Photosensitive lithographic form plate using an image-forming material

专利摘要:
A photosensitive lithographic form plate that can be directlyprepared by using digital signals from a computer or the like by usingan infrared laser or the like (i.e., a photosensitive lithographic formplate that can be directly prepared), through using an image-formingmaterial that can be directly inscribed with heat generated byirradiation of a laser light and is suitable for use in a lithographicform plate. The image-forming material used in the present inventioncomprises an infrared light absorbing agent having a hydrophobicgroup which changes to hydrophilic due to heat. The image-formingmaterial may further contain a macromolecular binder insoluble inwater and soluble in an aqueous solution of an alkali, or amacromolecular binder that is decomposed by heat or with an acid andbecomes soluble in water or an alkali. In an exposed portion of thephotosensitive layer, the infrared light absorbing agent is decomposeddue to heat by irradiation of infrared light, and an acid is generated.
公开号:EP0938972A1
申请号:EP99102807
申请日:1999-02-25
公开日:1999-09-01
发明作者:Koichi Kawamura；Ippei Nakamura；Hidekazu Ohashi
申请人:Fuji Photo Film Co Ltd；
IPC主号:G03F7-00

专利说明:
[0001] The present invention relates to a photosensitive lithographic formplate using an image-forming material, and more particularly, to aphotosensitive lithographic form plate which uses an image-formingmaterial, which can be inscribed by light such as a laser light and by heatgenerated by irradiation of a laser light and is suitable as a material forthe lithographic form plate, and which plate can be used for directpreparation of plates from digital signals of a computer or the like by usingan infrared laser, i.e., a photosensitive lithographic form plate that can bedirectly prepared. Description of the Related Art
[0002] In preparation of a form plate for printing, a developing step and afinishing step must be conducted as wet processes after the step ofexposure to light. In the developing step, a portion of an image-recordinglayer disposed on the surface of a substrate is removed to leave theremaining portion in an image form. In the finishing step, the developedform plate is washed with water and treated with a rinsing liquidcontaining a surfactant and with a desensitizing liquid containing gumarabic and a starch derivative.
[0003] In the field of form plate preparation and printing, a problem ofenvironmental pollution arises because the waste water is alkaline. Atthe same time, streamlining of operations for preparation of form plates isbeing promoted. Therefore, a form plate that does not require the complicated wet developing processes described above and can be used as amachine plate for printing directly after exposure to light, i.e., a form platethat can be directly prepared, has been desired.
[0004] Progress in laser technology in recent years has been remarkable.In particular, solid lasers and semiconductor lasers, which can emitinfrared light of a wavelength in a range of 760 to 1200 nm and which havea high output and are of a small size, are easily available. When a formplate is prepared directly from digital data of a computer or the like, theabove laser is very useful as the light source for recording. Instrumentsfor preparation of form plates using a semiconductor laser that generateslight of about 830 nm and a YAG laser that generates light of about 1064nm are commercially available.
[0005] However, many photosensitive recording materials of practical usehave sensitive wavelengths in the region of visible light, i.e., 760 nm or less,and infrared lasers cannot be used for recording images with suchmaterials. Therefore, developing a material that can be used forrecording images with an infrared laser has been desired.
[0006] As the image-forming material that can be used for recording by aninfrared laser, a positive-type recording material using atetrahydropyranyl ester as a macromolecular compound soluble in analkali solution is described in European Patent No. 703499A1. Apositive-type recording material based on abrasion by an ultraviolet laseris described in Japanese Patent Application Laid-Open No. (hereinafter,abbreviated as JP-A) 8-310148. However, form plates using the aboveimage-forming materials have a problem in that image-forming propertymarkedly deteriorates when the form plates are kept in a condition of a high temperature and a high humidity.
[0007] Heat sensitive positive-type image-forming materials that contain amacromolecular compound soluble in an alkali (solution) and an infraredlight absorbing agent and can be inscribed by an infrared laser have alsobeen proposed.
[0008] As examples in which the above heat sensitive positive-type image-formingmaterial is used in a positive-type lithographic form platesensitive to an infrared laser light, a carboxylic ester which can bedecomposed with an acid is used with an infrared light absorbing colorantin an example disclosed in JP-A 7-186562 and an abrasion-type polymerand an infrared light absorbing colorant are used in an example disclosedin U. S. Patent No. 5,605,780.
[0009] As examples in which the above material is used in a negative-typelithographic form plate sensitive to an infrared laser light, combinations ofresol resins which can be thermally crosslinked, agents that generate anacid and infrared light absorbing agents are used in examples disclosed inJP-A 56-69193, JP-A 7-20629 and JP-A 7-271029.
[0010] In the above image-forming materials, images are formed byutilizing a difference in the rate of dissolution of the material in an exposedportion and in an unexposed portion. Therefore, to obtain good positiveimages, it is necessary that the difference in the rate of dissolution beincreased. Particularly, it is necessary that the rate of dissolution in theexposed portion be increased.
[0011] However, conventional infrared light absorbing agents have aproblem in that the infrared light absorbing agent does not completely loseits ability to suppress the rate of dissolution in the exposed portion because decomposition of the infrared light absorbing agent itself does not proceedso much in the exposed portion, although the infrared light absorbingagent can remarkably suppress the rate of dissolution of an alkali-solublemacromolecular compound into the alkali in the unexposed portion. Inother words, the difference in the rate of dissolution in the exposed portionand in the unexposed portion is not large and excellent image formationcannot be achieved.
[0012] In short, the conventional lithographic form plates such as thosedescribed above do not have a sufficient sensitivity from a practical point ofview and further improvement in sensitivity has been desired. SUMMARY OF THE INVENTION
[0013] The present invention has been made in view of the above problems.An object of the present invention is to provide a photosensitivelithographic form plate which uses an image-forming material havingproperties suitable for preparing a lithographic form plate for printing(machine plate) by directly writing digital data of a computer or the likeusing a solid laser or a semiconductor laser emitting infrared light (that is,suitable for direct preparation of a form plate) and which shows excellentimage-forming properties (sensitivity and developing latitude) and toprovide a photosensitive lithographic form plate that is highly sensitiveand forms no stains.
[0014] As the result of extensive studies by the present inventors, it wasfound that the above-mentioned disadvantages of the prior art can beovercome by using a photosensitive layer which is disposed on a(hydrophilic) substrate and which contains an infrared absorbing agent having a hydrophobic functional group which changes to hydrophilic due toheat.
[0015] Aspects of the present invention are as follows.
[0016] A first aspect of the present invention is a photosensitivelithographic form plate comprising: a substrate; and a photosensitivelayer disposed on the substrate, the photosensitive layer containingan infrared light absorbing agent having a hydrophobic functionalgroup which changes to hydrophilic due to heat.
[0017] A second aspect of the present invention is a photosensitivelithographic form plate comprising: a hydrophilic substrate; and aphotosensitive layer disposed on the substrate, the photosensitivelayer containing an infrared light absorbing agent having ahydrophobic functional group which changes to hydrophilic due toheat.
[0018] A third aspect of the present invention is a photosensitivelithographic form plate wherein, in the first aspect, the hydrophobicfunctional group which changes to hydrophilic due to heat is bound toan aromatic ring within the infrared light absorbing agent directly orvia a binding group.
[0019] A fourth aspect of the present invention is a photosensitivelithographic form plate wherein, in the first aspect, the infrared lightabsorbing agent is represented by following general formula (1):
[0020] A fifth aspect of the present invention is a photosensitivelithographic form plate wherein, in the first aspect, the photosensitivelayer includes a macromolecular compound which is decomposable byat least one of heat and an acid and as a result becomes soluble in atleast one of water and an alkali.
[0021] A sixth aspect of the present invention is a photosensitivelithographic form plate comprising: a substrate; and a photosensitivelayer disposed on the substrate, wherein the photosensitive layerincludes an image-forming material which comprises: amacromolecular binder insoluble in water and soluble in an aqueoussolution of an alkali; and an infrared light absorbing agent having athermally decomposable sulfonic ester group.
[0022] A seventh aspect of the present invention is a photosensitivelithographic form plate wherein, in the sixth aspect, before theinfrared light absorbing agent is decomposed by heating, the infraredlight absorbing agent has a function to decrease a rate of dissolution of the macromolecular binder into the aqueous solution of an alkali.
[0023] An eighth aspect of the present invention is a photosensitivelithographic form plate wherein, in the sixth aspect, the infrared lightabsorbing agent is decomposed with heating by irradiation of infraredlight to form the sulfonic acid in portions of the photosensitive layerexposed to the infrared light.
[0024] A ninth aspect of the present invention is a photosensitivelithographic form plate wherein, in the sixth aspect, the thermallydecomposable sulfonic ester group has a structure in which a sulfonicacid is bonded to an ester group and the ester group includes asubstituted or unsubstituted primary, secondary or tertiary alkylgroup, a substituted or unsubstituted aryl group, a substituted orunsubstituted alkenyl group, or a cyclic imide group.
[0025] A tenth aspect of the present invention is a photosensitivelithographic form plate comprising: a substrate and a photosensitivelayer disposed on the substrate, wherein the photosensitive layer isformed with an image-forming material, the image-forming materialcomprising: an infrared light absorbing agent having a thermallydecomposable sulfonic ester group; and a macromolecular compoundwhich decomposes due to heat or an acid and is soluble in water or analkali.
[0026] An eleventh aspect of the present invention is a photosensitivelithographic form plate wherein, in the tenth aspect, in the exposedportions of the photosensitive layer, decomposition of themacromolecular compound which is decomposed due to heat or an acidand becomes soluble in water or an alkali is accelerated by the sulfonic acid formed by exposure to the infrared light.
[0027] A twelfth aspect of the present invention is a photosensitivelithographic form plate wherein, in the tenth aspect, themacromolecular compound which is decomposed due to heat or an acidand becomes soluble in water or an alkali comprises a polymer of asulfonic ester or a polymer of a carboxylic ester.
[0028] A thirteenth aspect of the present invention is a radiation-sensitivelithographic form plate comprising: a binder having acrosslinked structure which has a functional group that changes fromhydrophobic to hydrophilic due to at least one of an acid, radiationand heat; and an infrared light absorbing agent having a hydrophobicfunctional group which changes to hydrophilic due to heat.
[0029] A fourteenth aspect of the present invention is a radiation-sensitivelithographic form plate wherein, in the thirteenth aspect,the hydrophobic functional group which changes to hydrophilic due toheat is bound to an aromatic ring within the infrared light absorbingagent directly or via a binding group.
[0030] A fifteenth aspect of the present invention is a radiation-sensitivelithographic form plate wherein, in the fourteenth aspect,the infrared light absorbing agent is represented by following generalformula (1):
[0031] A sixteenth aspect of the present invention is a radiation-sensitivelithographic form plate wherein, in the thirteenth aspect,the photosensitive layer includes a plurality of water-insoluble solidparticles.
[0032] A seventeenth aspect of the present invention is a radiation-sensitivelithographic form plate wherein, in the sixteenth aspect, thephotosensitive layer is structured such that the water-insoluble solidparticles are covered by the binder and are bound together by thebinder such that each particle is contacted by others at some portionsand gaps are formed between the water-insoluble particles.
[0033] An eighteenth aspect of the present invention is a radiation-sensitivelithographic form plate wherein, in the thirteenth aspect,the binder is a compound which is obtained by reacting: a compoundhaving, in the same molecule, a functional group which changes fromhydrophobic to hydrophilic due to at least one of an acid, radiationand heat, and a functional group which reacts with a hydrolysis polymerizible compound represented by following general formula (2);and the hydrolysis polymerizible compound represented by followinggeneral formula (2):(Q¹)_n―X―(OQ²)_4-n wherein Q¹ and Q² each represents an alkyl group or an aryl groupand may be the same or different; X represents Si, Al, Ti, or Zr; and nis an integer of from 0 to 2.
[0034] Specifically, for example, the inventors have found that an infraredlight absorbing agent (a colorant) having a specific sulfonic ester groupgenerates a sulfonic acid by thermal decomposition and the sulfonic acidthus formed remarkably increases the rate of dissolution of amacromolecular binder soluble in an alkali. The photosensitivelithographic form plate using the image-forming material of the presentinvention has been completed by forming a photosensitive layercomprising the infrared light absorbing agent having such a thermallydecomposable sulfonic ester group on a substrate.
[0035] A first image-forming material which contains the infraredabsorbing agent of the present invention and is used in a first embodiment,comprises (A) a macromolecular binder insoluble in water and soluble inan aqueous solution of an alkali and (B) an infrared light absorbing agenthaving a thermally decomposable sulfonic ester group.
[0036] A second image-forming material which contains the infraredabsorbing agent of the present invention and is used in a secondembodiment, comprises (C) a macromolecular compound which isdecomposed by heating or with an acid and becomes soluble in water or analkali and (B) an infrared light absorbing agent having a thermally decomposable sulfonic ester group.
[0037] A third image-forming material which contains the infraredabsorbing agent of the present invention and is used in a thirdembodiment (for a radiation-sensitive lithographic form plate),comprises: a binder having a crosslinked structure which has afunctional group that changes from hydrophobic to hydrophilic due toat least one of an acid, radiation and heat; and an infrared lightabsorbing agent having a hydrophobic functional group which changesto hydrophilic due to heat.
[0038] The present invention may further include the following aspect.
[0039] That is, a nineteenth aspect of the present invention is aphotosensitive lithographic form plate wherein, in the first aspect, thehydrophobic functional group which changes to hydrophilic due toheat is selected from the group consisting of the following structuresrepresented by general formulas (3) through (7):
[0040] In a photosensitive lithographic form plate in which the first image-formingmaterial described above is used, the rate of dissolution of themacromolecular binder soluble in an alkali is suppressed in an unexposedportion by the infrared light absorbing agent having a thermallydecomposable sulfonic ester group and the rate of dissolution of themacromolecular binder soluble in an alkali is increased in an exposedportion by the sulfonic acid formed by decomposition of the infrared lightabsorbing agent (a dye or a pigment). Therefore, the difference in the rateof dissolution between the two portions is large and an excellent image canbe formed.
[0041] In a photosensitive lithographic form plate in which the secondimage-forming material described above is used, the rate of dissolution ofthe macromolecular compound which is decomposed by heating or with anacid and becomes soluble in water or an alkali is increased by the sulfonicacid which is formed by decomposition of the infrared light absorbing agent (the dye or the pigment) in an exposed portion. Therefore, the differencein the height of the surface in the exposed portion and in the unexposedportion increases and an excellent image can be formed.
[0042] The second image-forming material described above may furthercomprise an agent for generating an acid where necessary.
[0043] In summary, the photosensitive (radiation-sensitive)lithographic form plate of the present invention can directly beprepared from digital data from a computer or the like by recording byusing a solid-state laser or a semiconductor laser emitting infraredlight. After image recording, there is no need for special processingssuch as wet developing processing or rubbing or the like, and further,the sensitivity is high. Moreover, the photosensitive layer of thephotosensitive lithographic form plate of the present inventionincludes an infrared light absorbing agent which contains ahydrophobic functional group which changes to hydrophilic due toheat. Thus, no residual film remains at the exposed portions, noscum-like solids are left in the wetting water used during printing,and stains are not formed.
[0044] Further, in the radiation-sensitive lithographic form plate ofthe sixteenth and seventeenth aspects of the present invention, aplurality of water-insoluble solid particles exist in the photosensitivelayer. The respective water-insoluble solid particles are covered bythe binder, and are bound together by the binder such that eachparticle is contacted by others at some portions and gaps are formedbetween the water-insoluble particles. As a result, the surface of theradiation-sensitive lithographic form plate is not smooth. With such a structure, if the binder covering the water-insoluble solid particles ishydrophilic, moisture is held at the gap portions between the particlesand the surface of the form plate is hydrophilic, and if the binder ishydrophobic, water does not seep into the gaps between the water-insolublesolid particles, and the surface is lipophilic. Accordingly,because the surface of the radiation-sensitive lithographic form plateof the sixteenth and seventeenth aspects of the present inventionchanges from hydrophobic to hydrophilic due to heat, radiation or anacid, printing is possible without the need for conducting developingprocessing after image formation, and satisfactory printed matter canbe obtained.
[0045] Further, in the radiation-sensitive lithographic form plate ofthe eighteenth aspect of the present invention, the hydrolysispolymerizible compound is hydrolysis polymerized, and an inorganicmatrix (hydrolysis polymerization reaction product) is formed withinthe coated film. Thus, the film strength of the photosensitive layer onthe whole improves. As a result, this radiation-sensitive lithographicform plate is extremely durable.
[0046] The mechanism of decomposition of the infrared light absorbingagent having a thermally decomposable sulfonic ester group is not clear atpresent. As described in a reference about thermal decomposition ofsulfonic esters (T. ENDO Macromolecules 1996, 29, 3317), it can beconsidered that the ester portion is removed by heat via a carbocation toform the sulfonic acid. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0047] A photosensitive lithographic form plate in which a first image-formingmaterial of the present invention is used is described inaccordance with a first embodiment of the present invention.
[0048] First, a composition of the first image-forming material will bedescribed in detail.
[0049] The first image-forming material described in the presentembodiment comprises (A) a macromolecular binder insoluble in water andsoluble in an aqueous solution of an alkali and (B) an infrared lightabsorbing agent having a thermally decomposable sulfonic ester group. [(B) Infrared light absorbing agent]
[0050] The infrared light absorbing agent (hereinafter referred to as the IRabsorbing agent, occasionally in the present invention) is a dye or apigment, and has a structure in which a hydrophobic group which changesto hydrophilic due to heat is bonded to a colorant portion.
[0051] This change must be a change to the extent that, when heat isgenerated by light-heat conversion at the time of laser exposure, inthe infrared light absorbing agent which does not exhibit affinity towater (e.g., is not soluble in water) at room temperature, thehydrophobic functional group capable of changing to hydrophilicwithin the infrared light absorbing agent molecule changes to ahydrophilic functional group, such that the infrared light absorbingagent exhibits affinity to water (e.g., becomes soluble in water).
[0052] The hydrophobic functional group which changes to hydrophilicdue to heat is a functional group which changes to a hydrophilicfunctional group through either of the following processes: a processin which a side chain functional group which is originally hydrophobic reacts and changes to hydrophilic due to heat, or a process in which aside chain functional group which is originally hydrophobicdecomposes and loses the hydrophobic functional group portion due toheat.
[0053] As the examples of the hydrophobic functional group which changeto hydrophilic due to heat and which can be preferably used in the presentinvention, the hydrophobic functional group represented by the followinggeneral formulas (3)-(7) may be included.
[0054] As the colorant portion, any compound that can absorb light ofwavelengths in a region of 700 to 1200 nm can be used. Preferableexamples include polymethine colorants, cyanine colorants, squaliliumcolorants, pyrylium colorants, diimmonium colorants, phthalocyaninecompounds, triarylmethane colorants, metal dithiole and carbon black.Among these compounds, polymethine colorants, cyanine colorants,squalilium colorants, pyrylium colorants, diimmonium colorants,phthalocyanine compounds and carbon black are more preferable. Fromthe standpoint of synthesis suitability, polymethine colorants, cyaninecolorants, phthalocyanine compounds and carbon black are mostpreferable.
[0055] As mentioned above, the change of the hydrophobic functional groupto a hydrophilic state due to heat must be a change to the extent that,when heat is generated by light-heat conversion at the time of laserexposure, in the infrared light absorbing agent which does not exhibitaffinity to water (e.g., is not soluble in water) at room temperature,the hydrophobic functional group capable of changing to hydrophilicwithin the infrared light absorbing agent molecule changes to ahydrophilic functional group, such that the infrared light absorbingagent exhibits affinity to water (e.g., becomes soluble in water).
[0056] Also as mentioned above, the hydrophobic functional group which changes to hydrophilic due to heat is to be a functional groupwhich changes to a hydrophilic functional group through either of thefollowing processes: a process in which a side chain functional groupwhich is originally hydrophobic reacts and changes to hydrophilic dueto heat, or a process in which a side chain functional group which isoriginally hydrophobic decomposes and loses the hydrophobicfunctional group portion due to heat.
[0057] The examples of such hydrophobic functional group which change tohydrophilic due to heat and which can be preferably used in the presentinvention may include the hydrophobic functional group represented bythe following general formulas (3)-(7).
[0058] Among hydrophobic functional groups which change tohydrophilic due to heat, a functional group which is particularlypreferable from the standpoints of reactivity, storage stability, andhydrophilicity/hydrophobicity is thermally-decomposable sulfonicester group.
[0059] The thermally decomposable sulfonic ester group described abovehas a structure in which a sulfonic acid is bonded to an ester group. Theester group is, for example, a substituted or unsubstituted primary,secondary or tertiary alkyl group, a substituted or unsubstituted arylgroup, a substituted or unsubstituted alkenyl group, or a cyclic imidegroup. Among these groups, a primary alkyl group which is substitutedwith electron-donating groups such as the alkyl group and the alkoxygroup or with electron-withdrawing groups such as the carbonyl group, thealkoxycarbonyl group, the cyano group and the halogens, secondary alkylgroups such as the cyclohexyl group, the isopropyl group and the 1-methoxy-2-propylgroup and tertiary alkyl groups such as the t-butylgroup are preferable.
[0060] Preferable examples of the alkyl group described as an example ofthe ester group of the thermally decomposable sulfonic ester group includelinear, branched and cyclic alkyl groups having 1 to 20 carbon atoms.Specific examples thereof include: the methyl group, the ethyl group, thepropyl group, the butyl group, the pentyl group, the hexyl group, the heptylgroup, the octyl group, the nonyl group, the decyl group, the undecyl group,the dodecyl group, the tridecyl group, the hexadecyl group, the octadecylgroup, the eicosyl group, the isopropyl group, the isobutyl group, the s-butylgroup, the t-butyl group, the isopentyl group, the neopentyl group,the 1-methylbutyl group, the isohexyl group, the 2-ethylhexyl group, the2-methylhexyl group, the cyclohexyl group, the cyclopentyl group and the2-norbornyl group. Among these groups, linear alkyl groups having 1 to12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms andcyclic alkyl groups having 5 to 10 carbon atoms are more preferable.
[0061] The alkyl group described as an example of the ester group of thethermally decomposable sulfonic ester group may be substituted. Thesubstituent group may be a group of monovalent non-metallic atomsexcluding hydrogen. Preferable examples of the group of monovalentnon-metallic atoms include: halogen atoms (-F, -Br, -Cl and -I), thehydroxyl group, the alkoxy group, the aryloxy group, the mercapto group,the alkylthio group, the arylthio group, the alkyldithio group, thearyldithio group, the amino group, the N-alkylamino group, the N,N-dialkylaminogroup, the N-arylamino group, the N,N-diarylamino group,the N-alkyl-N-arylamino group, the acyloxy group, the carbamoyloxygroup, the N-alkylcarbamoyloxy group, the N-arylcarbamoyloxy group, theN,N-dialkylcarbamoyloxy group, the N,N-diarylcarbamoyloxy group, the N-alkyl-N-arylcarbamoyloxy group, the alkylsulfoxy group, the arylsulfoxygroup, the acylthio group, the acylamino group, the N-alkylacylaminogroup, the N-arylacylamino group, the ureido group, the N'-alkylureidogroup, the N',N'-dialkylureido group, the N'-arylureido group, the N',N'-diarylureidogroup, the N'-alkyl-N'-arylureido group, the N-alkylureidogroup, the N-arylureido group, the N'-alkyl-N-alkylureido group, the N'-alkyl-N-arylureidogroup, the N',N'-dialkyl-N-alkylureido group, the N',N'-dialkyl-N-arylureidogroup, the N'-aryl-N-alkylureido group, the N'-aryl-N-arylureidogroup, the N',N'-diaryl-N-alkylureido group, the N',N'-arylureidogroup, the N'-alkyl-N'-aryl-N-alkylureido group, the N'-alkyl-N'-aryl-N-arylureidogroup, the alkoxycarbonylamino group, thearyloxycarbonylamino group, the N-alkyl-N-alkoxycarbonylamino group,the N-alkyl-N-aryloxycarbonylamino group, the N-aryl-N-alkoxycarbonylaminogroup, the N-aryl-N-aryloxycarbonylamino group,the formyl group, the acyl group, the carboxyl group, the alkoxycarbonylgroup, the aryloxycarbonyl group, the carbamoyl group, the N-alkylcarbamoylgroup, the N,N-dialkylcarbamoyl group, the N-arylcarbamoylgroup, the N,N-diarylcarbamoyl group, the N-alkyl-N-arylcarbamoylgroup, the alkylsulfinyl group, the arylsulfinyl group, thealkylsufonyl group, the arylsulfonyl group, the sulfonic group (-SO₃H) andgroups of conjugate bases thereof (hereinafter referred to as the sulfonatogroup), the alkoxysulfonyl group, the aryloxysulfonyl group, thesulfinamoyl group, the N-alkylsulfinamoyl group, the N,N-dialkylsufinamoylgroup, the N-arylsulfinamoyl group, the N,N-diarylsulfinamoylgroup, the N-alkyl-N-arylsulfinamoyl group, thesulfamoyl group, the N-alkylsulfamoyl group, the N,N-dialkylsufamoyl group, the N-arylsulfamoyl group, the N,N-diarylsulfamoyl group, the N-alkyl-N-arylsulfamoylgroup, the phosphono group (-PO₃H₂) and groups ofconjugate bases thereof (hereinafter referred to as the phosphonato group),the dialkylphosphono group (-PO₃(alkyl)₂), the diarylphosphono group(-PO₃(aryl)₂), the alkylarylphosphono group (-PO₃(alkyl)(aryl)), themonoalkylphosphono group (-PO₃H(alkyl)) and groups of conjugate basesthereof (hereinafter referred to as the alkylphosphonato group), themonoarylphosphono group (-PO₃H(aryl)) and groups of conjugate basesthereof (hereinafter referred to as the arylphosphonato group), thephosphonoxy group (-OPO₃H₂) and groups of conjugate bases thereof(hereinafter referred to as the phosphonatoxy group), thedialkylphosphonoxy group (-OPO₃(alkyl)₂), the diarylphosphonoxy group (-PO₃(aryl)₂),the alkylarylphosphonoxy group (-OPO₃(alkyl)(aryl)), themonoalkylphosphonoxy group (-OPO₃H(alkyl)) and groups of conjugatebases thereof (hereinafter referred to as the alkylphosphonatoxy group),the monoarylphosphonoxy group (-OPO₃H(aryl)) and groups of conjugatebases thereof (hereinafter referred to as the arylphosphonatoxy group), thecyano group, the nitro group, the aryl group, the alkyl group, the alkenylgroup, the alkynyl group, the acyl group and the alkylene group.
[0062] Preferable examples of the alkyl group described above as anexample of the substituent of the alkyl group as the thermallydecomposable ester group are the same as those described as thepreferable examples of the alkyl groups described as the ester group of thethermally decomposable sulfonic ester group.
[0063] Preferable examples of the aryl group described above as anexample of the substituent include: the phenyl group, the biphenyl group, the naphthyl group, the tolyl group, the xylyl group, the mesityl group, thecumenyl group, the chlorophenyl group, the bromophenyl group, thechloromethylphenyl group, the hydroxyphenyl group, the methoxyphenylgroup, the ethoxyphenyl group, the phenoxyphenyl group, theacetoxyphenyl group, the benzoyloxyphenyl group, the methylthiophenylgroup, the phenylthiophenyl group, the methylaminophenyl group, thedimethylaminophenyl group, the acetylaminophenyl group, thecarboxyphenyl group, the methoxycarbonyl-phenyl group, theethoxyphenylcarbonyl group, the phenoxycarbonylphenyl group, the N-phenylcarbamoylphenylgroup, the cyanophenyl group, the sulfophenylgroup, the sulfonatophenyl group, the phosphonophenyl group and thephosphonatophenyl group.
[0064] Preferable examples of the alkenyl group described above as anexample of the substituent of the alkyl group as the thermallydecomposable ester group include: the vinyl group, 1-propenyl group, 1-butenylgroup, cinnamyl group and 2-chloro-1-ethenyl group.
[0065] Preferable examples of the alkynyl group described above as anexample of the substituent of the alkyl group as the thermallydecomposable ester group include the ethynyl group, 1-propynyl group, 1-butynylgroup and trimethylsilylethynyl group.
[0066] In the acyl groups (G¹CO-) described above as examples of thesubstituent of the alkyl group as the thermally decomposable ester group,G¹ represents hydrogen or one of the alkyl groups and the aryl groupsdescribed above as preferable examples.
[0067] Preferable examples of the alkylene group described above as anexample of the substituent of the alkyl group as the thermally decomposable ester group include divalent organic group obtained byreplacing any one hydrogen atom of the above alkyl groups having 1 to 20carbon atoms with a substituent. Linear alkylene groups having 1 to 12carbon atoms, branched alkylene groups having 3 to 12 carbon atoms andcyclic alkylene groups having 5 to 10 carbon atoms are more preferable.Specific examples of preferable substituted alkyl groups which areobtained as combinations of the above substituents and the above alkylgroups include: the chloromethyl group, the bromomethyl group, the 2-chloroethylgroup, the trifluoromethyl group, the methoxymethyl group,the methoxyethoxyethyl group, the allyloxymethyl group, thephenoxymethyl group, the methylthiomethyl group, the tolylthiomethylgroup, the ethylaminoethyl group, the diethylaminopropyl group, themorpholinopropyl group, the acetyloxymethyl group, thebenzoyloxylmethyl group, the N-cyclohexylcarbamoyloxyethyl group, theN-phenylcarbamoyloxyethyl group, the acetylaminoethyl group, the N-methylbenzoylaminopropylgroup, the 2-oxoethyl group, the 2-oxopropylgroup, the carboxypropyl group, the methoxycarbonylethyl group, theallyloxycarbonylbutyl group, the chlorophenoxylcarbonylmethyl group, thecarbamoymethyl group, the N-methylcarbamoylethyl group, the N,N-dipropylcarbamoylmethylgroup, the N-(methoxyphenyl)carbamoylethylgroup, the N-methyl-N-(sulfophenyl)carbamoylmethyl group, thesulfobutyl group, the sulfonatobutyl group, the sulfamoylbutyl group, theN-ethylsulfamoylmethyl group, the N,N-dipropylsulfamoylpropyl group,the N-tolylsulfamoylpropyl group, the N-methyl-N-(phosphonophenyl)sulfamoyloctylgroup, the phosphonobutyl group, thephosphonatohexyl group, the diethylphosphonobutyl group, the diphenylphosphonopropyl the group, the methylphosphonobutyl group, themethylphosphonatobutyl group, the tolylphosphonohexyl group, thetolylphosphonatohexyl group, the phosphonoxypropyl group, thephosphonatoxybutyl group, the benzyl group, phenetyl group, the α -methylbenzyl group, the 1-methyl-1-phenylethyl group, the p-methylbenzylgroup, the cinnamyl group, the allyl group, the 2-propenylmethylgroup, the 2-butenyl group, the 2-methylallyl group, the2-methylpropenylmethyl group, the 2-propynyl group, the 2-butynyl groupand the 3-butynyl group.
[0068] More preferable examples of the substituent of the alkyl groupwhich was described as an example of the ester group of the abovethermally decomposable sulfonic ester group include: halogen atoms (-F,-Br, -Cl and -I), the alkoxy group, the aryloxy group, the alkylthio group,the arylthio group, the N-alkylamino group, the N,N-dialkylamino group,the acyloxy group, the N-alkylcarbamoyloxy group, the N-arylcarbamoyloxygroup, the acylamino group, the formyl group, the acylgroup, the carboxyl group, the alkoxycarbonyl group, the aryloxycarbonylgroup, the carbamoyl group, the N-alkylcarbamoyl group, the N,N-dialkylcarbamoylgroup, the N-arylcarbamoyl group, the N-alkyl-N-arylcarbamoylgroup, the sulfonic group, the sulfonato group, thesulfamoyl group, the N-alkylsulfamoyl group, the N,N-dialkylsulfamoylgroup, the N-arylsulfamoyl group, the N-alkyl-N-arylsulfamoyl group, thephosphono group, the phosphonato group, the dialkylphosphono group, thediarylphosphono group, the monoalkylphosphono group, thealkylphosphonato group, the monoarylphosphono group, thearylphosphonato group, the phosphonoxy group, the phosphonatoxy group, the aryl group and the alkenyl group.
[0069] Examples of the aryl group which is described as an example of theester group of the above thermally decomposable sulfonic ester groupinclude: that having a single benzene ring, that having a condensed ringformed with 2 or 3 benzene rings and that having condensed rings formedwith benzene rings and five-membered unsaturated rings. Preferablespecific examples of such aryl groups include: the phenyl group, thenaphthyl group, the anthryl group, the phenanthryl group, the indenylgroup, the acenaphthenyl group and the fluorenyl group. Among thesegroups, the phenyl group and the naphthyl group are more preferable.The aryl groups include heterocyclic aryl groups in addition to the abovearyl groups made of carbon rings. Examples of the heterocyclic arylgroups include: heterocyclic aryl groups having 3 to 20 carbon atoms and 1to 5 hetero atoms such as the pyridyl group, the furyl group and groups inwhich a benzene ring is condensed such as the quinolyl group, thebenzofuryl group, the thioxanthone group and the carbazole group.
[0070] The above aryl group as the ester group of the thermallydecomposable sulfonic ester group may have a substituent on carbon atomsforming the ring of the aryl group and the substituent may be a group ofnon-metallic atoms excluding hydrogen. Specific examples of the group ofnon-metallic atoms are the same as those described as examples of thealkyl group which is described as an example of the ester group in theabove thermally decomposable sulfonic ester group and the substituentstherefor. Preferable examples of the above substituted aryl groupinclude: the biphenyl group, the tolyl group, the xylyl group, the mesitylgroup, the cumenyl group, the chlorophenyl group, the bromophenyl group, the fluorophenyl group, the chloromethylphenyl group, thetrifluoromethylphenyl group, the hydroxyphenyl group, themethoxyphenyl group, the methoxyethoxyphenyl group, the allyloxyphenylgroup, the phenoxyphenyl group, the methylthiophenyl group, thetolylthiophenyl group, the ethylaminophenyl group, thediethylaminophenyl group, the morpholinophenyl group, theacetyloxyphenyl group, the benzoyloxyphenyl group, the N-cyclohexylcarbamoyloxyphenylgroup, the N-phenylcarbamoyloxyphenylgroup, the acetylaminophenyl group, the N-methylbenzoylaminophenylgroup, the carboxyphenyl group, the methoxycarbonylphenyl group, theallyloxycarbonyl-phenyl group, the chlorophenoxycarbonylphenyl group,the carbamoylphenyl group, the N-methylcarbamoylphenyl group, theN,N-dipropylcarbamoylphenyl group, the N-(methoxyphenyl)-carbamoylphenylgroup, the N-methyl-N-(sulfophenyl)carbamoylphenylgroup, the sulfophenyl group, the sulfonatophenyl group, thesulfamoylphenyl group, the N-ethylsulfamoylphenyl group, the N,N-dipropylsulfamoylphenylgroup, the N-tolylsulfamoylphenyl group, the N-methyl-N-(phosphonophenyl)sulfamoylphenylgroup, the phosphonophenylgroup, the phosphonatophenyl group, the diethylphosphonophenyl group,the diphenylphosphonophenyl group, the methylphosphonophenyl group,the methylphosphonatophenyl group, the tolylphosphonophenyl group, thetolylphosphonatophenyl group, the allyl group, the 1-propenylmethylgroup, the 2-butenyl group, the 2-methylallylphenyl group, the 2-methylpropenylphenylgroup, 2-propynylphenyl group, 2-butynylphenylgroup and 3-butynylphenyl group.
[0071] The alkenyl group described above as an example of the ester group of the thermally decomposable sulfonic ester group is preferably an alkenylgroup having a carbonyl group such as the cyclohexenyl group or theoxycylohexenyl group. The 3-oxycyclohexenyl group and the 5,5-dimethyl-3-oxycyclohexenylgroup are more preferable.
[0072] The alkenyl group described above as an example of the ester groupof the thermally decomposable sulfonic ester group may have a substituent.Examples of the substituent are the same as those described as thesubstituent of the alkyl group described as an example of the ester group ofthe thermally decomposable sulfonic ester group.
[0073] Examples of the cyclic imide group described above as an example ofthe ester group of the thermally decomposable sulfonic ester group include:cyclic imides having 4 to 20 carbon atoms such as succinimide, phthalimide,cyclohexanedicarboxylic acid imide and norbornene-dicarboxylic acidimide.
[0074] Among the substituents of alkyl groups, aryl groups and alkenylgroups described as examples of the ester group of the thermallydecomposable sulfonic ester group, primary or secondary alkyl groups aremore preferable from the standpoint of storage stability and thermaldecomposition.
[0075] Specific examples of the thermally decomposable sulfonic estergroup are shown in the following (1m-1 to 1m-34). However, the presentinvention is not limited to these examples.
[0076] Specific examples of the infrared light absorbing agent having ahydrophobic functional group which changes to hydrophilic due to heat areshown in the following (Compounds 1 to 73). However, the presentembodiment is not limited to these examples.
[0077] In the present embodiment, the infrared light absorbing agenthaving a hydrophobic functional group which changes to hydrophilic due toheat can be synthesized as shown in the following specific SynthesisExamples. Synthesis Example of Compound 1
[0078]
[0079] Into a 300 ml three-necked flask, 20.7 g of Compound (F) (refer tothe structural formula above), 50 ml of toluene and 21.6 g of 2-chloro-(1-methoxy-2-propyl)sulfonate were placed and the mixture was refluxed for2 hours by heating with steam. After finishing the heating, the mixturewas cooled to room temperature and 200 ml of acetone was added to thecooled mixture. The formed solid material was separated by filtration toobtain 30.4 g of Compound (G).
[0080] Compound (G) in an amount of 21 g and 8.9 g of Compound (H)(refer to the structural formula above) were dissolved in 100 ml ofmethanol. After adding 9.4 ml of acetic anhydride to the solution, the mixture was stirred at room temperature for 10 minutes and then 14.0 g oftriethylamine was added dropwise over 20 minutes. After the mixturewas further stirred at room temperature for 2 hours, 6.5 g of p-toluenesulfonicacid was added and the mixture was stirred at roomtemperature for 2 hours. The formed crystals were separated by filtrationand Compound 1 was obtained (yield: 23 g; the structure was identified byelement analysis and NMR). Synthesis Example of Compound 10
[0081] Into a 500 ml three-necked flask, 230 g of chlorosulfuric acid wasplaced. While the content was kept at a temperature in a range of 20 to50°C and stirred, 25 g of vanadyl phthalocyanine was added into the flaskover 0.5 hours. The mixture was then stirred for 3 hours while beingheated at a temperature of 130 to 140°C. After the mixture was cooled to60°C, 32 g of thionyl chloride was added dropwise over 20 minutes andthen the temperature inside the flask was raised to 80°C while the mixturewas stirred. The mixture was cooled to a temperature of 0 to 3°C andstirred for 15 minutes. The formed crystals were separated by filtrationand washed with cold water. After the product was dried, 28 g of asulfonyl chloride compound was obtained.
[0082] Into a 300 ml three-necked flask, 20 g of the above sulfonyl chloridecompound was placed and 10 g of 1-methoxy-2-propanol was added. Then,28 g of pyridine was added dropwise to the reaction mixture which waskept cool. When the addition was completed, cooling was discontinuedand the reaction mixture was stirred at room temperature for 8 hours.The obtained reaction solution was added to 300 ml of a 3N aqueous solution of hydrochloric acid. The formed crystals were separated byfiltration and washed with 500 ml of methanol. After the product wasdried, Compound 10 was obtained (yield: 19 g; the structure was identifiedby element analysis and NMR).
[0083] In the present embodiment, the infrared light absorbing agent isused in an amount of about 0.1 to 40% by weight, preferably 1 to 25% byweight and more preferably 3 to 15% by weight, of the total amount of solidcomponents of the photosensitive layer. When the amount of the infraredlight absorbing agent having a thermally decomposable sulfonic estergroup is less than 0.1%, sensitivity is low and stains tend to be formedduring printing. When the amount exceeds 40% by weight, the infraredlight absorbing agent tends to remain in the photosensitive layer andstains tend to be formed. [(A) Macromolecular binder insoluble in water and soluble in an aqueoussolution of an alkali]
[0084] The macromolecular binder insoluble in water and soluble in anaqueous solution of an alkali, which is used in the first image-formingmaterial of the present invention, is a compound or a mixture ofcompounds selected from macromolecular compounds having an acidicgroup in the structure of the main chain and/or the side chains. Amongthese compounds, compounds having one of the following acidic groups (a-1)to (a-6) in the structure of the main chain and/or the side chains arepreferable from the standpoint of solubility in an alkaline developer: (a-1) phenol group (-Ar-OH) (a-2) sulfonamide group (-SO₂NH-R) (a-3) an acid group derived from substituted sulfonamide(hereinafter referred to as the active imide group) (-SO₂NHCOR,-SO₂NHSO₂R, -CONHSO₂R) (a-4) carboxylic acid group (-CO₂H) (a-5) sulfonic acid group (-SO₃H) (a-6) phosphoric acid group (-OPO₃H₂)
[0085] In the above (a-1) to (a-6), Ar represents a substituted orunsubstituted divalent aryl group and R represents a substituted orunsubstituted hydrocarbon group.
[0086] Among the macromolecular binders which have one of acidic groups(a-1) to (a-6) and are insoluble in water and soluble in an aqueous solutionof an alkali, macromolecular binders which have the (a-1) phenol group,the (a-2) sulfonamide group or the (a-3) an active imide group and areinsoluble in water and soluble in an aqueous solution of an alkali arepreferable. Macromolecular binders which have the (a-1) phenol groupand are insoluble in water and soluble in an aqueous alkali solution aremore preferable from the standpoint of solubility in an alkaline developer,adhesion of ink and resistance to friction. Copolymers which have a (a-1)phenol group in the main chain and one of (a-1) to (a-3) in a portion of themain chain and/or in the side chains are also preferable from thestandpoint of developing latitude.
[0087] As the macromolecular binder which has the (a-1) phenol group andis insoluble in water and soluble in an aqueous solution of an alkali, forexample, novolak resins such as polycondensation products of phenol andformaldehyde (hereinafter referred to as phenol-formaldehyde resins), polycondensation products of m-cresol and formaldehyde (hereinafterreferred to as m-cresol-formaldehyde resins), polycondensation products ofp-cresol and formaldehyde, polycondensation products of a mixture of m-cresoland p-cresol and formaldehyde and polycondensation products ofphenol, cresol (any of m-cresol, p-cresol and a mixture of m-cresol and p-cresol)and formaldehyde; and polycondensation products of pyrogallol andacetone, can be used. Copolymers obtained by copolymerization ofmonomers having the phenol group in the side chain may also be used.Examples of the monomer having the phenol group in the side chaininclude acrylamide, methacrylamide, acrylic esters, methacrylic esters andhydroxystyrene, each having the phenol group. Specifically, N-(4-hydroxyphenyl)acrylamide,N-(4-hydroxyphenyl)methacrylamide, o-hydroxyphenylacrylate, m-hydroxyphenyl acrylate, p-hydroxyphenylacrylate, o-hydroxyphenyl methacrylate, m-hydroxyphenyl methacrylate,p-hydroxyphenyl methacrylate, o-hydroxystyrene, m-hydroxystyrne, p-hydroxystyrene,2-(4-hydroxyphenyl)ethyl acrylate and 2-(4-hydroxyphenyl)ethylmethacrylate can be advantageously used.
[0088] From the standpoint of image-forming property, it is preferable thatthe macromolecular compound has a weight-average molecular weight of5.0×10² to 2.0×10⁴ and a number-average molecular weight of 2.0×10² to1.0×10⁴. The above resins may be used singly or as a combination of twoor more types. When a combination of two or more types of the resins isused, the combination may contain condensation products of a phenolsubstituted with an alkyl group having 3 to 8 carbon atoms andformaldehyde such as polycondensation products of t-butylphenol andformaldehyde and polycondensation products of octylphenol and formaldehyde, as described in the specification of U. S. Patent No.4,123,279.
[0089] As the macromolecular binder which has the (a-2) sulfonamidegroup and is insoluble in water and soluble in an aqueous solution of analkali, for example, polymers obtained by using a monomer havingsulfonamide group as the main component of polymerization can be used.Examples of such a monomer include compounds having one or moresulfonamide groups in which at least one hydrogen atom is bonded to anitrogen atom and one or more polymerizable unsaturated bonds in themolecule. Among such compounds, low molecular weight compoundshaving: the acryloyl group, the allyl group or the vinyloxy group; andeither a substituted or monosubstituted aminosulfonyl group or asubstituted sulfonylimino group, are preferable. Examples of suchcompounds include compounds represented by the following generalformulae (8) to (12):
[0090] In the above formulae, X¹ and X² each independently represents -O-or-NA²⁷-; R²¹ and R²⁴ each independently represents a hydrogen atom or-CH₃; R²², R²⁵, R²⁹, R³² and R³⁶ each independently represents a substitutedor unsubstituted alkylene group, cycloalkylene group, arylene group oraralkylene group, each having 1 to 12 carbon atoms; R²³, R²⁷ and R³³ eachindependently represents a hydrogen atom or a substituted orunsubstituted alkyl group, cycloalkyl group, aryl group or aralkyl group,each having 1 to 12 carbon atoms; R²⁶ and R³⁷ each independentlyrepresents a substituted or unsubstituted alkyl group, cycloalkyl group,aryl group or aralkyl group, each having 1 to 12 carbon atoms; R²⁸, R³⁰ andR³⁴ each independently represents a hydrogen atom or -CH₃; R³¹ and R³⁵each independently represents a single bond or a substituted orunsubstituted alkylene group, cycloalkylene group, arylene group oraralkylene group, each having 1 to 12 carbon atoms; and Y¹ and Y² eachindependently represents a single bond or -CO-. Specifically, m-aminosulfonylphenylmethacrylate, N-(p-aminosulfonylphenyl)methacrylamideand N-(p-aminosulfonylphenyl)acrylamide can beadvantageously used.
[0091] As the macromolecular binder which has the (a-3) active imide group and is insoluble in water and soluble in an aqueous solution of analkali, for example, polymers obtained by using a compound having anactive imide group as the main monomer can be used. Examples of such acompound include compounds having in the molecule one or morepolymerizable unsaturated bonds and one or more active imide groupsexpressed by the following formula:
[0092] As specific examples of the above compound, N-(p-toluenesulfonyl)methacrylamideor N-(p-toluenesulfonyl)acrylamide can beadvantageously used.
[0093] As the macromolecular binder which has an (a-4) carboxylic acidgroup and is insoluble in water and soluble in an aqueous solution of analkali, for example, polymers obtained by using a compound having one ormore carboxylic acid groups and one or more polymerizable unsaturatedbond in the molecule as the main component of polymerization can be used.As the macromolecular binder which has the (a-5) sulfonic acid group andis insoluble in water and soluble in an aqueous solution of an alkali, forexample, polymers obtained by using a compound having one or moresulfonic acid groups and one or more polymerizable unsaturated bond inthe molecule as the main component of polymerization can be used. As the macromolecular binder which has an (a-6) phosphoric acid group and isinsoluble in water and soluble in an aqueous solution of an alkali, forexample, polymers obtained by using a compound having one or morephosphoric acid groups and one or more polymerizable unsaturated bondin the molecule as the main component of polymerization can be used.
[0094] In the present embodiment, it is not necessary that a single type ofthe monomer having one of the acidic groups (a-1) to (a-6) alone is used inthe macromolecular binder insoluble in water and soluble in an aqueoussolution of an alkali. Polymers obtained by copolymerization of two ormore types of the monomers having the same acidic group, or of two ormore types of the monomers having different acidic groups, may also beused. For example, copolymers obtained by copolymerization of amonomer having one of the acidic groups (a-1) to (a-6) with a polymerhaving one of acidic groups (a-1) to (a-6) in the main chain can be used.As the monomer having one of the acidic groups (a-1) to (a-6) which is usedfor the copolymerization, the compounds described above as examples canbe used. As described above, it is preferable that copolymers having a (a-1)phenol group in the main chain and one of the acidic groups (a-1) to (a-3)in a portion of the main chain and/or in the side chains is used because thedeveloping latitude can be improved.
[0095] For example, a copolymer, obtained by copolymerization of amonomer having the phenol group with a phenol-formaldehyde resinhaving the (a-1) phenol group in the main chain or with a m-cresol-formaldehyderesin which has the (a-1) phenol in the main chain, can beused. As the monomer having the phenol group, for example, acrylamide,methacrylamide, an acrylic ester, a methacrylic ester or hydroxystyrene, each having the phenol group, can be used. Specifically, N-(2-hydroxyphenyl)acrylamide,N-(3-hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)acrylamide,N-(2-hydroxyphenyl)methacrylamide, N-(3-hydroxyphenyl)methacrylamide,N-(4-hydroxyphenyl)methacrylamide, o-hydroxyphenylacrylate, m-hydroxyphenyl acrylate, p-hydroxyphenylacrylate, o-hydroxyphenyl methacrylate, m-hydroxyphenyl methacrylate,p-hydroxyphenyl methacrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene,2-(2-hydroxyphenyl)ethyl acrylate, 2-(3-hydroxyphenyl)ethylacrylate, 2-(4-hydroxyphenyl)ethyl acrylate, 2-(2-hydroxyphenyl)ethylmethacrylate, 2-(3-hydroxyphenyl)ethyl methacrylate and 2-(4-hydroxyphenyl)ethylmethacrylate, can be advantageously used.
[0096] As the process of polymerization, a conventional process such asrandom copolymerization, graft copolymerization and blockcopolymerization can be used.
[0097] It is preferable that the above copolymer contains the abovemonomer having one of the acidic groups (a-1) to (a-6) in an amount of 10%by mol or more and more preferably 20% by mol or more. When thecontent is less than 10% by mol, the effect of improving developing latitudetends to become insufficient.
[0098] In the above copolymer, a monomer which contains none of theacidic groups (a-1) to (a-6) can also be used. Examples of the monomerwhich contains none of the acidic groups (a-1) to (a-6) include monomersshown in the following (1) to (12): (1) Acrylic esters and methacrylic esters having an aliphatichydroxyl group such as 2-hydroxyethyl acrylate and 2-hydroxyethylmethacrylate. (2) Alkyl acrylates such as methyl acrylate, ethyl acrylate, propylacrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylatebenzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate and N-dimethylaminoethylacrylate. (3) Alkyl methacrylates such as methyl methacrylate, ethylmethacrylate, propyl methacrylate, butyl methacrylate, amylmethacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzylmethacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate and N-dimethylaminoethylmethacrylate. (4) Acrylamides and methacrylamides such as acrylamide,methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide,N-cyclohexylacrylamide, N-hydroxyethylacrylamide,N-phenylacrylamide, N-nitrophenylacrylamide and N-ethyl-N-phenylacrylamide. (5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether,hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinylether and phenyl vinyl ether. (6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinylbutyrate and vinyl benzoate. (7) Styrenes such as styrene, α-methylstyrene, methylstyrene andchloromethylstyrene. (8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone,propyl vinyl ketone and phenyl vinyl ketone. (9) Olefins such as ethylene, propylene, isobutylene, butadiene andisoprene. (10) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile and methacrylonitrile. (11) Unsaturated imides such as maleimide, N-acryloylacrylamide,N-acetylmethacrylamide, N-propionylmethacrylamide and N-(p-chlorobenzoyl)methacrylamide. (12) Unsaturated carboxylic acids such as acrylic acid, methacrylicacid, maleic anhydride and itaconic acid.
[0099] In the present embodiment, it is preferable from the standpoint offriction resistance during printing that the macromolecular binderinsoluble in water and soluble in an aqueous solution of an alkali has aweight-average molecular weight of 2.0×10³ or more and a number-averagemolecular weight of 5.0×10² or more when the binder is a homopolymerand also when the binder is a copolymer. It is more preferable that themacromolecular binder has a weight-average molecular weight of 5.0×10³to 3.0×10⁵, a number-average molecular weight of 8.0×10² to 2.5×10⁵ and adispersion (the weight-average molecular weight / the number-averagemolecular weight) of 1.1 to 10.
[0100] In the above copolymer, the ratio by weight of the monomer havingone of the acidic groups (a-1) to (a-6) constituting the main chain to othermonomers constituting a portion of the main chain and/or the side chainsis preferably in the range of 50:50 to 5:95 and more preferably in the rangeof 40:60 to 10:90 from the standpoint of solubility in an alkali and adhesionof ink and friction resistance during printing.
[0101] The macromolecular binder insoluble in water and soluble in anaqueous solution of an alkali described above can be used singly or as acombination of two or more types. The macromolecular binder is used inan amount of 30 to 99% by weight, preferably 40 to 95% by weight and more preferably 50 to 90% by weight, of the total amount of the solidcomponents in the image-forming material. When the amount of themacromolecular binder insoluble in water and soluble in an aqueoussolution of an alkali is less than 30% by weight, durability of the recordinglayer tends to become inferior. When the amount exceeds 99% by weight,sensitivity and durability tend to become inferior. [Other components]
[0102] In the image-forming material of the present embodiment, otherdyes and pigments may also be added to further improve the image-formingproperty. The dyes and pigments may be added into the layerthat contains the infrared light absorbing agent having the thermallydecomposable sulfonic ester group or into another layer formed separately.As the dye, generally known dyes such as those described above,commercially available dyes and dyes described in a reference, "SENRYOBINRAN", edited by YUKI GOSEI KAGAKU KYOKAI, published in 1970,can be used. Examples of the dye include azo dyes, metal complex azodyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes,carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, aminiumdyes, diimmonium dyes and squalilium dyes. As the pigment, pigmentswhich are generally known and commercially available and pigmentsdescribed in the Color Index (C.I.) Handbook, "SAISHIN GANRYOBINRAN" (edited by NIPPON GANRYO GIJUTSU KYOKAI, published in1977), "SAISHIN GANRYO OYOGIJUTSU" (published by CMCSHUPPAN in 1986), or "INSATSU INK GIJUTSU" (published by CMCSHUPPAN in 1984), can be used. Examples of the pigment include: black pigments, yellow pigments, orange pigments, brown pigments, redpigments, violet pigments, blue pigments, green pigments, fluorescentpigments, pigments of metal powder and coloring substances bound topolymers. Specific examples include: insoluble azo pigments, azo lakepigments, condensed azo pigments, chelate azo pigments, phthalocyaninepigments, anthraquinone pigments, perylene pigments, perynonepigments, thioindigo pigments, quinacridone pigments, dioxazinepigments, isoindolinone pigments, quinophthalone pigments, dyed lakepigments for inmold decoration, azine pigments, nitroso pigments, nitropigments, natural pigments, fluorescent pigments, inorganic pigments andcarbon black. Among these dyes and pigments, dyes and pigments thatabsorb infrared light or near infrared light are particularly preferable.The dyes and the pigments may be used singly or as a combination of twoor more types.
[0103] To the first image-forming material of the present embodiment,various additives can be added. For example, quinonediazide compounds,onium salts, aromatic sulfonic compounds and esters of aromatic sulfonicacids work as thermally decomposable substances. Therefore, a propertyof suppressing dissolution of image-forming portions into a developer canbe improved by addition of these substances.
[0104] As the onium compound, diazoium salts, ammonium salts,phosphonium salts, iodonium salts, sulfonium salts, selenonium salts andarsonium salts can be used. Examples of the onium salts that can beadvantageously used in the present invention include: diazonium saltsdescribed in S. I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T. S. Balet al., Polymer, 21, 423 (1980) and JP-A 5-158230; ammonium salts described in U. S. Patent Nos. 4,069,055 and 4,069,056 and JP-A 3-140140;phosphonium salts described in D. C. Necker et al., Macromolecules, 17,2468 (1984), C. S. Wen et al., Teh, Proc. Conf. Rad. Curing ASIA, p. 478,Tokyo, Oct. (1988) and U. S. Patent Nos. 4,069,055 and 4,069,056;iodonium salts described in J. V. Crivello et al., Macromolecules, 10(6),1307 (1977), Chem. & Eng. News, Nov. 28, p.31 (1988), European PatentNo. 104,143, U. S. Patent Nos. 339,049 and 410,201, JP-A 2-150848 andJP-A 2-296514; sulfonium salts described in J. V. Crivello et al., Polymer J.17, 73 (1985), J. V. Crivello et al., J. Org. Chem., 43, 3055 (1978), W. R.Watt et al., J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), J. V.Crivello et al., Polymer Bull., 14, 279 (1985), J. V. Crivello et al.,Macromolecules, 14(5), 1141 (1981), J. V. Crivello et al., J. Polymer Sci.,Polymer Chem. Ed., 17, 2877 (1979), European Patent Nos. 370,693,233,567, 297,443 and 297,442, U. S. Patent Nos. 4,933,377, 3,902,114,410,201, 339,049, 4,760,013, 4,734,444 and 2,833,827 and German PatentNos. 2,904,626, 3,604,580 and 3,604,581; selenonium salts described in J.V. Crivello et al., Macromolecules, 10(6), 1307 (1977) and J. V. Crivello etal., J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979); and arsoniumsalts described in C. S. Wen et al., Teh, Proc. Conf. Rad. Curing ASIA, p.478, Tokyo, Oct. (1988).
[0105] As the counter ion of the onium salt, boric acid tetrafluoride,phosphoric acid hexafluoride, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonicacid, 5-sulfosalicylic acid, 2,5-dimethylbenzene-sulfonicacid, 2,4,6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonicacid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonicacid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonicacid and p-toluenesulfonic acid, can be used. Among these counter ions,phosphoric acid hexafluoride and alkyl-substituted aromatic sulfonic acidssuch as triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzene-sulfonicacid can be advantageously used.
[0106] The added amount of the onium salt used as the additive ispreferably of 1 to 50% by weight, more preferably of 5 to 30% by weightand most preferably of 10 to 30% by weight.
[0107] In the present invention, it is preferable that the additives and thebinding agents are contained in the same layer.
[0108] To further improve the sensitivity, cyclic acid anhydrides, phenolsand organic acids may be added. As the cyclic acid anhydride, cyclic acidanhydrides which are described in the specification of U. S. Patent No.4,115,128, such as phthalic anhydride, tetrahydrophthalic anhydride,hexahydrophthalic anhydride, 3,6-endooxy-Δ⁴-tetrahydrophthalicanhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleicanhydride, α -phenylmaleic anhydride, succinic anhydride andpyromellitic anhydride, can be used. As the phenol, bisphenol A, p-nitrophenol,p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxy-benzophenone,4-hydroxybenzophenone, 4,4',4''-trihydroxytriphenyl-methaneand 4,4',3'',4''-tetrahydroxy-3,5,3',5'-tetramethyltriphenyl-methanecan be used. As the organic acid, sulfonicacids, sulfinic acids, alkylsulfuric acids, phosphonic acids, esters ofphosphoric acid and carboxylic acids which are described in JP-A 60-88942and JP-A 2-96755 can be used. Specific examples include: p-toluenesulfonicacid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethylsulfuric acid, phenylphosphonic acid, phenylphosphinic acid, phenylphosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid,p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid,4-cyclohexene-1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoicacid and ascorbic acid.
[0109] The amount of the above cyclic acid anhydrides, phenols and organicacid contained in the material of the form plate is preferably of 0.05 to 20%by weight, more preferably of 0.1 to 15% by weight and most preferably of0.1 to 10% by weight, of the total weight of the material of the form plate.
[0110] To the image-forming material of the present embodiment, nonionicsurfactants described in JP-A 62-251740 and JP-A 3-208514 andamphoteric surfactants described in JP-A 59-121044 and JP-A 4-13149may further be added to improve stability of processing, with respect todeveloping conditions. Specific examples of the nonionic surfactantinclude sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate,stearic acid monoglyceride and polyoxyethylene nonylphenyl ether.Specific examples of the amphoteric surfactant includealkyldi(aminoethyl)glycine, alkylpolyaminoethyl-glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethyl-imidazoliniumbetaine and N-tetradecyl-N,N-betaine(for example, AMOGEN K, a trade name;manufactured by DAIICHI KOGYO Co., Ltd.).
[0111] The contained amount of the above nonionic surfactants andamphoteric surfactants in the material of the form plate is preferably of0.05 to 15% by weight and more preferably of 0.1 to 5% by weight, of thetotal weight of the material of the form plate.
[0112] The image-forming material of the present embodiment may further comprise a print-out agent, to obtain visible images immediately afterheating by exposure to the light, and dyes and pigments, as agents forcoloring images. Examples of the print-out agent include combinations ofa compound that generates an acid by heating by exposure to the light (anagent generating an acid by light) and an organic dye that can form a salt.Specific examples of the above agent include combinations of o-naphthoquinonediazide-4-sulfonicacid halide and an organic dye whichcan form a salt, which are described in the specifications of JP-A 50-36209and JP-A 53-8128 and combinations of a trihalomethyl compound and anorganic dye which can form a salt, which are described in the specificationsof JP-A 53-36223, JP-A 54-74728, JP-A 60-3626, JP-A 61-143748, JP-A 61-151644and JP-A 63-58440. As the trihalomethyl compound, oxazolecompounds and triazine compounds are used and both provide clearprinted-out images having stable storage stability.
[0113] As the agent for coloring images, dyes other than the above organicdyes that can form salts can be used. Among various dyes including theorganic dyes that can form salts, dyes soluble in oils and basic dyes arepreferable. Specific examples of the preferable dye include OIL YELLOW#101, OIL YELLOW #103, OIL PINK #312, OIL GREEN BG, OIL BLUEBOS, OIL BLUE #603, OIL BLACK BY, OIL BLACK BS and OIL BLACKT-505 (all trade names; manufactured by ORIENT KAGAKUKOGYO Co.,Ltd.); victoria pure blue, crystal violet (CI 42555), methyl violet (CI 42535),ethyl violet, rhodamine B (CI 145170B), Malachite green (CI 42000) andmethylene blue (CI 52015). Dyes described in the specification of JP-A62-293247 are particularly preferable. The dye may be added to thematerial of the form plate in an amount of 0.01 to 10% by weight and preferably of 0.1 to 3% by weight, of the total amount of solid componentsof the form plate.
[0114] Addition of an epoxy compound, a vinyl ether compound, a phenolcompound having a hydroxymethyl group or an alkoxymethyl groupdescribed in Japanese Patent Application No. 7-18120 or a crosslinkingcompound increasing the to-alkali-dissolution-suppressing effect which isdescribed in Japanese Patent Application No. 9-328937 is preferablebecause friction resistance increases due to a burning treatment afterexposure to light and developing.
[0115] To the material of the image-forming material of the presentembodiment, plasticizers may further be added to provide layers withflexibility, where necessary. Examples of the plasticizer include butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutylphthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate,tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate andoligomers and polymers of acrylic acid or methacrylic acid.
[0116] To the material of the image-forming material of the presentembodiment, a surfactant, such as a surfactant containing fluorinedescribed in the specification of JP-A 62-170950, may further be added toimprove coatability. The amount is preferably of 0.01 to 1% by weightand more preferably of 0.05 to 0.5% by weight, of the total amount of thematerial of the form plate.
[0117] In the present embodiment, an agent generating an acid is notparticularly required. When a further increased sensitivity is desired, theuse of an agent generating an acid is preferable. The agent generating anacid is a compound that generates an acid by heat or light. Examples of such a compound generally include: photoinitiators for photocationicpolymerization, photoinitiators for photoradical polymerization, agentsdecoloring colorants by light, agents that change color by light,conventional compounds that generate an acid by light and are used formicroresists, and mixtures of these compounds. These compounds may besuitably selected and used as the above agent.
[0118] Examples of the agent generating an acid include the followingonium compounds: diazonium salts described in S. I. Schlesinger, Photogr.Sci. Eng., 18, 387 (1974) and T. S. Bal et al., Polymer, 21, 423 (1980);ammonium salts described in U. S. Patent Nos. 4,069,055 and 4,069,056and JP-A 3-140,140; phosphonium salts described in D. C. Necker et al.,Macromolecules, 17, 2468 (1984), C. S. Wen et al., Teh, Proc. Conf. Rad.Curing ASIA, p. 478, Tokyo, Oct. (1988) and U. S. Patent Nos. 4,069,055and 4,069,056; iodonium salts described in J. V. Crivello et al.,Macromolecules, 10(6), 1307 (1977), Chem. & Eng. News, Nov. 28, p. 31(1988), European Patent No. 104,143, U. S. Patent Nos. 339,049 and410,201, JP-A 2-150848 and JP-A 2-296514; sulfonium salts described in J.V. Crivello et al., Polymer J., 17, 73 (1985), J. V. Crivello et al., J. Org.Chem., 43, 3055 (1978), W. R. Watt et al., J. Polymer Sci., Polymer Chem.Ed., 22, 1789 (1984), J. V. Crivello et al., Polymer Bull., 14, 279 (1985), J. V.Crivello et al., Macromolecules, 14(5), 1141 (1981), J. V. Crivello et al., J.Polymer Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patent No.370,693, U. S. Patent No. 3,902,114, European Patent Nos. 233,567,297,443 and 297,442, U. S. Patent Nos. 4,933,377, 410,201, 339,049,4,760,013, 4,734,444 and 2,833,827 and German Patent Nos. 2,904,626,3,604,580 and 3,604,581; selenonium salts described in J. V. Crivello et al., Macromolecules, 10(6), 1307 (1977) and J. V. Crivello et al., J. Polymer Sci.,Polymer Chem. Ed., 17, 1047 (1979); and arsonium salts described in C. S.Wen et al., Teh, Proc. Conf. Rad. Curing ASIA, p. 478, Tokyo, Oct. (1988).
[0119] The above examples also include the following compounds: organichalogen compounds described in U. S. Patent No. 3,905,815, JapanesePatent Publication No. 46-4605, JP-A 48-36281, JP-A 55-32070, JP-A 60-239736,JP-A 61-169835, JP-A 61-169837, JP-A 62-58241, JP-A 62-212401,JP-A 63-70243 and JP-A 63-298339; organometallic/organohalogencompounds described in K. Meier et al., J. Rad. Curing, 13(4), 26 (1986), T.P. Gill et al., Inorg. Chem., 19, 3007 (1980), D. Astruc, Acc. Chem. Res.,19(12), 377 (1896) and JP-A 2-161445; agents generating an acid by lightand having a protective group of an o-nitrobenzyl type which are describedin S. Hayase et al., J. Polymer Sci., 25, 753 (1987), E. Reichman et al., J.Polymer Sci., Polymer Chem. Ed., 23, 1 (1985), Q. Q. Zhu et al., J.Photochem., 36, 85, 39, 317 (1987), B. Amit et al., Tetrahedron Lett., (24)2205 (1973), D. H. R. Barton et al., J. Chem. Soc., 3571 (1956), P. M.Collins et al., J. Chem. Soc., Perkin I, 1695 (1975), M. Rudinstein et al.,Tetrahedron Lett., (17), 1445 (1975), J. W. Walker et al., J. Am. Chem. Soc.,110, 7170 (1988), S. C. Busman et al., Imaging Technol., 11(4), (1985), H.M. Houlihan et al., Macromolecules, 21, 2001 (1988), P. M. Collins et al., J.Chem. Soc., Chem. Commun., 532 (1972), S. Hayase et al., Macromolecules,18, 1799 (1985), E. Reichmanis et al., J. Electrochem. Soc., Solid State Sci.Technol., 130(6), F. M. Houlihan et al., Macromolecules, 21, 2001 (1988),European Patent Nos. 0290,750, 046,083, 156,535, 271,851 and 0,388,343,U. S. Patent Nos. 3,901,710 and 4,181,531, JP-A 60-198538 and JP-A 53-133022;compounds which are decomposed by light to generate a sulfonic acid, typical examples of which are iminosulfonates described in Tunookaet al., Polymer Preprints Japan, 35(8), G. Berner et al., J. Rad. Curing,13(4), W. J. Mijs et al., Coating Technol., 55(697), 45 (1983), Akzo, H.Adachi et al., Polymer Preprints, Japan, 37(3), European Patent Nos.0199,672, 84515, 199,672, 044,115 and 0101,122, U. S. Patent Nos.4,618,554, 4,371,605 and 4,431,774, JP-A 64-18143, JP-A 2-245756 andJP-A 3-140109; and disulfonic compounds described in JP-A 61-166544.
[0120] Compounds obtained by introducing an agent generating an acid bylight into the main chain or the side chain of a polymer can also be used.Examples of such compounds include compounds described in M. E.Woodhouse et al., J. Am. Chem. Soc., 104, 5586 (1982), S. P. Pappas et al.,J. Imaging Sci., 30(5), 218 (1986), S. Kondo et al., Macromol. Chem. RapidCommun., 9, 625 (1988), Y. Yamada et al., Macromol. Chem., 152, 153, 163(1972), J. V. Crivello et al., J. Polymer Sci., Polymer Chem. Ed., 17, 3845(1979), U. S. Patent No. 3,849,137, German Patent No. 3914407, JP-A 63-26653,JP-A 55-164824, JP-A 62-69263, JP-A 63-14603, JP-A 63-163452,JP-A 62-153853 and JP-A 63-146029.
[0121] Compounds generating an acid by light which are described in V. N.R. Pillai, Synthesis, (1), 1 (1980), A. Abad et al., Tetrahedron Lett., (47)4555 (1971), D. H. R. Barton et al., J. Chem. Soc., (C), 329 (1970), U. S.Patent No. 3,779,778 and European Patent No. 126,712 can also be used.
[0122] In the present embodiment, the agent generating an acid by light isused generally in an amount of about 40% by weight or less, preferably inan amount of 20% by weight or less and more preferably in an amount of5% by weight or less, of the total amount of the solid components in thephotosensitive layer. When the amount of the acid generating agent exceeds 40% by weight, the property to prevent staining deteriorates andsuch an amount is not preferable. [Lithographic form plate]
[0123] When the above first image-forming material is used for alithographic form plate, the lithographic form plate is prepared inaccordance with the following general process. The above first image-formingmaterial is suited for application to a lithographic form plate butthe application of this material is not limited to the lithographic formplate.
[0124] The lithographic form plate is generally prepared by dissolvingcomponents described above in a solvent and applying the result to asuitable substrate. Examples of the solvent used in this step include:ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol,ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol,2-methoxyethyl acetate, 1-methoxy-2-propyl acetate,dimethoxyethane, methyl lactate, ethyl lactate, N,N-dimethylacetoamide,N,N-dimethylformamide, tetramethylurea, N-methylpyrrolidone,dimethylsulfoxide, sulfolane, γ-butyrolactone and toluene. However, thesolvent is not limited to these examples. The solvent can be used singly oras a mixture of two or more types. The concentration of the abovecomponents, i.e., the total solid components including the additives, in thesolvent is preferably of 1 to 50% by weight. The amount of the materialcoated on the substrate after application and drying, i.e., the amount of thesolid components, is different depending on the application. When theproduct is used as a photosensitive form plate, it is generally preferable that the amount is 0.5 to 5.0 g/m². Various methods may be used to applythe solution to the substrate. For example, coating by a bar coater,rotation coating, spray coating, curtain coating, dip coating, coating by anair knife, coating by a blade or coating by a roll can be used. The smallerthe coated amount, the better the apparent sensitivity but the moreinferior the film characteristic of the photosensitive layer. This coatinglayer forms the photosensitive layer in the lithographic form plate.
[0125] The substrate is dimensionally stable with a plate shape.Examples of the substrate include paper, paper laminated with plastics(such as polyethylene, polypropylene and polystyrene), metal plates suchas plates of aluminum, zinc and copper, plastic films such as films ofcellulose diacetate, cellulose triacetate, cellulose propionate, cellulosebutyrate, cellulose acetate butyrate, cellulose nitrate, polyethyleneterephthalate, polyethylene, polystyrene, polypropylene, polycarbonateand polyvinylacetal, and paper and plastic films laminated or depositedwith the above metal. As the substrate in the present invention,polyester films and aluminum plates are preferable and aluminum platesare more preferable because aluminum plates have excellent dimensionalstability and are relatively inexpensive. Preferable aluminum plates areplates of pure aluminum and plates of alloys containing aluminum as themain component and small amounts of other elements. The substratemay be a plastic film laminated or deposited with aluminum. The otherelements contained in the aluminum alloy are silicon, iron, manganese,copper, magnesium, chromium, zinc, bismuth, nickel and titanium. Thecontained amount of the other elements in the alloy is to be 10% by weightor less. It is particularly preferable in the present invention that pure aluminum is used. However, a small amount of other metals may becontained because producing completely pure aluminum is technicallydifficult. The aluminum plate used in the present invention is notrequired to have a specific composition but conventionally availablealuminum plates can be suitably used. The thickness of the aluminumplate used in the present invention is about of 0.1 mm to 0.6 mm,preferably of 0.15 to 0.4 mm and more preferably of 0.2 to 0.3 mm.
[0126] The aluminum plate is used after the surface has been made rough.Before making the surface rough, the degreasing treatment using, forexample, a surfactant, an organic solvent or an alkaline aqueous solutionmay be conducted to remove oil used in rolling from the plate surface,where necessary.
[0127] The surface-roughening treatment for the aluminum plate can beconducted in accordance with various methods, such as a mechanicalmethod in which the surface is mechanically made rough, anelectrochemical method in which the surface is made rough byelectrochemically dissolving the surface and a chemical method in whichthe surface is chemically dissolved selectively. As the mechanical method,a conventional method such as abrading by balls, abrading by brushes,abrading by blasting and abrading by buffing can be used. As theelectrochemical method, an aluminum plate may be treated by analternating electric current or a direct electric current in an electrolytecontaining hydrochloric acid or nitric acid. A combination of thesemethods can also be conducted as shown in the specification of JP-A 54-63902.
[0128] The aluminum plate the surface of which has been made rough is treated by an alkali etching treatment and a neutralization treatment andthen treated by anode oxidation to improve a property of the surface tohold water and to increase wear resistance, where necessary. As theelectrolyte used for anode oxidation of the aluminum plate, variouselectrolytes that can form porous oxide films can be used. In general,sulfuric acid, phosphoric acid, oxalic acid, chromic acid or a mixture ofthese acids is used. The concentration of the electrolyte is suitablyselected in accordance with the type of the electrolyte.
[0129] The conditions for anode oxidation varies depending on the usedelectrolyte and may be generally decided. In general, a concentration ofthe electrolyte of 1 to 80% by weight, a temperature of the liquid of 5 to70°C, a current density of 5 to 60 A/dm², a voltage of 1 to 100 V and a timeof electrolysis of 10 seconds to 5 minutes are suitable. When the amountof the film formed by anode oxidation is less than 1.0 g/m², resistance toprinting stress is occasionally insufficient. Moreover, non-image portionsof the lithographic form plate tend to have scratches and this tends tocause so-called scratch stains due to ink attaching to the scratches duringprinting.
[0130] The aluminum plate, which has been treated by anode oxidation,may have a hydrophilizing treatment carried out on the surface, wherenecessary. As the hydrophilizing treatment used in the present invention,an alkali metal silicate process such as a process using an aqueous solutionof sodium silicate, which is disclosed in U. S. Patent Nos. 2,714,066,3,181,461, 3,280,734 and 3,902,734, can be used. In this process, thesubstrate is treated with an aqueous solution of sodium silicate by dippingthe substrate into the solution or by electrolysis. Alternatively, the substrate may be treated with potassium fluorozirconate as disclosed inthe specification of Japanese Patent Application Publication 36-22063 orwith polyvinylphosphonic acid as disclosed in U. S. Patent Nos. 3,276,868,4,153,461 and 4,689,272.
[0131] An undercoat layer (a primer) may be formed between the substrateand the photosensitive layer, where necessary. As the component of theundercoat layer, various organic compounds can be used. The componentmay be selected, for example, from among the followingcarboxymethylcellulose; dextrin; gum arabic; organophosophonic acidssuch as a phosphonic acid having the amino group such as 2-aminoethylphosphonicacid, substituted and unsubstitutedphenylphosphonic acids, naphthylphosphonic acids, alkylphosphonic acids,glycerophosphonic acids, methylenediphosphonic acids andethylenediphosphonic acids; organophosphoric acids such as substitutedand unsubstituted phenylpohosphoric acids, naphthyl-phosphoric acids,alkylphospohoric acids and glycerophosphoric acids; organophosphinicacids such as substituted and unsubstituted phenylphosphinic acids,naphthylphosphinic acids, alkylphosphinic acids and glycerophosphinicacid; amino acids such as glycine and β-alanine; and amine hydrochlorideshaving a hydroxyl group such as triethanolamine hydrochlorides. Theabove compounds may be used singly or as a mixture of two or more types.
[0132] The organic undercoat layer can be formed in accordance with one ofthe following processes. In one process, a solution prepared by dissolvingthe above organic compound in water, an organic solvent such as methanol,ethanol or methyl ethyl ketone, or a mixture of water and such an organicsolvent, is applied to the aluminum plate and dried. In another process, the aluminum plate is dipped into a solution prepared by dissolving theabove organic compound in water, an organic solvent such as methanol,ethanol or methyl ethyl ketone, or a mixture of water and such an organicsolvent, so that the above compound is sorbed onto the aluminum plateand the treated aluminum plate is then washed with water or the like anddried to form the organic undercoat layer. In the first process, a solutionof the above organic compound having a concentration of 0.005 to 10% byweight can be applied by various methods. In the second process, theconcentration of the organic compound in the solution is of 0.01 to 20% byweight and preferably of 0.05 to 5% by weight, the temperature of dippingis of 20 to 90°C and preferably of 25 to 50°C and the time period for dippingis 0.1 seconds to 20 minutes and preferably 2 seconds to 1 minute. Thesolution used in these processes can be adjusted to a pH of 1 to 12 using abasic substance such as ammonia, triethylamine and potassium hydroxideor an acidic substance such as hydrochloric acid or phosphoric acid. Ayellow dye may be added to improve the color-tone-reproduction propertyof the image-forming material.
[0133] It is suitable that the applied amount of the organic primer layer isof 2 to 200 mg/m² and preferably of 5 to 100 mg/m². When the appliedamount is less than 2 mg/m², sufficient resistance to printing stress cannotbe obtained. Similarly, when the amount exceeds 200 mg/m², sufficientresistance to printing stress cannot be obtained.
[0134] The prepared lithographic form plate is generally exposed toimagewise exposure, developing processing is applied, and the images areformed on the form plate. As a light source of an active light used forimagewise exposure, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp or a carbon arc lamp, for example, can be used. Otherirradiations such as an electron beam, X-ray, ion beam, far infrared light,g-ray, i-ray, deep-UV light and high density energy beam (laser beam) canalso be used. As the laser beam, beams from helium-neon lasers, argonlasers, krypton lasers, helium-cadmium lasers, Kr-F excimer lasers, solidlasers and semiconductor lasers can be used. In the present invention, alight source emitting light of a wavelength in the near infrared to infraredregion is preferable and light from a solid laser and a semiconductor laseris more preferable.
[0135] As the developer and a replenisher used for processing,conventionally used aqueous solutions of an alkali can be used. Examplesof the alkali include: inorganic alkali salts such as sodium silicate,potassium silicate, sodium tertiary phosphate, potassium tertiaryphosphate, ammonium tertiary phosphate, sodium secondary phosphate,potassium secondary phosphate, ammonium secondary phosphate, sodiumcarbonate, potassium carbonate, ammonium carbonate, sodiumhydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate,sodium borate, potassium borate, ammonium borate, sodiumhydroxide, potassium hydroxide, ammonium hydroxide and lithiumhydroxide. Other examples of the alkali include: organic alkalis such asmonomethylamine, dimethylamine, trimethylamine, monoethylamine,diethylamine, triethylamine, monoisopropylamine, diisopropylamine,triisopropylamine, n-butylamine, monoethanolamine, diethanolamine,triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine,ethylenediamine and pyridine.
[0136] The alkali may be used singly or as a combination of two or more types.
[0137] Among the above solutions of an alkali, solutions of silicates such assodium silicate and potassium silicate are particularly preferably used asthe developer because the property for developing can be adjusted bychanging the ratio of silicon dioxides SiO₂ the components of the silicate tothe oxide of the alkali metal M₂O and by changing the concentrations ofthese components. For example, alkali metal silicates described in JP-A54-62004 and Japanese Application Patent Publication No. 57-7427 areeffectively used.
[0138] When developing is conducted using an automatic processer, it isknown that a large number of PS plates can be processed withoutexchanging the developer in the developer tank for a long time if anaqueous solution having a higher alkali strength than that of the developer(a replenisher) is added to the developer. In the present invention, thismethod of replenishing can be advantageously adopted. To the developerand the replenisher, various surfactants and organic solvents can be addedin accordance with necessity to promote or suppress developing, todisperse waste substances formed by developing or to increase affinity ofthe formed image portion of the form plate to ink. Examples of preferablesurfactants include: anionic surfactants, cationic surfactants, nonionicsurfactants and amphoteric surfactants. Moreover, reducing agents suchas hydroquinone, resorcinol and sodium salts, and potassium salts ofinorganic acids such as sulfurous acid and hydrogensulfurous acid; organiccarboxylic acids; defoaming agents; and softeners for hard water may beadded to the developer and the replenisher, where necessary.The lithographic form plate to which developing processing has been applied with the developer and the replenisher is then subjected toposttreatments such as with washing water, with a rinsing liquidcontaining a surfactant or with a desensitization liquid containing gumarabic and a starch derivative. As the posttreatment of the form plateusing the image-forming material of the present invention, variouscombinations of the above posttreatments can be applied.
[0139] Recently, automatic processor for form plates are widely used in theform-plate manufacturing and printing industries, to rationalize andstandardize operations of making form (machine) plates. Thelithographic form plate of the present invention can be processed by suchautomatic processor. Automatic processor are generally composed of adeveloping portion and a posttreatment portion and contain apparatusesfor transferring form plates, tanks of various processing solutions andspraying apparatuses. While form plates which have been exposed tolight are transferred in a horizontal direction, various processing solutionspumped up from tanks are sprayed through nozzles for developingtreatment. In some recent machines, form plates are processed bydipping into processing solutions in tanks filled with the processingsolutions and transferred through the solutions by guide rolls. In theseautomatic treatments, processing can be conducted while the replenisheris supplied in accordance with the amount of processing and the time ofoperation. The so-called single-use method in which processing isconducted using substantially fresh processing solutions can also be used.
[0140] After imagewise exposure, developing, washing with water and/orrinsing and/or coating with gum, unnecessary images on the lithographicform plate such as film edges of the original plate, if any, may be eliminated. As a method of elimination, a method described in JapanesePatent Publication No. 2-13293, in which an elimination liquid is appliedto an unnecessary image portion and, after being left standing for aprescribed time, the portion is washed with water, is preferable. Amethod described in JP-A 59-174842, in which the unnecessary imageportion is irradiated with an active light through optical fibers and thendeveloped, may also be used.
[0141] The lithographic form plate which has been treated as describedabove is coated with desensitizing gum, where necessary, and used in aprinting step. The form plate may be subjected to a burning treatment toimprove resistance to printing stress. When a lithographic form plate issubjected to the burning treatment, it is preferable that, before theburning treatment, the lithographic form plate is treated with anaffinitizing liquid such as those described in the specifications of JapanesePatent Application Publication Nos. 61-2518 and 55-28062, JP-A 62-31859and JP-A 61-159655. In the treatment, the affinitizing liquid is applied tothe surface of the lithographic form plate using a sponge or absorbentcotton impregnated with the affinitizing liquid or the lithographic formplate is dipped into a vat filled with the affinitizing liquid. An automaticcoater may also be used for this purpose. It is more preferable that thecoating is made uniform by a squeegee or a squeegee roller. It isgenerally suitable that the applied amount of the affinitizing liquid is of0.03 to 0.8 g/m² (weight after being dried).
[0142] The lithographic form plate which has been treated with theaffinitizing liquid and dried may be heated to a high temperature by aburning processor such as a burning processor BP-1300, a trade name, marketed by FUJI PHOTO FILM Co., Ltd. The temperature and the timeof heating are varied depending on the type of components forming theimages. It is preferable that heating is conducted at a temperature in therange of 180 to 300°C for 1 to 20 minutes.
[0143] The lithographic form plate which has been subjected to burningprocessing may suitably be subjected to conventional treatments such aswashing with water or coating with gum. When an affinitizing liquidcontaining a macromolecular compound soluble in water is used, the so-calleddesensitizing processing such as coating with gum may be omitted.
[0144] The lithographic form plate obtained after the above treatments isset in an offset printer or the like and used for printing. EXAMPLES
[0145] Photosensitive lithographic form plates using the first image-formingmaterial of the present embodiment will be described morespecifically with reference to the following examples. However, thepresent invention is not limited by the examples. Example 1Preparation of a substrate
[0146] An aluminum plate (material 1050) having a thickness of 0.3 mmwas degreased by washing with trichloroethylene. The washedaluminum plate was treated with a nylon brush and with pumice-watersuspension of 400 mesh in water to roughen the surface and then washedwell with water. The treated plate was dipped into a 25% aqueoussolution of sodium hydroxide at 45°C for 9 seconds for etching, washed with water, then dipped into a 2% nitric acid for 20 seconds and washedwith water. The amount of etching of the roughened surface was about 3g/m². An oxide coating layer of 3 g/m² was formed on the plate by directcurrent anode oxidation using a 7% sulfuric acid as the electrolyte at adensity of electric current of 15 A/dm² and then the plate was washed withwater and dried. The following undercoat liquid was applied to the plateand the undercoat layer was dried at 90°C for 1 minute. The amount ofthe dried undercoat layer was 10 mg/m². Composition of the undercoat liquid β-alanine 0.5 g methanol 95 g water 5 g
[0147] Photosensitive Liquid 1 shown in the following was applied to theobtained substrate in such an amount that the amount of coating was 1.8g/m² and a lithographic form plate of Example 1 was obtained. Composition of Photosensitive Liquid 1 m-, p-cresol novolak (a macromolecular binder soluble in water and insoluble in an aqueous solution of an alkali) 1.0 g m/p ratio=6/4; weight-average molecularweight, 3500; contained amount ofunreacted cresol, 0.5% by weight; infrared light absorbing agent (Compound 3) 0.2 g a dye obtained by converting the counter anion of VICTORIA PURE BLUE BOH to 1-naphthalenesulfonate anion 0.02 gsurfactant containing fluorine (MEGAFAC F-177, a trade name; manufactured by DAINIPPON INK KAGAKU KOGYO Co., Ltd.) 0.05 g γ-butyrolactone 3 g methyl ethyl ketone 8 g 1-methoxy-2-propanol 7 g Example 2
[0148] In accordance with the same procedures as those conducted inExample 1 except that another infrared light absorbing agent (Compound12) was used in place of Compound 3, a lithographic form plate of Example2 was obtained. Comparative Example 1
[0149] In accordance with the same procedures as those conducted inExample 1 except that another infrared light absorbing agent (ReferenceCompound 1 shown in the following) was used in place of Compound 3, alithographic form plate of Comparative Example 1 was obtained.
[0150] In accordance with the same procedures as those conducted inExample 1 except that another infrared light absorbing agent (ReferenceCompound 2 shown in the following) was used in place of Compound 3, a lithographic form plate of Comparative Example 2 was obtained.
[0151] Into a 100 ml three-necked flask equipped with a stirrer, a coolerand a dropping funnel, 5.04 g (0.0210 mol) of N-(p-aminosulfonylphenyl)-methacrylamide,2.05 g (0.0180 mol) of ethyl methacrylate, 1.11 g (0.021mol) of acrylonitrile and 20 g of N,N-dimethylacetoamide were placed andthe mixture was stirred while being heated at 65°C in a hot water bath.To this mixture, 0.15 g of V-65 (a trade name, manufactured by WAKOJUN'YAKU Co., Ltd.) was added and the resultant mixture was stirred for2 hours under a nitrogen stream while the temperature was kept at 65°C.To this reaction mixture, a mixture of 5.04 g of N-(p-aminosulfonylphenyl)methacrylamide,2.05 g of ethyl methacrylate, 1.11 g ofacrylonitrile, 20 g of N,N-dimethylacetoamide and 0.15 g of V-65 wasadded dropwise from the dropping funnel over 2 hours. After the additionwas completed, the reaction mixture was further stirred at 65°C for 2hours. After the reaction was completed, 40 g of methanol was added to the reaction mixture and the mixture was cooled. The obtained mixturewas added into 2 liters of water which was kept being stirred. After themixture was stirred for 30 minutes, the formed precipitate was separatedby filtration and dried to obtain 15 g of a white solid (Copolymer 1). Theweight-average molecular weight of Copolymer 1 was measured by the gelpermeation chromatography using polystyrene as the reference and wasfound to be 53,000.
[0152] On a substrate which was similar to the substrate obtained inExample 1, a Photosensitive Liquid 2 shown in the following was appliedso that a film of 1.8 g/m² was formed and a lithographic form plate ofExample 3 was obtained. Composition of Photosensitive Liquid 2 Copolymer 1 prepared above 1.0 g infrared light absorbing agent (Compound 1) 0.1 g a dye obtained by converting the counter anion of VICTORIA PURE BLUE BOH to 1-naphthalenesulfonate anion 0.02 g surfactant containing fluorine (MEGAFAC F-177, a trade name; manufactured by DAINIPPON INK KAGAKU KOGYO Co., Ltd.) 0.05 g γ-butyrolactone 8 g methyl ethyl ketone 8 g 1-methoxy-2-propanol 4 g Example 4
[0153] In accordance with the same procedures as those conducted in Example 1 except that another infrared light absorbing agent (Compound8) was used in place of Compound 3, a lithographic form plate of Example 4was obtained. Example 5
[0154] In accordance with the same procedures as those conducted inExample 1 except that another infrared light absorbing agent (Compound9) was used in place of Compound 3, a lithographic form plate of Example 5was obtained. Example 6
[0155] In accordance with the same procedures as those conducted inExample 1 except that another infrared light absorbing agent (Compound13) was used in place of Compound 3, a lithographic form plate of Example6 was obtained. [Evaluation of lithographic form plates]
[0156] Properties of the lithographic form plates of Examples 1 to 6 andComparative Examples 1 and 2 were evaluated in accordance with thefollowing methods. The results are shown in Table 1. (Evaluation of the sensitivity and the developing latitude (the image-formingproperties)
[0157] The obtained lithographic form plate was exposed to light using asemiconductor laser emitting light of a wavelength of 830 nm. Afterexposure, developing was conducted using an automatic processor (PS PROCESSOR 900 VR, manufactured by FUJI PHOTO FILM Co., Ltd.)with a developer DP-4, and a rinsing solution FR-3 (diluted at a ratio of 1:7),both manufactured by FUJI PHOTO FILM Co., Ltd. The developer DP-4was diluted to prepare two solutions, i.e., one solution diluted at a ratio of1:6 and another solution diluted at a ratio of 1:12. The line width in theportion which did not have images was measured in each case in whicheach developer was used. Then, the energy of laser irradiationcorresponding to the line width was obtained and the obtained value wasregarded as the sensitivity (mJ/cm²). Difference between the sensitivityobtained by using the developer diluted by the ratio of 1:6, which was usedas the reference, and the sensitivity obtained by using the developerdiluted by the ratio of 1:12 was obtained. The smaller the difference, thebetter the developing latitude. A developing latitude of 20 mJ/cm² or lessindicates a practically useful level.infrared light absorbing agent image-forming properties sensitivity (mJ/cm²) developing latitude Example 1 Compound 3 120 5 Example 2 Compound 12 115 5 Comparative Example 1 Reference Compound 1 180 25 Comparative Example 2 Reference Compound 2 200 30 Example 3 Compound 1 130 10 Example 4 Compound 8 110 10 Example 5 Compound 9 100 15 Example 6 Compound 13 140 10 Evaluation of storage stability
[0158] After the obtained lithographic form plate was stored at 60°C for 3days, the lithographic form plate was exposed to laser light and developedin accordance with the same procedures as those described above for theevaluation of the sensitivity and the developing latitude (the image-formingproperties). The sensitivity of the developed form plate wasmeasured and the obtained value was compared with the value obtainedbefore the storage. All lithographic form plates showed a change in thesensitivity of 20 mJ/cm² or less.
[0159] The results in Table 1 show that the lithographic form plates of Examples 1 to 6 showed higher sensitivities to the infrared laser light andbetter developing latitudes, i.e., more excellent image-forming properties,than those of the lithographic form plates of Comparative Examples 1 and2. The lithographic form plates each showed a small change in sensitivityafter storage and thus have excellent storage stability.
[0160] In summary, in accordance with the present embodiment, thelithographic form plate onto which digital data of computers can bedirectly inscribed by a solid laser and a semiconductor laser that emitsinfrared light and shows excellent image-forming properties (sensitivityand developing latitude) and storage stability can be obtained by using theabove first image-forming material.
[0161] The photosensitive lithographic form plate in which the secondimage-forming material of the present invention is used will be describedas the second embodiment.
[0162] The composition of the second image-forming material will be firstdescribed in detail.
[0163] The second image-forming material described in the presentembodiment comprises (C) a macromolecular compound which isdecomposed by heating or with an acid and becomes soluble in water or analkali and (B) an infrared light absorbing agent having a hydrophobicfunctional group which changes to hydrophilic due to heat.
[0164] The infrared light absorbing agent having a hydrophobic functionalgroup which changes to hydrophilic due to heat as component (B) is thesame as the infrared light absorbing agent having a hydrophobicfunctional group which changes to hydrophilic due to heat of component (B) contained in the first image-forming material described in the firstembodiment and a detailed description of component (B) is omitted.
[0165] The second image-forming material used in the present embodimentmay further comprise an agent generating an acid and other substances inaddition to components (B) and (C) described above in accordance with theobject. [(C) Macromolecular compound which is decomposed by heating or with anacid and becomes soluble in water or an alkali]
[0166] In the present embodiment, the macromolecular compound which isdecomposed by heating or with an acid and becomes soluble in water or analkali means a macromolecular compound which becomes soluble in wateror an alkali under heating and/or by the action of an acid. Examples ofthe compound which becomes soluble in water or an alkali under heatingor by the action of an acid include polymers of sulfonic esters and polymersof carboxylic esters.
[0167] As the polymer of sulfonic ester of the present embodiment,polymers described in Japanese Patent Application Nos. 9-26878, 9-89451,9-85328 and 9-89816 can be used. As the polymer of carboxylic ester,polymers of alkoxyalkylesters described in Japanese Patent ApplicationNo. 9-248994 and t-alkylcarboxylic esters and benzyl carboxylatesdescribed in JP-A 7-186562 can be used. Among these compounds,sulfonic esters represented by General Formula (1) described in Claim 1 ofJapanese Patent Application No. 9-26878, sulfonic esters described inclaims of Japanese Patent Application No. 9-85328 and t-alkylcarboxylicesters, benzyl carboxylates and pyranyl carboxylates described in Claim 3 of JP-A 7-186562 are preferably used.
[0168] Specific examples of the macromolecular compound which isdecomposed by heating or with an acid and becomes soluble in water or analkali, which is used in the present embodiment, are shown in thefollowing. Examples of the polymer of sulfonic ester are shown as 1p-1 to1p-8 and examples of the polymer of carboxylic ester are shown as a1 toa10. However, the present invention is not limited to these examples.
[0169] In the present embodiment, when the macromolecular compoundwhich is decomposed by heating or with an acid and becomes soluble inwater or an alkali is used, the compound is used in an amount of about 3 to98% by weight, preferably 5 to 80% by weight and more preferably 10 to60% by weight, of the total amount of the solid components in thephotosensitive layer. An amount of the macromolecular compound whichis decomposed by heating or with an acid and becomes soluble in water oran alkali less than 3% by weight is not preferable from the standpoint ofthe image-forming properties and an amount exceeding 98% by weight isnot preferable from the standpoint of sensitivity. [The agent generating an acid]
[0170] In the present embodiment, the agent generating an acid is notparticularly required because the infrared absorbing agent having athermally decomposable ester group plays the role of the agent generatingan acid. When further increased sensitivity is desired, it is preferablethat the agent generating an acid is used.
[0171] The agent generating an acid is a compound that generates an acidby heat or light. Examples of such a compound generally includephotoinitiators used in photocationic polymerization, photoinitiators usedin photoradical polymerization, agents for decoloring colorants by light,agents that change color by light, conventional compounds that generateacid by light and are used for microresists, and mixtures of thesecompounds. These compounds may be suitably selected and used as theabove agent.
[0172] The agents generating an acid that are described above in the first embodiment may be used as the agent generating an acid. Therefore, adetailed description of this agent is omitted. [Other components]
[0173] In the second image-forming material used in the presentembodiment for forming a photosensitive layer of the photosensitivelithographic form plate, various other additives may also be added, wherenecessary, in addition to the above components to obtain variousproperties of the lithographic form plate.
[0174] For example, a dye having a large absorption in the visible regioncan be used as the coloring agent of images.
[0175] Specific examples of the preferable dye include: OIL YELLOW #101,OIL YELLOW #103, OIL PINK #312, OIL GREEN BG, OIL BLUE BOS,OIL BLUE #603, OIL BLACK BY, OIL BLACK BS and OIL BLACK T-505(all trade names; manufactured by ORIENT KAGAKUKOGYO Co., Ltd.);victoria pure blue, crystal violet (CI 42555), methyl violet (CI 42535), ethylviolet, rhodamine B (CI 145170B), Malachite green (CI 42000), methyleneblue (CI 52015); and dyes described in the specification of JP-A 62-293247.
[0176] It is preferable that the dye is added because difference between theimage portions and non-image portions can be made clearer after theimages are formed. The amount of the dye is of 0.01 to 10% by weight, ofthe total amount of the solid components in the photosensitive layer.
[0177] It is advantageous in the present embodiment that an additive suchas a silane coupling agent is added to the liquid used for forming thephotosensitive layer of the lithographic form plate so that themacromolecular compound which becomes soluble in water or in an alkali is used in a cured condition.
[0178] In the photosensitive layer of the lithographic form plate preparedby using the second image-forming material of the present embodiment,nonionic surfactants described in JP-A 62-251740 and JP-A 3-208514 andamphoteric surfactants described in JP-A 59-121044 and JP-A 4-13149may be further used to improve stability of processing with respect todeveloping conditions.
[0179] Specific examples of the nonionic surfactant include sorbitantristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acidmonoglyceride and polyoxyethylene nonylphenyl ether.
[0180] Specific examples of the amphoteric surfactant include:alkyldi(aminoethyl)glycines, alkylpolyaminoethylglycine hydrochlorides,2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N,N-betaine(for example, AMOGEN K, a trade name;manufactured by DAIICHI KOGYO Co., Ltd.). The contained amount ofthe above nonionic surfactants and amphoteric surfactants is preferably of0.05 to 15% by weight and more preferably of 0.1 to 5% by weight, of thephotosensitive layer of the photosensitive lithographic form plate.
[0181] To the photosensitive layer of the lithographic form plate preparedby using the second image-forming material of the present embodiment, aplasticizer may further be added to impart flexibility to the coating layer,where necessary. Examples of the plasticizer include: butyl phthalyl,polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate,dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributylphosphate, trioctyl phosphate, tetrahydrofurfuryl oleate and oligomers andpolymers of acrylic acid or methacrylic acid.
[0182] To the photosensitive layer of the lithographic form plate of thepresent embodiment, the above onium salts, s-triazine and substitutedwith a haloalkyl group, epoxy compounds, vinyl ethers, phenol compoundshaving a hydroxymethyl group and phenol compounds having analkoxymethyl group which are described in Japanese Patent ApplicationNo. 7-18120, and phenol novolak resins and cresol novolak resins may befurther added. [Lithographic form plate]
[0183] The above second image-forming material is suited for application toa photosensitive lithographic form plate but application of this material isnot limited to the lithographic form plate. The general process forpreparation of the photosensitive lithographic form plate in the presentembodiment will be described in the following.
[0184] The photosensitive lithographic form plate of the presentembodiment is generally prepared by dissolving components describedabove in a solvent and applying the result to a suitable substrate to formthe coating layer. Examples of the solvent used in this step include:ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol,ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol,2-methoxyethyl acetate, 1-methoxy-2-propyl acetate,dimethoxyethane, methyl lactate, ethyl lactate, N,N-dimethylacetoamide,N,N-dimethylformamide, tetramethylurea, N-methylpyrrolidone,dimethylsulfoxide, sulfolane, γ-butyrolactone, toluene and water.However, the solvent is not limited to these examples. The solvent can beused singly or as a mixture of two or more types. The concentration of the above components in the solution i.e., the total solid components includingthe additives in the solution is preferably of 1 to 50% by weight. Theamount of the material coating the substrate after applying and drying thesolution, i.e., the amount of the solid components of the coating, is differentdepending on the application. When the product is used as thephotosensitive lithographic form plate, it is generally preferable that theamount is of 0.5 to 5.0 g/m². Various methods may be used to apply thesolution to the substrate. For example, the following can be used: coatingby a bar coater, rotation coating, spray coating, curtain coating, dip coating,coating by an air knife, coating by a blade or coating by a roll. Thesmaller the amount of the coating, the better the apparent sensitivity butthe more inferior the properties of the layer.
[0185] To the photosensitive layer of the photosensitive lithographic formplate of the present embodiment, a surfactant such as a surfactantcontaining fluorine, which is described in the specification of JP-A 62-170950,may be added to improve coatability. The amount is preferably of0.01 to 1% by weight and more preferably of 0.05 to 0.5% by weight, of thetotal amount of the solid components in the photosensitive layer.
[0186] The substrate used in the present embodiment is dimensionallystable with a plate shape. Examples of the substrate include: paper;paper laminated with plastics such as polyethylene, polypropylene andpolystyrene; metal plates such as plates of aluminum, zinc and copper;plastic films such as films of cellulose diacetate, cellulose triacetate,cellulose propionate, cellulose butyrate, cellulose acetate butyrate,cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene,polypropylene, polycarbonate and polyvinylacetal; and paper and plastic films, which are laminated or deposited with the above metals.
[0187] As the substrate in the present invention, polyester films andaluminum plates are preferable and aluminum plates are more preferablebecause aluminum plates have excellent dimensional stability and arerelatively inexpensive. Preferable aluminum plates are plates of purealuminum and plates of alloys containing aluminum as the maincomponent and small amounts of other elements. The substrate may be aplastic film laminated or deposited with aluminum. The other elementscontained in the aluminum alloy may be silicon, iron, manganese, copper,magnesium, chromium, zinc, bismuth, nickel and titanium. Thecontained amount of the other elements is to be 10% by weight or less.
[0188] It is particularly preferable in the present invention that purealuminum is used. However, small amounts of other metals may becontained because producing completely pure aluminum is technicallydifficult. The aluminum plate used in the present invention is notrequired to have a specific composition but conventionally availablealuminum plates can be suitably used. The thickness of the aluminumplate used in the present invention is about 0.1 mm to 0.6 mm, preferably0.15 to 0.4 mm and more preferably 0.2 to 0.8 mm.
[0189] Before the surface of the aluminum plate is made rough, atreatment for degreasing using, for example, a surfactant, an organicsolvent or an alkaline aqueous solution may be conducted, to remove oilused in rolling, where necessary.
[0190] The aluminum plate used in the present embodiment may have theabove degreasing treatment, the surface-roughening treatment, theetching treatment with an alkali, the neutralization treatment, anode oxidation treatment and the hydrophilizing treatment in the same manneras the aluminum plate used in the above first embodiment. Thesetreatments are essentially the same as the corresponding treatments ofthe aluminum plate described in the first embodiment. Therefore,detailed descriptions on these treatments are omitted.
[0191] An undercoat (primer) layer may be formed on the substrate of thephotosensitive lithographic form plate of the present embodiment, wherenecessary.
[0192] As the component of the undercoat layer, various organiccompounds can be used. The component is selected, for example, from:carboxymethylcellulose; dextrin; gum arabic; organophosphonic acids suchas a phosphonic acid having the amino group such as 2-aminoethylphosphonicacid, substituted and unsubstitutedphenylphosphonic acids, naphthylphosphonic acids, alkylphosphonic acids,glycerophosphonic acids, methylenediphosphonic acids andethylenediphosphonic acids; organophosphoric acids such as substitutedand unsubstituted phenylpohosphoric acids, naphthylphosphoric acids,alkylphospohoric acids and glycerophosphoric acids; organophosphinicacids such as substituted and unsubstituted phenylphosphinic acids,naphthylphosphinic acids, alkylphosphinic acids and glycerophosphinicacids; amino acids such as glycine and β-alanine; and aminehydrochlorides having a hydroxyl group such as triethanolaminehydrochloride. The above compounds may be used singly or as a mixtureof two or more types.
[0193] It is suitable that the applied amount of the organic undercoat layeris 2 to 200 mg/m².
[0194] The photosensitive lithographic form plate of the presentembodiment can be prepared as described above. The preparedphotosensitive lithographic form plate is exposed to light from a solid laseror a semiconductor laser emitting infrared light of a wavelength of 760 to1200 mm and images are formed. In the case of the photosensitivelithographic form plate of the present embodiment, the plate can be set inan offset printer or the like immediately after being exposed to light andused to print many sheets. EXAMPLES
[0195] The present embodiment will be described more specifically withreference to following examples. However, the present embodiment is notlimited by the examples. Example 1Preparation of a lithographic form plate that can be directly used
[0196] An aluminum plate (material 1050) having a thickness of 0.3 mmwas degreased by washing with trichloroethylene. The washedaluminum plate was surface-roughened with a nylon brush and withpumice-water suspension of 400 mesh and then washed well with water.The processed plate was dipped into a 25% aqueous solution of sodiumhydroxide at 45°C for 9 seconds for etching, washed with water, thendipped into a 2% nitric acid for 20 seconds and washed with water. Theamount of etching of the roughened surface was about 3 g/m². An oxidecoating layer of 3 g/m² was formed on the plate by direct current anodeoxidation using a 7% sulfuric acid as the electrolyte at a density of electric current of 15 A/dm² and then the plate was washed with water and dried.
[0197] Then, a photosensitive liquid having the following composition wasprepared and applied to the aluminum plate treated above. The coatedaluminum plate was dried at 100°C for 2 minutes to obtain thelithographic original plate. The dried weight of the layer was 1.2 g/m². Composition of photosensitive liquid thermally decomposable polymer (1p-4) (molecular weight, 20,000) 1.00 g infrared light absorbing agent (Compound 1) 0.15 g a dye obtained by converting the counter anion of VICTORIA PURE BLUE BOH to 1-naphthalenesulfonate anion 0.05 g surfactant containing fluorine (MEGAFAC F-177, a trade name; manufactured by DAINIPPON INK KAGAKU KOGYO Co., Ltd.) 0.06 g methyl ethyl ketone 20 g methanol 7 g
[0198] The obtained lithographic original form plate was exposed to lightfrom an IR laser emitting infrared light of a wavelength of 830 nm(diameter of beam: 28 µm). After exposure, the plate was heated at 110°Cfor 1 minute and then used directly for printing with a LITHRON printer.Formation of stains in non-image portions during printing was examinedby visual observation. Forty thousand excellent printed sheets withoutstains in the non-image portions were obtained.
[0199] The lines generated by scanning of the laser lights in the obtainedform plates were observed by a microscope. The sensitivity of the form plate was evaluated from the measured line width. The nearer the linewidth to the beam of irradiation diameter of 28 µm, the higher thesensitivity. Example 2
[0200] A lithographic original form plate was prepared and evaluated inaccordance with the same procedures as those conducted in Example 1except that Compound 2 was used as the infrared light absorbing agent inplace of Compound 1. Example 3
[0201] A lithographic original form plate was prepared and evaluated inaccordance with the same procedures as those conducted in Example 1except that Compound 3 was used as the infrared light absorbing agent inplace of Compound 1. Example 4
[0202] A lithographic original form plate was prepared and evaluated inaccordance with the same procedures as those conducted in Example 1except that Compound 8 was used as the infrared light absorbing agent inplace of Compound 1. Example 5
[0203] A lithographic original form plate was prepared and evaluated inaccordance with the same procedures as those conducted in Example 1except that Compound 11 was used as the infrared light absorbing agent in place of Compound 1. Comparative Example 1
[0204] A lithographic original form plate was prepared and evaluated inaccordance with the same procedures as those conducted in Example 1except that Reference Compound 3 shown in the following was used as theinfrared light absorbing agent in place of Compound 1.
[0205] The results of the evaluation of the lithographic original form platesof Examples 1 to 5 and Comparative Example 1 are shown in Table 2.infrared light absorbing agent sensitivity (µm) stain Example 1 Compound 1 25 none Example 2 Compound 2 25 none Example 3 Compound 3 25 none Example 4 Compound 8 25 none Example 5 Compound 11 25 none Comparative Example 1 Reference Compound 3 18 found
[0206] The results in Table 2 show that the lithographic form plates of thepresent embodiment demonstrate high sensitivity and do not form stains.
[0207] Next, a radiation-sensitive lithographic form plate in which thethird image-forming material of the present invention is used will bedescribed as the third embodiment.
[0208] The composition of the third image-forming material will be firstdescribed in detail.
[0209] The third image-forming material described in the presentembodiment comprises in its photosensitive layer a binder of cross-linkedstructure which contains a functional group that changes fromhydrophobic to hydrophilic due to the action caused by at least one of heat,radiation and an acid, and an infrared absorption agent which has anhydrophobic functional group that changes to hydrophilic due heat.
[0210] The present embodiment is basically the same as the secondembodiment, except that the present embodiment makes more detailed description on the binder and includes a plurality of water-insoluble solidparticles as a unique component.
[0211] Accordingly, a detailed description of the components which hasbeen already described in the second embodiment will be omitted. Forexample, as the structure of the infrared light absorbing agent having ahydrophobic functional group which changes to hydrophilic due to heat ofthe present embodiment is the same as that used in the secondembodiment as component (B), a detailed description thereof is omitted.
[0212] The structure and characteristics of the binder will be firstdescribed hereinafter.
[0213] In the present embodiment, the binder is a crosslinkedcompound having a functional group which is changed fromhydrophobic to hydrophilic by acid, radiation, or heat.
[0214] Here, "changing from hydrophobic to hydrophilic" means clearlychanging to hydrophilic to the extent that the function of the printingsurface of the lithographic form plate can be exhibited. To this end, itis preferable that the compound can reduce the in-atmosphere waterdroplet contact angle by 15° or more. Namely, it is preferable that theangle at which a water droplet contacts the compound in the ambientenvironment is reduced by 15° or more due to the action of acid,radiation, or heat, such that the compound which was originallyhydrophobic becomes hydrophilic. Further, it is more preferable thatthe in-atmosphere water droplet contact angle of the compound isreduced by 40° or more. Concretely, it is preferable that a compoundwhose in-atmosphere water droplet contact angle is originally 60° ormore is reduced by the action of acid, radiation or heat to become 20° or less.
[0215] In the present invention, if the compound is a compound whichhas the above property and is crosslinked, the compound can bepreferably used as a binder. Specific examples of the group whichchanges from hydrophobic to hydrophilic due to heat are preferably atleast one of sulfonic ester group and alkoxyalkylester group(hereinafter referred to as the functional group X).
[0216] Specific examples of the functional group X will be described indetail hereinafter.
[0217] The sulfonic ester group can be represented by followinggeneral formula (13).―L²―SO₂―O―R₁₁
[0218] In the above general formula (13), L² represents an organicgroup formed from polyvalent nonmetal atoms which are necessary inorder to bind the functional group represented by general formula (13)to the polymer skeleton, and R₁₁ represents a substituted orunsubstituted aryl group, a substituted or unsubstituted alkyl group,or a cyclic imide group.
[0219] When R₁₁ is an aryl group or a substituted aryl group, R₁₁ mayinclude a carbocyclic aryl group and a heterocyclic (hetero) aryl group.Examples of the carbocyclic aryl group are groups having from 6 to 19carbon atoms such as phenyl group, naphthyl group, anthracenylgroup, pyrenyl group, and the like. Examples of the heterocyclic arylgroup are groups having from 3 to 20 carbon atoms and from 1 to 5 hetero atoms such as pyridyl group, furyl group, and groups in whicha benzene ring is condensed such as the quinolyl group, benzofurylgroup, thioxanthone group, and carbazole group. When R₁₁ representsan alkyl group or a substituted alkyl group, the alkyl group may be astraight, branched, or cyclic alkyl group having from 1 to 25 carbonatoms such as methyl group, ethyl group, isopropyl group, t-butylgroup, cyclohexyl group, and the like.
[0220] Among the above, especially preferred examples of R₁₁ are arylgroups substituted with an electron-withdrawing group such as ahalogen group, a cyano group, or a nitro group; alkyl groupssubstituted with an electron-withdrawing group such as a halogengroup, a cyano group, or a nitro group; a secondary or tertiarybranched alkyl group; a cyclic alkyl group; and cyclic imides.
[0221] The polyvalent binding group formed from nonmetal atoms andrepresented by L² is formed from 1 to 60 carbon atoms, 0 to 10nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0to 20 sulfur atoms.
[0222] The alkoxyalkylester group can be represented by followinggeneral formula (14).
[0223] In general formula (14), R₂₁ represents a hydrogen atom, R₂₂represents a hydrogen atom or an alkyl group having 18 or fewer carbon atoms, and R₂₃ represents an alkyl group having 18 or fewercarbon atoms. Of R₂₁, R₂₂, and R₂₃, two may be bonded together. Inparticular, it is preferable to bond R₂₂ and R₂₃ so as to form a 5- or 6-memberring.
[0224] In the present invention, the groups represented by abovegeneral formula (13) and general formula (14) are given as examplesof the functional group X. However, it is particularly preferable thatthe functional group X is the sulfonic ester group represented bygeneral formula (13).
[0225] It is preferable that the binder is a compound formed bycrosslinking by some method macromolecular compounds obtained byradical polymerization of monomers selected from those having thefunctional group represented by general formula (13) or (14). Themacromolecular compound may be a homopolymer using only one typeof monomer having the functional group represented by generalformula (13) or (14). Or, the macromolecular compound may be acopolymer of two or more types of monomers having the functionalgroup represented by general formula (13) or (14), or may be acopolymer of a monomer having the functional group represented bygeneral formula (13) or (14) and other monomer(s).
[0226] Preferable examples of such an other monomer includecrosslinkable monomers such as glycidylmethacrylate, N-methylolmethacrylamide,2-isocyanate ethylacrylate, or the like.
[0227] Particularly optimal examples of such an other monomer whichis used for the copolymer are acrylic esters, methacrylic esters,acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acids, methacrylic acids, and acrylonitriles, all having 20 or fewer carbonatoms.
[0228] The ratio of the monomer having the functional grouprepresented by general formula (13) or (14), which monomer is used insynthesizing the copolymer, is preferably 5 to 99 wt%, and morepreferably 10 to 95 wt%, with respect to the entire amount ofmonomer.
[0229] Next, a compound, which is used in the radiation-sensitivelithographic form plate of the present invention and which is aparticularly preferable example of the binder, will be described.Hereinafter, this compound will be referred to as "compound A".
[0230] Compound A is a compound of a cross-linked structure whichcontains, in the same molecule, the above-described functional groupX as well as at least one functional group Y which is a functionalgroup selected from ―OH, ―NH₂, ―COOH, ―NH―CO―Q³,―Si(OQ⁴)₃, wherein Q³ and Q⁴ each represent an alkyl group or anaryl group, and in a case in which both Q³ and Q⁴ exist in thecompound having these functional groups, Q³ and Q⁴ may be the sameor different. Here, the functional group Y is a group used forcrosslinking.
[0231] Specific examples of ―NH―CO―Q³ are ―NH―CO―CH₃,―NH―CO―C₂H₅, and the like. Specific examples of ―Si(OQ⁴)₃ are―Si(OCH₃)₃, ―Si(OC₂H₅)₃, and the like.
[0232] Compound A which is used in the present invention is acompound formed by crosslinking macromolecular compoundsobtained by radical polymerization of the monomer having the functional group Y and the monomer having the functional group X(preferably, selected from the functional group represented by generalformula (13) or (14)).
[0233] The mixing ratio of the monomer having the functional group Xand the monomer having the functional group Y, which are used insynthesizing the copolymer, is, as a weight ratio, preferably 10:90 to99:1, and more preferably 30:70 to 97:3.
[0234] Further, when a copolymer formed by using the othermonomer(s) is used as the macromolecular compound, the ratio of theother monomer to the total amount of the monomer having thefunctional group X and the monomer having the functional group Ywhich are used in synthesizing the copolymer is preferably 5 to 99wt% and more preferably 10 to 95 wt%.
[0235] Specific examples of the copolymer used in the presentinvention are given hereinafter. The numbers to the lower right of theparentheses in the chemical formulas denote the copolymer ratios. (I-1) through (I-17)
[0236]
[0237] Next, the hydrolysis polymerizible compound of the eighteenthaspect of the present invention will be described. This hydrolysispolymerizible compound is a compound which crosslinks the above-describedcopolymer.
[0238] The hydrolysis polymerizible compound used in the presentinvention is a compound represented by following general formula(15).(Q¹)_n―X―(OQ²)_4-n
[0239] In general formula (15), Q¹ and Q² each represent an alkylgroup or an aryl group, and may be the same or different. X representsSi, Al, Ti, or Zr, and n is an integer of from 0 to 2. When R₁ or R₂represents an alkyl group, the number of carbon atoms is preferably 1to 4. Further, the alkyl group and the aryl group may have asubstituent group. It is preferable that the compound is a lowmolecular weight compound having a molecular weight of 1000 or less.
[0240] Examples of the hydrolysis polymerizible compound whichcontains aluminum are trimethoxyaluminate, triethoxyaluminate,tripropoxyaluminate, tetraethoxyaluminate, and the like. Examplesof the hydrolysis polymerizible compound which contains titanium aretrimethoxytitanate, tetramethoxytitanate, triethoxytitanate,tetraethoxytitanate, tetrapropoxytitanate, chlorotrimethoxytitanate,chlorotriethoxytitanate, ethyltrimethoxytitanate,methyltriethoxytitanate, ethyltriethoxytitanate, diethyldiethoxytitanate, phenyltrimethoxytitanate,phenyltriethoxytitanate, and the like. Examples of the hydrolysispolymerizible compound which contains zirconium are the same asthose compounds listed above for titanium, except that they containzirconate rather than titanate.
[0241] Examples of the hydrolysis polymerizible compound whichcontains silicon are trimethoxysilane, triethoxysilane,tripropoxysilane, tetramethoxysilane, tetraethoxysilane,tetrapropoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane,propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane,propyltriethoxysilane, dimethyldimethoxysilane,diethyldiethoxysilane, γ-chloropropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane,phenyltrimethoxysilane,phenyltriethoxysilane, phenyltripropoxysilane,diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.Particularly preferred among these are tetramethoxysilane,tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane,methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane,diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.
[0242] A single type of hydrolysis polymerizible compound may be used,or two or more types of hydrolysis polymerizible compounds may beused. Further, after partial hydrolysis, dehydration condensation maybe carried out.
[0243] In the eighteenth aspect of the present invention, the amount of the hydrolysis polymerizible compound is preferably 3 to 95 wt%, andmore preferably 10 to 80 wt% with respect to the total amount ofsolids in the photosensitive layer. [Water-Insoluble Solid Particles]
[0244] Next, the water-insoluble solid particles as the aforementionedfourth and fifth aspects of the present invention will be described.These water-insoluble solid particles are at least one type of solidparticles selected from the group consisting of inorganic particles,organic particles, and metal particles.
[0245] The average particle diameter of each of the particles is about10 µm or less, preferably 0.01 to 10 µm, and more preferably 0.1 to 5µm. When the average particle diameter is less than 0.01 µm, thewater holding property of the portions irradiated by laser light isinsufficient, and it is easy for stains to form. When the averageparticle diameter exceeds 10 µm, the resolution of the printed matterdeteriorates, adhesion to the substrate deteriorates, and it becomeseasy for the particles in the vicinity of the surface to be removed.
[0246] Examples of the inorganic particles include metal oxides suchas iron oxide, zinc oxide, titanium dioxide, zirconia, and the like;silicon-containing oxides (also called white carbons) such as silicicacid anhydride, calcium silicate hydrate, aluminum silicate hydrateand the like which themselves do not absorb light in the visible range;clay mineral particles such as clay, talc, kaolin, zeolite, and the like;and the like.
[0247] Examples of metal particles are particles of iron, aluminum,copper, nickel, silver, and the like.
[0248] The contained amount of inorganic particles or metal particlesis about 2 to 90 volume %, preferably 5 to 80 volume %, and morepreferably 10 to 50 volume %, with respect to the entire amount ofsolids in the photosensitive layer. When the contained amount is lessthan 2 volume %, the water holding property at the laser lightilluminated portions of the surface of the radiation sensitivelithographic form plate is insufficient, and it becomes easy for stainsto form. When the contained amount exceeds 90 volume %, thestrength of the coated film deteriorates, the durability deteriorates,and the adhesion between the coated film layer and the substratedeteriorates.
[0249] The contained amount of organic particles is about 3 to 70volume %, preferably 5 to 60 volume %, and more preferably 10 to 50volume %, with respect to the entire amount of solids in thephotosensitive layer. When the contained amount is less than 3volume %, the water holding property is insufficient, and it becomeseasy for stains to form. When the contained amount exceeds 70volume %, the strength of the photosensitive layer deteriorates, thedurability deteriorates, and it becomes easy for the adhesion betweenthe photosensitive layer and the substrate to deteriorate.
[0250] Examples of the organic particles are polystyrene particles(particle diameter: 4 to 10 µm), silicone resin particles (particlediameter: 2 to 4 µm), and the like. Examples of crosslinked resinparticles include microgel (particle diameter: 0.01 to 1 µm) formedfrom two or more ethylene unsaturated monomers, crosslinked resinparticles (particle diameter: 4 to 10 µm) formed from styrene and divinylbenzene, crosslinked resin particles (particle diameter: 4 to 10µm) formed from methylmethacrylate anddiethyleneglycoldimethacrylate, and the like. Namely, acrylic resinmicrogels, crosslinked polystyrenes, crosslinked methylmethacrylates,and the like are examples of the crosslinked resin particles. Theseorganic particles are prepared by any of general methods such asemulsion polymerization, soap-free emulsion polymerization, seedemulsion polymerization, dispersion polymerization, suspensionpolymerization, or the like.
[0251] The inorganic particles may be prepared from a solution. Forexample, a metal lower alkoxide may be added to a solvent such asethanol so as to obtain inorganic particles containing metal in thepresence of water and an acid or an alkali. An inorganic particledispersed solution may be prepared by adding the obtained inorganicparticle solution to a thermoplastic polymer solution which is solublein solvent. Or, inorganic particles containing metal may be obtainedby first adding a metal lower alkoxide to a thermoplastic polymersolution, and thereafter, adding water and an acid or an alkali.
[0252] In a case in which inorganic particles are prepared by adding ametal lower alkoxide to a thermoplastic polymer precursor solution, acomplex of the metal and the polymer is obtained when thethermoplastic polymer precursor is made to be to a thermoplasticpolymer by heat. Tetraethoxysilane, tetraethoxytitanium and the likemay be used as the metal lower alkoxide.
[0253] Before discussing the Examples of the present invention,several path schemes for forming the photosensitive layer, which is a water insoluble structure, will be given hereinafter by usingschematic diagrams.
[0254] In the above schematic diagrams, schemes 1 and 2 are examplesin which the photosensitive layer, which is a porous structure, isprepared by mixing compound A, a hydrolysis polymerization reactionproduct and water-insoluble solid particles. In scheme 1, silicaparticles are used as the water-insoluble solid particles, and inscheme 2, silica particles which are surface-modified in advance areused as the water-insoluble solid particles. In the schematic diagrams,R is a substituent group such as a modifier group for each compoundor solid, or the like. The respective Rs may be the same or different.
[0255] In schemes 3 and 4, after a silane coupling agent (hydrolysispolymerization reaction product) is made to act on the silica particlesin advance, a hydrolysis polymerization reaction product, which maybe different than that mentioned above, is added such that a reactiontakes place to form the porous structure. In scheme 3, the surfaces ofthe particles have been modified with a polymerizible monomer.
[0256] In scheme 5, organic polymer particles are first formed byemulsion polymerization or dispersion polymerization.
[0257] More specifically, in scheme 3, particle surfaces havingpolymerizible groups are formed by using a silane coupling agent asthe hydrolysis polymerization reaction product. Thereafter, acompound having a sensitive group and particles having reactivegroups are prepared, and then the porous structure is prepared byusing the hydrolysis polymerization reaction product.
[0258] In scheme 4, particles having the intended sensitivity aredirectly prepared by using a silane coupling agent. Thereafter, theporous structure is prepared by using the hydrolysis polymerization reaction product. EXAMPLES
[0259] The present invention will be described in further detailhereinafter in accordance with the following Examples. However, it isto be understood that the present invention is not limited to theseExamples. (Examples 1-8)
[0260] 40 mg of a 50%phosphoric acid aqueous solution was added to asolution containing 0.4 g of above compound I-11 as compound A (thebinder), 0.4 g of tetraethoxysilane as the hydrolysis polymeriziblecompound, 40 mg of one of the infrared light absorbing agents listed infollowing Table 3, and 1.6 g of methylethylketone, and the resultantmixture was stirred for 10 minutes. Thereafter, to this dispersionliquid was added 4 g of a 10% methylethylketone dispersion liquid ofsilica gel particles (trade name: Silicia #445, manufactured by: FujiSilicia Kagaku Co., particle diameter as measured by the Coultercounter method: 3.5 µm) dispersed in a paint shaker by using glassbeads, so as to form a coating liquid. The coating liquid was applied byusing a rod bar #20 onto the surface of a PET substrate which hadbeen subjected to corona charging processing.
[0261] The obtained radiation-sensitive lithographic form plate wassubjected to image formation by using a semiconductor laser(wavelength: 830 nm; beam diameter: 14 µm) which was adjusted to alinear velocity of 10 m/sec and a plate surface output of 200 mW. Thelithographic form plate was not subjected to any processings thereafter. Printing was then carried out on a Heidelberg printer.After printing 3000 copies, the 3000th copy was observed to determinewhether there were stains in the non-image portions. The results arelisted in following Table 3. (Comparative Examples 1-2)
[0262] Radiation-sensitive lithographic form plates were prepared inthe same manner as in Examples 1-8, except that the infrared lightabsorbing agents used in Examples 1-8 were replaced by the followingReference Compound 4 (for Comparative Example 1) and ComparativeExample Compound 5 (for Comparative Example 2). Printing wascarried out in the same manner as for Examples 1-8, and the 3000thcopy was observed to determine whether there were stains in thenon-image portions. The results are listed in following Table 3.
[0263] As can be seen from Table 3, in accordance with the presentinvention, good printed matter, in which there were no stains in theexposed portions up through the 3000th copy, was obtained. However,in the radiation-sensitive lithographic form plate of each ComparativeExample, there were stains in the exposed portions which isunsatisfactory. (Examples 9-11 and Comparative Examples 3-4)
[0264] Radiation-sensitive lithographic form plates were obtained inthe same manner as in Examples 1-8, except that no silica gel wasadded, and the infrared light absorbing agents listed in Table 4 were used in place of those listed in Table 3. Printing was carried out in thesame manner as in Examples 1-8, and staining of the non-imageportions of the 1000th copy and the 3000th copy was observed. Theresults are listed in following Table 4. Example/Comp. Ex. Number Infrared Light Absorbing Agent Stains in Non-Image Portions after Printing 1000th Copy 3000th Copy Example 9 Compound 1 None Very few stains Example 10 Compound 23 None Very few stains Example 11 Compound 26 None Very few stains Comp. Ex. 3 Reference Compound 4 Stains Stains Comp. Ex. 4 Carbon black Stains Stains
[0265] As can be seen from Table 4, even if silica gel particles are notadded, by using the infrared light absorbing agent of the presentinvention which has a thermally decomposable sulfonic ester group,good printed matter, in which there were no stains in the exposedportions up through the 1000th copy, was obtained. In contrast, in theradiation-sensitive lithographic form plate of each ComparativeExample, there were stains in the exposed portions which isunsatisfactory. (Examples 12-19 and Comparative Examples 5-6)
[0266] Radiation-sensitive lithographic form plates were obtained inthe same manner as in Examples 1-8, except that the infrared lightabsorbing agents listed in Table 5 were used in place of those listed inTable 3. Printing was carried out in the same manner as in Examples1-8, and staining of the non-image portions of the 5000th copy wasobserved. The results are listed in following Table 5. Example/Comp. Ex. Number Infrared Light Absorbing Agent Stains in Non-Image Portions after Printing 5000 Copies Example 12 Compound 27 None Example 13 Compound 28 None Example 14 Compound 29 None Example 15 Compound 30 None Example 16 Compound 31 None Example 17 Compound 32 None Example 18 Compound 33 None Example 19 Compound 34 None Comp. Ex. 5 Reference Compound 4 Some stains Comp. Ex. 6 Reference Compound 5 Some stains
[0267] As can be seen from Table 5, in accordance with the presentinvention, good printed matter, in which there were no stains in the exposed portions up through the 5000th copy, was obtained. However,in the radiation-sensitive lithographic form plate of each ComparativeExample, there were stains in the exposed portions which isunsatisfactory. (Examples 19-21 and Comparative Examples 7-8)
[0268] Radiation-sensitive lithographic form plates were obtained inthe same manner as in Examples 1-8, except that no silica gel wasadded, and the infrared light absorbing agents listed in Table 4 wereused in place of those listed in Table 3. Printing was carried out in thesame manner as in Examples 1-8, and staining of the non-imageportions of the 3000th copy and the 5000th copy was observed. Theresults are listed in following Table 6. Example/Comp. Ex. Number Infrared Light Absorbing Agent Stains in Non-Image Portions after Printing 3000th Copy 5000th Copy Example 20 Compound 27 None Very few stains Example 21 Compound 36 None Very few stains Example 22 Compound 30 None Very few stains Comp. Ex. 7 Reference Compound 4 Stains Stains Comp. Ex. 8 Carbon black Stains Stains The infrared light absorbing agents of the present invention in aboveTable 6 have on an aromatic ring, either directly or via a bindinggroup, a hydrophobic functional group which changes to hydrophilicdue to heat. As can be seen from Table 6, even if silica gel particles arenot added, by using these infrared light absorbing agents of thepresent invention, good printed matter, in which there were nostains in the exposed portions up through the 3000th copy, wereobtained. In contrast, in the radiation-sensitive lithographic formplate of each Comparative Example, there were stains in the exposedportions which is unsatisfactory.

权利要求:
Claims (18)
[1] A photosensitive lithographic form plate comprising:
a substrate; and
a photosensitive layer disposed on the substrate, thephotosensitive layer containing an infrared light absorbing agenthaving a hydrophobic functional group which changes to hydrophilicdue to heat.
[2] A photosensitive lithographic form plate comprising:
a hydrophilic substrate; and
a photosensitive layer disposed on the substrate, thephotosensitive layer containing an infrared light absorbing agenthaving a hydrophobic functional group which changes to hydrophilicdue to heat.
[3] A photosensitive lithographic form plate according to claim 1,wherein the hydrophobic functional group which changes tohydrophilic due to heat is bound to an aromatic ring within theinfrared light absorbing agent directly or via a binding group.
[4] A photosensitive lithographic form plate according to claim 1,wherein the infrared light absorbing agent is represented by followinggeneral formula (1):
[5] A photosensitive lithographic form plate according to claim 1,wherein the photosensitive layer includes a macromolecularcompound which is decomposable by at least one of heat and an acidand as a result becomes soluble in at least one of water and an alkali.
[6] A photosensitive lithographic form plate comprising:
a substrate; and
a photosensitive layer disposed on the substrate, wherein the photosensitive layer includes an image-formingmaterial which comprises:
a macromolecular binder insoluble in water and soluble in anaqueous solution of an alkali; and
an infrared light absorbing agent having a thermallydecomposable sulfonic ester group.
[7] A photosensitive lithographic form plate according to claim 6,wherein, before the infrared light absorbing agent is decomposed byheating, the infrared light absorbing agent has a function to decreasea rate of dissolution of the macromolecular binder into the aqueoussolution of an alkali.
[8] A photosensitive lithographic form plate according to claim 6,wherein the infrared light absorbing agent is decomposed withheating by irradiation of infrared light to form the sulfonic acid inportions of the photosensitive layer exposed to the infrared light.
[9] A photosensitive lithographic form plate according to claim 6,wherein the thermally decomposable sulfonic ester group has astructure in which a sulfonic acid is bonded to an ester group and theester group includes a substituted or unsubstituted primary,secondary or tertiary alkyl group, a substituted or unsubstituted arylgroup, a substituted or unsubstituted alkenyl group, or a cyclic imidegroup.
[10] A photosensitive lithographic form plate comprising:
a substrate and a photosensitive layer disposed on thesubstrate,wherein the photosensitive layer is formed with an image-formingmaterial, the image-forming material comprising:
an infrared light absorbing agent having a thermallydecomposable sulfonic ester group; and
a macromolecular compound which decomposes due to heat oran acid and is soluble in water or an alkali.
[11] A photosensitive lithographic form plate according to claim 10,wherein, in the exposed portions of the photosensitive layer,decomposition of the macromolecular compound which is decomposeddue to heat or an acid and becomes soluble in water or an alkali isaccelerated by the sulfonic acid formed by exposure to the infraredlight.
[12] A photosensitive lithographic form plate according to claim 10,wherein the macromolecular compound which is decomposed due toheat or an acid and becomes soluble in water or an alkali comprises apolymer of a sulfonic ester or a polymer of a carboxylic ester.
[13] A radiation-sensitive lithographic form plate comprising:
a binder having a crosslinked structure which has a functionalgroup that changes from hydrophobic to hydrophilic due to at leastone of an acid, radiation and heat; and
an infrared light absorbing agent having a hydrophobicfunctional group which changes to hydrophilic due to heat.
[14] A radiation-sensitive lithographic form plate according to claim 13,wherein the hydrophobic functional group which changes tohydrophilic due to heat is bound to an aromatic ring within theinfrared light absorbing agent directly or via a binding group.
[15] A radiation-sensitive lithographic form plate according to claim 14,wherein the infrared light absorbing agent is represented by followinggeneral formula (1):
[16] A radiation-sensitive lithographic form plate according to claim 13,wherein the photosensitive layer includes a plurality of water-insolublesolid particles.
[17] A radiation-sensitive lithographic form plate according to claim 16,wherein the photosensitive layer is structured such that the water-insolublesolid particles are covered by the binder and are boundtogether by the binder such that each particle is contacted by othersat some portions and gaps are formed between the water-insolubleparticles.
[18] A radiation-sensitive lithographic form plate according to claim 13,wherein the binder is a compound which is obtained by reacting:
a compound having, in the same molecule, a functional groupwhich changes from hydrophobic to hydrophilic due to at least one ofan acid, radiation and heat, and a functional group which reacts witha hydrolysis polymerizible compound represented by following generalformula (2); and
the hydrolysis polymerizible compound represented byfollowing general formula (2):(Q¹)_n―X―(OQ²)_4-n wherein Q¹ and Q² each represents an alkyl group or an aryl groupand may be the same or different; X represents Si, Al, Ti, or Zr; and nis an integer of from 0 to 2.

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法律状态:
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优先权:

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申请号 | 申请日 | 专利标题

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JP4771398||1998-02-27||

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JP4771398||1998-02-27||

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JP7463098A|JPH11268438A|1998-03-23|1998-03-23|Image forming material|

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JP7463098||1998-03-23||

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JP37120998||1998-12-25||

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JP37120998A|JP3627903B2|1998-02-27|1998-12-25|Photosensitive planographic printing plate|

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JP848899||1999-01-14||

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JP00848899A|JP3745550B2|1998-04-15|1999-01-14|Infrared sensitive lithographic printing plate|

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