbon atoms, which is specificallyexemplified by, for example, a methyl group, an ethyl group,a n-propyl group, an isopropyl group, a n-butyl group, anisobutyl group, a sec-butyl group, a tert-butyl group, a n-pentylgroup, an isopentyl group, a sec-pentyl group, atert-pentyl group, a neopentyl group, a n-hexyl group, anisohexyl group, a sec-hexyl group, a tert-hexyl group, a neohexylgroup, a cyclopropyl group, a cyclobutyl group, a cyclopentylgroup and a cyclohexyl group.
The alkyl group shown by R¹⁹ may be straight chained,branched or cyclic, and includes one having generally 1 to 10carbon atoms, which is specifically exemplified by, for example,a methyl group, an ethyl group, a n-propyl group, an isopropylgroup, a n-butyl group, an isobutyl group, a sec-butyl group,a tert-butyl group, a n-pentyl group, an isopentyl group, asec-pentyl group, a tert-pentyl group,- a neopentyl group, a2-methylbutyl group, a 1-ethylpropyl group, a n-hexyl group,an isohexyl group, a sec-hexyl group, a tert-hexyl group, aneohexyl group, a 2-methylpentyl group, a 1,2-dimethylbutylgroup, a 1-ethylbutyl group, a n-heptyl group, an isoheptyl group,a sec-heptyl group, a tert-heptyl group, a neoheptyl group, a n-octyl group, an isooctyl group, a sec-octyl group, a tert-octylgroup, a neooctyl group, a n-nonyl group, an isononyl group,a sec-nonyl group, a tert-nonyl group, a neononyl group, an-decyl group, an isodecyl group, a sec-decyl group, a tert-decylgroup, a neodecyl group, a cyclopropyl group, a cyclobutyl group,a cyclopentyl group, a cyclohexyl group, a cyclohexylmethylgroup, a 2-cyclohexylethyl group, a cycloheptyl group, acyclooctyl group, a cyclononyl group and a cyclodecyl group.
The haloalkyl group shown by R¹⁹ may be straight chained,branched or cyclic, and includes one, wherein a part of or allof the hydrogen atoms of the alkyl group having generally 1 to6 carbon atoms are substituted by a halogen atom (e.g. a fluorineatom, a chlorine atom, a bromine atom and an iodine atom), whichis specifically exemplified by, for example, a fluoromethylgroup, a chloromethyl group, a bromomethyl group, an iodomethylgroup, a difluoromethyl group, a dichloromethyl group, adibromomethyl group, a trifluoromethyl group, a trichloromethylgroup, a triiodomethyl group, a tetrafluoroethyl group, atetrachloroethyl group, a tetrabromoethyl group, atetraiodoethyl group, a heptafluoropropyl group, aheptachloropropyl group, a heptabromopropyl group, aheptaiodopropyl group, a nonafluorobutyl group, anonachlorobutyl group, a nonabromobutyl group, a nonaiodobutylgroup, a perfluoropentyl group, a perchloropentyl group, aperbromopentyl group, a periodopentyl group, a perfluorohexylgroup, a perchlorohexyl group, a perbromohexyl group, aperiodohexyl group, a pentafluorocyclohexyl group, apentachlorocyclohexyl group, a pentabromocyclohexyl group anda pentaiodocyclohexyl group.
The aralkyl group shown by R¹⁹ includes one having generally7 to 12 carbon atoms, which is specifically exemplified by, forexample, a benzyl group, a phenethyl group, a phenylpropyl group,a phenylbutyl group, a phenylpentyl group, a phenylhexyl groupand a 1-naphthylethyl group.
The acid labile group shown by R²⁰ includes, for example,a tert-butyl group, a 1-methylcyclohexyl group, a tert-butoxycarbonyl group, a tetrahydropyranyl group, atrimethylsilyl group and a tert-butoxycarbonylmethyl group.
In the general formula [40], the alkoxycarbonyl groupshown by R²¹ may be straight chained, branched or cyclic, andincludes one having generally 2 to 7 carbon atoms, which isspecifically exemplified by, for example, a methoxycarbonylgroup, an ethoxycarbonyl group, a n-propoxycarbonyl group, anisopropoxycarbonyl group, a n-butoxycarbonyl group, anisobutoxycarbonyl group, a sec-butoxycarbonyl group, atert-butoxycarbonyl group, a n-pentyloxycarbonyl group, anisopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, atert-pentyloxycarbonyl group, a neopentyloxycarbonyl group, an-hexyloxycarbonyl group, an isohexyloxycarbonyl group, asec-hexyloxycarbonyl group, a tert-hexyloxycarbonyl group, aneohexyloxycarbonyl group, a cyclopropyloxycarbonyl group, acyclobutoxycarbonyl group, a cyclopentyloxycarbonyl group anda cyclohexyloxycarbonyl group.
In the general formula [41], the group derived from apolymer shown by R²³ includes, for example, one which turnsalkali-soluble through a scission of cross-linked part by anaction of a co-existing acid, which is specifically exemplifiedby, for example, one derived from the dissolution-inhibitingresin shown by the general formulae [38] and [39].
The specific examples of the dissolution-inhibiting resinshown by the general formula [38] include, for example,poly(p-hydroxystyrene/styrene/tert-butyl acrylate), poly(p-hydroxystyrene/styrene/1-methylcyclohexyl acrylate),poly(p-hydroxystyrene/styrene/2-methyl-2-adamantyl acrylate),poly(p-hydroxystyrene/styrene/tert-butyl methacrylate),poly(2-methyl-2-adamantyl acrylate/mevalonic lactoneacrylate), poly (2-methyl-2-adamantyl methacrylate/mevaloniclactone methacrylate), poly(p-hydroxystyrene/2-methyl-2-adamantylacrylate), poly(p-tert-butoxystyrene/p-hydroxystyrene) [composition ratio: 20↑/80↓], poly(p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene) [compositionratio: 20↑/80↓], poly(p-tetrahydropyranyloxystyrene/p-hydroxystyrene) [composition ratio: 20↑/80↓], poly(p-tromethylsilyloxystyrene/p-hydroxystyrene) [compositionratio: 20↑/80↓], poly(p-tert-butoxycarbonylmethoxystyrene/p-hydroxystyrene) [compositionratio: 20↑/80↓], poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene) [composition ratio: 20↑/80↓], poly(p-1-cyclohexyloxyethoxystyrene/p-hydroxystyrene)[compositionratio: 20↑/80↓], poly[-1-(2-cyclohexylethoxy)ethoxystyrene/p-hydroxystyrene][composition ratio: 20↑/80↓], poly(p-1-methoxy-1-ethoxyethoxystyrene/p-hydroxystyrene)[composition ratio:20↑/80↓], poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/tert-butyl methacrylate), poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/1-methylcyclohexylacrylate), poly(p-1-ethoxyethoXystyrene/p-hydroxystyrene/2-methyl-2-adamantylacrylate), poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/1-adamantylacrylate),poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/styrene),poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/p-methylstyrene), poly(p-1-cyclohexyloxyethoxystyrene/p-hydroxystyrene/tert-butyl acrylate), poly(p-1-cyclohexyloxyethoxystyrene/p-hydroxystyrene/tert-butylmethacrylate), poly(p-1-cyclohexyloxyethoxystyrene/p-hydroxystyrene/1-methylcyclohexyl acrylate), poly (p-1-cyclohexyloxyethoxystyrene/p-hydroxystyrene/2-methyl-2-adamantylacrylate), poly(p-1-cyclohexyloxyethoxystyrene/p-hydroxystyrene/1-adamantyl acrylate), poly(p-1-cyclohexyloxyethoxystyrene/p-hydroxystyrene/styrene),poly(p-1-cyclohexyloxyethoxystyrene/p-hydroxystyrene/p-methylstyrene), poly(p-1-methoxy-1-ethoxyethoxystyrene/p-hydroxystyrene/tert-butyl acrylate), poly(p-1-methoxy-1-ethoxyethoxystyrene/p-hydroxystyrene/tert-butylmethacrylate), poly(p-1-methoxy-1-ethoxyethoxystyrene/p-hydroxystyrene/1-methylcyclohexyl acrylate), poly(p-1-methoxy-1-ethoxyethoxystyrene/p-hydroxystyrene/2-methyl-2-adamantylacrylate), poly(p-1-methoxy-1-ethoxyethoxystyrene/p-hydroxystyrene/1-adamantyl acrylate),poly(p-1-methoxy-1-ethoxyethoxystyrene/p-hydroxystyrene/styrene), poly(p-1-methoxy-1-ethoxyethoxystyrene/p-hydroxystyrene/p-methylstyrene),poly(styrene/p-hydroxystyrene/p-trimethylsilyloxystyrene),poly(styrene/p-hydroxystyrene/tert-butyl acrylate),poly(styrene/p-hydroxystyrene/p-tert-butoxycarbonylmethoxystyrene), poly(p-tert-butoxystyrene/p-hydroxystyrene/tert-butyl methacrylate), poly(p-tert-butoxystyrene/p-hydroxystyrene/1-methylcyclohexyl acrylate),poly(p-tert-butoxystyrene/p-hydroxystyrene/2-methyl-2-adamantyl acrylate), poly(p-tert-butoxystyrene/p-hydroxystyrene/1-adamantyl acrylate), poly(p-tert-butoxystyrene/p-hydroxystyrene/styrene), poly(p-tert-butoxystyrene/p-hydroxystyrene/p-methylstyrene), poly(p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene/tert-butyl methacrylate), poly(p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene/1-methylcyclohexyl acrylate), poly(p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene/2-methyl-2-adamantylacrylate), poly(p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene/1-adamantylacrylate), poly(p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene/styrene), poly(p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene/p-methylstyrene),poly(p-tetrahydropyranyloxystyrene/p-hydroxystyrene/tert-butyl methacrylate), poly(p-tetrahydropyranyloxystyrene/p-hydroxystyrene/1-methylcyclohexyl acrylate), poly(p-tetrahydropyranyloxystyrene/p-hydroxystyrene/2-methyl-2-adamantyl acrylate), poly(p-tetrahydropyranyloxystyrene/p-hydroxystyrene/1-adamantyl acrylate), poly(p-tetrahydropyranyloxystyrene/p-hydroxystyrene/styrene),poly(p-tetrahydropyranyloxystyrene/p-hydroxystyrene/p-methylstyrene), poly(p-tert-butoxycarbonylmethoxystyrene/p-hydroxystyrene/tert-butyl methacrylate), poly(p-tert-butoxycarbonylmethoxystyrene/p-hydroxystyrene/1-methylcyclohexylacrylate), poly(p-tert-butoxycarbonylmethoxystyrene/p-hydroxystyrene/2-methyl-2-adamantyl acrylate), poly(p-tert-butoxycarbonylmethoxystyrene/p-hydroxystyrene/1-adamantylacrylate), poly(p-tert-butoxycarbonylmethoxystyrene/p-hydroxystyrene/styrene) and poly(p-tert-butoxycarbonylmethoxystyrene/p-hydroxystyrene/p-methylstyrene).
The specific examples of the dissolution-inhibiting resinshown by the general formula [39] include, for example,poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/p-tert-butoxystyrene), poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/p-tert-butoxycarbonyloxystyrene), poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/p-tetrahydropyranyloxystyrene), poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/p-trimethylsilyloxystyrene), poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/p-tert-butyl acrylate), poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/p-tert-butoxycarbonylmethoxystyrene), poly(p-1-cyclohexyloxyethoxystyrene/p-hydroxystyrene/p-tert-butoxystyrene), poly(p-1-cyclohexyloxyethoxystyrene/p-hydroxystyrene/p-tert-butoxycarbonyloxystyrene), poly(p-1-cyclohexyloxyethoxystyrene/p-hydroxystyrene/p-tetrahydropyranyloxystyrene),poly(p-1-cyclohexyloxyethoxystyrene/p-hydroxystyrene/p-trimethylsilyloxystyrene),poly(p-1-cyclohexyloxyethoxystyrene/p-hydroxystyrene/p-tert-butoxycarbonylmethoxystyrene),poly(p-1-methoxy-1-ethoxyethoxystyrene/p-hydroxystyrene/p-tert-butoxystyrene),poly(p-1-methoxy-1-ethoxyethoxystyrene/p-hydroxystyrene/p-tert-butoxycarbonyloxystyrene), poly(p-1-methoxy-1-ethoxyethoxystyrene/p-hydroxystyrene/p-tetrahydropyranyloxystyrene),poly(p-1-methoxy-1-ethoxyethoxystyrene/p-hydroxystyrene/p-trimethylsilyloxystyrene),poly(p-1-methoxy-1-ethoxyethoxystyrene/p-hydroxystyrene/p-tert-butoxycarbonylmethoxystyrene), poly(p-1-methoxy-1-ethoxyethoxystyrene/p-hydroxystyrene/p-isopropoxystyrene)and poly(p-1-methoxy-1-ethoxyethoxystyrene/p-hydroxystyrene/p-pivaloyloxystyrene).
The specific examples of the dissolution-inhibiting resinshown by the general formula [40] include, for example,poly(tert-butyl 5-norbornene-2-carboxylate/maleicanhydride/cyclohexyl acrylate), poly(tert-butyl1,2,3,4,4a,5,8, 8a-octahydro-1,4:5,8-dimethanonaphthalene-2-carboxylate/maleicanhydride), poly(tert-butyl1,2,3,4,4a,5,8, 8a-octahydro-1,4:5,8-dimethanonaphthalene-2-carboxylate/maleicanhydride/methyl acrylate), poly(tert-butyl 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene-2-carboxylate/maleicanhydride/5-norbornene-2-carbonitrile)and poly(tert-butyl1,2,3,4,4a,5,8, 8a-octahydro-1,4:5,8-dimethanonaphthalene-2-carboxylate/maleicanhydride/methyl 5-norbornene-2-carboxylate).
A weight-average molecular weight (Mw) of thedissolution-inhibiting resin which turns alkali-solublethrough a chemical change in the presence of an acid is generally3, 000 to 50, 000, preferably 5, 000 to 25, 000, and molecular weightdistribution (Mw/Mn) thereof is generally 1.0 to 3.0, preferably1.0 to 2.0.
The specific examples of solubility inhibitors which turnsalkali-soluble through a chemical change in the presence of anacid include, for example, 2,2'-bis(4-tert-butoxyphenyl)propane, 2,2'-bis(4-tert-butoxycarbonyloxyphenyl)propane, 2,2'-bis(4-tetrahydropyranyloxyphenyl)propane,2,2'-bis[4-(1-ethoxyethoxy)phenyl]propane,2,2'-bis(4-tert-butoxycarbonylmethoxyphenyl)propane, 4,4',4''-tris(4-tert-butoxyphenyl)methane, 4,4',4''-tris(4-tert-butoxycarbonyloxyphenyl)methane, 4,4',4''-tris(4-tetrahydropyranyloxyphenyl)methane,4,4',4''-tris[4-(1-ethoxyethoxy)phenyl]methane,4,4',4''-tris(4-tert-butoxycarbonylmethoxyphenyl) methane, α,α,α'-tris(4-tert-butoxyphenyl)-1-ethyl-4-isopropylbenzene, α,α,α'-tris(4-tert-butoxycarbonyloxyphenyl)-1-ethyl-4-isopropylbenzene,α,α,α'-tris(4-tetrahydropyranyloxyphenyl)-1-ethyl-4-isopropylbenzene,α,α,α'-tris[4-(1-ethoxyethoxy)phenyl]-1-ethyl-4-isopropylbenzene,α,α,α'-tris(4-tert-butoxycarbonylmethoxyphenyl)-1-ethyl-4-isopropylbenzene,1,1,1-tris(4-tert-butoxyphenyl)ethane, 1,1,1-tris(4-tert-butoxycarbonyloxyphenyl)ethane, 1,1,1-tris(4-tetrahydropyranyloxyphenyl)ethane,1,1,1-tris[4-(1-ethoxyethoxy)phenyl)ethane,1,1,1-tris(4-tert-butoxycarbonylmethoxyphenyl)ethane, 1,1,1-tris(4-trimethylsilyloxyphenyl)ethane,3,4-dihydro-4-[2,4-di-(4-tert-butoxyphenyl)]-7-(4-tert-butoxyphenyl)-2,2,4-trimethyl-2H-benzo-1-pyran,3,4-dihydro-4-[2,4-di-(4-tert-butoxycarbonyloxyphenyl)]-7-(4-tert-butoxycarbonyloxyphenyl)-2,2,4-trimethyl-2H-benzo-1-pyran,3,4-dihydro-4-[2,4-di-(4-tetrahydropyranyloxyphenyl)]-7-(4-tetrahydropyranyloxyphenyl)-2,2,4-trimethyl-2H-benzo-1-pyran,3,4-dihydro-4-[2,4-di-[4-(1-ethoxyethoxy)phenyl])-7-[4-(1-ethoxyethoxy)phenyl]-2,2,4-trimethyl-2H-benzo-1-pyran,3,4-dihydro-4-[2,4-di-(4-tert-butoxycarbonylmethoxyphenyl)]-7-(4-tert-butoxycarbonylmethoxyphenyl)-2,2,4-trimethyl-2H-benzo-1-pyran,3,4-dihydro-4-[2,4-di-(4-trimethylsilyloxyphenyl)]-7-(4-trimethylsilyloxyphenyl)-2,2,4-trimethyl-2H-benzo-1-pyran,tert-butyl 2,2-bis(4-tert-butoxyphenyl)pentanoate,tert-buty 2,2-bis(4-tert-butoxycarbonyloxyphenyl)pentanoate,tert-butyl 2,2-bis(4-tetrahydropyranyloxyphenyl)pentanoate,tert-butyl 2,2-bis[4-(1-ethoxyethoxy)phenyl]pentanoate andtert-butyl 2,2-bis(4-tert-butoxycarbonylmethoxyphenyl) pentanoate. They may be used aloneor in a suitable combination of two or more kinds thereof.
An amount of these compounds to be used is generally 0.1to 30 wt%, preferably 0.5 to 20 wt%, relative to a base polymer.
The cross-linkable compound which makes a resin hardly alkali-soluble through a chemical change by heating in thepresence of an acid, include, for example, 2,4,6-tris(methoxymethyl)amino-1,3,5-s-triazine,2,4,6-tris(ethoxymethyl)amino-1,3,5-s-triazine,tetramethoxymethylglycol urea, tetramethoxymethyl urea, 1,3,5-tris(methoxymethoxy)benzene,1,3,5-tris(isopropoxymethoxy)benzene,α,α,α'-tris(isopropoxymethoxyphenyl)-1-ethyl-4-isopropylbenzene,α,α,α'-tris(methoxymethoxyphenyl)-1-ethyl-4-isopropylbenzene,CY-179 (a trade name of a product from CibaGeigy Ltd.). They may be used alone or in a suitable combinationof two or more kinds thereof.
An amount of these cross-linkable compounds to be used isgenerally 5 to 50 wt%, preferably 10 to 35 wt%, relative to abase polymer.
With regard to the bisimide compound shown by the generalformula [1] , at least one kind of said compound may be used asan acid generator, but they may also be used in combination withat least one kind of conventional acid generator including, forexample, various diazosulfone compounds, various sulfoniumsalts, various iodonium salts and variouspyrogalloltrisulfonate compounds.
In a chemically amplified resist composition, a solventand a basic compound are used, along with a surfactant, a UVabsorber, an acid compound including an organic carboxylic acid,if necessary, in addition to the above-described solidcomponents (the resin, the bisimide compound shown by the generalformula [1], the dissolution-inhibiting agent and thecross-linking agent).
The specific examples of the solvent include, for example,methyl cellosolve acetate, ethyl cellosolve acetate, propyleneglycol monomethyl ether, propylene glycol monomethyl etheracetate, propylene glycol monoethyl ether acetate, methyllactate, ethyl lactate, propyl lactate, 2-ethoxyethyl acetate,methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate,ethyl 3-methoxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide, cyclohexanone, methyl ethyl ketone, 2-heptanone,β-propiolactone, β-butyrolactone, γ-butyrolactone,γ-valerolactone, δ-valerolactone, 1,4-dioxane, diethyleneglycol monomethyl ether, diethylene glycol dimethyl ether,ethylene glycol monoisopropyl ether and N-methyl-2-pyrrolidone.They may be used alone or in a suitable combination of two ormore kinds thereof.
An amount of these solvents to be used is generally 3 to25 parts by weight, preferably 3 to 20 parts by weight, relativeto 1 part by weight of the total solid components in any typeof resist.
The basic compound is used to adjust sensitivity and thelike, and specifically includes, for example, pyridine,picoline, triethylamine, tri-n-butylamine, tri-n-octylamine,dioctylmethylamine, dicyclohexylmethylamine, N-methylpyrrolidine,N-methylpiperidine, 4-N,N-dimethylaminopyridine,triethanolamine, triisopropanolamine,dimethyldodecylamine, dimethylhexadecylamine, tribenzylamine,tris[2-(2-methoxyethoxy)ethyl]amine, tetramethylammoniumhydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, polyvinylpyridine andpoly(vinylpyridine/methyl methacrylate). They may be used aloneor in a suitable combination of two or more kinds thereof.
The specific examples of the surfactant optionally usedinclude, for example, a fluorine-containing nonionic typesurfactant such as "Fluorad" (a trade name of a product fromSumitomo 3M, Ltd.), "Surflon" (a trade name of a product fromAsahi Glass Co., Ltd.), "Unidyne" (a trade name of a productfrom Daikin Ind., Ltd.), "Megafac" (a trade name of a productfrom Dainippon Ink & Chem., Inc.) and "Eftop" (a trade name ofa product from Tohkem Products Corp.), polyethylene glycol,polypropylene glycol and polyoxyethylene cetyl ether. They maybe used alone or in a suitable combination of two or more kindsthereof.
The specific examples of the UV absorber optionally usedinclude, for example, 9-diazofluorenone, 9-(2-methoxyethoxymethyl)anthracene, 9-(2-ethoxyethoxymethyl)-anthracene,9-fluorenone, 2-hydroxycarbazole, o-naphthoquinonediazidederivatives and 4-diazo-1,7-diphenylpentane-3,5-dione.They may be used alone or in asuitable combination of two or more kinds thereof.
The acid compounds including the organic carboxylic acidoptionally used include, for example, salicylic acid, m-hydroxybenzoicacid, p-hydroxybenzoic acid, o-acetylbenzoicacid, diphenolic acid, phthalic acid, succinic acid, malonicacid, salicylaldehyde, succinimide, phthalimide, saccharin andascorbic acid. They may be used alone or in a suitable combinationof two or more kinds thereof.
An amount of the basic compound or the optionally usedsurfactant, UV absorber and acid compound including the organiccarboxylic acid to be used is each generally 0.000001 to 1 wt%,preferably 0.00001 to 1 wt%, relative to the base polymers inany type of resist.
The method for pattern formation using a chemicallyamplified resist composition containing the bisimide compoundshown by the general formula [1] as an acid generator is, forexample, as follows.
Namely, a resist composition of the present invention isspin-coated on a semiconductor substrate such as a silicon wafer,followed by pre-baking at 70 to 150°C for 60 to 120 sec. on ahot plate to obtain a resist film with 0.1 to 1.0 µm thickness.Then said resist film is irradiated with radioactive rays toform an objective pattern, followed by baking (PEB) at 70 to150°C for 60 to 120 sec. on a hot plate and developing usingan alkaline developing solution for 30 to 120 sec, by, for example,a spraying method, a paddle method or a dip method, and washingwith water to form a desired resist pattern.
The alkaline developing solution includes an aqueoussolution dissolving at least one kind of alkaline compoundincluding, for example, inorganic alkalis such as sodiumhydroxide, potassium hydroxide and ammonia; organic alkalissuch as triethanolamine, choline and tetraalkylammonium hydroxide, in an amount of generally 0.01 to 20 wt%, preferably1 to 5 wt%, and among others, an aqueous solution oftetraalkylammonium hydroxide is preferable.
Further, in the developing solution consisting of saidaqueous alkaline solution, an aqueous organic solvent such asmethanol and ethanol, and a surfactant may be addedappropriately.
A chemically amplified resist composition containing thecompounds of the present invention, that is, thebisimidesulfonate compound shown by the general formula [4] andthe bisphthalimidesulfonate compound shown by the generalformula [26] as an acid generator generates an acid in accordancewith the following schemes [1] and [2] in an area irradiated.
(wherein R² and A₃ are the same as described above),
(wherein R⁴ and A₂ are the same as described above).
When a positive resist composition is used, a chemicalchange shown by the following scheme [3] occurs by, for example,heating, if necessary, in the presence of an acid generated, thereby the irradiated area turns soluble in an alkalinedeveloping solution, and forms a positive resist pattern (anelimination reaction of the acid labile group).

While, when a negative resist composition is used, achemical change shown by the following scheme [4] occurs by,for example, heating, if necessary, in the presence of an acidgenerated, thereby the irradiated area turns hardly soluble inan alkaline developing solution, and form a negative resistpattern (a cross-linking reaction of the resin).

Since the bisimide compound of the present invention,shown by the general formula [1] has high solubility in a resistsolvent, use of said compound as an acid generator for achemically amplified resist composition can generate an acidhomogeneously and in high sensitivity, without causing a problemsuch as easy formation of fine particles due to low solubilityin a solvent, observed in using an acid generator such as aconventional sulfonium salt.
In addition, a chemically amplified resist compositioncontaining the bisimide compound of the present invention caneasily generate an acid in response to various radioactive rayssuch as i-line (365 nm) , KrF excimer laser (248 nm) , ArF excimerlaser (193 nm), F₂ laser (157 nm) , EUV (1 to 30 nm bond) , electronbeams and X-rays, and thus provides high sensitivity, highresolution and superior pattern profile.
Furthermore, the bisimide compound of the presentinvention is useful not only for said resist composition, butalso for a chemically amplified resist composition for i-line,using a photosensitive polyimide resin.
Furthermore, the bis(N-hydroxy)phthalimide compound ofthe present invention, shown by the general formula [25], isuseful not only as a synthesis intermediate of thebisphthalimidesulfonate compound of the present invention,shown by the general formula [26], but also as, for example,a raw material for synthesizing a heat resistant polymer suchas a cross-linking agent for a polyimide resin, a functionalorganic material such as synthetic intermediate for aphotosensitive compound, and a functional material inbiochemical fields such as peptide synthesis.
In the following, the present invention will be explainedin further detail referring to Examples, Reference Examples andComparative Examples, but the present invention is not limitedthereto by any means. EXAMPLE
Reference Example 1. Synthesis of tetrahydro-2,5-dihydroxycyclobuta-[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone
In 210 ml of pyridine solution dissolving 15.3 g (0.22mol) of hydroxylamine hydrochloride, 19.6 g (0.10 mol) ofcyclobutane-1,2,3,4-tetracarboxylic dianhydride, obtainedfrom maleic anhydride by photoreaction in accordance with themethod disclosed in JP-A-59-212495, was added at roomtemperature, and the solution was reacted at 90°C for 15 minutes with stirring. After completion of the reaction, the obtainedreaction solution was concentrated under reduced pressure, and210 ml of an aqueous solution of 6% acetic acid was poured tothe resulting residue, followed by filtering precipitated crudecrystalline substance, washing with water and drying underreduced pressure to obtain 17.0 g of tetrahydro-2,5-dihydroxycyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetroneas colorless powder crystal.¹HNMR(DMSO-d₆) δ ppm: 3.38-3.40 (4H, d, CH×4), 11.09(2H, s, OH×2)Reference Example 2. Synthesis of 3a,4,4a,7a,8,8a-hexahydro-2,6-dihydroxy-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone
The similar procedure as in Reference Example 1 wasconducted except that 24.8 g (0.10 mol) ofbicycle[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydridewas used instead of cyclobutane-1,2,3,4-tetracarboxylicdianhydride in Reference Example 1, to obtain 16.5 g of3a,4,4a,7a,8,8a-hexahydro-2,6-dihydroxy-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetroneascolorless powder crystal.¹HNMR(DMSO-d₆) δ ppm: 3.31-3.37(6H, m, CH×6) , 6. 08-6.09 (2H, d,-CH=×2) , 10.76(2H, s, OH×2)Reference Example 3. Synthesis of 2,6-dihydroxybenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone
The similar procedure as in Reference Example 1 wasconducted except that 21. 8 g (0.10 mol) of pyromellitic anhydridewas used instead of cyclobutane-1,2,3,4-tetracarboxylicdianhydride in Reference Example 1, to obtain 24.0 g of2,6-dihydroxybenzo[1,2-c:4,5-c'] dipyrrole-1,3,5,7(2H,6H)-tetroneas orange powder crystal.¹HNMR(DMSO-d₆) δ ppm: 8.13(2H, s, pyromellitic ring H×2),11.16(2H, s, OH×2) Reference Example 4. Synthesis of N-10-camphorsulfonyloxy-5-norbornene-2,3-dicarboxyimide
In 20 ml of acetone, 1.25 g (0.007 mol) of N-hydroxy-5-norbornene-2,3-dicarboxyimideand 2.01 g (0.008 mol) of10-camphorsulfonyl chloride were suspended, then 0.81 g (0.008mol) of triethylamine was added dropwise thereto at roomtemperature, and the suspension was reacted for 2 hours withstirring. After completion of the reaction, the obtainedreaction solution was poured into 100 ml of water forcrystallization, followed by filtering precipitated crystalthus obtained, washing with water and drying to obtain crudecrystal. Then, the crude crystal was recrystallized from a mixedsolvent of ethyl acetate/ethyl ether to obtain 1.8 g of N-10-camphorsulfonyloxy-5-norbornene-2,3-dicarboxyimideascolorless prism crystal.Mp.: 163-165°C¹HNMR(CDCl₃) δ ppm: 0.90(3H, s, CH₃), 1.11(3H, s, CH₃), 1.46-1.54(2H,m, H-C-H and bridged alicyclic H), 1.77-1.79(2H, m,H-C-H and bridged alicyclic H), 1.93-1.98(1H, d, bridgedalicyclic H), 2.07-2.13(2H, m, bridged alicyclic H×2),2.30-2.42(2H, m, bridged alicyclic H×2), 3.32(2H, bs, bridgedalicyclic H×2), 3.46(2H, bs, bridged alicyclic HX2), 3.54-3.58(1H, d, H-C-H-SO₃ ^-) , 3.91-3.95 (1H, d, H-C-H-SO₃ ^-), 6.17-6.20(2H,d, -CH=×2)Reference Example 5. Synthesis of N-pentafluorobenzenesulfonyloxy-5-norbornene-2,3-dicarboxyimide
In 10 ml of acetone, 0.63 g (0.0035 mol) of N-hydroxy-5-norbornene-2,3-dicarboxyimideand 1.07 g (0.004 mol)of pentafluorobenzenesulfonyl chloride were dissolved, then0.40 g (0.004 mol) of triethylamine was added dropwise theretoat room temperature, and the solution was reacted for 2 hourswith stirring. After completion of the reaction, the obtainedreaction solution was poured into 50 ml of water forcrystallization, followed by filtering precipitated crystal thus obtained, washing with water and drying to obtain crudecrystal. Then, the crude crystal was recrystallized from a mixedsolvent of ethyl acetate/ethyl ether to obtain 0.8 g of N-pentafluorobenzenesulfonyloxy-5-norbornene-2,3-dicarboxyimideas colorless prism crystal.Mp.: 153-155 °C¹HNMR(CDCl₃) δ ppm: 1.49-1.51(1H, d, H-C-H), 1.78-1.81(lH, d,H-C-H), 3.29-3.30(2H, d, bridged alicyclic H×2), 3.45(2H, s,bridged alicyclic H×2), 6.16(2H, s, -CH=×2)Reference Example 6. Synthesis of 2,6-bis(methanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone
In 1.5 ml of pyridine and 10 ml of N, N-dimethylacetamide,1.00 g (0.004 mol) of 2,6-dihydroxybenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,obtained in ReferenceExample 3, was suspended, then 2.94 g (0.012 mol) ofmethanesulfonyl chloride was added dropwise thereto at roomtemperature, and the suspension was reacted for 1 hour withstirring. After completion of the reaction, the obtainedreaction solution was poured into 150 ml of water forcrystallization, followed by filtering precipitated crudecrystal thus obtained, washing with water and drying to obtaincrude crystal. Then, the crude crystal was recrystallized fromN,N-dimethylacetamide to obtain 1.1 g of 2,6-bis(methanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone as colorless powder crystal.Mp.: 300°C or more¹HNMR(DMSO-d₆) δ ppm: 8.47 (2H, s, pyromellitic ring H×2)Reference Example 7. Synthesis of 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(n-butanesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone
In 1.5.ml of pyridine and 10 ml of N, N-dimethylacetamide,1.11 g (0.004 mol) of 3a,4,4a,7a,8,8a-hexahydro-2,6-dihydroxy-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, obtained in Reference Example 2, wasdissolved, then 2.94 g (0.012 mol) of n-butanesulfonyl chloridewas added dropwise thereto at room temperature, and the solutionwas reacted for 1 hour with stirring. After completion of thereaction, the obtained reaction solution was poured into 150ml of water for crystallization, followed by filteringprecipitated crude crystal, washing with water and drying toobtain crude crystal. Then, the crude crystal thus obtained wasrecrystallized from ethyl acetate to obtain 1.1 g of3a,4,4a,7a,8,8a-hexahydro-2,6-bis(n-butanesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetroneascolorless flaky crystal.Mp.: 239-241 °C¹HNMR (DMSO-d₆) δ ppm: 0.88-0.92 (6H, t, CH₃×2), 1.38-1.44 (4H, q,CH₂×2), 1.79-1.83 (4H, m, CH₂ ×2), 3.43(6H, s, CH×6), 3.61-3.65(4H, m, CH₂×2), 6.18(2H, s, -CH=×2)Example 1. Synthesis of tetrahydro-2,5-bis(3-trifluoromethylphenylsulfonyloxy)cyclobuta [1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone
In 1.5 ml of pyridine and 10 ml of N,N-dimethylacetamide,0.90 g (0.004 mol) of tetrahydro-2,5-dihydroxycyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone,obtained in Reference Example 1, was suspended, then2.94 g (0.012 mol) of 3-trifluoromethylbenzenesulfonyl chloridewas added dropwise thereto at room temperature, and thesuspension was reacted for 1 hour with stirring. After completionof the reaction, the obtained reaction solution was poured into150 ml of water for crystallization, followed by filteringprecipitated crude crystal, washing with water and drying toobtain crude crystal. Then, the crude crystal was recrystallizedfrom a mixed solvent of methylene chloride/acetone to obtain1.5 g of tetrahydro-2,5-bis(3-trifluoromethylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetroneas colorless prism crystal(yield: 58.4 %). Mp.: 245-247 °C¹HNMR(DMSO-d₆) δ ppm: 3. 58 (4H, s, CH×4), 7.92-8.01(2H, t,aromatic ring H×2), 8.31-8.34 (2H, d, aromatic ring H×2),8.39-8.43(4H, t, aromatic ring H×4)IR(KBr-Disk) ν cm^-1 : 3076, 3017, 1765 (C=O) , 1327 (SO₂O) ,1196 (SO₂O)MS(m/z) : 641(M⁺)Examples 2 to 5. Synthesis of the compounds shown by the generalformula [10] (the ones wherein tetra-valent alicyclichydrocarbon groups are derived from a cyclobutane ring)
The similar procedures as in Example 1 were conductedexcept that various sulfonyl chlorides were used instead of3-trifluoromethylbenzenesulfonyl chloride used in Example 1,desired bisimidesulfonate compounds were obtained. The resultsare shown in Table 1. Example R⁷ Shape(cryst. solvent) Physical property ¹H NMR (DMSO-d₆) (δ ppm),. IR (KBr-Disk) (ν cm^-1), and others 2 n-butyl colorless flaky crystal (MeCN)Mp.: 278°C ¹HNMR: 0.89-0.93(6H, t, CH₃×2), 1.40-1.46 (4H, q, CH₂×2), 1.84-1.88(4H, m, CH₂×2), 3.72(4H, s, CH ×4), 3.74-3.78(4H, m, CH₂×2) 3 p-methyl phenyl colorless powder crystal (DMAc) Mp.: ≧300°C ¹HNMR: 2.46(6H, s, CH₃×2), 3.53(4H, s,CH×4), 7.53-7.55(2H, d, aromatic ring H×2), 7.94-7.96(2H, d, aromatic ring H×2) IR: 3007, 1796(C=O), 1750(C=O), 1392(SO₂O), 1179(SO₂O) 4 2,5-di chloro phenyl pale yellow prism crystal (DMAc) Mp.: 289°C ¹HNMR: 3.57(4H, s, CH×4), 7.88-7.91(2H, d, aromatic ring H×2), 7.95-7.98(2H, m, aromatic ring H×2), 8.01-8.09(2H, d, aromatic ring H×2) 5 10-camphor colorless prism crystal (EtOAc/MeCN) Mp.: 210°C ¹HNMR: 0.84(6H, s, CH₃×2), 1.04 (6H, s, CH₃×2), 1.47-1.49(2H, m, bridged alicyclic HX2), 1.67-1.70(2H, m, bridged alicyclic H×2), 1.96-2.01(4H, m, bridged alicyclic H×4), 2.11-2.13(2H, t, bridged alicyclic H×2), 2.21-2.23(2H, m, bridged alicyclic H×2), 2.38-2.42(2H, m, bridged alicyclic H×2), 3.69-3.80(4H, dd, CH×4), 3.86-3.90(2H, d, H-C-H×2), 3.96-4.00 (2H, d, H-C-H×2), IR: 2980, 2946, 2892, 1757(C=O), 1395 (SO₂O) , 1188 (SO₂O) MS(m/z): 653(M⁺-H) * MeCN: acetonitrile, DMAc: N,N-dimethylacetamide, EtOAc: ethyl acetate Example 6. Synthesis of 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(3-trifluoromethylphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone
In 1.5 ml of pyridine and 10 ml of N, N-dimethylacetamide,1.11 g (0.004 mol) of 3a,4,4a,7a,8,8a-hexahydro-2,6-dihydroxy-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,obtained in Reference Example 2, wasdissolved, then 2.94 g (0.012 mol) of 3-trifluoromethylbenzenesulfonylchloride was added dropwise thereto at room temperature, and the solution was reacted atroom temperature for 1 hour with stirring. After completion ofthe reaction, the obtained reaction solution was poured into150 ml of water for crystallization, followed by filteringprecipitated crude crystal, washing with water and drying toobtain crude crystal. Then, the crude crystal was recrystallizedfrom a mixed solvent of ethyl acetate/methanol to obtain 1.8g of 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(3-trifluoromethylphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone as colorlessflaky crystal (yield: 64.8 %).Mp.: 226 °C¹HNMR(DMSO-d₆) δ ppm: 3.25-3.29(2H, d, CH×2), 3.31-3.36 (4H, m,CH×4), 6.17-6.19(2H, t, -CH=×2), 7.98-8.02(2H, t, aromaticring H×2), 8.23(2H, s, aromatic ring H×2), 8.31-8.33(4H, d,aromatic ring H×4)IR (KBr-Disk) ν cm^-1 : 3088, 2951, 1750 (C=O) , 1327 (SO₂O) ,1200 (SO₂O)MS(m/z) : 694 (M⁺)Examples 7 to 9. Synthesis of the compounds shown by the generalformula [11]
The similar procedures as in Example 1 were conductedexcept that various sulfonyl chlorides were used instead of3-trifluoromethylbenzenesulfonyl chloride used in Example 6,to obtain desired bisimidesulfonate compounds. The results areshown in Table 2. Example R⁸ Shape(cryst. solvent) Physical property IR ¹H NMR (DMSO-d₆) (δ ppm) ,(KBr-Disk) ( ν cm^-1), and others 7 p-methyl phenyl colorless powder crystal (DMAc/Me₂CO)Mp.: ≧300°C ¹HNMR: 2.47(6H, s, CH₃× 2), 3.38(6H, s, CH×6), 6.22(2H, s, CH= ×2), 7.53-7.55 (2H, d, aromatic ring H×2), 7.85-7.87(2H, d, aromatic ring H×2) IR: 3057, 2934, 1805(C=O), 1742(C=O), 1397 (SO₂O) , 1196 (SO₂O) 8 3,5-di trifluoro methyl phenyl colorless short needle-like crystal (Et₂O/MeCN)Mp.: 196-198°C ¹HNMR: 3.34(6H, s, CH X 6), 6.10(2H, s, -CH=×2), 8.59(4H, s, aromatic ring H×4), 8.78(2H, s, aromatic ring H×2) IR: 3086, 2965, 1809(C=O), 1752(C=O), 1417 (SO₂O), 1183 (SO₂O) MS(m/z): 830(M⁺) 9 10-camphor colorless short needle-like crystal (EtOAc)Mp.: 226°C ¹HNMR: 0.82(6H, s, CH₃, × 2), 1.01(6H, s, CH₃×2), 1.45(2H, m, bridged alicyclic H×2), 1.62 (2H, m, bridged alicyclic H ×2), 1.95-1.99(4H, m, bridged alicyclic H×4), 2.11-2.15(4H, t, bridged alicyclic H×4), 2.36-2.41(2H, m, bridged alicyclic H×2), 3.46(6H, s, CH×₆), 3.71-3.75(2H, d, H-C-H×2), 3.85-3.89 (2H, d, H-C-H×2) , 6.18 (2H, s, - CH= ×2) IR: 2966, 1794 (C=O), 1730 (C=O), 1404 (SO₂O), 1196 (SO₂O) MS (m/z) : 705 (M⁺-H) *DMAc: N,N-dimethylacetamide, Me₂CO: acetone, Et₂O: ethyl ether, MeCN: acetnitrile, EtOAc: ethyl acetate Example 10. Synthesis of 2,6-bis(3-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone
In 1.5 ml of pyridine and 10 ml of N, N-dimethylacetamide,1.00 g (0.004 mol) of 2,6-dihydroxybenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,obtained in ReferenceExample 3, was suspended, then 2.94 g (0.012 mol) of 3-trifluoromethylbenzenesulfonylchloride was added dropwisethereto at room temperature, and the suspension was reacted at room temperature for 1 hour with stirring. After completion ofthe reaction, the obtained reaction solution was poured into150 ml of water, followed by extraction of oily substanceprecipitated with 20 ml of methylene chloride three times,washing the organic layer with water (50 ml×4) and concentratingunder reduced pressure. Then, the crude crystal residue wasrecrystallized from a mixed solvent of methylenechloride/acetone to obtain 1.7 g of 2,6-bis(3-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7-(2H,6H)-tetroneas pale yellow flakycrystal (yield: 64.0 %).Mp.: 226-228 °C¹HNMR(DMSO-d₆) δ ppm: 7.96-8.00 (2H, t, aromatic ring H×2),8.32-8.34(2H, d, aromatic ringH×2), 8.37(2H, s, pyromelliticring H×2), 8.41-8.45(4H, t, aromatic ring H×4)IR(KBr-Disk) ν cm^-1 : 3100, 3036, 1798(C=O), 1759 (C=O) ,1392 (SO₂O) , 1194 (SO₂O)MS(m/z) : 664 (M⁺)Examples 11 to 21. Synthesis of the compounds shown by the generalformula [12]
The similar procedures as in Example 10 were conductedexcept that various sulfonyl chlorides were used instead of3-trifluoromethylbenzenesulfonyl chloride used in Example 10,to obtain desired bisimidesulfonate compounds. The results areshown in Tables 3 to 5. Example R⁹ Shape(cryst. solvent)Physical property ¹H NMR (DMSO-d₆) (δppm) ,IR and others (ν cm^-1),and others 11 n-butyl colorless flaky crystal (MeCN)Mp.: 226-2289°C ¹HNMR: 0.91-0.95(6H, t, CH₃×2), 1,43-1.49(4H, q. CH₂×2). 1.91(4H, m, CH₂×2), 3.82-3.85(4H, m, CH₂× 2), 8.46 (2H, s, pyromerilliticring H×2) IR: 3110, 3061, 2963, 2876, 1765 (c=O), 1387 (SO₂O) , 1177 (SO₂O) 12 benzyl pale yellow prism crystal (DMAc/Me₂CO)Mp.: 227°C ¹HNMR: 5.24(4H, s, CH₂×2), 7.46-7.(6H, t, aromatic ring H×6), 7.62-7.63 (4H, d, aromatic ring H ×4), 8.55(2H, s, pyromellitic ring H×2) IR: 2990, 1796(C=O), 1757(C-O), 1402 (SO₂O) , 1179 (SO₂O) 13 phenyl pale yellow powder crystal (DMAc)Mp.: ≧300°C ¹HNMR: 7.69-7.73(4H, t, aromatic ring H × 4), 7.89-7.93(2H, t, aromatic ring H×2), 8.07-9.09(4H, d, aromatic ring H×4) , 8.36 (2H, s, pyromellitic ring H×2) * MeCN: acetonitrile, Me₂CO: acetone, DMAc: N,N-dimethylacetamide, Example R⁹ Shape(cryst. solvent)Physical property ¹H NMR (DMSO-d₆) (δ ppm),IR (KBr-Disk) (νcm^-1, and others 14 p-methylphenyl colorless powder crystal (DMAc) Mp. 293°C ¹HNMR: 2.47(6H,s,CH₃×2), 7.51-7.54 (4H, d, aromatic ring H×4). 7.95-7.97 (4H, d, aromatic ring H×4), 8.38(2H, s, pyromellitic ring H×2) IR: 3100, 3040, 2984, 1782(C=O), 1757 (C=O) , 1593, 1377 (SO₂O) , 1181 (SO₂O) 15 p-methoxyphenyl pale yellow powder crystal (DMAc)Mp. 274°C ¹HNMR: 3.90(6H, s, CH₃O×2), 7.19-7.21(4H, d, aromatic ring H×4), 7.99-8.01 (4H, d, aromatic ring H×4) 8.37 (2H, s, pyromellitic ring H×2) 16 p-fluorophenyl pale yellow powder crystal (DMAc) Mp.: ≧300°C ¹HNMR: 7.55-7.60 (4H, t, aromatic ring H×4), 8.18-8.22 (4H, m, aromatic ring H×4), 8.40(2H, s, pyromellitic ring H×2) 17 o-tri fluoromethylphenyl pale yellow powder crystal (DMAc)Mp. 277-279°C ¹HNMR: 7.89-7.92(2H, t, aromatic ring H×2), 8.08-8.12 (2H, t, aromatic ring H×2), 8.21-8.23 2H, d, aromatic ring H×2), 8.28-8.30(2H, d, aromatic ring H×2), 8.32(2H, s, pyromellitic ring H×2) 18 2,5-dichlorophenyl pale yellow powder crystal (DMAc/MeOH)Mp. 297-299°C ¹HNMR: 7.93-8.00(4H, m, aromatic ring H×4), 8.08-8.09(2H, d, aromatic ring H×2), 8.38 (2H, s, pyromellitic ring H×2) 19 2-thiophene pale yellow flaky crystal (DMAc/MeCN)Mp. : 296°C Mp.: 296°C ¹HNMR: 7.36(2H, bs, thiophene ring H×2), 8.15(2H, bs, thiophene ring H×2), 8.41 (4H, bs, thiophene ring H×2), 8.41(4H, bs, thiophene ring H×2 and pyromellitic ring H×2) IR: 3100, 3040, 1796 (C=O), 1744(C=O) 1379(SO₂O), 1190(SO₂O) * DMAc: N,N-dimethylacetamide, MeOH: methanol, MeCN: acetonitrile Example R⁹ Shape(cryst. solvent)Physical property ¹H NMR (DMSO-d₆) (<5ppm).IR (KBr-Disk) and others (νcm^-1), and others 20 10-camphor pale yellow powder crystal (Et₂O/MeCN)Mp. 187°C ¹HNMR: 0.85 (6H, s, CH₃×2) , 1.01(6H, s, CH3 × 2) , 1.48-1.50 (2H, m, bridged alicyclic H×2), 1.70(2H, m, bridged alicyclic H × 2), 1.97-2.02 (4H, m, bridged alicyclic H × 4), 2.11-2.13 (2H, t, bridged alicyclic H×2), 2.23-2.26(2H, m, bridged alicyclic H×2), 2.38-2.43 (2H. m, bridged alicyclic H×2), 3.91-3.95(2H, d, H-C-H × 2), 3.99-4.03(2H, d, H-C-H × 2), 8.52(2H, s. pyromellitic ring H× 2) IR: 2965, 1798(C=O), 1754(C=O), 1402 (SO₂O) , 1186 (SO₂O) MS (m/z) : 677 (M') 21 p-trifluoro methyl phenyl pale yellow powder crystal (DMAc)Mp. 288°C ¹HNMR: 8.11-8.13(4H, d, aromatic ring H × 4), .8.34-8.36(4H, d, aromatic ring H×4), 8.42(2H, s, pyromellitic ring H×2) IR: 3106, 3058. 1800(C=O), 1763(C=O), 1410 (SO₂O). 1183 (SO₂O) * Et₂O: diethylether, MeCN: acetonitrile, DMAc: N,N-dimethylacetamide Example 22. Synthesis of 2,6-bis(pentafluorobenzenesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone
In 20 ml of acetone, 1.00 g (0.004 mol) of 2,6-dihydroxybenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,obtained in Reference Example 3, and 2.67 g (0.01 mol)of pentafluorobenzenesulfonyl chloride were dissolved, then1.01 g (0.01 mol) of triethylamine was added dropwise theretoat room temperature, and the solution was reacted for 2 hourswith stirring. After completion of the reaction, the obtainedreaction solution was poured into 150 ml of water, followed byextracting oily substance precipitated with 50 ml of chloroform4 times, washing of the organic layer with water (50 ml×4) andconcentrating under reduced pressure. Then, the crude crystalresidue was recrystallized from a mixed solvent of methylene chloride/ethyl acetate to obtain 1.8 g of 2,6-bis(pentafluorobenzenesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetroneas pale yellow prismcrystal (yield: 63.5 %).Mp.: 299 °C¹HNMR(DMSO-d₆) δ ppm: 8.44(2H, s, pyromellitic ring H×2)IR(KBr-Disk) ν cm^-1 : 3108, 3042, 1784 (C=O), 1289 (SO₂O),1120 (SO₂O)MS(m/z) : 708 (M+)Example 23. Synthesis of 2,6-bis(3,5-di-trifluoromethylphenysulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone
The similar reaction as in Example 23 was conducted exceptthat 3,5-di-trifluoromethylphenylsulfonyl chloride was usedinstead of pentafluorobenzenesulfonyl chloride used in Example22, and the obtained reaction solution was poured into 150 mlof water for crystallization, followed by filtering crystalprecipitated, washing with water and drying to obtain crudecrystal. Then, the crude crystal was recrystallized from a mixedsolvent of ethyl ether/acetonitrile to obtain 2.0 g of 2,6-bis(3,5-di-trifluoromethylphenylsulfonyloxy)benzo[1,2-,c:4,5-c'] dipyrrole-1,3,5,7(2H,6H)-tetrone as pale yellowflaky crystal (yield: 62.5 %).Mp.: 210-212 °C¹HNMR (DMSO-d₆) δ ppm: 8.31 (2H, s, pyromellitic ring H×2),8.74(6H, s, aromatic ring H×6)IR (KBr-Disk) ν cm^-1 : 3098, 3042, 1802 (C=O), 1757(C=O),1284 (SO₂O), 1196 (SO₂O)MS (m/z): 800 (M⁺)Example 24. Synthesis of 2,6-bis(nonafluorobutanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone
In 1.5 ml of 2,6-lutidine and 10 ml of N,N-dimethylacetamide,1.00 g (0.004 mol) of 2,6-dihydroxybenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone, obtained in Reference Example 3, was suspended, then3.62 g (0.012 mol) of nonafluorobutanesulfonyl fluoride wasadded dropwise thereto at room temperature, and the suspensionwas reacted for 30 minutes with stirring. After completion ofthe reaction, the obtained reaction solution was poured into150 ml of water for crystallization, followed by filteringprecipitated crystal, washing with water and drying to obtaincrude crystal. Then, the crude crystal residue wasrecrystallized from acetonitrile to obtain 1.1 g of 2,6-bis(nonafluorobutanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetroneas pale yellow powdercrystal (yield: 39.9 %).Mp.: 300°C or more¹HNMR(DMSO-d₆) δ ppm: 8.12 (2H, s, pyromellitic ring H×2)Example 25. Synthesis of 2,6-bis(trifluoromethanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone
In 20 ml of methylene chloride, 1.00 g (0.004 mol) of2,6-dihydroxybenzo[1,2-c:4,5-c')dipyrrole-1,3,5,7(2H,6H)-tetrone,obtained in Reference Example 3 and 1.20 g (0.008 mol)of trifluoromethanesulfonic acid were suspended, then 10 ml ofmethylene chloride solution dissolving 1.65 g (0.008 mol) ofdicyclohexylcarbodiimide was added dropwise thereto at roomtemperature, and the suspension was reacted for 8 hours withstirring. After completion of the reaction, the obtainedreaction solution was filtered, followed by washing the filtratewith water and concentrating to obtain 2.3 g of crude crystal.Then, the crude crystal was recrystallized from methanol toobtain 0.6 g of 2,6-bis(trifluoromethanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetraneas colorless prism crystal(yield: 29.3 %).Mp.: 231-233 °C¹HNMR(DMSO-d₆) δ ppm: 8.12(2H, s, pyromellitic ring H×2) Example 26. Synthesis of 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(pentafluorobenzenesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone
In 20 ml of acetone, 1.11 g (0.004 mol) of3a,4,4a,7a,8,8a-hexahydro-2,6-dihydroxy-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone,obtained in Reference Example 2 and 2.67 g (0.01 mol) ofpentafluorobenzenesulfonyl chloride were dissolved, then 1.01g (0.01 mol) of triethylamine was added dropwise thereto at roomtemperature, and the solution was reacted for 2 hours withstirring. After completion of the reaction, the obtainedreaction solution was poured into 150 ml of water forcrystallization, followed by filtering precipitated crudecrystal, washing with water and drying to obtain crude crystal.Then, the crude crystal was recrystallized from a mixed solventof acetonitrile/methanol to obtain 1.7 g of3a,4,4a,7a,8,8a-hexahydro-2,6-bis(pentafluorobenzenesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone as colorless flaky crystal (yield: 57.6 %).Mp.: 300 °C or more¹HNMR (DMSO-d₆) δ ppm: 3.32-3.36(6H, m, CH×4), 5.95(2H, bs, -CH= ×2)IR(KBr-Disk) ν cm-1 . 2961, 1815(C=O), 1759(C=O), 1313 (SO₂O) ,1109 (SO₂O)MS(m/z) : 736 (M⁺ -2H)Example 27.
A resist composition consisting of the followingingredients was prepared. poly (p-hydroxystyrene/styrene/tert-butyl acrylate) 6.0 g [composition ratio: 7/2/1, weight-average molecular weight (Mw) = 10,000, molecular weight distribution (Mw/Mn) = 1.9] 2,6-bis(3-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone 0.3 g[the compound of Example 10] dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed as follows using the above-describedresist composition.
Namely, the resist composition was filtered using amembrane filter with 0.1 µm pore size, followed by spin-coatingon a silicon substrate, pre-baking at 130 °C for 90 sec. on ahot plate, to obtain a resist film with thickness of 0.3 µm. Thena pattern was drawn using EB direct writing equipment(acceleration voltage of 50 KeV), followed by baking at 120 °Cfor 60 sec. on a hot plate, developing using a 2.38 % aqueoussolution of tetramethylammonium hydroxide and washing withwater, to form a positive resist pattern. The positive resistpattern thus obtained showed resolution of 100 nm L&S (0.1 µmL&S) with sensitivity of 4.0 µ C/cm². Pattern profile was nearlyrectangular.Example 28.
A pattern was formed similarly as in Example 27 exceptthat exposure was carried out using a KrF excimer laser stepper(NA 0.55) instead of EB direct writing equipment in Example 27.The positive resist pattern thus obtained showed resolution of0.15µm L&S with sensitivity of 5 mJ/cm². Pattern profile wasnearly rectangular.Example 29.
A resist composition consisting of the followingingredients was prepared. poly (p-1-ethoxyethoxystyrene/p-hydroxystyrene/p-tert-butoxystyrene) 6.0 g [composition ratio: 26/64/10, Mw = 10,000, Mw/Mn = 1.02] 2,6-bis(3-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone 0.3 g[the compound of Example 10] tris[2-(2-methoxyethoxy) ethyl] amine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
The above-described resist composition was filteredusing a membrane filter with 0.1 µm pore size, followed byspin-coating on a silicon substrate, pre-baking at 130 °C for90 sec. on a hot plate, to obtain a resist film with thicknessof 0.3 µm. Then a pattern was drawn using an EB direct writingequipment (acceleration voltage of 50 KeV), followed by bakingat 105 °C for 60 sec. on a hot plate, developing using a 2.38 %aqueous solution of tetramethylammonium hydroxide and washingwith water, to form a positive resist pattern. The positiveresist pattern thus obtained showed resolution of 100 nm L&S(0.1 µm L&S) with sensitivity of 2.8 µC/cm². Pattern profile wasnearly rectangular.Example 30.
A pattern was formed similarly as in Example 29 exceptthat exposure was carried out using a KrF excimer laser stepperinstead of the EB direct writing equipment in Example 29. Thepositive resist pattern thus obtained showed resolution of 0.15µm L&S with sensitivity of 3 mJ/cm². Pattern profile was nearlyrectangular.Example 31.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g [composition ratio: 33/67, Mw = 10,000, Mw/Mn = 1.02] 2,6-bis(3-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H, 6H)-tetrone 0.3 g [the compound of Example 10] dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g[commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 27 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1 µm L&S) withsensitivity of 3.0 µ C/cm². Pattern profile was nearlyrectangular.Example 32.
A pattern was formed similarly as in Example 27 exceptthat exposure was carried out using a KrF excimer laser stepperinstead of the EB direct writing equipment in Example 31. Thepositive resist pattern thus obtained showed resolution of 0.15µm L&S with sensitivity of 3 mJ/cm². Pattern profile was nearlyrectangular.Example 33.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g [composition ratio: 1/9, Mw = 2,500, Mw/Mn = 1.02] 2,6-bis(pentafluorobenzenesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-l,3,5,7(2H,6H)-tetrone 0.3 g [the compound of Example 22] 2,4,6-tris(methoxymethyl)amino-1,3,5-s-triazine 2.0 g dicyclohexylmethylamine' 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 58.0 g
A pattern was formed similarly as in Example 27 using theabove-described resist composition. The negative resist patternthus obtained showed resolution of 100 nm L&S (0.1 µm L&S) withsensitivity of 7.0 µ C/cm². Pattern profile was nearlyrectangular.Example 34.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g [composition ratio: 2/8, Mw = 8,500, Mw/Mn = 1.05] 2,6-bis(pentafluorobenzenesulfonyloxy)benzo[1,2-c:4,5-c')dipyrrole-1,3,5,7(2H,6H)-tetrone 0.3 g [the compound of Example 22] 4,4',4''-tris(4-tert-butoxycarbonylmethoxyphenyl)methane 1.5 g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 58.0 g
A pattern was formed similarly as in Example 27 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1 µm L&S) withsensitivity of 4.0 µ C/cm². Pattern profile was nearlyrectangular.Example 35.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxycarbonylmethoxystyrene/styrene/p-hydroxystyrene) 6.0 g [composition ratio: 25/10/65, Mw = 10,000, Mw/Mn = 1.85] 2,6-bis(nonafluorobutanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone 0.3 g [the compound of Example 24] dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] ethyl lactate 30.0 g ethyl 3-ethoxypropionate 30.0 g
A pattern was formed similarly as in Example 27 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1 µm L&S) with sensitivity of 4.0 µ C/cm². Pattern profile was nearlyrectangular.Example 36.
A resist composition consisting of the followingingredients was prepared. poly (p-hydroxystyrene/styrene/tert-butyl acrylate) 6.0 g [composition ratio: 7/2/1, Mw = 10,000, Mw/Mn = 1.9] 2,6-bis(3,5-di-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone 0.3 g [the compound of Example 23] dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 27 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1 µm L&S) withsensitivity of 4.0 µ C/cm². Pattern profile was nearlyrectangular.Example 37.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g [composition ratio: 33/67, Mw = 10,000, Mw/Mn = 1.02] 2,6-bis(10-camphorsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone 0.3 g [the compound of Example 20] 4-N,N-dimethylaminopyridine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 27 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1 µm L&S) with sensitivity of 5.0 µ C/cm². Pattern profile was nearlyrectangular.Example 38.
A resist composition consisting of the followingingredients was prepared. poly (p-1-ethoxyethoxystyrene/p-hydroxystyrene/p-tert-butoxystyrene) 6.0 g [composition ratio: 26/64/10, Mw = 10,000, Mw/Mn = 1.02] tetrahydro-2,5-bis(10-camphorsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone 0.3 g [the compound of Example 5] trioctylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 30 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 0.15 µm L&S with sensitivityof 4 mJ/cm². Pattern profile was nearly rectangular.Example 39.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g [composition ratio: 33/67, Mw = 10,000, Mw/Mn = 1.02] 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(3-trifluoromethylphenylsulfonyloxy-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone 0.3 g [the compound of Example 6] dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] ethyl lactate 60.0 g
A pattern was formed similarly as in Example 27 using theabove-described resist composition. The positive resist pattern thus obtained showed resolution of 100 nm L&S (0.1 µ m L&S) withsensitivity of 4.0 µ C/cm². Pattern profile was nearlyrectangular.Example 40.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g [composition ratio: 33/67, Mw = 10,000, Mw/Mn = 1.02] 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(10-camphorsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone [the compound of Example 9] 0.3 g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 30.0 g ethyl 3-ethoxypropionate 30.0 g
A pattern was formed similarly as in Example 28 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 0.15 µm L&S with sensitivityof 5 mJ/cm². Pattern profile was nearly rectangular.Example 41.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g [composition ratio: 33/67, Mw = 10,000, Mw/Mn = 1.02] 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(pentafluorobenzenesulfonyloxy)-4,8-ethenobenzo[2,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone 0.3 g [the compound of Example 26] dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 27 using the above-described resist composition. A positive resist patternthus obtained showed resolution of 100 nm L&S (0.1µm L&S) withsensitivity of 4.0 µ C/cm². Pattern profile was nearlyrectangular.Comparative Example 1.
A resist composition consisting of the followingingredients was prepared. poly (p-hydroxystyrene/styrene/tert-butyl acrylate) 6.0 g [composition ratio: 7/2/1, Mw = 10,000, Mw/Mn = 1.9] 2,6-bis(methanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone 0.3 g [the compound of Reference Example 6] dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
Preparation of the above-described composition wasconducted, but could not be succeeded due to no dissolution ofthe acid generator.Comparative Example 2.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g [composition ratio: 33/67, Mw = 10,000, Mw/Mn = 1.02] N-10-camphorsulfonyloxy-5-norbornene-2,3-dicarboxyimide 0.3g [the compound of Reference Example 4] dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 28 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 0.18 µm L&S with sensitivityof 10 mJ/cm², but 0.18 µm L&S could not be resolved. The pattern was poor with tapered profile.Comparative Example 3.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g [composition ratio: 33/67, Mw = 10,000, Mw/Mn = 1.02] N-pentafluorobenzenesulfonyloxy-5-norbornene-2,3-dicarboxyimide [the compound of Reference Example 5] 0.3 g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 27 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 110 nm L&S (0.11 µm L&S) withsensitivity of 8.0 µC /cm², but 100 nm L&S could not be resolved.The pattern was poor with reversely tapered profile.Comparative Example 4.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxycarbonylmethoxystyrene/styrene/p-hydroxystyrene) 6.0 g [composition ratio: 25/10/65, Mw = 10,000, Mw/Mn =.1.85] 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(n-butanesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone [the compound of Reference Example 7] 0.3 g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 27 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 120 nm L&S (0.12 µm L&S) withsensitivity of 10 µ C/cm², but 100 nm L&S could not be resolved. The pattern was poor with tapered profile.Comparative Example 5.
A resist composition consisting of the followingingredients was prepared. poly (p-hydroxystyrene/styrene/tert-butyl acrylate) 6.0 g [composition ratio: 7/2/1, Mw = 10,000, Mw/Mn = 1.9] N-10-camphorsulfonyloxy-5-norbornene-2,3-dicarboxyimide 0.3g [the compound of Reference Example 5] dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 27 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 120 nm L&S (0.12 µm L&S) withsensitivity of 12 mJ/cm², but 100 nm L&S could not be resolved.The pattern was poor with tapered profile.
As is clear from the results of each Example, thebisimidesulfonate compound shown by the general formula [4],among the compounds of the present invention, was found to bevery useful as an acid generator for a chemically amplifiedresist composition. While, a conventional compound very similarto the compound shown by the general formula [4] was found notto provide a resist composition due to poor solubility as isclear from the results of Comparative Example 1, or was difficultto be used due to low sensitivity, low resolution and poor profileas is clear from the comparison of the results of ComparativeExample 4 and Example 35.
Furthermore, a conventional compound similar to thecompound shown by the general formula [4] was confirmed to showlow sensitivity, low resolution and poor profile by thecomparisons among Examples 27 to 32, Examples 35 to 41 andComparative Examples 2, 3 and 5. Example 42. Synthesis of 5,5'-oxybis[2-hydroxyl-1H-isoindole-1,3(2H)-dione]
In 150 ml of a pyridine solution dissolving 11.9 g (0.17mol) of hydroxylamine hydrochloride, 24.1 g (0.078 mol) of4,4'-oxydiphthalic anhydride was added at room temperature, andthe solution was reacted at 90°C for 15 minutes with stirring.After completion of the reaction, the obtained reaction solutionwas concentrated under reduced pressure, and the resultingresidue was added with 150 ml of an aqueous solution of 6 % ofacetic acid, followed by filtering precipitated crystal,washing with water and recrystallization from ethanol, to obtain24.6 g of desired substance as pale yellow powder crystal.Mp.: 286-287 °C¹HNMR (DMSO-d₆) δ ppm: 7.49-7.51 (4H, m, phthalimide ring H×4),7.88-7.90 (2H, d, phthalimide ring H×2), 10.85 (2H, s, OH×2)IR (KBr-Disk) ν cm^-1 : 3175, 1785 (C=O), 1716 (C=O)Example 43. Synthesis of 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxyl-1H-isoindole-1,3(2H) -dione]
The similar reaction and treatment as in Example 42 werecarried out using 20.0 g (0.045 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and 6.9 g(0.099 mol) of hydroxylamine hydrochloride salt. The obtainedprecipitated oily substance was fractionated and recrystallizedfrom ethyl acetate. The obtained precipitated crystal wasfiltered, followed by washing with water and drying under reducedpressure, to obtain 19.8 g of desired substance as orange yellowpowder crystal.Mp.: 102-110 °C¹HNMR (DMSO-d₆) δ ppm: 7.62 (2H, s, phthalimide ring H × 2),7.82-7.84(2H, d, phthalimide ring H×2). 7.97-7.99(2H, d,phthalimide ring H×2), 11.01(2H, s, OH×2)IR (KBr-Disk) ν cm^-1 . : 3275, 1792(C=O), 1717(C=O)Example 44. Synthesis of 5,5'-bis[2-hydroxyl-1H-isoindole-1,3(2H) -dione]
The similar reaction and treatment as in Example 42 werecarried out using 25.0 g (0.085 mol) of 4 , 4 ' -biphthalic anhydrideand 13.0g (0.187 mol) of hydroxylamine hydrochloride, to obtain27.4 g of desired substance as yellow powder crystal.Mp.: 300 °C or more¹HNMR (DMSO-d₆) δ ppm: 7.93-7.95(2H, d, phthalimide ring H×2),8.23(2H, s, phthalimide ring H×2) , 8.23-8.26(2H, d, phthalimidering H×2), 10.89(2H, s, OH×2)IR (KBr-Disk) ν cm^-1 : 3212, 1782 (C=O) , 1725 (C=O)Example 45. Synthesis of 5,5'-oxybis[2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione]
In 1.5 ml of pyridine and 10 ml of N,N-dimethylacetamide,1.36 g (0.004 mol) of 5,5'-oxybis[2-hydroxyl-1H-isoindole-1,3 (2H) -dione] , obtained in Example 42, was dissolved, and then2.94 g (0.012 mol) of 3-trifluoromethylbenzenesulfonyl chloridewas added dropwise thereto at room temperature, and the solutionwas reacted at room temperature for 3 hours with stirring. Aftercompletion of the reaction, the obtained reaction solution waspoured into 150 ml of water for crystallization, followed byfiltering precipitated crude crystal, washing with water thenwith methanol, and recrystallizing from acetonitrile, to obtain1.9 g of desired substance as pale yellow flaky crystal.Mp.: 189-192 °C¹HNMR (DMSO-d₆) δ ppm: 7.60-7.62 (4H, m, phthalimide ring H×4),7.98-8.01 (4H, dd, phthalimide ring H×2 and aromatic ring H×2), 8.31-8.33(2H, d, aromatic ring H×2), 8.37(2H, s, aromaticring H×2), 8.40-8.42(2H, d, aromatic ring H×2)IR (KBr-Disk) ν cm^-1 : 3112, 1793(C=O), 1761(C=O), 1329 (SO₂) ,1194 (SO₂)Example 46. Synthesis of 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione]
The similar reaction and post-treatment as in Example 45were carried out using 1.90 g (0.004 mol) of 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxyl-1H-isoindole-1,3(2H)-dione],obtained in Example 43, and 2.94 g(0.012 mol) of 3-trifluoromethylbenzenesulfonyl chloride. Theobtained crude crystal was recrystallized from n-hexane/ethylether to obtain 2.54 g of desired substance as pale yellow flakycrystal.¹HNMR (DMSO-d₆) δ ppm: 7.66(2H, s, aromatic ring H×2), 7.91-7.93(2H,d, aromatic ring H×2) , 7.96-8.00(2H, t, aromatic ringH×2), 8.08-8.10(2H, d, aromatic ring H×2), 8.31-8.32(2H, d,aromatic ring H×2), 8.40(2H, s, aromatic ring H×2), 8.42-8.45(2H,d, aromatic ring H×2)Example 47. Synthesis of 5,5'-bis[2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione]
The similar reaction and post-treatment as in Example 45were carried out using 0.68 g (0.002 mol) of 5,5'-bis[2-hydroxyl-1H-isoindole-1,3 (2H) -dione] , obtained in Example 44,and 1.55 g (0.006 mol) of 3-trifluoromethylbenzenesulfonylchloride. The obtained crude crystal was recrystallized fromacetonitrile to obtain 0.5 g of desired substance as pale yellowpowder crystal.Mp.: 235-236°C¹HNMR (DMSO-d₆) δ ppm: 7.97-8.04 (4H, m, phthalimide ring H×2 andaromatic ring H×2), 8.32-8.45 (10H, m, phthalimide ring H×4 andaromatic ring H×6)IR (KBr-Disk) ν cm^-1: 3092, 1792(C=O), 1755(C=O), 1329 (SO₂) ,1198 (SO₂)Example 48. Synthesis of 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-toluenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione]
The similar reaction and post-treatment as in Example 45 were carried out using 1.90 g (0.004 mol) of 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis(2-hydroxyl-1H-isoindole-1,3(2H)-dione],obtained in Example 43, and 2.29 g(0.012 mol) of p-toluenesulfonyl chloride. The obtained crudecrystal was recrystallized from methanol to obtain 1.25 g ofdesired substance as pale yellow powder crystal.Mp.: 122-131 °C¹HNMR (DMSO-d₆) δ ppm: 2.50(6H, s, CH₃×2), 7 .52-7. 54 (4H, d,aromatic ring H×4), 7.70(2H, s, phthalimide ring H×2),7.93-7.95(2H, d, phthalimide ring H×2), 7.97(4H, d, aromaticring H×4), 8.07-8.10(2H, d, phthalimide ring H×2)IR (KBr-Disk) ν cm^-1 : 3073, 1806 (C=O) , 1759 (C=O) , 1400 (SO₂) ,1196(SO₂)Example 49. Synthesis of 5,5'-oxybis[2-(camphorsulfonyl)oxy-1H-isoindole-1,3(2H)-dione]
In 1.5 ml of pyridine and 10 ml of N,N-dimethylacetamide,1.36 g (0.004 mol) of 5,5'-oxybis(2-hydroxyl-1H-isoindole-1,3 (2H) -dione] , obtained in Example 42, was dissolved, then 3.01g (0.012 mol) of 10-camphorsulfonyl chloride was added dropwisethereto at room temperature, and the solution was reacted atroom temperature for 1 hour with stirring. After completion ofthe reaction, the obtained reaction solution was poured into150 ml of water for crystallization, followed by extracting whiteoily substance with methylene chloride (50 m1×3), washing theorganic layer with water(100 m1×3) and concentrating underreduced pressure, to obtain 2.3 g of pale yellow viscous oilysubstance. Then, the obtained oily substance was separated bya column chromatography ["Wakogel C-200", eluent: methylenechloride/methanol = 16/1 (v/v)], followed by recrystallizationfrom n-hexane/ethyl acetate, to obtain 1.2 g of desired substanceas colorless short needle-like crystal.Mp.: 169-174 °C¹HNMR (DMSO-d₆) δ ppm: 0.83 (6H, s, CH₃×2) , 1.04(6H, s, CH₃×2),1.46-1.48(2H, m, bridged aliphatic ring H×2), 1.68(2H, m,bridged aliphatic ring H×2) , 1.95-2.00 (4H, m, bridged aliphatic ring H×4), 2.11(2H, t, bridged aliphatic ring H×2), 2.21-2.24(2H,m, bridged aliphatic ring HX2), 2.36-2.40(2H, m,bridged aliphatic ring H × 2), 3.87-3.98(4H, q, CH₂ × 2),7.65-7.66(2H, d, phthalimide ring H×2) , 7.70 (2H, s, phthalimidering H×2), 8.08-8.10 (2H, d, phthalimide ring H×2)IR (KBr-Disk) ν cm^-1 : 3102, 2969, 1798 (C=O) , 1750 (C=O) , 1399 (SO₂) ,1186 (SO₂)UV (MeCN) λmax: 318 nm( E 5760)Example 50. Synthesis of 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(10-camphorsulfonyl)oxy-1H-isoindole-1,3(2H)-dione]
The similar reaction as in Example 49 was carried out using1.90 g (0.004 mol) of 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]-bis[2-hydroxyl-1H-isoindole-1,3(2H)-dione],obtained in Example 43, and 3.01 g (0.012 mol)of 10-camphorsulfonyl chloride. The obtained reaction solutionwas poured into 150 ml of water for crystallization, followedby filtering the obtained crystal, washing with water and drying,to obtain 3.8 g of crude crystal. Then, the crude crystal wasrecrystallized from methanol to obtain 0.5 g of desired substanceas colorless prism crystal.Mp.: 140-145 °C¹HNMR (DMSO-d₆) δ ppm: 0.83 (6H, s, CH₃×2), 1.04(6H, s, CH₃×2),1.46-1.48(2H, m, bridged aliphatic ring H×2), 1.67(2H, m,bridged aliphatic ring H×₂) , 1.95-2.00 (4H, m, bridged aliphaticring H×4), 2.11(2H, t, bridged aliphatic ring H×2), 2.22-2.25(2H,m, bridged aliphatic ring H×2), 2.36-2.41(2H, m,bridged aliphatic ring H×2), 3.87-3 .98 (4H, q, CH₂×2) , 7.74 (2H,s, phthalimide ring H×₂), 7.98-8.00(2H, d, phthalimide ring H×2), 8.18-8.20(2H, d, phthalimide ring H×2)IR (KBr-Disk) ν cm^-1 : 3113, 2969, 1802 (C=O) , 1757 (C=O) , 1391 (SO₂),1188 (SO₂)Example 51. Synthesis of 5,5'-oxybis[2-(pentafluorobenzenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione]
In 25 ml of acetone, 1.36 g (0.004 mol) of 5,5'-oxybis[2-hydroxyl-1H-isoindole-1,3(2H)-dione], obtained inExample 42, and 2.67 g (0.01 mol) of pentafluorobenzenesulfonylchloride were suspended, then 1.01 g (0.01 mol) of triethylaminewas added dropwise thereto at 18 to 25 °C, and the suspensionwas reacted at room temperature for 2 hours with stirring. Thereaction solution was poured into 150 ml of water, followed byextracting the precipitated viscous oily substance withmethylene chloride (50 ml×3), washing the organic layer withwater(100 ml×3) and concentrating under reduced pressure, toobtain 2.5 g of pale yellow crude crystal. Then, the crude crystalwas recrystallized from methylene chloride/acetonitrile, toobtain 0.8 g of desired substance as pale yellow powder crystal.Mp.: 224-229 °C¹HNMR (DMSO-d₆) δ ppm: 7.61-7.64 (4H, m, phthalimide ring H×4),8.02-8.04(2H, d, phthalimide ring H×2)IR (KBr-Disk) ν cm^-1 . 3108, 1848(C=O), 1765(C=O), 1429(SO₂),1203(SO₂)UV (MeCN) λ max : 313 nm (ε 7800), 275 nm (ε 11910)MS(m/z) : 800 [M-H]Example 52. Synthesis of 5,5'-bis[2-n-butanesulfonyloxy-1H-isoindole-1,3(2H)-dione]
The similar reaction and post-treatment as in Example 45were carried out using 1.30 g (0.04 mol) of 5,5'-bis[2-hydroxyl-1H-isoindole-1,3(2H)-dione),obtained in Example 44,and 1.88 g (0.012 mol) of n-butanesulfonyl chloride. The obtainedpale yellow crude crystal was recrystallized fromacetone/methanol to obtain 1.5 g of desired substance ascolorless flaky crystal.Mp.: 213-214 °C¹HNMR (DMSO-d₆) δ ppm: 0.92-0.95(6H, t, CH₃×2), 1.43-1.49(4H,q, CH₂×2), 1.90-1.94(4H, m, CH₂×2), 3.79-3.83 (4H, m, CH₂×2),8.09-8.11(2H, d, phthalimide ring H×2), 8.39-8.41(2H, d,phthalimide ring H×2), 8.46(2H, s, phthalimide ring hydeogen×2) IR (KBr-Disk) ν cm^-1 : 2969, 1790 (C=O) , 1744 (C=O) , 1387 (SO₂),1173 (SO₂)Example 53. Synthesis of 5,5'-oxybis[2-(3,5-di-trifluoromethylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione]
The similar reaction and post-treatment as in Example 45were carried out using 1.36 g (0.004 mol) of 5,5'-oxybis[2-hydroxyl-1H-isoindole-1,3(2H)-dione],obtained in Example 42,and 3.13 g (0.01 mol) of 3,5-di-trifluoromethylphenylsulfonylchloride, to obtain 3.1 g of pale yellow crude crystal. Then,by recrystallizing the crude crystal was recrystallized fromisopropyl ether/acetonitrile, to obtain 1.5 g of desiredsubstance as colorless prism crystal.Mp.: 179-183 °C¹HNMR (DMSO-d₆) δ ppm: 7.56-7.61 (4H, m, phthalimide ring H×4),7.99-8.01(2H, d, phthalimide ring H×2), 8.73(4H, s, aromaticring H×4), 8.75(2H, s, aromatic ring H×2)IR (KBr-Disk) ν cm^-1 : 3092, 1796 (C=O) , 1746 (C=O) , 1410 (SO₂).1202 (SO₂)Example 54. Synthesis of 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(pentafluorobenzenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione]
The similar reaction and post-treatment as in Example 46were carried out using 1.90 g (0.004 mol) of 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxyl-1H-isoindole-1,3(2H)-dione],obtained in Example 43, and 2.67 g(0.01 mol) of pentafluorobenzenesulfonyl chloride, to obtain3.6 g of pale yellow crude crystal. Then, the crude crystal wasrecrystallized from methylene chloride/acetonitrile, to obtain2.0 g of desired substance as pale yellow prism crystal.Mp.: 227-230 °C¹HNMR (DMSO-d₆) δ ppm: 7.67(2H, s, phthalimide ring H×2),7.91-7.93(2H, d, phthalimide ring H×2), 8.11-8.13 (2H, d,phthalimide ring H×2)IR (KBr-Disk) ν cm^-1 : 3108, 1811 (C=O) , 17 65 (C=O) , 1426 (SO₂), 1200 (SO₂)MS (m/z) : 933 [M-H]Example 55. Synthesis of 5,5'-bis[2-(4-toluenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione]
The similar reaction and post-treatment as in Example 45were carried out using 1.30 g (0.04 mol) of 5,5'-bis[2-hydroxyl-1H-isoindole-1,3(2H)-dione],obtained in Example 44,and 2.29 g (0.012 mol) of p-toluenesulfonyl chloride, to obtain4.1 g of pale yellow crude crystal. Then, the crude crystal wasrecrystallized from acetonitrile, to obtain 1.4 g of 5,5'-bis[2-(4-toluenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione] aspale yellow short needle-like crystal.Mp.: 287-288 °C¹HNMR (DMSO-d₆) δ ppm: 2.50(6H, s, CH₃×2), 7.53-7.55(4H, d,aromatic ring H × 4), 7.95-7.97(4H, d, aromatic ring H×4),8.02-8.04(2H, d, phthalimide ring H×2), 8.34-8.36(2H, d,phthalimide ring H×2), 8.39(2H, s, phthalimide ring H×2)IR (KBr-Disk) ν cm^-1 : 3069, 1790 (C=O) , 1755(C=O), 1395 (SO₂),1196 (SO₂)Examples 56 to 65. Synthesis of the compounds shown by the generalformula [13]
The similar reactions and post-treatments as in Example51 were conducted except that various sulfonyl chlorides wereused instead of pentafluorobenzenesulfonyl chloride used inExample 51, to obtain desired bisimidesulfonate compounds afterpurifying the obtained crude crystals. The results are shownin Tables 6 to 9. Example R¹ Shape(cryst. solvent)Physical property ¹H NMR, IR, and others 56 phenyl pale yellow flaky crystal (MeCN)Mp.: 255-256°C ¹HNMR (DMSO - d₆) δ ppm: 7.60-7.61 (4H, m, phthalimide ring H×4), 7.70-7.74 (4H, m, aromatic ring H×4), 7.89-7.93 (2H, t, aromatic ring H×2), 7.98-8.00(2H, d, phthalimide ring H×2), 8.06-8.08(4H, d, aromatic ring H×4) IR (KBr-Disk) ν cm^-1: 3081, 1792 (C=O) , 1755 (C=O) , 1787(SO₂), 1194(SO₂) 57 4-methoxy phenyl pale yellow prism crystal (MeCN)Mp.: 227-229°C ¹HNMR (DMSO-d₆) δ ppm: 3.09(6H, s, CH₃O×2), 7.20-7.22(4H,d, aromatic ring H×4), 7.60-7.61(4H, d, phthalimide ring H×4), 7.97-8.00(6H, dd, aromatic ring H×4 and phthalimide ring H×2) IR(KBr-Disk) ν cm^-1: 3106, 2951, 1790 (C=O), 1752(C=O), 1385(SO₂), 1173 (SO₂) * MeCN: acetonitrile Example R¹⁰ Shape(cryst. solvent)Physical property ¹H NMR, IR, and others 58 4-n-butyl phenyl orange yellow prism crystal (MeCN)Mp. : 184-185°C ¹HNMR (DMSO-d₆) δ ppm: 0.88-0.92(6H, t, CH₃×2), 1.28-1.31(4H, m, CH₂×2), 1.57-1.61(4H, m, CH₂ ×2), 2.72-2.75 (4H, m, CH₂×2), 7.53-7.55(4H, d, aromatic ring H×4), 7.60-7.62(4H, m, phthalimide ring H×4), 7.95-8.00(6H, dd, aromatic ring H×4 and phthalimide ring H ×2) IR(KBr-Disk) ν cm^-1: 3077, 2955, 2867, 1792(C=O), 1750(C=O), 1387(SO₂), 1196 (SO₂) UV (THF) λ max: 312nm(ε 6800) 59 benzyl colorlessprism crystal (MeCN/Me₂CO)Mp.: 217°C ¹HNMR (DMSO-d₆) δ ppm : 5.18 (4H, s, CH₂×2), 7.44-7.46(6H, m, aromatic ring H×6), 7.60-6.61(4H, m, aromatic ring H×4), 7. 71-7.73 (4H, m, phthalimide ring H×4), 8.06-8.08(2H, d, phthalimide ring H×2) IR(KBr-Disk) νcm^-1: 3071, 2996, 1795(C=O), 1748(C=O), 1387(SO₂), 1181 (SO₂) 60 4-trifluoro methyl phenyl pale yellow short needle-like crystal (EtOH/Me₂CO) Mp. : 184-186°C Mp.: 184-186°C ¹HNMR (DMSO-d₆) δ ppm: 7.60-7.62(4H, m, phthalimide ring H×4), 8.00-8.03 (2H, d, phthalimide ring H×2), 8.10-8.12(4H, d, aromatic ring H×4), 8.31-8.33(4H, d, aromatic ring H×4) IR(KBr-Disk) ν cm^-1 : 3106, 1794(C=O), 1755 (C=O) , 1325 (SO₂) , 1198 (SO₂) * MeCN: acetonitrile, Me₂CO: dimethylketone, EtOH: ethanol Example R¹⁰ Shape (cryst. solvent) Physical property ¹H NMR, IR, and others 61 2,5-di chloro phenyl colorless powder crystal (DMAc/MeCN)Mp. : 287°C ¹HNMR (DMSO-d₆) δ ppm: 7.59-7.60(4H, m, phthalimide ring H×4), 7.92-8 .00 (6H, m, phthalimide ring H×2 and aromatic ring H×4), 8.08-8.09(2H, m, aromatic ring H×2) IR (KBr-Disk) ν cm^-1: 3096, 1800 (C=O) , 1755(C=O), 1410(SO₂), 1196(SO₂) 62 2-thienyl pale yellow powder crystal (MeCN)Mp.: 255-256°C ¹HNMR(DMSO-d₆) δ ppm: 7.34-7.36(2H, t, thiophene ring H ×2), 7.61-7.63(4H, m, phthalimide ring H×4), 8.00-8.02(2H, d, phthalimide ring H×2), 8.11-8.12 (2H, d, thiophene ring HX2), 8.37-8.38(2H, d, thiophene ring H×2) IR (KBr-Disk) ν cm^-1 : 3102, 1794 (C=O) , 1750(C=O), 1393(SO₂), 1190(SO₂) 63 4-ethyl phenyl pale yellowshort needle-like crystal(MeCN)Mp.: 211-213°C ¹HNMR(DMSO-d₆) δ ppm: 1.20-1.24(6H, t, CH₃×2). 2.75-2.77 (4H, m, CH₂×2), 7.55-7.57 (4H, d, aromatic ring H× 4), 7.60-7.62 (4H, m, phthalimide ring H × 4), 7.96-8.01 (6H, dd, aromatic ring H×4 and phthalimide ring H×2) IR(KBr-Disk) νcm^-1: 3075, 2973, 2876, 1792(C=O), 1750(C=O), 1385(SO₂), 1198(SO₂) * DMAc: N,N-dimethylacetamide, MeCN: acetonitrile Example R¹⁰ Shape(cryst. solvent) Physical property ¹H NMR, IR, and others 64 4-n-propyl phenyl pale orange yellow short needle-like crystal (MeCN)Mp. 195-197°C ¹HNMR(DMSO-d₆) δ ppm: 0.87-0.91(6H, t, CH₃×2), 1.61-1.66(4H), m, CH₂×2), 2.69-2.73(4H, m, CH₂ × 2), 7.53-7.55(4H, d, aromatic ring H×4), 7.60-7.61(4H, m, phthalimide ring H×4 7.98-8.00(6H, dd, aromaticring H×4 and phthalimide ring H×2) IR(KBr-Disk) νcm^-1: 3079, 2963, 2874, 1792(C=O), 1761(C=O), 1389(SO₂), 1198(SO₂) 65 4-tert-butyl phenyl pale yellowprism crystal (MeCN/MeOH)Mp. 170-173°C ¹HNMR (DMSO-d₆) (δ ppm: 1.33(18H, s, CH₃ × 6), 7.61-7.63(4H, m, phthalimide ringH×4), 7.74-7.76 (4H, d, aromatic ring H × 4), 7.97-8.02(6H, dd, aromatic ring H × 4 and phthalimide ring HX2) IR (KBr-Disk) νcm^-1: 3102, 1794 (C=O), 1750 (C=O) , 1393 (SO₂) , 1190 (SO₂) * MeCN: acetonitrile, MeOH: methanol Examples 66. Synthesis of 5,5'-oxybis[2-nonafluorobutanesulfonyloxy-1H-isoindole-1,3(2H)-dione]
In 2 ml of pyridine and 10 ml of N,N-dimethylacetamide,1.50 g (0.0044 mol) of 5,5'-oxybis[2-hydroxyl-1H-isoindole-1,3 (2H) -dione] , obtained in Example 42, was suspended, then 3.63g (0.012 mol) of nonafluorobutanesulfonyl fluoride was addeddropwise thereto at 0 to 5 °C, and the suspension was reactedat the same temperature for 1 hour and then at room temperaturefor 3 hours with stirring. After the completion of the reaction,the reaction solution was poured into 150 ml of water, followedby filtering precipitated crystal, washing with 50 ml of water2 times, then 50 ml of methanol one time and drying under reducedpressure, to obtain 2.9 g of pale yellow crude crystal. Then,the obtained crude crystal was recrystallized from N,N-dimethylacetamide/acetonitrileto obtain 1.5 g of 5,5'-oxybis[2-nonafluorobutanesulfonyloxy-1H-isoindole-1,3 (2H) -dione] as pale yellow powder crystal. ¹HNMR (DMSO-d₆) δ ppm: 7.53-7.57(4H, m, phthalimide ring H×4) ,7.95-7.97(2H, d, phthalimide ring H×2)IR (KBr-Disk) ν cm^-1 . 3088, 1808 (C=O), 1754 (C=O), 1348 (SO₂) ,1213 (SO₂)Reference Example 8. Synthesis of 5,5'-oxybis[2-(4-toluenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione]
The similar reaction and post-treatment as in Example 45were carried out using 1.36 g (0.004 mol) of 5,5'-oxybis[2-hydroxyl-1H-isoindole-1,3(2H)-dione],obtained in Example 42,and 2.29 g (0.012 mol) of p-toluenesulfonyl chloride. Theobtained crude crystal was recrystallized from acetonitrile,to obtain 0.8 g of desired substance as colorless needle-likecrystal.Mp.: 250-251 °C¹HNMR (DMSO-d₆) δ ppm: 2.50(6H, s, CH₃×2), 7.52-7.54 (4H, d,aromatic ring H×4), 7.60-7.62(4H, m, phthalimide ring H×4),7.93-7.95(4H, d, aromatic ring H×4), 7.98-8.00(2H, d,phthalimide ring H×2)IR (KBr-Disk) ν cm^-1: 3077, 1790(C=O), 1750 (C=O), 1385 (SO₂) ,1196 (SO₂)Reference Example 9. Synthesis of 5,5'-oxybis[2-trifluoromethanesulfonyloxy-1H-isoindole-1,3(2H)-dione]
The similar reaction and post-treatment as in Example 51were carried out using 1.36 g (0.004 mol) of 5,5'-oxybis[2-hydroxyl-1H-isoindole-1,3(2H) -dione] , obtained in Example 42,and 1.69 g (0.01 mol)of trifluoromethanesulfonyl chloride. Theobtained crude crystal was recrystallized from a mixed solventof acetonitrile/ethyl ether, to obtain 0 . 3 g of desired substanceas pale yellow powder crystal.Mp.: 300°C or more¹HNMR (DMSO-d₆) δ ppm: 7.46-7.47(2H, bs, phthalimide ring H×2), 7.51-7.54(2H, d, phthalimide ring H×2), 7.89-7.91(2H, d,phthalimide ring H×2)IR (KBr-Disk) ν cm^-1: 3073, 1771(C=O), 1717(C=O), 1364 (SO₂) , 1229(SO₂)Example 67.
A resist composition consisting of the followingingredients was prepared. poly (p-hydroxystyrene/styrene/tert-butyl acrylate) 6.0 g [composition ratio: 7/2/1, weight-average molecular weight (Mw) = 10,000, molecular weight distribution (Mw/Mn) = 1.9] 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione] [the compound of Example 46] 0.3 g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed as follows using the above-describedresist composition. Each of the processes thereof is shown inFig. 1.
Namely, the resist composition was filtered using amembrane filter with 0.1 µm pore size, followed by spin-coatingon a silicon substrate 1, pre-baking at 130 °C for 90 sec. ona hot plate, to obtain a resist film 2 with thickness of 0.3µ m (Fig. 1 (a)) . Then EB-drawn pattern 3 was drawn using an EBdirect writing equipment (acceleration voltage of 50 KeV) (Fig.1(b)) , followed by baking at 120 °C for 60 sec. on a hot plate(Fig. 1 (c)), developing using a 2.38 % aqueous solution oftetramethylammonium hydroxide and washing with water, to forma positive resist pattern 2a (Fig. 1 (d)). The positive resistpattern thus obtained showed resolution of 100 nm L&S (0.1 µmL&S) with sensitivity of 4.0 µ C/cm². Pattern profile wasrectangular.
In Fig. 1, each number has the following meaning: 1: silicon substrate 2: resist film of the present invention 3: EB-drawn pattern 4: bake 2a: pattern. Example 68.
A pattern was formed similarly as in Example 67 exceptthat exposure was carried out using a KrF excimer laser stepper(NA 0.55) instead of the EB direct writing equipment in Example67. The positive resist pattern thus obtained showed resolutionof 0.15 µm L&S with sensitivity of 5 mJ/cm². Pattern profile wasnearly rectangular.Example 69.
A resist composition consisting of the followingingredients was prepared. poly (p-1-ethoxyethoxystyrene/p-hydroxystyrene /p-tert-butoxystyrene) 6.0 g [composition ratio: 26/64/10, Mw = 10,000, Mw/Mn = 1.02] 5,5'-oxybis[2-(10-camphorsulfonyl)oxy-1H-isoindole-1,3(2H)-dione] [the compound of Example 49] 0.3 g tris[2-(2-methoxyethoxy)ethyl]amine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
The above-described resist composition was filteredusing a membrane filter with 0.1 µm pore size, followed byspin-coating on a silicon substrate, pre-baking at 130°C for90 sec. on a hot plate, to obtain a resist film with a thicknessof 0.3 µm. Then a pattern was transcripted by irradiation usingan EB direct writing equipment (acceleration voltage of 50 KeV) ,followed by baking at 105°C for 60 sec. on a hot plate, developingusing a 2.38 % aqueous solution of tetramethylammonium hydroxideand washing with water, to form a positive resist pattern. Thepositive resist pattern thus obtained showed resolution of 100nm L&S (0.1 µm L&S) with sensitivity of 2.8 µ C/ cm². Patternprofile was nearly rectangular.Example 70.
A pattern was formed similarly as in Example 69 exceptthat exposure was carried out using a KrF excimer laser stepperinstead of the EB direct writing equipment in Example 69. Thepositive resist pattern thus obtained showed resolution of 0.15µm L&S with sensitivity of 3 mJ/cm². Pattern profile was nearlyrectangular.Example 71.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g [composition ratio: 33/67, Mw = 10,000, Mw/Mn = 1.02] 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-toluenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione] 0.3 g [the compound of Example 48] dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 67 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1µm L&S) withsensitivity of 3.0 µ C/cm². Pattern profile was nearlyrectangular.Example 72.
A pattern was formed similarly as in Example 67 exceptthat exposure was carried out using a KrF excimer laser stepperinstead of the EB direct writing equipment in Example 71. Thepositive resist pattern thus obtained showed resolution of 0.15µm L&S with sensitivity of 3 mJ/cm². Pattern profile was nearlyrectangular.Example 73.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g [composition ratio: 1/9, Mw = 2,500, Mw/Mn = 1.02] 5,5'-oxybis[2-(pentafluorobenzenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione] [the compound of Example 51] 0.3 g 2,4,6-tris (methoxymethyl)amino-1,3,5-s-triazine 2.0 g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 58.0 g
A pattern was formed as follows using the above-describedresist composition. Each of the processes thereof is shown inFig. 2.
Namely, the above-described resist composition wasfiltered using a membrane filter with 0.1 µm pore size, followedby spin-coating on a silicon substrate 1, pre-baking at 130 °Cfor 90 sec. on a hot plate, to obtain a resist film 5 with thicknessof 0.3 µm (Fig. 2 (a)). Then a EB-drawn pattern was drawn usingan EB direct writing equipment (acceleration voltage of 50 KeV)(Fig. 2 (b)), followed by baking at 130 °C for 60 sec. on a hotplate (Fig. 2 (c)), developing using a 2.38 % aqueous solutionof tetramethylammonium hydroxide and washing with water, to forma negative resist pattern 5a (Fig. 2 (d)). The negative resistpattern thus obtained showed resolution of 100 nm L&S (0.1 µmL&S) with sensitivity of 4.5 µC/cm². Pattern profile was nearlyrectangular.
In Fig. 2, each number has the following meaning: 1: silicon substrate 4: resist film of the present invention 6: EB-drawn pattern 7: bake 5a: pattern. Example 74.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g[composition ratio: 2/8, Mw = 8,500, Mw/Mn = 1.05] 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-pentafluorobenzenesulfonyl]oxy-1H-isoindole-1,3(2H)-dione] [the compound of Example 54] 0.3 g 4,4',4"-tris (4-tert-butoxycarbonylmethoxyphenyl)methane 1.5g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 58.0 g
A pattern was formed similarly as in Example 67 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1 µm L&S) withsensitivity of 4.0 µ C/cm². Pattern profile was nearlyrectangular.Example 75.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxycarbonylmethoxystyrene/styrene/p-hydroxystyrene) 6.0 g [composition ratio: 25/10/65, Mw = 10,000, Mw/Mn = 1.85] 5,5'-oxybis[4-trifluoromethylphenylsulfonyloxy-2H-isoindole-1,3(2H)-dione] 0.3 g [the compound of Example 60] dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] ethyl lactate 30.0 g ethyl 3-ethoxypropionate 30.0 g
A pattern was formed similarly as in Example 67 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1 µ m L&S) wi thsensitivity of 4.0 µ C/cm². Pattern profile was nearlyrectangular. Example 76.
A resist composition consisting of the followingingredients was prepared. poly (p-hydroxystyrene/styrene/tert-butyl acrylate) 6.0 g [composition ratio: 7/2/1, weight-average molecular weight (Mw) = 10,000, molecular weight distribution (Mw/Mn) = 1.9] 5,5'-oxybis[2-(3,5-di-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione) [the compound of Example 53] 0.3 g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 67 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1 µ m L&S) withsensitivity of 4.0 µ C/cm². Pattern profile was nearlyrectangular.Example 77.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxystyrene/p-hydroxystyrene) 0.3 g [composition ratio: 33/67, Mw = 10,000, Mw/Mn = 1.02] 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(10-camphorsulfonyl)oxy-1H-isoindole-1,3(2H)-dione] 6.0 g [the compound of Example 50] 4-N,N-dimethylaminopyridine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 67 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1 µm L&S) withsensitivity of 5.0 µ C/cm². Pattern profile was nearlyrectangular. Example 78.
A resist composition consisting of the followingingredients was prepared. poly (p-1-ethoxyethoxystyrene/p-hydroxystyrene/p-tert-butoxystyrene) 6.0 g [composition ratio: 26/64/10, Mw = 10,000, Mw/Mn = 1.02] 5,5'-bis[2-n-butanesulfonyloxy-1H-isoindole-1,3(2H)-dione] [the compound of Example 52] 0.3 g trioctylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 70 using theabove-described resist composition. The positive resist patternthus obtained showed resolution 0.15 µm L&S with sensitivity of4 mJ/cm². Pattern profile was nearly rectangular.Example 79.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g [composition ratio: 30/70, Mw = 8,000, Mw/Mn = 1.01] 5,5'-oxybis[2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione] 0.3 g [the compound of Example 45] dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] ethyl lactate 60.0 g
A pattern was formed similarly as in Example 67 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1 µm L&S) withsensitivity of 4.0 µ C/cm². Pattern profile was nearlyrectangular.Example 80.
A resist composition consisting of the followingingredients was prepared. poly (p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g [composition ratio: 30/70, Mw = 8,000, Mw/Mn = 1.01] 5,5'-oxybis[2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione] 0.3 g [the compound of Example 45] dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] ethyl lactate 50.0 g γ-butyrolactone 10.0 g
A pattern was formed similarly as in Example 68 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 0.15 µm L&S with sensitivityof 5 mJ/cm². Pattern profile was nearly rectangular.Example 81.
A resist composition consisting of the followingingredients was prepared. poly (p-hydroxystyrene/styrene/tert-butyl acrylate) 5.0 g [composition ratio: 7/2/1, weight-average molecular weight (Mw) = 10,000, molecular weight distribution (Mw/Mn) = 1.9] poly(p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene) 1.0 g [composition ratio: 35/65, Mw = 10,000, Mw/Mn = 1.02] 5,5'-oxybis[2-(3,5-di-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione] 0.2 g [the compound of Example 53] 2,4,6-trimethylphenyldiphenylsulfonium pentafluorobenzenesulfonate 0.1 g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 67 using theabove-described resist composition. The positive resist pattern thus obtained showed resolution of 100 nm L&S (0.1 µm L&S) withsensitivity of 4.0 µ C/cm². Pattern profile was nearlyrectangular.Example 82.
A resist composition consisting of the followingingredients was prepared. poly(p-hydroxystyrene/styrene/tert-butyl acrylate) 5.0 g [composition ratio: 7/2/1, weight-average molecular weight (Mw) = 10,000, molecular weight distribution (Mw/Mn) = 1.9] poly(p-tert-butoxystyrene/p-hydroxystyrene) 1.0 g [composition ratio: 30/70, Mw = 8,000, Mw/Mn = 1.01] 5,5'-oxybis[2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione] 0.2 g [the compound of Example 45] triphenylsulfonium pentafluorobenzenesulfonate 0.1 g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] ethyl lactate 60.0 g
A pattern was formed similarly as in Example 67 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1 µm L&S) withsensitivity of 4.0 µ C/cm². Pattern profile was nearlyrectangular.Example 83.
A resist composition consisting of the followingingredients was prepared. poly(p-hydroxystyrene/styrene/tert-butyl acrylate) 5.0 g [composition ratio: 7/2/1, weight-average molecular weight (Mw) = 10,000, molecular weight distribution (Mw/Mn) = 1.9] poly(p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene) 1.0 g [composition ratio: 35/65, Mw = 10,000, Mw/Mn = 1.02] 5,5'-oxybis[2-(pentafluorobenzenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione] [the compound of Example 51] 0.2 gbis(4-tolyl)iodonium nonafluorobutanesulfonate 0.1 g cyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 40.0 g ethyl lactate 20.0 g
A pattern was formed similarly as in Example 67 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1 µm L&S) withsensitivity of 4.0 µ C/cm². Pattern profile was nearlyrectangular.Example 84.
A resist composition consisting of the followingingredients was prepared. poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/p-tert-butoxystyrene) 4.5 g [composition ratio: 25/65/10, Mw = 15,000, Mw/Mn = 1.85] poly(p-1-isobutoxyethoxystyrene/p-hydroxystyrene) 1.5 g [composition ratio: 30/70, Mw = 10,000, Mw/Mn = 1.02] 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(10-camphorsulfonyl)oxy-1H-isoindole-1,3(2H)-dione] 0.2 g [the compound of Example 50] 4-tolyldiphenylsulfonium 4-toluenesulfonate 0.1 g tris[2-(2-methoxyethoxy)ethyl]amine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 69 using theabove-described resist composition. The contact hole patternthus obtained showed resolution of 100 nm (0.1 µm) withsensitivity of 4.0 µ C/cm². Pattern profile was nearly vertical.Example 85.
A resist composition consisting of the followingingredients was prepared. poly(p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g [composition ratio: 33/67, Mw = 10,000, Mw/Mn = 1.02] 5,5'-oxybis[2-(4-n-propylbenzenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione] [the compound of Example 64] 0.3 g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] ethyl lactate 60.0 g
A pattern was formed similarly as in Example 67 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1 µm L&S) withsensitivity of 4.0 µ C/cm². Pattern profile was nearlyrectangular.Example 86.
A resist composition consisting of the followingingredients was prepared. poly(p-hydroxystyrene/styrene/tert-butyl acrylate) 6.0 g [composition ratio: 7/2/1, weight-average molecular weight (Mw) = 10,000, molecular weight distribution (Mw/Mn) = 1.9] 5,5'-oxybis[2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione] [the compound of Example 45] 0.3 g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethvl ether acetate 60.0 g
A pattern was formed similarly as in Example 67 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1 µm L&S) withsensitivity of 4.4 µ C/cm². Pattern profile was nearlyrectangular.Example 87.
A resist composition consisting of the followingingredients was prepared. poly(p-hydroxystyrene/styrene/tert-butyl acrylate) 6.0 g[composition ratio: 7/2/1, weight-average molecular weight (Mw) = 10,000, molecular weight distribution (Mw/Mn) = 1.9] 5,5'-oxybis[2-(4-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione] 0.3 g [the compound of Example 60] dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 67 using theabove-described resist composition. The positive resist patternthus obtained showed resolution of 100 nm L&S (0.1 µm L&S) withsensitivity of 4.6 µ C/cm². Pattern profile was nearlyrectangular.Comparative Example 6.
A resist composition consisting of the followingingredients was prepared. poly(p-hydroxystyrene/styrene/tert-butyl acrylate) 6.0 g [composition ratio: 7/2/1, weight-average molecular weight (Mw) = 10,000, molecular weight distribution (Mw/Mn) = 1.9] 5,5'-oxybis[2-(4-toluenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione] [the compound of Reference Example 8] 0.3 g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
Preparation of the resist composition comprising the aboveingredients was conducted but could not be succeeded due to nodissolution of the acid generator.Comparative Example 7.
A resist composition consisting of the followingingredients was prepared. poly(p-tert-butoxystyrene/p-hydroxystyrene) [composition ratio: 33/67, Mw = 10,000, Mw/Mn = 1.02] 6.0 g5,5'-oxybis[2-(4-toluenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione] [the compound of Reference Example 8] 0.3 g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] ethyl lactate 60.0 g
Preparation of the resist composition comprising the aboveingredients was conducted but could not be succeeded due to nodissolution of the acid generator.Comparative Example 8.
A resist composition consisting of the followingingredients was prepared. poly(p-tert-butoxystyrene/p-hydroxystyrene) 6.0 g [composition ratio: 33/67, Mw = 10,000, Mw/Mn = 1.02] 5,5'-oxybis[2-trifluoromethanesulfonyloxy-1H-isoindole-1,3(2H)-dione] [the compound of Reference Example 9] 0.3 g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed similarly as in Example 67 using theabove-described resist composition. Each of the processesthereof is shown in Fig. 3.
Namely, the resist composition was filtered using amembrane filter with 0.1 µm pore size, followed by spin-coatingon a silicon substrate 1, pre-baking at 130 °C for 90 sec. ona hot plate to obtain a resist film 8 with a thickness of 0.3µm (Fig. 3 (a)). Then EB-drawn pattern 3 was drawn using an EBdirect writing equipment (acceleration voltage of 50 KeV) (Fig.3 (b)), followed by baking at 120 °C for 60 sec. on a hot plate(Fig. 3 (c)), developing using a 2.38 % aqueous solution oftetramethylammonium hydroxide and washing with water, to forma positive resist pattern 8a (Fig. 3 (d)). The positive resistpattern 8a thus obtained showed resolution of 110 nm L&S (0.11µm L&S) with sensitivity of 8. 0 µ C/cm², but could not resolve 100 nm L&S. The pattern 8a was poor with reversely taperedprofile.
In Fig. 3, each number has the following meaning: 1: silicon substrate 3: EB-drawn pattern 4: bake 8: a resist film of the Comparative Example 8a: pattern Comparative Example 9.
A resist composition consisting of the followingingredients was prepared. poly(p-hydroxystyrene) [weight-average molecular weight (Mw) = 10,000, molecular weight distribution (Mw/Mn) = 1.9] 6.0 g 5,5'-oxybis[2-trifluoromethanesulfonyloxy-1H-isoindole-1,3(2H)-dione] [the compound of Reference Example 9] 0.3 g 2,4,6-tris(methoxymethyl)amino-1,3,5-s-triazine 0.12g dicyclohexylmethylamine 0.01 g fluorine-containing nonionic surfactant 0.1 g [commercial product] propylene glycol monomethyl ether acetate 60.0 g
A pattern was formed as follows similarly as in Example85 using the above-described resist composition. Each of theprocesses thereof is shown in Fig. 4.
Namely, the resist composition was filtered using amembrane filter with 0.1 µm pore size, followed by spin-coatingon a silicon substrate 1, pre-baking at 130 °C for 90 sec. ona hot plate, to obtain a resist film 9 with a thickness of 0.3µm (Fig. 4 (a)) . Then EB-drawn pattern 6 was drawn using an EBdirect writing equipment (acceleration voltage of 50 KeV) (Fig.4 (b)), followed by baking at 130°C for 60 sec. on a hot plate(Fig. 4 (c)), developing using a 2.38 % aqueous solution oftetramethylammonium hydroxide and washing with water, to forma negative resist pattern 9a (Fig. 4 (d)). The negative resistpattern thus obtained showed resolution of 120 nm L&S (0.12µm L&S) with sensitivity of 9.5µC/cm², but could not resolve 110 nm L&S. The pattern 9a had poor profile.
In Fig. 4, each number has the following meaning: 1: silicon substrate 6: EB-drawn pattern 7: bake 9: a resist film of the Comparative Example 9a: pattern
As is clear from the result of each Example, thebisphthalimidesulfonate compound of the present invention shownby the general formula [26], was found to be very useful as anacid generator for a chemically amplified resist composition.While, the conventional compound very similar to the compoundshown by the general formula [26] was found not to provide aresist composition due to poor solubility as is clear from theresults of Comparative Examples 6 and 7, or was difficult tobe used due to low sensitivity, low resolution and poor profileas is clear from the comparison of Comparative Examples 8 and9. INDUSTRIAL APPLICABILITY
Among the bisimide compounds of the present invention,shown by the general formula [1] , the one, wherein R is one shownby the general formula [2], has advantages such as uniform acidgeneration and high sensitivity, due to high solubility to aresist solvent, and little occurrence of problems including anincrease of fine particle during storage, and is different froma conventional ionic compound such as a sulfonium salt, whenused as an acid generator for a chemically amplified resistcomposition.
In addition, since said bisimide compound can easilygenerate an acid in response to various energy lines such asKrF excimer laser, ArF excimer laser and electron beams, apattern having high sensitivity, high resolution and goodpattern profile can be obtained, when a chemically amplifiedresist composition comprising said compound is used in
Furthermore, the bis(N-hydroxy)phthalimide compound ofthe present invention, shown by the general formula [25], isnot only an important synthetic intermediate of thebisphthalimidesulfonate compound of the present invention,shown by the general formula [26] , but also useful as, for example,a cross-linking agent for a polyimide resin, a raw material ofvarious functional materials such as a synthetic intermediateof a photosensitive compound, and a functional material inbiochemical fields such as peptide synthesis.
Furthermore, the bisimide compound of the presentinvention, shown by the general formula [1] is also useful notonly as an acid generator for a resist used for fine fabrication,but also as an acid generator for photosensitive polyimidematerial aimmed at high sensitivity or a cross-linking agentfor a polyimide resin.

权利要求:
Claims (31)
[1] A bisimide compound shown by the general formula [1]:
[2] The compound according to claim 1, wherein the compoundshown by the general formula [1] is one shown by the generalformula [4]:
[3] The compound according to claim 2, wherein the tetra-valentalicyclic hydrocarbon group having 4 to 10 carbon atomsshown by A₃ is a group shown by the general formula [7]:
[4] The compound according to claim 2, wherein the compoundshown by the general formula [4] is one shown by the generalformula [10] :
[5] The compound according to claim 4, wherein R⁵ and R⁶ areboth direct-linkages.
[6] The compound according to claim 5, wherein the compoundshown by the general formula [10] is: tetrahydro-2,5-bis(nonafluorobutanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone;tetrahydro-2,5-bis(heptadecafluorooctanesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone;tetrahydro-2,5-bis(10-camphorsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone; tetrahydro-2,5-bis(4-trifluoromethylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone;tetrahydro-2,5-bis(3-trifluoromethylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone;tetrahydro-2,5-bis(3,5-di-trifluoromethylphenylsulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone;or tetrahydro-2,5-bis(pentafluorobenzenesulfonyloxy)cyclobuta[1,2-c:3,4-c']dipyrrole-1,3,4,6(2H,5H)-tetrone.
[7] The compound according to claim 4, wherein one of R⁵ andR⁶ is a direct-linkage and the other is a methylene group.
[8] The compound according to claim 7, wherein the compoundshown by the general formula [10] is: hexahydro-2,6-bis(nonafluorobutanesulfonyloxy)-cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone; hexahydro-2,6-bis(heptadecafluorooctanesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone; hexahydro-2,6-bis(10-camphorsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone;hexahydro-2,6-bis(4-trifluoromethylphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone; hexahydro-2,6-bis(3-trifluoromethylphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone; hexahydro-2,6-bis(3,5-di-trifluoromethylphenylsulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone; or hexahydro-2,6-bis(pentafluorobenzenesulfonyloxy)cyclopenta[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone.
[9] The compound according to claim 2, wherein the compoundshown by the general formula [4] is one shown by the generalformula [11] :
[10] The compound according to claim 9, wherein the compoundshown by the general formula [11] is: 3a,4,4a,7a,8,8a-hexahydro-2,6-bis(nonafluorobutanesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone;3a,4,4a,7a,8,8a-hexahydro-2,6-bis(heptadecafluorooctanesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone;3a,4,4a,7a,8,8a-hexahydro-2,6-bis(10-camphorsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone;3a,4,4a,7a,8,8a-hexahydro-2,6-bis(4-trifluoromethylphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone;3a,4,4a,7a,8,8a-hexahydro-2,6-bis(3-trifluoromethylphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone;3a,4,4a,7a,8,8a-hexahydro-2,6-bis(3,5-di-trifluoromethylphenylsulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone;or3a,4,4a,7a,8,8a-hexahydro-2,6-bis(pentafluorobenzenesulfonyloxy)-4,8-ethenobenzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone.
[11] The compound according to claim 2, wherein the compoundshown by the general formula [4] is one shown by the generalformula [12]:
[12] The compound according to claim 11, wherein the compoundshown by the general formula [12] is: 2,6-bis(nonafluorobutanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone;2,6-bis(heptadecafluorooctanesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone;2,6-bis(10-camphorsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone;2,6-bis(4-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone;2,6-bis(3-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone:2,6-bis(3,5-di-trifluoromethylphenylsulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone;or 2,6-bis(pentafluorobenzenesulfonyloxy)benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetrone.
[13] The compound according to claim 1, wherein the compoundshown by the general formula [1] is one shown by the generalformula [5]:
[14] The compound according to claim 13, wherein R³ is a hydrogenatom.
[15] The compound according to claim 13, wherein R³ is a groupshown by the general formula [6].
[16] The compound according to claim 15, wherein the compoundshown by the general formula [5] is one shown by the generalformula [13]:
[17] The compound according to claim 16, wherein the compoundshown by the general formula [13] is: 5,5'-oxybis[2-nonafluorobutanesulfonyloxy-1H-isoindole-1,3(2H)-dione];5,5'-oxybis[2-heptadecafluorooctanesulfonyloxy-1H-isoindole-1,3(2H)-dione]; 5,5'-oxybis[2-(10-camphorsulfonyl)oxy-1H-isoindole-1,3(2H)-dione];5,5'-oxybis[2-(4-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione];5,5'-oxybis[2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione];5,5'-oxybis[2-(3,5-di-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione];or 5,5'-oxybis[2-(pentafluorobenzenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione].
[18] The compound according to claim 15, wherein the compoundshown by the general formula [5] is one shown by the generalformula [14]:
[19] The compound according to claim 18, wherein the compoundshown by the general formula [14] is: 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-nonafluorobutanesulfonyloxy-1H-isoindole-1,3(2H)-dione];5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-heptadecafluorooctanesulfonyloxy-1H-isoindole-1,3(2H)-dione];5, 5'- [2, 2, 2 - trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(10-camphorsulfonyl)oxy-1H-isoindole-1,3(2H)-dione];5,5'- [2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(4-trifluoromethylphenylsulfonyl)]oxy-1H-isoindole-1,3(2H)-dione];5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(3-trifluoromethylphenylsulfonyl)]oxy-1H-isoindole-1,3(2H)-dione]; 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-(3,5-di-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione];or 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene] bis [2-(pentafluorobenzenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione].
[20] The compound according to claim 15, wherein the compoundshown by the general formula [5] is one shown by the generalformula [15]:
[21] The compound according to claim 20, wherein the compoundshown by the general formula [15] is: 5,5'-bis[2-nonafluorobutanesulfonyloxy-1H-isoindole-1,3(2H)-dione];5,5'-bis[2-heptadecafluorooctanesulfonyloxy-1H-isoindole-1,3(2H)-dione];5,5'-bis[2-(10-camphorsulfonyl)oxy-1H-isoindole-1,3(2'H)-dione); 5,5'-bis[2-(4-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione];5,5'-bis[2-(3-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione]; 5,5'-bis[2-(3,5-di-trifluoromethylphenylsulfonyl)oxy-1H-isoindole-1,3(2H)-dione];or 5,5'-bis[2-(pentafluorobenzenesulfonyl)oxy-1H-isoindole-1,3(2H)-dione].
[22] An acid generator for a chemically amplified resist, whichcomprises the bisimide compound in claim 2.
[23] An acid generator for a chemically amplified resist, whichcomprises the bisimide compound in claim 15.
[24] A positive resist composition, which comprises at leastone or more kinds of the bisimide compound in claim 2.
[25] A positive resist composition, which comprises at leastone or more kinds of the bisimide compound in claim 15.
[26] A negative resist composition, which comprises at leastone or more kinds of the bisimide compound in claim 2.
[27] A negative resist composition, which comprises at leastone or more kinds of the bisimide compound in claim 15.
[28] A method for pattern formation, which comprises:
a process of forming a positive resist composition in claim24 on a substrate as a resist film;
a process of exposing an arbitrary pattern on the said resistfilm; and
a process of forming a positive resist pattern by developing.
[29] A method for pattern formation, which comprises:
a process of forming a positive resist composition in claim25 on a substrate as a resist film;
a process of exposing an arbitrary pattern on the said resistfilm; and
a process of forming a positive resist pattern by developing.
[30] A method for pattern formation, which comprises:
a process of forming a negative resist composition accordingto claim 26 on a substrate as a resist film;
a process of exposing an arbitrary pattern on the said resistfilm; and
a process of forming a negative resist pattern by developing.
[31] A method for pattern formation, which comprises:
a process of forming a negative resist composition accordingto claim 27 on a substrate as a resist film;
a processs of exposing an arbitrary pattern on the said resistfilm; and
a process of forming a negative resist pattern by developing.

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同族专利:

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公开号 | 公开日

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EP1449833A4|2005-11-30|

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KR20040063156A|2004-07-12|

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KR100840635B1|2008-06-24|

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AU2002354114A1|2003-06-10|

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TW200301400A|2003-07-01|

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JP4439915B2|2010-03-24|

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US7374857B2|2008-05-20|

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CN100343232C|2007-10-17|

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CN1592738A|2005-03-09|

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EP1449833B1|2009-09-09|

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JPWO2003045915A1|2005-04-07|

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TWI312907B|2009-08-01|

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DE60233675D1|2009-10-22|

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WO2003045915A1|2003-06-05|

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US20050038261A1|2005-02-17|

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优先权:

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JP2001366005||2001-11-30||

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JP2001366005||2001-11-30||

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JP2002120769||2002-04-23||

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JP2002120769||2002-04-23||

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PCT/JP2002/012434|WO2003045915A1|2001-11-30|2002-11-28|Bisimide compound, acid generator and resist composition each containing the same, and method of forming pattern from the composition|

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