Pasty composition and cosmetics containing the same

专利摘要:
This invention is a cosmetic material containing a pastycomposition obtained by adding at least one acidicsubstance selected from a group comprising organic acids,phosphoric acid and phosphates to a mixture comprising acrosslinking type organopolysiloxane polymer having apolyoxyalkylene group and a liquid oil, adding a basicneutralizing agent to adjust the pH to 5-8, and removingvolatile components by heating and/or decompression . Thispasty composition is a composition wherein thepropionaldehyde amount produced by adding an identicalamount of water to the composition and heating at 60°C for24 hours is 100 ppm or less.
公开号:EP1424365A1
申请号:EP02762991
申请日:2002-09-03
公开日:2004-06-02
发明作者:Koji Shin-Etsu Chemical Co. Ltd. Sakuta
申请人:Shin Etsu Chemical Co Ltd；
IPC主号:A61K-8

专利说明:
[0001] This invention relates to a pasty composition comprisinga crosslinking type organopolysiloxane polymer having ahydrophilic organic group, and a liquid oil, and moreparticularly relates to a pasty composition which not onlydoes not have an odor, but whereof the pH does not falland which does not generate an unpleasant odor over timeeven when blended with an emulsifying system. It furtherrelates to a method of manufacturing this composition, andto a cosmetic material with which this composition isblended. Background of the Invention
[0002] Silicone oil, on account of its safety, has long beenused as a base oil in various compositions in many fields,including cosmetics.
[0003] In particular, low viscosity silicone oil of not morethan 100mm ²/S is attracting attention with a view toextensive use in cosmetic skin care and make-up on accountof its outstanding extensibility, fresh feeling and safety.
[0004] However, if a pasty composition without fluidity isprepared using low viscosity silicone oil as a base oil,the addition amount of thickener must be increased, so itis difficult to obtain a smooth, uniform composition, andas the low viscosity silicone oil easily separated and was released from the composition so obtained, its stabilitywas low. In order to solve this problem, the use of organicmaterials as thickeners for low viscosity silicone oil hasbeen proposed, examples being dextrin fatty acid esters(Tokkai Sho 62-121764, 62-143971, 62-143970, 63-159489),sucrose fatty acid esters (Tokkai Sho 63-235366),trimethylsilyl polyvinyl alcohol and trimethylsilylpolysaccharides (Tokkai Sho 62-240335), fatty acid estergroup-containing cellulose ether (Tokkai Sho 63-260955),and organically-modified clay minerals (Tokkai Sho62-45656, 62-54759, 63-72779).
[0005] However, when these organic or inorganic materials areused as thickeners, there is a problem that the inherentfresh feeling and high extensibility of the low viscositysilicone oil, decline.
[0006] A method of obtaining a uniform pasty composition wastherefore proposed using a specific organopolysiloxanepolymer as a thickener, and treating it with a low viscositysilicone oil under a shear force (Tokkai Hei 02-43263)
[0007] In the field of cosmetics, not only oil but water isoften blended as a required component of the composition.In such a case, although a surfactant is used accordingto conventional methods, it is difficult to distribute thesilicone oil and water uniformly and stably, and althoughthe silicone thickener disclosed in Tokkai Hei 02-43263has excellent thickening qualities with regard to siliconeoil, it has the disadvantage that when water is blended,it does not disperse uniformly. In addition, somesurfactants irritate the skin; which is undesirable.
[0008] In order to solve this problem, Tokkai Hei 04-272932 and05-140320 propose introducing apolyoxyalkylene group intothe molecule of the silicone thickener.
[0009] Although the composition disclosed therein has excellentemulsifying characteristics, it has the disadvantage thatif the composition is stored over a long period of time,the pH falls, and the emulsion emits an unpleasant odor.
[0010] A polyether-modified organopolysiloxane can bepurified by treating it with an acidic solution (Tokko Hei07-91389) or by treating unsaturated groups byhydrogenation (Tokkai Hei 07-330907). If thesepurification methods are applied to this crosslinking typepolymer, when treating with corrosive aqueous acids suchas hydrochloric acid solution, if the apparatus used doesnot have a glass lining, the apparatus may be corroded.Moreover, even if the odor can be reduced, the fall in pHcannot be suppressed.
[0011] If hydrogenation treatment is performed, heavy metalcatalysts such as palladium and nickel are required, butas these catalysts cannot be removed by filtration, heavymetal catalysts may remain in the composition and aretherefore unsuitable for use in cosmetics.
[0012] As a result of intensive studies to resolve the abovedisadvantage, the Inventor found that in a compositioncomprising a crosslinking type organopolysiloxane polymerwherein the crosslinks are formed by hydrophilic organicgroups (polyoxyalkylene chains) and a liquid oil, acomposition with good storage stability and which did notemit an unpleasant odor could be obtained by adding an acidic substance to this polymer, performing heat treatment,neutralizing with a basic substance and removing volatilecomponents, and thereby arrived at the present invention.
[0013] It is therefore an object of this invention to providea paste-like composition comprising a crosslinking typeorganopolysiloxane polymer and an oil which has anemulsifying function, which has excellent storagestability and does not emit an unpleasant odor, to providea method of manufacturing same, and to provide a cosmeticmaterial containing this composition. Summary of the Invention
[0014] This invention is a paste-like composition obtained byadding at least one acidic substance selected from a groupcomprising an organic acid, phosphoric acid and phosphateto a mixture comprising a crosslinking typeorganopolysiloxane polymer wherein the crosslinks areformed by polyoxyalkylene chains and a liquid oil, addinga basic neutralizer so that the pH is 5-8, and removingvolatile components by heating and/or reduced pressure,this paste-like composition being characterized in thatthe amount of propionaldehyde generated when an identicalamount of water is added to this composition and heatedat 60°C for 24 hours, is 100 ppm or less.
[0015] Herein, the mixture comprising the crosslinking typeorganopolysiloxane polymer and the liquid oil includes amixture comprising the crosslinking typeorganopolysiloxane polymer and liquid oil are simply mixedtogether, and a mixture wherein the crosslinking type organopolysiloxane polymer and the liquid oil are kneadedtogether.
[0016] This invention is also a method of manufacturing apaste-like composition obtained by adding at least oneacidic substance selected from a group comprising anorganic acid, phosphoric acid and phosphate to a mixturecomprising a crosslinking type organopolysiloxane polymerwherein the crosslinks are formed by polyoxyalkylene chainsand a liquid oil, adding a basic neutralizer so that pHis 5-8, and removing volatile components by heating and/orreduced pressure, this method of manufacturing thepaste-like composition being characterized in that theamount of propionaldehyde generated when an identicalamount of water is added to this composition and heatedat 60°C for 24 hours, is 100 ppm or less.
[0017] The salt produced by the acidic substance and the basicneutralizer preferably has a buffer effect, the acidicsubstance being at least one moiety selected from a groupcomprising citric acid, lactic acid, malic acid, glutamicacid, tartaric acid, acetic acid, glycine, succinic acidand potassium dihydrogen phosphate, and the basicneutralizer being at least one moiety selected from a groupcomprising sodium carbonate, sodium hydrogen carbonate,sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate and sodium acetate. The proportions of theacidic substance andbasic neutralizer are 0.01-10 wt partsrelative to 100 wt parts of the crosslinking typeorganopolysiloxane, respectively, and preferably, heatingis performed to 20-150°C after adding the acidic substance, and heating is performed to 20-150°C after adding the basicneutralizer.
[0018] The crosslinking type organopolysiloxane polymer isobtained by addition polymerization of at least one moietyselected from a group comprisingorganohydrogenpolysiloxanes expressed by the followinggeneral formula (A1) and the following general formula (A2),and at least one moiety selected from a group comprisingunsaturated compounds expressed by the following generalformulae (B1), (B2), (B3), andpreferably, the crosslinkingtype organopolysiloxane polymer is insoluble in organicsolvents, and can be made to swell up by including at leastits own weight of decamethyl cyclopentasiloxane.R¹ _aR² _bH_cSiO_(4-a-b-c)/2 R¹ _dH_eSiO_(4-d-e)/2 C_fH_2f-1O (C_gH_2gO) _hC_fH_2f-1
[0019] In these formulae, R¹ are monofunctional hydrocarbongroups which may be respectively identical or different,may be substituted or unsubstituted, have 1-30 carbon atomsand do not contain an alkenyl group. R² are organic groupswhich may identical or different, and are expressed by thegeneral formula-C_fH_2fO(C_gH_2gO)_hR⁶.
[0020] R³ is a hydrogen atom, or a monofunctional hydrocarbongroup having 1-10 carbon atoms which may or may not besubstituted, and which does not contain an alkenyl group.R⁴ are organic groups which are respectively identical ordifferent, identical to R³ or expressed by -C_fH_2f-1, andR⁶ is a hydrogen atom, or a monofunctional hydrocarbon groupnot containing an aliphatic unsaturated group which mayor may not be substituted, or an acetyl group.
[0021] a, b, c, d, e, j, k are 1.0≤a≤2.3, 0.001≤b≤1.0, 0.001≤c≤1.0,1.0≤d≤2.3, and 0.001≤e≤1.0, respectively, and are positiveintegers satisfying the relations 1.5≤a+b+c≤2.6 and 1.5≤d+e≤2.6.
[0022] f is an integer from 2-6, g is an integer from 2-4,h is an integer from 1-200, i is an integer from 1-20, andx is 0 or 1.
[0023] It is particularly preferred that this crosslinkingtype organopolysiloxane polymer is a polymer comprisingthe organohydrogen polysiloxane (A2) and polyoxyalkylene(B1). Description of the Preferred Embodiments
[0024] Hereafter, this invention will be described in moredetail.
[0025] The component (A1) is expressed by the average empiricalformula R¹ _aR² _bH_cSiO_(4-a-b-c)/2. In the formula, R¹ is amonofunctional hydrocarbon group having 1-30 carbon atomswhich may be substituted or unsubstituted, and does notcontain an alkenyl group. R² is an organic group expressedby the general formula -C_fH_2fO(C_gH_2gO)_hR⁶. a, b, c arepositive integers satisfying the relations 2.0≤a≤2.3,0.001≤b≤1.0, 0.001≤c≤1.0 and 1.5 ≤a+b+c≤2.6. f is aninteger from 2-6, g is an integer from 2-4, h is an integerfrom 1-200, and R⁶ is a hydrogen atom, or a monofunctionalhydrocarbon group not containing an aliphatic unsaturatedgroup which may or may not be substituted, or an acetylgroup.
[0026] Examples of R¹ are alkyl groups such as methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl;saturated alicyclic hydrocarbon groups such as cyclopentyland cyclohexyl; aryl groups such as phenyl and tolyl; andfluorinated alkyl groups such as trifluoropropyl,nonafluorohexyl and heptadecylfluorodecyl. a is 1.0-2.3,but preferably 1.2-2.1; b is 0.001-1.0, but preferably0.005-0.5; and c is 0.001-1.0, but preferably 0.005-0.5.If a is less than 1.0, the degree of crosslinking is toohigh, so the component cannot contain at least its own weightof decamethyl cyclopentasiloxane, .whereas if it is morethan 2.3, the degree of crosslinking is too low, so it isdifficult to form a three-dimensional crosslinkedstructure. If b is less than 0.001, the hydrophilicityis low, so it is difficult to form a water-in-oil type (W/O)emulsion composition, whereas if it is more than 1.0, the, hydrophilicity is too high, and it is again difficult toform a water-in-oil type emulsion composition. If c isless than 0.001, the degree of crosslinking is low, so itis difficult to form a three-dimensional crosslinkedstructure, whereas if it is more than 1.0, the degree ofcrosslinking is too high, so the component cannot containat least its own weight of decamethyl cyclopentasiloxane.
[0027] a+b+c is 1.5-2.6, but preferably 1.8-2.2. f is 2-6,but preferably 3-6. g is an integer from 2-4. Thecomponent preferably comprises at least one unit selectedfrom among an ethylene oxide unit, a propylene oxide unitand a butylene oxide unit, but is preferably an ethyleneoxide unit, or a copolymer comprising an ethylene oxideunit and a propylene oxide unit. h is an integer from 1-200,but preferably 3-100.
[0028] Examples of R⁶ are hydrogen, methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl or acetyl, buthydrogen or methyl is preferred.
[0029] This organopolysiloxane may be straight chain, branchedor cyclic, but to make the polymerization reaction gosmoothly, it is preferably straight chain, or is mainlystraight chain containing some branched units.
[0030] Component (A2) is expressed by the average empiricalformula R¹ _dH_eSiO_(4-d-e)/2. In the formula, R¹ is the same asin the case of (A1), and d, e are positive integers satisfyingthe relations 1.0≤d≤2.3 and 0.001≤e≤1.0.
[0031] d is 1.0-2.3, but preferably 1.2-2.1, and e is 0.001-1.0,but preferably 0.005-0.5. If d is less than 1.0, the degreeof crosslinking is too high, so the component cannot contain at least its own weight of decamethyl cyclopentasiloxane,and if d is more than 2.3, the degree of crosslinking istoo low, so formation of a three-dimensional crosslinkedstructure is difficult.
[0032] If e is less than 0.001, the degree of crosslinkingis too low, so formation of a three-dimensional crosslinkedstructure is difficult. If e is more than 1.0, the degreeof crosslinking is too high, so the component cannot containat least its own weight of decamethyl cyclopentasiloxane.
[0033] This organopolysiloxane may be straight chain, branchedor cyclic, but to make the polymerization reaction gosmoothly, it is preferably straight chain, or is mainlystraight chain containing some branched units.
[0034] Component (B1) is expressed by the average empiricalformula C_fH_2f-1O(C_gH_2gO)_hC_fH_2f-1.
[0035] f, g, h in the formula have an identical significanceto the above.
[0036] Component (B2) is expressed by the average empiricalformula:
[0037] In the formula, R³ is a monofunctional hydrocarbon grouphaving 1-10 carbon atoms which may be substituted orunsubstituted, and does not contain unsaturated group bonds.f, g, h are identical to the above, and x is 0 or 1.
[0038] Examples of R³ are hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, but hydrogen,methyl, ethyl and propyl are particularly preferred.
[0039] Component (B2) can be obtained for example by usingglycerol or trimethylolpropane as a starting material,adding an alkylene oxide to this, and performing an alkenyletheration on the ends of the chain.
[0040] All three polyoxyalkylene end groups are alkenyletherated, but only two may be sealed by alkenyl etherationand the remaining group left as a hydroxyl group.
[0041] If this component (B2) uses glycerol monoallyl etheror trimethylol propane monoallyl ether as startingmaterials, and after adding an alkylene oxide thereto, theterminal groups are alkenyl etherated, a structure isobtained containing two polyoxyalkylene units in onemolecule and three terminal alkenyl groups in one molecule.This polyoxyalkylene compound can also be used.
[0042] Component (B3) has the average empirical formula:
[0043] In the formula, R⁴ is identical to R³ or an organic groupexpressed by -C_fH_2f-1, f, g, h are identical to thosedescribed before, and i is an integer from 1-20.
[0044] i is 1-20, but preferably 2-10. If i is more than 20,the degree of crosslinking is too high, so the componentcannot contain at least its own weight of decamethylcyclopentasiloxane.
[0045] Component (B3) may for example be obtained by addingan alkylene oxide and allyl glycidyl ether to a loweralcohol or allyl alcohol, or after addition, performingalkylation or alkenyl etheration of the terminal.
[0046] The crosslinking type organopolysiloxane polymer ofthis invention can be obtained by carrying out additionpolymerization of the organohydrogen polysiloxaneexpressed by (A1) and/or (A2), and at least one moietyselected from the unsaturated compounds expressed by anyof (B1), (B2) and (B3).
[0047] Further, to the extent that it does not interfere withthe purpose of this invention, addition polymerization canbe carried out with the organohydrogen polysiloxaneexpressed by (A1) and/or (A2) using the organopolysiloxaneexpressed by the following general formula (B4), or theunsaturated compound expressed by the following generalformula (B5).
[0048] Component (B4) is expressed by the average empiricalformula R¹ _jR⁵ _kSiO_(4-j-k)/2.
[0049] In the formula, R¹ is identical to that described before,R⁵ is a monofunctional hydrocarbon group having 2-10 carbonatoms with a terminal vinyl group, j and k are integerssatisfying the relations 1.0≤j≤2.3 and 0.001≤k≤1.0.
[0050] Examples of R⁵ are vinyl, allyl, butenyl, pentenyl,hexenyl, heptenyl, octenyl, nonenyl and decenyl, but vinylis preferred.
[0051] j is 1.0-2.3, but preferably 1.2-2.1, and k is 0.001-1.0,but preferably 0.005-0.5.
[0052] If j is less than 1.0, the degree of crosslinking istoo high, so the component will be unable to contain atleast its own weight of decamethyl cycloheptasiloxane,whereas if j is larger than 2.3, the degree of crosslinkingis too low, so formation of a three-dimensional structureis difficult.
[0053] If k is less than 0.001, the degree of crosslinkingis too low, so formation of a three-dimensional structureis difficult, whereas if k is larger than 1.0, the degreeof crosslinking is too high, so the component will be unableto contain at least its own weight of decamethylcycloheptasiloxane.
[0054] This organopolysiloxane may be straight chain, branchedor cyclic, but to make the polymerization reaction gosmoothly, it is preferably straight chain, or is mainlystraight chain containing some branched units.
[0055] Component (B5) is expressed by the average empiricalformula C_mH_2m-1 (CH₂)_yC_mH_2m-1, and m is an integer from 2-6.y is an integer equal to 1 or more, but preferably an integerfrom 1-10.
[0056] If unreacted polyether wherein the double bond of theterminal allyl group has migrated is not present as animpurity in component (A1), ketones and aldehydes whichcause odor are not generated even if components (B4) or(B5) are reacted with this component (A1).
[0057] For example, if all the polyoxyethylene monoallyl etheris added first to the component (A2) to prepare anintermediate without unsaturated groups by removing theodor of the remaining unreacted polyether with hydrochloric acid or performing a hydrogenation, introducing a sourceof Si-H by an equilibrium reaction or the like to synthesizethe component (A1), and then reacting this with components(B4) or (B5); or if part of the polyoxyethylene monoallylether is added to component (A2), and the remainingpolyether is treated by removing the odor with hydrochloricacid or by hydrogenation to synthesize the component (A1)without unsaturated groups, which is then reacted withcomponents (B4) or (B5), a crosslinked product can beobtained even without the processing steps of the invention.However, in practice, if part of the polyoxyethylenemonoallyl ether is added to component (A2), a crosslinkedproduct might be obtained by reacting components (B4) or(B5) without removing the remaining unsaturated groups.In this case, writing a general equation, the stage wherethe polyether is partially added corresponds to component(A1), and as unreacted polyether containing unsaturatedgroups is present, the crosslinked product obtained byreaction of components (B4) or (B5) will generate anunpleasant odor. Therefore, to the extent that the purposeof this invention is not lost, a polymer within the scopeof this invention can be obtained not only by usingcomponents (B4) and/or (B5) in conjunction with theunsaturated compounds expressed by (B1), (B2) , (B3), butalso by crosslinking components (B4) and/or (B5) alone.
[0058] The crosslinking type organopolysiloxane polymer ofthis invention obtained by the aforesaid additionpolymerization is an organopolysiloxane polymer whereinthe organopolysiloxane structure is crosslinked by the polyoxyalkylene chains. Moreover, a paste-likecomposition can be obtained by kneading theorganopolysiloxane addition polymer obtained in this waywith a liquid oil. This paste-like composition may alsobe obtained by manufacturing an organic polysiloxanepolymer by the addition polymerization of theorganohydrogen polysiloxane expressed by (A1) and/or (A2)with a mixture comprising the polyoxyalkylene expressedby (B1), (B2) or (B3), and as arbitrary components, theorganic polysiloxane expressed by (B4) and at least onemoiety selected from among unsaturated compounds expressedby (B5), and part of the liquid oil, and then kneading thisorganopolysiloxane polymer with the remaining liquid oil.
[0059] Another method of obtaining the paste-likeorganopolysiloxane composition of this invention is tofirst purify the addition polymer, and then mix and kneadit with the liquid oil. It may also be obtained by purifyingthe addition polymer while still containing the organicsolvent used for the reaction, mixing with the liquid oilafter removing volatile components such as the solvent andodorous components, and kneading. However, even if anaqueous solution of an organic acid is added to an additionpolymer which does not contain liquid oil, as the efficiencyof contact with the treatment solution is low, it isdifficult to improve the degree of purity and perform aneutralization reaction.
[0060] To obtain the organopolysiloxane polymer of thisinvention, the reaction may be performed in the presenceof a platinum compound (for example, chloroplatinic acid, alcohol-modified chloroplatinic acid or chloroplatinicacid-vinyl siloxane complex), or a rhodium compound, atroom temperature or by heating (about 50-120°C). Thereaction may be performed without a solvent, or an organicsolvent may be used if required. Examples of such organicsolvents are aliphatic alcohols such as methanol, ethanol,2-propanol and butanol; aromatic hydrocarbons such asbenzene, toluene and xylene; aliphatic or alicyclichydrocarbons such as n-pentane, n-hexane and cyclohexane;halogenated hydrocarbons such as dichloromethane,chloroform and carbon tetrachloride; and ketone solventssuch as acetone and methyl ethyl ketone. However, in orderto widen application as a cosmetic material, no solvent,or ethanol or 2-propanol are preferred.
[0061] In this addition reaction, the same problem as wasalready pointed out in Tokko Hei 07-91389 and Tokkai Hei07-330907 occurs. Specifically, a part of thepolyoxyalkylene of (B1) - (B3) causes an internalrearrangement according to a side reaction based on theaction of the platinum catalyst, and remains withoutreacting with the -SiH group of the organohydrogenpolysiloxane of (A1) and (A2).
[0062] For example, when an allyl etherated polyoxyalkyleneis used as the polyoxyalkylene, the allyl group undergoesan internal rearrangement as a side reaction, and propenyletherated polyoxyalkylene is produced. This propenyletherated polyoxyalkylene remains without undergoing anaddition reaction with the -SiH group, decomposing withtime to generate ketones and aldehydes which are responsible for odor.
[0063] The organopolysiloxane addition polymer of thisinvention has a three-dimensional crosslinkage which isinsoluble in organic solvents, the organic solventsmentioned here being aliphatic organic solvents such asstraight chain or branched pentane, hexane, decane,dodecane, hexadecane and octadecane, aromatic organicsolvents such as benzene, toluene and xylene, alcoholicorganic solvents such as methanol, ethanol, propanol,butanol, hexanol anddecanol, halogenated organic solventssuch as chloroform and carbon tetrachloride, ketone organicsolvents such as acetone and methyl ethyl ketone, andsilicone solvents such as low viscositydimethylpolysiloxane, ethylphenylpolysiloxane and cyclicdimethylpolysiloxane.
[0064] The organopolysiloxane addition polymer of thisinvention is characterized by swelling with at least itsown weight of decamethylcyclopentasiloxane, and this canbe confirmed as follows.
[0065] Equal weights of the organopolysiloxane additionpolymer and decamethyl cyclopentasiloxane are mixed, andallowed to stand at room temperature. After standing, itis verified that there is no separation ofdecamethylcyclopentasiloxane even if the sample is placedon a 100 mesh sieve and left for 5 minutes.
[0066] In manufacturing the silicone composition of thisinvention, kneading of the organopolysiloxane additionpolymer and liquid oil may be performed by an ordinarystirrer, but this is preferably performed under a shear force. This is because, as the organopolysiloxaneaddition polymer has a three-dimensional crosslinkedstructure which is insoluble in solvents, a paste-likecomposition of smooth appearance is obtained by givingsufficient dispersibility to the organopolysiloxaneaddition polymer and liquid oil.
[0067] The kneading can be performed by, for example, athree-roll mill, two-roll mill, side grinder, colloidalmill, Gaulin homogenizer or disper, but a three-roll millor disper are particularly preferred.
[0068] The liquid oil used in this invention may be suitablyselected from among those demonstrating fluidity at 25°C.Examples are silicone oil, hydrocarbon oil, ester oil,natural animal and vegetable oils and semi-synthetic oil.
[0069] As examples of other silicone oils which can be mixed,mention may be made of organopolysiloxanes having from lowto high viscosities, such as dimethylpolysiloxane,methylphenylpolysiloxane, anddimethylsiloxane-methylphenylsiloxane copolymer; cyclicsiloxanes, such as octamethylcyclotetrasiloxane,decamethylcyclopentasiloxane,dodecamethylcyclohexasiloxane,tetramethyltetraphenylcyclotetrasiloxane; branchedsiloxanes such as tristrimethyl siloxymethylsilane andtetrakistrimethylsiloxysilane, silicone gum, such asgummy dimethylpolysiloxanes having high polymerizationdegrees and gummy dimethylsiloxane-methylphenylsiloxanecopolymers having high polymerization degrees; andcyclosiloxane solutions of silicone gum.
[0070] Examples of hydrocarbon oils are straight chain orbranched volatile hydrocarbon oils, specifically,alpha-olefin oligomers, light isoparaffin, light flowingisoparaffin, squalane, synthetic squalane, vegetablesqualane, squalene, liquid paraffin and liquidisoparaffin.
[0071] Examples of an ester oil which can be mixed thereininclude diisobutyl adipate, 2-hexyldecyl adipate,di-2-heptylundecyl adipate, N-alkylglycolmonoisostearates, isocetyl isostearate,trimethylolpropane triisostearic acid ester, ethyleneglycol di-2-ethylhexanoic acid ester, cetyl2-ethylhexanoate, trimethylolpropanetri-2-ethylhexanoic acid ester, pentaerythritoltetra-2-ethylhexanoic acid ester, cetyl octanoate,octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate,decyl oleate, neopentyl glycol dicapric acid ester,triethyl citrate, 2-ethylhexyl cinnamate, amyl acetate,ethyl acetate, butyl acetate, isocetyl stearate, butylstearate, diisopropyl sebacate, di-2-ethylhexyl sebacate,cetyl lactate, myristyl lactate, isopropyl palmitate,2-ethylhexyl palmitate, 2-hexyldecyl palmitate,2-heptylundecyl palmitate, cholesteryl12-hydroxystearate, dipentaerythritol fatty acid esters,isopropylmyristate, octyldodecylmyristate, 2-hexyldecylmyristate, myristyl myristate, hexyldecyldimethyloctanoate, ethyl laurate, hexyl laurate,N-lauroyl-L-glutaminic acid 2-octyldodecyl ester anddiisostearyl malic acid.
[0072] Examples of ester oil which are glyceride oils areacetoglyceryl, glyceryl trioctanoate, glyceryltriisostearate, glyceryl triisopalmitate, glycerylmonostearate, glyceryl di-2-heptyl undecanoate, glyceryltrimyristate and diglyceryl myristate-isostearate.
[0073] Examples of higher fatty acids are undecylenic acid, oleicacid, linolic acid, linolenic acid, arachidonic acid,eicosapentaenoic acid (EPA), docosa-hexaenoic acid (DHA),isostearic acid and lactic acid, and examples of higher alcoholsare oleyl alcohol, isostearyl alcohol, hexyl decanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol andmonooleyl glyceryl ether (selachyl alcohol).
[0074] Examples of natural animal and vegetable oils and fats, andsemi-synthetic oils and fats, are avocado oil, almond oil, oliveoil, liver oil, beef foot tallow, apricot kernel oil, wheat germoil, sesame oil, rice germ oil, rice bran oil, sasanqua oil,safflower oil, cinnamon oil, turtle oil, soybean oil, tea fruitoil, camellia oil, evening primrose oil, corn oil, rapeseed oil,Japanese kiri oil, germ oil, par chic oil, castor oil, castoroil fatty acidmethyl ester, sunflower seedoil, grapeoil, jojobaoil, macadamia nut oil, mink oil, medoform oil, cotton seed oil,tricoconut oil fatty acid glycerides, arachis oil, liquefiedlanolin, acetic acid lanolin alcohol, lanolin fatty acidpolyethylene glycol and egg yolk oil.
[0075] The blending proportion of the organopolysiloxanepolymer crosslinked by the aforesaid polyoxyalkylenechains and liquid oil is preferably 1/20-20/1 (weightratio), but more preferably 1/10-1/1.
[0076] The addition amount of acidic substance is 0.01-10 wt parts, but preferably 0.02-5 wt parts, relative to 100 wtparts of the crosslinking type organopolysiloxane polymercrosslinked by polyoxyalkylene chains. If it is less than0.01 wt parts, the odor removal effect is poor, and if itis more than 10 wt parts, neutral salts separate from thecomposition after treatment which is undesirable. Theseorganic acids may be added as they are, but it is preferredto add them as a 1-50% aqueous solution.
[0077] The pasty composition comprising the crosslinking typepolyoxyalkylene compound crosslinked by polyoxyethylenechains and liquid oil may also be prepared, and treatedby adding an acidic substance to this pasty composition.As for treatment conditions after adding the acidicsubstance, heating is unnecessary, but heating may beperformed to 20-150°C, and preferably 50-100°C.
[0078] The basic neutralizing agent may be added as it is,but it is preferably added as a 1-50% aqueous solution.The addition amount is adjusted so that the functional groupequivalent of the aforesaid acidic substance and basicneutralizing agent is 1/0.1-0.1/1, but preferably1/0.3-0.3/1, and the acidity or alkanility afterneutralization is 5-8.
[0079] The treatment conditions after addition of the basicneutralizing agent are 20-150°C, but preferably 20-80°C.
[0080] Examples of the acidic substance are citric acid, lacticacid, tartaric acid, malic acid, glutamic acid, acetic acid,glycine, potassium dihydrogenphosphate and succinic acid,but citric acid, lactic acid, and glutamic acid arepreferred.
[0081] Examples of the basic neutralizer are sodium carbonate,sodium hydrogen carbonate, sodium hydroxide, potassiumhydroxide, disodium hydrogen phosphate and sodium acetate,but sodium carbonate, sodium hydrogen carbonate and sodiumhydroxide are preferred.
[0082] By selecting this acidic substance andbasic neutralizerfrom mixtures such that the salt produced by neutralizationhas a pH buffer effect, not only is the odor reduced, butthe pH of the composition can be stabilized.
[0083] This invention is a cosmetic material formed by blendingany of the aforesaid pasty compositions. This cosmeticmaterial may comprise at least one moiety selected froma group comprising (C) water, (D) a compound having analcoholic hydroxyl group in the molecule, (E) awater-soluble or water-swelling polymer, (F) a powderand/or colorant, (G) a surfactant, (H) a compositioncomprising a non-hydrophilic crosslinking typeorganopolysiloxane compound and liquid oil, and (I) asilicone resin.
[0084] At least part of (F), the powder and/or colorant, ispreferably a crosslinking type spherical silicone finepowder having a structure wherein dimethylpolysiloxane iscrosslinked, a crosslinking type sphericalpolymethylsilsesquioxane fine powder, or a fine powderobtained by coating a crosslinking type spherical siliconerubber surface with polymethylsilsesquioxane particles.
[0085] Afore mentioned (G), the surfactant, is preferably astraight-chain or branched silicone having apolyoxyalkylene chain in the molecule, and more preferably, its HLB is 2-8.
[0086] The aforesaid (I) silicone resin is preferably anacrylic silicone resin, and is more preferably a siliconeresin having at least one organic group selected from amonga pyrrolidone group, long chain alkyl group,polyoxyalkylene group, fluoroalkyl group and anioniccarboxyl group in the molecule. In particular, it is atleast one type of silicone resin selected from resinscomprising a R¹ ₃SiO_0.5 unit and SiO₂ unit, resins comprisinga R¹ ₃SiO_0.5 unit, R¹ ₂SiO unit and SiO₂ unit, resins comprisinga R¹ ₃SiO_0.5 unit and R¹SiO_1.5 unit, resins comprising aR¹ ₃SiO_0.5 unit, R¹ ₂SiO unit and R¹SiO_1.5 unit, and resinscomprising a R¹ ₃SiO_0.5 unit, R¹ ₂SiO unit, R¹SiO_1.5 unit andSiO₂ unit, but among these, silicone resins comprising atleast one organic group selected from among a pyrrolidonegroup, long chain alkyl group, polyoxyalkylene group,fluoroalkyl group and anionic group of a carboxyl groupare preferred.
[0087] (C), water, can also be blended with the cosmeticmaterial of this invention according to the purpose. Theblending amount may conveniently be within the range of1-95% of the total weight of cosmetic material.
[0088] In the cosmetic material of this invention, one,(D)two or more compounds having an alcoholic hydroxyl groupin the molecular structure may be used according to thepurpose. Examples of compounds having an alcoholichydroxyl group which can be added in this invention arelower alcohols such as ethanol and isopropanol, sugaralcohols such as sorbitol and maltose, and sterol such as cholesterol, sitosterol, phytosterol, lanosterol,polyhydric alcohols such as butylene glycol, propyleneglycol and dibutylene glycol, but normally, water-solublemonohydric alcohols and water-soluble polyhydric alcoholsare used.
[0089] The blending proportion of component (D) mayconveniently be 0.1-98% of the total weight of the cosmeticmaterial.
[0090] In the cosmetic material of this invention, one, twoor more of (E) water-soluble or water -swelling polymerscan also be used according to the purpose. Examples ofthese polymers are: plant polymers such as gum arabic,tragacanth, galactan, carob gum, guar gum, karaya gum,carrageenan, pectin, agar, quince seed, starch (rice, corn,potato, wheat), alge colloid, tranto gum and locust beangum; microbial polymers, such as xanthan gum, dextran,succinoglucan and pullulan; animal polymers, such ascollagen, casein, albumin and gelatin; starch polymers,such as carboxymethyl starch and methylhydroxypropylstarch; cellulose polymers, such as methyl cellulose, ethylcellulose, methylhydroxypropyl cellulose, carboxymethylcellulose, hydroxymethyl cellulose, hydroxypropylcellulose, nitrocellulose, sodium cellulose sulfate,sodium carboxymethylcellulose, crystalline cellulose andpowdery cellulose; alginic acid polymers, such as sodiumalginate and propylene glycol ester of alginic acid; vinylpolymers, such as polyvinyl methyl ether and carboxyvinylpolymer; polyoxyethylene polymers;polyoxyethylene-polyoxypropylene copolymers; acrylic polymers, such as sodium polyacrylate, polyethylacrylateand polyacrylamide; other synthetic water-solublepolymers, such as polyethyleneimines and cationicpolymers; and inorganic water-soluble polymers, such asbentonite, aluminum magnesium silicate, montmorillonite,beidellite, nontronite, saponite, hectorite and silicicacid anhydride.
[0091] Film-forming agents, such as polyvinyl alcohol andpolyvinyl pyrrolidone, are also contained in thesewater-soluble polymers. The blending amount of component(E) is conveniently within the range of 0.1-25 wt% of thetotal cosmetic material.
[0092] In the cosmetic material of this invention, one, twoor more of the powder and/or colorant (F) may also be usedaccording to the purpose.
[0093] If the powder is used in ordinary cosmetic materials,it maybe used regardless of its shape (spherical, acicular,plate), particle diameter (fume, fine particles or pigmentgrade), or particle structure (porous, non-porous). Suchpowders may for example be inorganic fine particles,organic fine particles, surfactant metal salt fineparticles, a colored pigment, a pearl pigment, a metalpowder pigment or natural coloring matter.
[0094] Examples of inorganic fine particles are titanium oxide,zirconium oxide, zinc oxide, cerium oxide, magnesium oxide,barium sulfate, calcium sulfate, magnesium sulfate,calcium carbonate, magnesium carbonate, talc, mica, kaolin,sericite, muscovite, syntheticmica, phlogopite, redmica,biotite, lithiamica, silicic acid, silicic acid anhydride, aluminium silicate, magnesium silicate, magnesiumaluminium silicate, calcium silicate, barium silicate,strontium silicate, tungstic acid metal salts,hydroxyapatite, vermiculite, haidilite, bentonite,montmorillonite, hectorite, zeolite, ceramic powder,dibasic calcium phosphate, alumina, aluminium hydroxide,boron nitride, boron nitride and silica.
[0095] Examples of organic fine particles are polyamide powder,polyester powder, polyethylene powder, polypropylenepowder, polystyrene powder, polyurethane, benzoguanaminepowder, polymethyl benzoguanamine powder,tetrafluoroethylene powder, polymethylmethacrylatepowder, cellulose, silk powder, nylon powder, 12 nylon,6 nylon, crosslinking type silicone fine powder having astructure wherein dimethylsilicone is crosslinked,polymethylsilsesquioxane fine powder, styrene-acrylicacid-copolymer, divinylbenzene styrene copolymer, vinylresin, urea resin, phenol resin, fluororesin, silicon resin,acrylate resin, melamine resin, epoxy resin, polycarbonateresin, microcrystalline fiber fine particles, starchpowder and lauroyl lysine.
[0096] Examples of surfactant metal salt fine particles (metalsoap) are zinc stearate, aluminum stearate, calciumstearate, magnesium stearate, zinc myristate, magnesiummyristate, zinc cetyl phosphate, calcium cetyl phosphateand zinc sodium cetyl phosphate.
[0097] Examples of colored pigments are inorganic red pigmentssuch as iron oxide, iron hydroxide and iron titanate,inorganic brown pigments such as γ-iron oxide, inorganic yellow pigments such as yellow iron oxide and ocher,inorganic black pigments such as black iron oxide and carbonblack, inorganic purple pigments such as manganese violetand cobalt violet, inorganic green pigments such aschromium hydroxide, chromium oxide, cobalt oxide andcobalt titanate, inorganic blue pigments such as Berlinblue and ultramarine blue, tar pigment lake, naturalpigment lake and synthetic resin powders which arecomplexes of these powders.
[0098] Examples of pearl pigments are titanium oxide-coatedmica and titanium oxide-coated mica, bismuth oxychloride,titanium oxide-coated bismuth oxychloride, titaniumoxide-coated talc, scales foil and titanium oxide-coatedcolored mica; examples of metal powder pigments arealuminium powder, copper powder and stainless steel powder
[0099] Examples of tar dyes are Red No. 3, Red No. 104, RedNo. 106, Red No. 201, Red No. 202, Red No. 204, Red No.205, Red No. 220, Red No. 226, Red No. 227, Red No. 228,Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, YellowNo. 5, YellowNo. 202, YellowNo. 203, YellowNo. 204, YellowNo. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No.404, Green No. 3, Green No. 201, Green No. 204, Green No.205, Orange No. 201, Orange No. 203, Orange No. 204, OrangeNo. 206 and Orange No. 207; examples of natural pigmentsare powders selected from among carminic acid, laccainicacid, carthamin, bradilin and crocin.
[0100] Of these powders and/or colorants, those wherein atleast part is a crosslinking type silicone fine powderhaving a structure wherein dimethylsilicone is crosslinked, polymethylsilsesquioxane fine powder, hydrophobic silica,or a composite fine powder wherein a spherical siliconerubber surface is coated by polymethylsilsesquioxaneparticles, or those wherein at least part of the powderand/or colorant has a fluorine group, are often used.Further, to the extent that it does not interfere with theeffect of this invention, composite powders or those whichhave been treated with ordinary oils, silicone oil,fluorine compounds or surfactants may be used, one, twoor more of these being used as required. The blendingproportion is conveniently within the range of 0. 1-99 wt%of the total cosmetic material. In particular, theblending proportion in a powder solidified cosmeticmaterial is conveniently within the range of 80-99 wt% ofthe total cosmetic material.
[0101] The cosmetic material of this invention may also useone, two or more of the surfactants (G) according to thepurpose. The surfactants may be anionic, cationic,non-ionic or amphoteric active agents and are notparticularly limited, and any of those used in ordinarycosmetic materials may be used herein.
[0102] Examples of a usable anionic surfactant include fattyacid soap, such as sodium stearate or triethanolaminepalmitate; alkyl ether carboxylic acids and salts thereof;salts of aminoacid-fatty acid condensates;alkanesulfonates; alkenesulfonates; sulfonated fatty acidesters; sulfonated fatty acid amides; sulfonates offormaldehyde condensate type; alkylsulfates; highersecondary alcohol sulfates; alkyl and aryl ether sulfates; fatty acid ether sulfates, fatty acid alkylolamidesulfates; ether sulfates such as Turkey red oil; alkylphosphates; ether phosphates; alkyl aryl ether phosphates;amide phosphates; and active agents of N-acylaminoacidtype; examples of a usable cationic surfactant includeamine salts, such as alkylamine salts, polyamines andaminoalcohol fatty acid derivatives, quaternaryalkylammonium salts, quaternary arylammonium salts,pyridinium salts and imidazolium salts.
[0103] Examples of a usable nonionic surfactant includesorbitan fatty acid esters, glycerin fatty acid esters,polyglycerin fatty acid esters, propylene glycol fatty acidesters, polyethylene glycol fatty acid esters, sucrosefatty acid esters, polyoxyethylene alkyl ethers,polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters,polyoxyethylene sorbitan fatty acid esters,polyoxyethylene sorbitol fatty acid esters,polyoxyethylene glycerin fatty acid esters,polyoxyethylene propylene glycol fatty acid esters,polyoxyethylene castor oil, polyoxyethylene hydrogenatedcastor oil, polyoxyethylene phytostanol ehter,polyoxyethylene phytosterol ether, polyoxyethylenecholestanol ether, polyoxyethylene cholesteryl ether,polyoxyalkylene-modified organopoly-siloxanes,organopolysiloxanes modified with both polyoxyalkyleneand alkyl groups, alkanolamides, sugar ethers and sugaramides; and examples of a usable amphoteric surfactantinclude betaine, aminocarboxylate, imidazoline derivatives and amidoamines.
[0104] Of these surfactants, surfactants which arestraight-chain or branched organopolysiloxane having apolyoxyalkylene chain in the molecule, and surfactantswhereof the HLB is 2-8, are often used.
[0105] The blending proportion of the component (G) ispreferably in the range of 1-20 wt%, but more preferably0.2-10 wt%, of the total cosmetic material.
[0106] In the cosmetic material of this invention, one, twoor more crosslinking type organopolysiloxanes which do notcontain a polyoxyalkylene chain which swells up when itcontains a low viscosity organopolysiloxane of from0.65mm²/s (25°C) to 100.0mm²/s (25°C) in an amount largerthan its own weight, may also be used as the component (H)according to the purpose. This crosslinking typeorganopolysiloxane preferably swells up with at least itsown weight of the low viscosity organopolysiloxane relativeto the low viscosity organopolysiloxane of from 0.65mm²/s(25°C) to 100.0mm²/s (25°C). The blending amount of thiscrosslinking type organopolysiloxane is preferably 0.1-50wt% but more preferably 1-30 wt%, of the total amount ofcosmetic material. These are not limiting, but examplesare the organopolysiloxane composition described in Tokkyo1925781, the organopolysiloxane polymer described in thesame patent, or a composition comprising an oil other thanthe organopolysiloxane oil.
[0107] One, two or more of the silicone resins (I) can alsobe used for the cosmetic material of this inventionaccording to the purpose,
[0108] This silicone resin is preferably an acrylic/siliconegraft resin or block copolymer acrylic silicone resin. Anacrylic silicone resin comprising at least one moeity inthe molecule selected from among pyrrolidone, long chainalkyl, polyoxyalkylene, fluoroalkyl and anions such ascarboxylic acid, can also be used.
[0109] Further, this silicone resin is preferably a siliconereticular compound represented by MQ, MDQ, MT, MDT or MDTQas a constituent component. This M, D, T, Q respectivelyexpress a R³SiO_0.5 unit, R²SiO unit, RSiO_1.5 unit or SiO₂unit, and are commonly used in the silicone industry. Asilicone reticular compound containing at least one moeityin the molecule selected from among pyrrolidone, long chainalkyl, polyoxyalkylene, fluoroalkyl and amino can also beused.
[0110] The blending amount of the silicone resin which is thecomponent (I), such as an acrylic silicone resin or asilicone reticular compound, is preferably 0.1-20 wt%, butmore preferably 1-10 wt%, relative to the total amount ofcosmetic material.
[0111] To the present cosmetic material, the ingredients usedin general cosmetic materials, such as an oil-solublegelling agent, clay minerals modified with organiccompounds, resins,antiperspiration, ultravioletabsorbents, an ultraviolet absorption and scattering agent,a moisture-holding agent, antiseptics, an antimicrobialagent, perfume, salts, antioxidants, pH regulators, achelatingagent, refrigerant, an anti-inflammatory agent,skin beautifying components (a skin whitener, a cell activator, a rough dry skin improver, a blood circulationpromoter, a skin astringent and an anti-seborrheic agent),vitamins, aminoacids, nucleic acids, hormones, clathratecompounds and hair firming agents can be added so far asthey have no adverse influence on the effects of the presentinvention.
[0112] Examples of an oil-soluble gelling agent which can beadded include metal soaps, such as aluminum stearate,magnesium stearate and zinc myristate; aminoacidderivatives, such as N-lauroyl-L-glutamic acid andα,γ-di-n-butylamine; dextrin fatty acid esters, such asdextrin palmitic acid ester, dextrin stearic acid esterand dextrin 2-ethylhexaminic acid palmitic acid ester;sucrose fatty acid esters, such as sucrose palmitic acidester and sucrose stearic acid ester; benzylidenederivatives of sorbitol, such as monobenzylidene sorbitoland dibenzylidene sorbitol; and clay minerals modified withorganic compounds, such as dimethylbenzyldodecyl ammoniummontmorillonite clay and dimethyldioctadecyl ammoniummontmorillonite clay.
[0113] Examples of an antiperspirant which can be added may beselected from among aluminum chlorohydrate, aluminumchloride, aluminum sesquichlorohydrate, zirconylhydroxychloride, aluminum zirconium hydroxychloride andaluminum zirconium glycine complex.
[0114] Examples of an ultraviolet absorbent which can be addedinclude ultraviolet absorbents of benzoic acid type, suchas p-aminobenzoic acid; those of anthranilic acid type,such as methyl anthranilate; those of salicylic acid type, such as methyl salicylate; those of succinic acid type,such as octyl p-methoxysuccinate; those of benzophenonetype, such as 2, 4-dihydroxybenzophenone; those of urocanicacid type, such as ethyl urocanate; and those ofdibenzoylmethane type, such as4-t-butyl-4'-methoxydibenzoylmethane. Examples of anultraviolet absorption and scattering agent which can beadded are powders which absorb and scatter ultravioletlight such as fine particle titanium oxide, fine particleiron-containing titanium oxide, fine particle zinc oxide,fine particle cerium oxide and their complexes.
[0115] Examples of a moisture-holding agent which can be addedinclude glycerin, sorbitol, propylene glycol, dipropyleneglycol, 1,3-butylene glycol, glucose, xylitol, maltitol,polyethylene glycol, hyaluromic acid, chondroitinsulfuric acid, pyrrolidone carboxylic acid,polyoxyethylene glycoside, and polyoxypropylenemethylglycoside.
[0116] Examples of preservatives which can be added includealkyl p-oxybenzoates, benzoic acid, sodium benzoate,sorbic acid, potassium sorbate and phenoxyethanol; andthose of an antimicrobial agent which can be added includebenzoic acid, salicylic acid, carbolic acid, sorbic acid,alkyl p-hydroxybenzoates, p-chlorometacresol,hexachlorophene, benzalkonium chloride, chlorhexidinechloride, trichlorocarbanilide, photosensitizer andphenoxyethanol.
[0117] Examples of an antioxidant which can be added includetocopherol, butylhydroxyanisole, dibutylhydroxytoluene and phytic acid; those of a pH regulator which can be addedinclude lactic acid, citric acid, glycolic acid, succinicacid, tartaric acid, dl-malic acid, potassium carbonate,sodium hydrogen carbonate and ammonium hydrogen carbonate;those of a chelating agent which can be added include alanine,sodium ethylenediaminetetraacetate, sodium polyphosphate,sodium metaphosphate and phosphoric acid; those of arefrigerant which can be added include L-menthol andcamphor; and those of an anti-inflammatory agent which canadded include allantoin, glycyrrhizin and salts thereof,glycyrrhetinic acid and stearyl glycyrrhetinate,tranexamic acid and azulene.
[0118] Examples of a skin-beautifying component which can beadded include whitening agents, such as placenta extract,arbutin, glutathione and Yukinoshita extract; cellactivators, such as royal jelly, photosensitizer,cholesterol derivatives and calf blood extract; rough dryskin improvers; blood circulation improvers, such asnonylic acid vanillyl amide, benzyl nicotinate,β-butoxyethyl nicotinate, capsaicin, zingerone, cantharistincture, ichtammol, caffeine, tannic acid, α-borneol,tocopheryl nicotinate, inositol hexanicotinate,cyclandelate, cinnarizine, tolazoline, acetyl choline,verapamil, cepharanthin and γ-oryzanol; skin astringents,such as zinc oxide and tannic acid; and anti-seborrheicagents, such as sulfur and thianthol.
[0119] Examples of vitamins which can be added include vitaminA, such as vitamin A oil, retinol, retinyl acetate andretinyl palmitate; vitamin B, including vitamin B2 such as riboflavin, riboflavin butyrate and flavin adeninenucleotide, vitamin B6 such as pyridoxine hydrochloride,pyridoxine dioctanoate and pyridoxine tripalmitate,vitamin B12 and its derivatives, and vitamin B15 and itsderivatives; vitaminc, such as L-ascorbic acid, L-ascorbicacid dipalmitic ester, sodium (L-ascorbic acid) -2-sulfateand dipotassium L-ascorbic acid diphosphate; vitamin D,such as ergocalciferol and cholecarciferol; vitamin E, suchas α-tocopherol, β-tocopherol, γ-tocopherol,dl-α-tocopheryl acetate, dl-α-tocopheryl nicotinate anddl-α-tocopheryl succinate; vitamin H; vitamin P; nicotinicacids, such as nicotinic acid, benzyl nicotinate andnicotinic acid amide; pantothenic acids, such as calciumpantothenate, D-pantothenyl alcohol, pantothenyl ethylether and acetylpantothenyl ethyl ether; and biotin.
[0120] Examples of an aminoacid which can be added includeglycine, valine, leucine, isoleucine, serine, threonine,phenylaranine, alginine, lysine, aspartic acid, glutamicacid, cystine, cysteine, methionine, andtryptophan; thoseof a nucleic acid which can be added includedeoxyribonucleic acid; and those of a hormone which canbe added include estradiol and ethenyl estradiol.
[0121] Examples of a hair firming polymer compound areamphoteric, anionic, cationic or nonionic polymercompounds, e.g., polyvinyl pyrrolidone-polymer compoundssuch as polyvinyl pyrrolidone and vinyl pyrrolidone/vinylacetate copolymer, acidic vinyl ether polymer compoundssuch as methyl vinyl ether/maleic anhydride alkyl halfester copolymer, acidic polyvinyl acetate-polymers such as vinyl acetate/crotonic acid copolymer, acidic acrylicpolymer compounds such as (meth)acrylicacid/alkyl(meth)acrylate copolymer and (meth)acrylicacid/alkyl (meth) acrylate/alkyl acrylamide copolymer, andamphoteric acrylic-polymer compounds such asN-methacryloylethyl-N,N-dimethylammonium-alpha-N-methyl, carboxybetaine/alkyl(meth)acrylate copolymer,hydroxypropyl(meth)acrylate/butylaminoethylmethacrylate/acrylic acid octylamide copolymer. Also,naturally-occurring polymer compounds such as celluloseor its derivatives, keratin, and collagen or itsderivatives, can also be used.
[0122] Examples of a higher alcohol which can be mixed thereininclude lauryl alcohol, myristyl alcohol, palmityl alcohol,stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleylalcohol, isostearyl alcohol, hexyldodecanol,octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol,cholesterol, phytosterol, POE cholesterol ether,monostearyl glycerin ether (batyl alcohol) and monooleylglyceryl ether (cerakyl alcohol).
[0123] As examples of other silicone oils which can be mixed,mention may be made of higher alkoxy-modified siliconessuch as stearoxysilicone, higher fatty acid-modifiedsilicones, alkyl-modified silicones, amino-modifiedsilicones and fluorine-modified silicones.
[0124] Examples of fluorinated oils are fluoropolyether,perfluorodecalin and perfluorooctane.
[0125] The "cosmetic material" of this invention formed by blending the aforesaid cosmetic material components maybe a skincare product such as a milky lotion, cream, facecleansing cream, packs, oily liquid, massage material,rinsing agent, deodorants, hand cream or lip cream; a makeupproduct such as a foundation, powder, liquid foundation,oily foundation, rouge, eye shadow, mascara, eyeliner,eyebrow, makeup such as lipstick; a hairdressing product,such as a shampoo, rinse, treatment and set; anantiperspirant, or an ultraviolet defense cosmeticmaterial such as suncut milky lotion or suncut cream.
[0126] Additionally, the present cosmetic material may haveany form, including liquid, emulsion, cream, solid, paste,gel, powder, compress, layers, mousse, spray or stick.
[0127] The oily composition comprising the crosslinking typeorganopoly siloxane having hydrophilic organic groupswhich has been purified and liquid oil according to thisinvention does not easily suffer a drop of pH during longstorage or when heated and left, and the unpleasant odorgenerated over time is largely suppressed even when blendedwith an emulsion. Therefore, a highly stable cosmeticmaterial may be obtained by the use of this composition. Examples
[0128] Hereafter, this embodiment will be described by specificexamples, but it should be understood that this inventionis not limited in any way thereby. Composition 1.
[0129] 100.0g of an organohydrogen polysiloxane expressed bythe average formula (1):
[0130] 30 wt parts of the obtained organopolysiloxane additionpolymer (P1) and 70 wt parts of a dimethylpolysiloxanehaving a viscosity of 10mm²/s at 25°C, were mixed anddispersed, and kneaded by a three roll mill to obtain apasty composition (C1). Composition 2.
[0131] 100.0g of an organohydrogen polysiloxane expressed bythe average formula (3):
[0132] 34.7g of the polyoxyalkylene compound expressed by theaverage formula (4), 34.3g of dimethylpolysiloxane havinga viscosity of 20mm²/s at 25°C, 150.0g of ethanol and 0.3gof a 3 wt% ethanol solution of chloroplatinic acid wereintroduced into a reactor, and stirred for 2 hours while maintaining the internal temperature at 70-80°C. Thesolvent was removed under reduced pressure, and anorganopolysiloxane addition polymer (P2) was obtained.CH₂=CHCH₂O(C₂H₄O)₃₀ (C₃H₆O)₁₀CH₂ CH=CH₂
[0133] Next, 25 wt parts of the obtained organopolysiloxaneaddition polymer (P2) and 75 wt parts of adimethylpolysiloxane having a viscosity of 20mm²/s at 25°C,were mixed and dispersed, and kneaded by a three roll millto obtain a pasty composition (C2). Composition 3.
[0134] 323.0g of an organohydrogen polysiloxane expressed bythe average formula (5):
[0135] Next, 30 wt parts of this organopolysiloxane additionpolymer (P3) and 70 wt parts of a fluid paraffin were mixedand dispersed, and kneaded by a three roll mill to obtaina pasty composition (C3). Composition 4.
[0136] 20 wt parts of the organohydrogen polysiloxane (P3.)and 80 wt parts of cetyl isooctanoate were mixed anddispersed, and kneaded by a three roll mill to obtain apasty composition (C4). Composition 5.
[0137] 156.3g of an organohydrogen polysiloxane expressed bythe average empirical formula (6):
[0138] 21.0g of the polyoxyalkylene compound expressed by theaverage formula (7), 70.0g of 2-propanol and 0.1g of a 3wt% ethanol solution of chloroplatinic acid were introducedinto a reactor, and stirred for 2 hours while maintainingthe internal temperature at 70-80°C. The solvent wasremoved under reduced pressure, and an organopolysiloxaneaddition polymer (P4) was obtained.CH₂=C (CH₃) CH₂O(C₂H₄O) ₂₀CH₂C (CH₃) = CH₂
[0139] Next, 30 wt parts of this organopolysiloxane additionpolymer (P4) and 70 wt parts of squalane were mixed anddispersed, and kneaded by a three roll mill to obtain apasty composition (C5). Composition 6.
[0140] 30 wt parts of the organohydrogen polysiloxane (P3)and 70 wt parts of macadamia nut oil were mixed and dispersed,and kneadedby a three roll mill to obtain a pasty composition (C6). Composition 7.
[0141] 676.0g of an organohydrogen polysiloxane expressed bythe average formula (8):
[0142] 165.0g of the polyoxyalkylene compound expressed by theaverage y formula (9), 300.0g of 2-propanol and 0.3g ofa 3 wt% ethanol solution of chloroplatinic acid wereintroduced into a reactor, and stirred for 2 hours whilemaintaining the internal temperature at 70-80°C. Thesolvent was removed under reduced pressure, and anorganopolysiloxane addition polymer (P5) was obtained.
[0143] Next, 30 wt parts of this organopolysiloxane additionpolymer (P5) and 70 wt parts of glyceryl trioctanoate weremixed and dispersed, and kneaded by a three roll mill toobtain a pasty composition (C7). Composition 8.
[0144] 368.0g of an organohydrogen polysiloxane expressed bythe average formula (10):
[0145] 100.0g of the polyoxyalkylene compound expressed by theaverage formula (11) and 0.3g of a 3 wt% ethanol solutionof chloroplatinic acid were introduced into a reactor, andstirred for 2 hours while maintaining the internaltemperature at 70-80°C. The solvent was removed underreduced pressure, and an organopolysiloxane additionpolymer (P6) was obtained.
[0146] Next, 30 wt parts of this organopolysiloxane additionpolymer (P6) and 70 wt parts of the fluorinatedorganopolysiloxane (viscosity 100mm²/s) expressed by (12)were mixed and dispersed, and kneaded by a three roll millto obtain a pasty composition (C8).
[0147] A refining treatment was performed under the followingconditions using the compositions shown in Table 1 usingthe pasty composition C1.
[0148] First, the 2% organic acid aqueous solution (10g) wasadded to the pasty composition C1 (100g), and thoroughlymixed. Next, the internal temperature was maintained at70-80°C, and mixing and heat-treatment was performed for3 hours. Cooling was performed until the internaltemperature reached 50°C or less, a predetermined amountof 5% sodium hydrogen carbonate aqueous solution was added,the internal temperature was maintained at 40-50°C, andstirring was performed for 1 hour. After stirring wascomplete, the internal temperature was raised to 100°Cunder reduced pressure, and volatile components wereremoved to obtain the target substance. Comparative Example 1.
[0149] The target substance was obtained without performing therefining treatment of this invention on the pastycomposition. Comparative Example 2 (method disclosed in Tokkai Hei07-91389).
[0150] 10g (reference is 6g) of 10^-2N (reference is 10^-3N) aqueoushydrochloric acid was added to the pasty composition C1(100g), and stirring was performed at 90°C for 4 hours.
[0151] After performing a reduced pressure strip, purificationfiltration was performed to obtain the target substance.
[0152] 5g of purified composition and 5g of water were mixed,introduced into a special 20ml container, sealed, andheated at 60°C for 24 hours. A headspace gas chromatographyanalysis was performed, and the amount of propionaldehydegenerated was measured. As a result, it was found thatin the case of the examples as compared to ComparativeExample 1, the unpleasant odor very much decreased. pH value measurement test
[0153] 10g of the aforesaid treated product was taken up ina 100ml glass bottle, and heated for one week at 70°C. Itwas then cooled to room temperature, and the pH of theextracted water was measured. The result is shown in Table2.
[0154] The treated composition of this invention had a smallpH change even after heating, whereas the pH of the untreatedproduct of Comparative Example 1 dropped considerably, andthe composition changed from a paste to a liquid. Thetreated composition of Comparative Example 2 did lose itsodor, but the drop of pH and apparent liquefaction couldnot be prevented. Examples 6-11.
[0155] Using compositions C2-C8, the production amount ofpropionaldehyde of the target substance treated underidentical conditions to those of Example 1, and the pH ofthe extracted water after heating, were measured. Theresults are shown in Table 3.
[0156] (Component)Weight (parts)1.Treated composition of Example 110.02.Dimethylpolysiloxane (6mm²/s (25°C)12.03.Decamethylcyclopentasiloxane10.04.Glyceryl trioctanoate5.05.1, 3-butylene glycol5.06.AntisepticsSuitable amount7.PerfumeSuitable amount8.Purified water58.0(Manufacturing method)A: Components 1-5 were mixed uniformly.B: After mixing components 6-8, they were added to A and emulsified.
[0157] The W/O emulsion thus obtained was not tacky, spreadlightly, had good skin contact, good setting qualities andsheen. Example 14: W/O type cream
[0158] (Component)Weight (parts)1.Treated composition of Example 36.02.Liquid paraffin13.53.Macadamia nut oil4.04.Alkyl/polyether comodified silicone (Note 1)1.55.Sodium citrate0.6.Propylene glycol8.07.Glycerol3.08.AntisepticSuitable amount9.PerfumeSuitable amount 10.Purified water60.8(Note 1) Shin-Etsu Chemical Co., Ltd.: KF-6026 (commercial name)(Manufacturing method)A: Components 1-4 were mixed.B: Components 5-10 were mixed, added to A, stirred and emulsified.
[0159] The W/O cream thus obtained was not oily or, tacky, spreadlightly, had good skin contact, good setting qualities andsheen. Example 15: W/O type cream
[0160] (Component)Weight (parts)1.Treated composition of Example 67.02.Liquid paraffin13.53.Macadamia nut oil5.04.Alkyl/polyether co-modified silicone (Note 1)0.55.Hybrid silicone composite powder (Note 2)3.06.Sodiumcitrate0.27.Propylene glycol8.08.Glycerol3.09.AntisepticsSuitable amount10.PerfumeSuitable amount11.Purified water59.8(Note 1) Shin-Etsu Chemical Co., Ltd.: KF-6026 (commercial name)(Note 2) Shin-Etsu Chemical Co., Ltd.: KSP-100 (commercial name)(Manufacturing method) A: Components 1-5 were mixed.B: Components 6-11 were mixed, added to A, stirred and emulsified.
[0161] The W/O emulsion thus obtained was not oily or tacky,spread lightly, had good skin contact, good settingqualities and sheen. Example 16: O/W type cream
[0162] (Component)Weight (parts)1.Treated composition of Example 28.02.Crosslinking type methyl phenyl polysiloxane (Note 1)2.03.Isotridecyl isononoate5.04.Dipropylene glycol7.05.Glycerol5.06.Methyl cellulose (2% aqueous solution) (Note 2)7.07.Polyacrylamide emulsifier (Note 3)2.08.Guanine1.09.AntisepticSuitable amount10.PerfumeSuitable amount11.Purified water63.0(Note 1) Shin-Etsu Chemical Co., Ltd.: KSG-18(Note 2) Shin-Etsu Chemical Co., Ltd.: Metrose SM-4000(Note 3) SEPIC: Sepgel 305(Manufacturing method)A: Components 4-11 were mixed.B: Components 1-3 were mixed and dissolved, A was added, and stirred and emulsified.
[0163] The O/W cream thus obtained was fine, spread lightly, was not tacky or oily, was moist and fresh, and left a cleanfeel. The cosmetic preparation lasted very well, showedno change with temperature or time, and had excellent.stability. Example 17: W/O type cream
[0164] (Component)Weight (parts)1.Treated composition of Example 17.02.Dimethylpolysiloxane (6mm²/s (25°C))10.03.Polyether-modified silicone (Note 1)0.54.Dipropylene glycol10.05.Sodium citrate0.26.Ethanol5.07.AntisepticSuitable amount8.PerfumeSuitable amount9.Purifiedwater67.8(Note 1) Shin-Etsu Chemical Co., Ltd.: KF-6017 (commercial name)(Manufacturing method)A: Components 1-3 were heated and dissolved.B: Components 4-10 were mixed and dissolved, added to A, stirred andemulsified.
[0165] The W/O cream thus obtained was moist and fresh, notoily or tacky, spread lightly, and had a fresh, clean feel.It had good skin contact and setting qualities, and gavea matt finish. Example 18: W/O type makeup foundation
[0166] (Component)Weight (parts)1.Treated composition of Example 45.02.Crosslinking type dimethylpolysiloxane (Note 1)1.03.Polyether-modifiedsilicone (Note 2)0.54.Dimethylpolysiloxane (6mm²/s (25°C))6.05.Dimethylpolysiloxane (20mm²/s (25°C))2.06.Decamethylcyclopentasiloxane3.07.Titanium oxide/cyclopentasiloxane dispersion (Note3)10.08.Dipropylene glycol5.09.Sodium citrate0.210.Methyl cellulose (2% aqueous solution) (Note 4 )2.511.Ethanol3.012.AntisepticSuitable amount13.PerfumeSuitable amount14.Purified water62.8(Note 1) Shin-Etsu Chemical Co., Ltd.: KSG-15 (commercial name)(Note 2) Shin-Etsu Chemical Co., Ltd.: KF-6017 (commercial name)(Note 3) Shin-Etsu Chemical Co., Ltd. SPD-T1S (commercial name)(Note 4) Shin-Etsu Chemical Co., Ltd. Metrose 65-SH4000 (commercial name)
[0167] (Manufacturing method)A: Components 1-7 were mixed.B: Components 8-15 were mixed and dissolved, added toA, stirred andemulsified.
[0168] The W/O makeup foundation thus obtained was not oilyor tacky, spread lightly, and had a fresh, clean feel. Ithad good skin contact and setting qualities, and gave amatt finish. Moreover, it had an ultraviolet cut actionand lasted well in cosmetics. Example 19: O/W type cream
[0169] (Component)Weight (parts)1.Treated composition of Example 12.02.Crosslinking type dimethylpolysiloxane (Note 1)15.03.Decamethylcyclopentasiloxane10.04.Dimethylpolysiloxane (6mm²/s (25°C))18.05.Polyether-modified silicone (Note 2)0.76.Propylene glycol3.07.Polyacrylamide mixture (Note 3)0.88.Xanthan gum (2% aqueous solution)8.09.AntisepticSuitable amount10.PerfumeSuitable amount11.Purified water42.5(Note 1) Shin-Etsu Chemical Co., Ltd.: KSG-16 (commercial name)(Note 2) Shin-Etsu Chemical Co., Ltd.: KF-6011 (commercial name)(Note 3) SEPIC Sepgel 305 (commercial name)(Manufacturing method)A: Components 1-4 were heated and mixed.B: Components 5-11 were mixed and dissolved.C: A was added to B, stirred and emulsified.
[0170] The O/W cream thus obtained was fine, spread lightly, was not tacky or oily, was moist and fresh, and left a cleanfeel. The cosmetic preparation lasted very well, showedno change with temperature or time, and had excellentstability. Example 20: Lipstick
[0171] (Component)Weight (parts)1.Polyethylene wax12.02.Microcrystalline wax4.03.Polybutene5.04.Acrylate/dimethyl silicone copolymer (Note 1)12.05.Treatment composition of Example 77.06.Cetyl octanoate20.07.Cane sugar fatty acid ester3.08.Glyceryl isostearate37.09.PigmentSuitable amount10.AntisepticsSuitable amount11.PerfumeSuitable amount(Note 1) Shin-Etsu Chemical Co., Ltd.: KP-561(Manufacturing method)A: Components 1-7 and part of Component 8 were heated, mixed and dissolved.B: Component 9 and the remainder of Component 8 were uniformly mixed, added to A, and homogenized.
[0172] The lipstick thus obtained spread lightly, was not oilyor powdery, and left a clean feel. It had good waterresistance and water repellence, lasted well, and hadexcellent stability. Example 21: Powder foundation
[0173] (Component)Weight (parts)1.Vaseline2.52.Squalane3.03.Treatment composition of Example 50.54.Glyceryl trioctanoate2.05.Silicone-treated mica40.06.Silicone-treated talcRemainder7.Silicone-treated titanium oxide10.08.Silicone-treated particulate titanium oxide5.09.Silicone-treated barium sulfate10.010.PigmentSuitable amount11.Fluorine-modified hybrid silicone composition powder (Note 1)2.012.Silicone powder (Note 2)2.513.AntisepticsSuitable amount14.PerfumeSuitable amount(Note 1) Shin-Etsu Chemical Co., Ltd.: KSP-200 (commercial name)(Note 2) Shin-Etsu Chemical Co., Ltd.: KMP-590 (commercial name)(Manufacturing method)A: Components 4-13 were mixed, and homogenized.B: Components 1-3 were mixed uniformly, added to A, and homogenized.C: Component 14 was added to B, and press molded into a mold to obtain a foundation.
[0174] The powder foundation thus obtained was not tacky, spread lightly, had good skin contact, good settingqualities and sheen. Example 22: Cream foundation
[0175] (Component)Weight (parts)1.Treatment composition of Example 75.52.Glyceryl trioctanoate4.03.Dimethylpolysiloxane (6mm²/s (25°C))5.04.Decamethyl cyclopentasiloxane6.05.Fluorine-modified hybrid silicone composition powder (Note 1)2.56.Pigment8.07.Acrylic silicone resin (Note 2)5.08.Dipropylene glycol5.09.Sodium citrate0.210.AntisepticsSuitable amount11.PerfumeSuitable amount12.Purified water59.3(Note 1) Shin-Etsu Chemical Co., Ltd. KSP-200 (commercial name)(Note 2) Shin-Etsu Chemical Co., Ltd. KP-545 (commercial name)(Manufacturing method)A: Components 1-5 were heated and mixed.B: Components 8-12 were mixed and dissolved, added to A, stirred and emulsified.C: Components 6-7 were mixed, added to B, and homogenized.
[0176] The cream foundation thus obtained was not tacky, spreadlightly, had good skin contact, good setting qualities, and gave a matt finish. Example 23: W/O compact foundation
[0177] (Component)Weight (parts)1.Ceresin5.52.Microcrystalline wax1.03.Liquidparaffin3.04.Treatment compositionof Example 39.05.Dicapricacidpolypropyleneglycol3.06.Alkyl/polyether co-modified organopolysiloxane (Note)1.07.Dimethylpolysiloxane (6mm²/s (25°C))15.58.Oil-treated titanium oxide10.09.PigmentSuitable amount10.Lecithin0.311.Monooleic acid polyoxyethylene sorbitan0.512.Dipropylene glycol8.013.Sodium citrate0.214.Purified waterRemainder(Note 1) Shin-Etsu Chemical Co., Ltd. KF-6026 (commercial name)(Manufacturing method)A: Components 1-7 were heated and mixed.B: Components 8-12 were mixed uniformly.C: Components 13-14 were mixed, B was added, mixed uniformly and heated.D: C was added to A and emulsified.
[0178] It was found that although this W/O compact foundationcontained a large amount of oil, it was not oily or tacky, spread lightly, had a clean feel, good skin contact andgood setting qualities. Example 24: Eye shadow
[0179] (Component)Weight (parts)1.Sericite40.02.Mica10.03.TalcRemainder4.Titanium oxide10.05.Particulate titanium oxide5.06.Magnesium stearate3.07.PigmentSuitable amount8.Octyl dodecanol3.09.Dimethylpolysiloxane (6mm²/s (25°C))4.010.Treatment composition of Example 26.011.AntisepticsSuitable amount12.PerfumeSuitable amount(Manufacturing method)A: Components 8-11 were heated and mixed.B: Components 1-7 were mixed, A was added and mixed uniformly.C: Component A was added to B.
[0180] The eye shadow thus obtained was not tacky, spreadlightly, had good skin contact, good setting qualities andsheen, and lasted well in cosmetics. Example 25: Powder eyebrow
[0181] (Component)Weight (parts)1.Vaseline2.5 2.Dimethylpolysiloxane (6mm²/s (25°C))1.53.Treatment composition of Example 40.54.Glyceryl trioctanoate4.05.Silicone-treated mica40.06.Silicone-treated talcRemainder7.Silicone-treated titanium oxide10.08.Silicone-treated.barium sulfate15.09.Silicone-treated pigmentSuitable amount10.Hybrid silicone composite powder (Note 1)1.511.Spherical polymethylsilsesquioxane (Note 2)fine particles 2.512.AntisepticSuitable amount13.PerfumeSuitable amount(Note 1) Shin-Etsu Chemical Co., Ltd.: KSP-100 (commercial name)(Note 2) Shin-EtsuChemical Co., Ltd. KMP-590 (commercial name)(Manufacturing method)A: Components 5-12 were mixed and homogenized.B: Components 1-4 were mixed uniformly, added to A, and the mixture homogenized.C: Component 13 was added to B, and the mixture pressed in a mold to obtain a powder eyebrow.
[0182] The eyebrow thus obtained was not tacky, spread lightly,had good skin contact, good setting qualities and sheen,and lasted well in cosmetics. Example 26: Hair cream
[0183] (Component)Weight (parts) 1.Treatment composition of Example 12.02.Dimethylpolysiloxane (6mm²/s (25°C))5.03.Decamethyl cyclopentasiloxane8.04.Stearyl trimethylammonium chloride1.55.Glycerol3.06.Propylene glycol5.07.Hydroxyethylcellulose0.28.AntisepticSuitable amount9.PerfumeSuitable amount10.Purified water75.3(Manufacturing method)A: Components 1-3 were heated and dissolved.B: Components 4-8 and 10 were uniformly mixed and dissolved.C: B was added to A, emulsified, cooled, and Component 9 was added.
[0184] The hair cream thus obtained spread easily, and left thehair very soft, smooth, manageable, moist and glossy. Example 27: Conditioning mousse
[0185] (Component)Weight (parts)1.Treatment composition of Example 60.52.Dimethylpolysiloxane (6mm²/s (25°C))2.03.Crosslinking type dimethylpolysiloxane (Note 1)0.54.Glyceryl trioctanoate1.55.Glycerol3.06.Stearyldimethyl benzylammonium chloride0.57.Polyoxyethylene-hardenedcastoroil0.58.Ethanol7.0 9.AntisepticSuitable amount10.PerfumeSuitable amount11.Purified waterRemainder12.Liquefied petroleum gas5.0(Note 1) Shin-Etsu Chemical Co., Ltd. KSG-16 (commercial name)(Manufacturing method)A: Components 1-4 were heated and dissolved.B: Components 5-9 and 11 were mixed uniformly and dissolved.C: B was added to A, emulsified, cooled, and Component 10 was added.D: An aerosol can was filled with C, and a conditioning mousse was obtained.The conditioning mousse thus obtained was moist, flexible, very smooth, not oily and left a good feeling. It also had good skin contact and setting qualities, and gave a matt finish. Example 28: Roll-on type antiperspirant
[0186] (Component)Weight (parts)1.Treatment composition of Example 125.02.Dimethylpolysiloxane(6mm²/s(25°C))10.03.Crosslinking type dimethylpolysiloxane (Note 1)15.04.Decamethyl cyclopentasiloxane30.05.Aluminiumzirconiumtetrachlorohydrate20.06.PerfumeSuitable amount(Note 1) Shin-Etsu Chemical Co., Ltd. KSG-15 (commercial name)(Manufacturing method) A: Components 1-4 were heated and mixed.B: Components 5 and 6 were added to A, and dispersed uniformly.
[0187] The roll-on antiperspirant thus obtained spreadlightly, was cool and fresh, not tacky or oily, showed nochange with temperature or time, was easy to use, and verystable. Example 29: W/O type antiperspirant
[0188] (Component)Weight (parts)1.Treatment composition of Example 29.02.Decamethyl cyclopentasiloxane7.03.Glyceryl trioctanoate8.04.1,3-butyleneglycol5.05.Sodium citrate0.26.Aluminium chlorohydrate20.07.PerfumeSuitable amount8.Purifiedwater50.8(Manufacturing method)A: Components 1-3 were heated and mixed.B: Components 4-5 and 8 were mixed, and Components 6 and 7 were added and dissolved. C: B was added to A, stirred and emulsified.
[0189] The W/O antiperspirant thus obtained spread lightly,was cool and fresh, not tacky or oily, showed no changewith temperature or time, was easy to use, and very stable. Example 30: W/O type UV cut cream
[0190] (Component)Weight (parts) 1.Silicone-treated zinc oxide20.02.Acrylate/dimethylpolysiloxane copolymer (Note 1)12.03.Decamethylcyclopentasiloxane20.04.Glyceryl trioctanoate3.05.Treatment composition of Example 87.06.Polyether-modified silicone (Note 2)1.07.Alkyl/polyetherco-modifiedsilicone (Note 3)1.08.Octyl methoxycinnamate6.09.Sodium citrate0.210.Dipropylene glycol3.011.AntisepticSuitable amount12.PerfumeSuitable amount13.Purified water26.8(Note 1) Shin-Etsu Chemical Co., Ltd. : KP-545 (commercial name)(Note 2) Shin-Etsu Chemical Co., Ltd.: KF-6017 (commercial name)(Note 3) Shin-Etsu Chemical Co., Ltd.: KF-6026 (commercial name)(Manufacturing method)A: Part of Component 3 and Components 4-8 were heated and mixed.B: Components 9-11 and 13 were mixed, added to A, stirred and emulsified.C: Components 1, 2 and the remainder of Component 3 were mixed and dispersed, Component 12 was added to B, and the mixture homogenized.
[0191] The W/O UV cut cream thus obtained spread lightly, was fresh, not tacky or oily, was transparent, lasted well incosmetics, showed no change with temperature or time, waseasy to use, and very stable. Example 31: W/O type UV cut milky lotion
[0192] (Component)Weight (parts)1.Dimethylpolysiloxane (6mm²/s (25°C))5.02.Glyceryl trioctanoate2.03.Treatment composition of Example 16.04.Polyether-modified silicone (Note 1)1.05.Titanium oxide/decamethyl cyclopentasiloxane dispersion (Note 2)30.06.Zinc oxide/decamethyl cyclopentasiloxane dispersion (Note 3)30.07.Dipropylene glycol3.08.Sodium citrate0.29.AntisepticSuitable amount10.PerfumeSuitable amount11.Purified water22.8(Note 1) Shin-Etsu Chemical Co., Ltd.: KF-6017 (commercial name)(Note 2) Shin-Etsu Chemical Co., Ltd. SPD-T1S (commercial name)(Note 3) Shin-Etsu Chemical Co., Ltd. : SPD-Z1 (commercial name)(Manufacturing method)A: Components 1-4 were heated and mixed.B: Components 7-9 and Component 11 were mixed and dissolved, added to A, stirred and emulsified. C: Components 5, 6 and 10 were added to B, and homogenized.
[0193] The UV cut milky lotion thus obtained was a W/O UV cutmilky lotion which spread lightly, was fresh, not tackyor oily, was transparent, lasted well in cosmetics, showedno change with temperature or time, was easy to use, andvery stable. Example 32: O/W type UV cut cream
[0194] (Component)Weight (parts)1.Crosslinking type organopolysiloxane (Note 1)5.02.Cetyl isooctanoate5.03.Treatment composition of Composition 41.04.Titanium oxide/decamethyl cyclopentasiloxane dispersion (Note 2)15.05.Polyether-modified silicone (Note 3)1.06.Polyether-modified silicone (Note 4)1.07.Acrylic acid amide mixture (Note 5)2.08.Propylene glycol5.09.Methylcellulose (2% aqueous solution) (Note 6)5.010.AntisepticSuitable amount11.PerfumeSuitable amount12.Purified water60.0(Note 1) Shin-Etsu Chemical Co., Ltd.: KSG-18 (commercial name)(Note 2) Shin-Etsu Chemical Co., Ltd.: SPD-T1S (commercial name)(Note 3) Shin-Etsu Chemical Co., Ltd.: KF-6027 (commercial name)(Note 4) Shin-Etsu Chemical Co., Ltd.: KF-6011 (commercial name)(Note 5) Seppic: Sepigel 305 (commercial name)(Note 6) Shin-Etsu Chemical Co., Ltd.: Metrose SM-4000 (commercial name)(Manufacturing method)A: Components 5-8, 10 and 12 were mixed.B: Components 1-3 were heated and mixed, added to A, stirred andemulsified.C: Component 4 was added to B, Components 9 and 10 were added, andhomogenized.
[0195] The UV cut cream thus obtained was a W/O UV cut creamwhich spread lightly, was fresh, not tacky or oily,transparent, lasted well in cosmetics, showed no changewith temperature or time, was easy to use, and very stable. Example 33: Nonaqueous emulsion
[0196] (Component)Weight (parts)1.Crosslinking type silicone resin/deca methyl cyclopentasiloxane (Note 1)30.02.Decamethyl cyclopentasiloxane15.03.Dimethylpolysiloxane (6mm²/s)7.04.Treatment composition of Example 13.05.Dimethyl distearyl ammonium hectorite2.06.Sodium chloride0.17.1,3-butylene glycol40.9(Note 1) Crosslinking type silicone resin/decamethyl cyclopentasiloxane:KSG15 (Shin-Etsu Chemical Co., Ltd.) (Manufacturing method)A: Components 1-5 were mixed uniformly.B: Components 6 and 7 were mixed.C: B was added to A and emulsified uniformly.
[0197] The nonaqueous emulsion thus obtained spread lightly,was not tacky or oily, left the skin feeling soft, and wasvery stable. Example 34: W/O/W type cream
[0198] (Component)Weight (parts)1.Cetyl isooctanoate5.02.Treatment composition of Example 56.03.Decamethyl cyclopentasiloxane5.04.Dioleic acid methyl glucose1.55.Isohexadecane3.56.Magnesium sulfate0.57.Propylene glycol5.08.Purifiedwater39.59.Cetyl alcohol1.010.PEG-10 soya sterol2.011.AntisepticSuitable amount12.PerfumeSuitable amount13.Purified water31.0(Manufacturing method)A: Components 6-8 were mixed.B: Components 1-5 were mixed, added to A, stirred and emulsified.C: Components 9-11 and 13 were mixed, B was added with stirring, andemulsified.D: Component 12 was added to C, and homogenized.
[0199] The W/O/W cream thus obtained spread lightly, left aclean feeling, was not tacky or oily, was transparent,lasted well in cosmetics, showed no change with temperatureor time, was easy to use and very stable. Example 35: O/W/O type milky lotion
[0200] (Component)Weight (parts)1.Glyceryl trioctanoate15.02.Treatment composition of Example 78 : 03.Cane sugar monostearate3.04.Glycerol5.05.1, 3-butylene glycol5.06.AntisepticSuitable amount7.Purifiedwater60.08.Macadamia nut oil2.09.Cetyl alcohol2.010.PerfumeSuitable amount(Note 1) Shin-Etsu Chemical Co., Ltd.: KSG-21 (commercial name)(Manufacturing method)A: Components 1-2 were mixed uniformly.B: Components 3-7 were heated and mixed, and homogenized.C: Components 8-10 were heated and mixed.D: B was stirred, C was added and emulsified, and cooled.D: A was stirred, and D was added and emulsified.
[0201] The O/W/O cream thus obtained spread lightly, left a clean feeling, was not tacky or oily, was transparent,lasted well in cosmetics, showed no change with temperatureor time, was easy to use and very stable. Example 36: O/W/O type facial liquid foundation
[0202] (Component)Weight (parts)1.Treatment composition of Example 57.02.Decanoic acid propylene glycol5.03.Isopropyl myristate5.04.Pigment10.05.Egg yolk-derived hydrogenated phospholipid1.06.Glycerol2.07.1,3-butyleneglycol10.08.AntisepticSuitable amount9.Purifiedwater52.010.Squalane3.011.Cetyl alcohol5.012.PerfumeSuitable amount(Manufacturing method)A: Components 1-3 were mixed uniformly.B: Components 4-9 were heated and mixed.C: Components 10-12 were heated and mixed.D: B was stirred, C was added, emulsified, and cooled.D: A was stirred, D 'was added, and emulsified,.
[0203] The O/W/O liquid foundation thus obtained spreadlightly, left a clean feeling, was not tacky or oily, wastransparent, lasted well in cosmetics, showed no changewith temperature or time, was easy to use and very stable. Industrial Field of Application
[0204] The cosmetic material formed by blending the hydrophilicorganic group-containing crosslinking typeorganopolysiloxane polymer purified according to thisinvention and an oil, is not tacky or heavy when it isapplied, feels soft, spreads lightly, and leaves the skinfeeling clean and smooth. When it is applied, it impartsflexibility, smoothness and an emollient effect withoutlosing moisture by evaporation. It imparts a natural sheenor matte finish, is very easy to use, and has good stabilityover time. Moreover, according to this invention, acosmetic material which has good storage stability and canprevent unpleasant odors can be provided, therefore thisinvention has considerably wide industrial application.

权利要求:
Claims (36)
[1] A pasty composition obtained by adding at least oneacidic substance selected from a group comprising organicacids, phosphoric acid and phosphates to a mixturecomprising a crosslinking type organopolysiloxane polymerhaving a polyoxyalkylene group and a liquid oil, addinga basic neutralizing agent to adjust the pH to 5-8, andremoving volatile components by heating and/ordecompression, wherein the propionaldehyde amountproduced by adding an identical amount of water to thiscomposition and heating at 60°C for 24 hours is 100 ppmor less.
[2] The pasty composition according to Claim 1, whereinafter adding an identical amount of water to the compositionand heating to 70°C for one hour, the pH of the extractedwater is 6.0 or less.
[3] The pasty composition according to Claim 1, whereinsaid acidic substance is at least one moiety selected fromamong citric acid, lactic acid, maleic acid, glutamic acid,tartaric acid, acetic acid, glycine, succinic acid andsodium dihydrogen phosphate, and said basic neutralizeris at least one moiety selected from among sodium carbonate,sodium hydrogen carbonate, sodium hydroxide, potassiumhydroxide, disodium hydrogen phosphate and sodium acetate.
[4] The pasty composition according to Claim 1, whereinthe proportions of said acidic substance and basic neutralizer are respectively 0.01-10 wt parts relative to100 wt parts of said crosslinking type organopolysiloxanepolymer, said composition is heated to 20-150°C afteradding said acidic substance, and it is heated to 20-150°Cafter adding said basic neutralizer.
[5] The pasty composition according to Claim 1, whereinsaid crosslinking type organopolysiloxane polymer isformed by an addition polymerization of at least one moietyselected from a group comprising organohydrogenpolysiloxanes expressed by the following general formula(AI) and the following general formula (A2), and at leastone moiety selected from a group comprising unsaturatedcompounds expressed by the following general formula (B1),(B2) or (B3), said polymer is insoluble in organic solvents,and can swell by containing at least its own weight ofdecamethyl cyclopentasiloxane.R¹ _aR² _bH_cSiO_(4-a-b-c)/2 R¹ _dH_eSiO_(4-d-e)/2 C_fH_2f-1O (C_gH_2gO) _hC_fH_2f-1
[6] The pasty composition according to Claim 5, whereinsaid crosslinking type organopolysiloxane polymer is apolymer comprising the organohydrogen polysiloxane (A2) and polyoxyalkylene (B1).
[7] The pasty composition according to Claim 1, wherein saidliquid oil is at least one moiety selected from amongsilicone oil, hydrocarbon oil, ester oil, naturalanimal/vegetable oil and semi-synthetic oil.
[8] A cosmetics formed by blending the paste-likecomposition according to Claim 1.
[9] The cosmetics according to Claim 8, further comprisingwater as Component C).
[10] The cosmetics according to Claim 8, containing acompound having an alcoholic hydroxyl group in themolecular structure as Component D).
[11] The cosmetics according to Claim 8, containing awater-soluble or water-swelling polymer as Component E).
[12] The cosmetics according to Claim 8, containing a powderand/or colorant as Component F).
[13] The cosmetics according to Claim 12, wherein at leastpart of F), the powder and/or colorant, is a crosslinkingtype spherical silicone fine powder having a structurewherein dimethylpolysiloxane is crosslinked, across linking type spherical polymethylsilsesquioxane finepowder, or a fine powder formed by coating a crosslinked spherical silicone rubber surface withpolymethylsilsesquioxane particles.
[14] The cosmetics according to Claim 8, further containinga surfactant as Component G).
[15] The cosmetics according to Claim 14, wherein saidsurfactant G) is a straight-chain or branchedorganopolysiloxane having a polyoxyalkylene chain in themolecule.
[16] The cosmetics according to Claim 14, wherein the HLBof said surfactant G) is 2-8.
[17] The cosmetics.according to Claim 8, containing acomposition comprising a crosslinking typeorganopolysiloxane polymer without hydrophilicity and aliquid oil as Component H).
[18] The cosmetics according to Claim 8, containing asilicone resin as Component I).
[19] The cosmetics according to Claim 18, wherein saidsilicone resin I) is an acrylic silicone resin.
[20] The cosmetics according to Claim 18, wherein saidsilicone resin I) is an acrylic silicone resin containingat least one anionic organic group selected from among apyrrolidone group, long-chain alkyl group, polyoxyalkylene group, fluoroalkyl group and carboxylgroup.
[21] The cosmetics according to Claim 18, wherein saidComponent I) is at least one silicone resin selected fromamong resins comprising a R¹ ₃SiO_0.5 unit and SiO₂ unit, resinscomprising a R¹ ₃SiO_0.5 unit, R¹ ₂SiO unit and SiO₂ unit, resinscomprising a R¹ ₃SiO_0.5 unit and R¹SiO_1.5 unit, resinscomprising a R¹ ₃SiO_0.5 unit, R¹ ₂SiO unit and R¹SiO_1.5 unit,and resins comprising a R¹ ₃SiO_0.5 unit, R¹ ₂SiO unit, R¹SiO_1.5unit and SiO₂ unit.
[22] The cosmetics according to Claim 18, wherein saidComponent I) is a silicone resin containing at least oneanionic organic group selected from among a pyrrolidonegroup, long-chain alkyl group, polyoxyalkylene group,fluoroalkyl group and carboxyl group.
[23] A skin care cosmetics containing the cosmetic materialaccording to Claim 8.
[24] A makeup cosmetics containing the cosmetic materialaccording to Claim 8.
[25] A hair care cosmetics containing the cosmetic materialaccording to Claim 8.
[26] An antiperspirant cosmetics containing the cosmeticmaterial according to Claim 8.
[27] An ultraviolet cut cosmetics containing the cosmeticmaterial according to Claim 8.
[28] A cosmetics containing the cosmetic materialaccording to Claim 8, which is in the form of a liquid,emulsion, cream, solid, paste, gel, powder, multi layer,laminate, mousse, spray or stick.
[29] A method for manufacturing a pasty compositionobtained by adding at least one acidic substance selectedfrom a group comprising organic acids, phosphoric acid andphosphates to a mixture comprising a crosslinking typeorganopolysiloxane polymer having a polyoxyalkylene groupand a liquid oil, adding a basic neutralizing agent to adjustthe pH to 5-8, and removing volatile components by heatingand/or decompression, wherein the propionaldehyde amountproduced by adding an identical amount of water to thiscomposition and heating at 60°C for 24 hours is 100 ppmor less.
[30] The method of manufacturing the pasty compositionaccording to Claim 29, wherein the salt produced by saidacidic substance and said basic neutralizer has a buffereffect.
[31] The method of manufacturing the pasty compositionaccording to Claim 1, wherein said acidic substance is atleast one moiety selected from among citric acid, lactic acid, maleic acid, glutamic acid, tartaric acid, aceticacid, glycine, succinic acid and sodium dihydrogenphosphate, and said basic neutralizer is at least one moietyselected from among sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide,disodium hydrogen phosphate and sodium acetate.
[32] The method of manufacturing the pasty compositionaccording to Claim 29, wherein the proportions of saidacidic substance and basic neutralizer are respectively0.01-10 wt parts relative to 100 wt parts of saidcrosslinking type organopolysiloxane polymer, heating isperformed to 20-150°C after adding said acidic substance,andheating is performed to 20-150°C after adding said basicneutralizer.
[33] The method of manufacturing the pasty compositionaccording to Claim 29, wherein said crosslinking typeorganopolysiloxane polymer is formed by an additionpolymerization of at least one moiety selected from a groupcomprising organohydrogen polysiloxanes expressed by thefollowing general formula (AI) and the following generalformula (A2), and at least one moiety selected from a groupcomprising unsaturated compounds expressed by thefollowing general formula (B1), (B2) or (B3), said polymeris insoluble in organic solvents, and can swell bycontaining at least its own weight of decamethylcyclopentasiloxane. R¹ _aR² _bH_cSiO_(4-a-b-c)/2 R¹ _dH_eSiO_(4-d-e)/2 C_fH_2f-1O (C_gH_2gO) _hC_fH_2f-1
[34] The method of manufacturing the pasty compositionaccording to Claim 29, wherein said crosslinking typeorganopolysiloxane polymer is formed by an additionpolymerization of an organohydrogen polysiloxaneexpressed by the following general formula (AI) and anunsaturated compound expressed by the following generalformula (B4) and/or (B5), not containing unreactedpolyether wherein the double bond of the terminal allylgroup has migrated as an impurity, said polymer is insolublein organic solvents, and can swell by containing at leastits own weight of decamethyl cyclopentasiloxane.(A1):   R¹ _aR² _bH_cSiO_(4-a-b-c)/2    wherein, in these formulae, R¹ are monofunctionalhydrocarbon groups which may be respectively identical ordifferent, may be substituted or unsubstituted, have 1-30carbon atoms and do not contain an alkenyl group, R² areorganic groups which may identical or different, and areexpressed by the general formula -C_fH_2fO(C_gH_2gO) hR⁶, R⁶ isa hydrogen atom, or a monofunctional hydrocarbon group notcontaining an aliphatic unsaturated group which may or maynot be substituted, or an acetyl group, and a, b, c arerespectively 1.0≤a≤2.3, 0.001≤b≤1.0, 0.001≤c≤1.0, and a+b+c≤2.6.(B4) :   R¹ _jR⁵ _kSiO_(4-j-k)/2)    wherein, in this formula, R¹ is identical to R¹ of (A1),R⁵ is a monofunctional hydrocarbon having 2-10 carbon atomswith a terminal vinyl group, and j, k are integers satisfying1.0≤j≤2.3, 0.001≤k≤1.0.(B5) :   C_mH_2m-1 (CH₂) yC_mH_2m-1    wherein, m is an integer from 2-6, and y is an integerequal to or larger than 1.
[35] The method of manufacturing the pasty compositionaccording to Claim 34, wherein the unsaturated compoundexpressed by (A1) is synthesized by first performing a fulladdition of the polyoxyethylene monoallyl ether to thefollowing component (A2), treating the remaining unreactedpolyether to form an intermediate from which unsaturatedgroups have been removed, and then introducing a Si-H sourceby an equilibrization reaction.(A2) :   R¹ _dH_eSiO_(4-d-e)/2    wherein, R¹ is identical to that of (A1), and d, e areintegers satisfying 1.0≤d≤2.3, 0.001≤e≤1, 1.5≤d+e≤2.6.
[36] The method of manufacturing the pasty compositionaccording to Claim 34, wherein the unsaturated compoundexpressed by (A1) is synthesized by first performing apartial addition of the polyoxyethylene monoallyl etherto the following component (A2), and treating the remainingunreacted polyether.(A2) :   R¹ _dH_eSiO_{(4-d-e) /2}    wherein, R¹ is identical to that of (A1), and d, e areintegers satisfying 1.0≤d≤2.3, 0.001≤e≤1, 1.5≤d+e≤2.6.

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同族专利:

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公开号 | 公开日

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JP3969728B2|2007-09-05|

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JPWO2003020828A1|2004-12-16|

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KR100898453B1|2009-05-21|

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US20040253197A1|2004-12-16|

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KR20040029466A|2004-04-06|

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DE60211532T2|2007-05-10|

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WO2003020828A1|2003-03-13|

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EP1424365A9|2004-12-15|

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DE60211532D1|2006-06-22|

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KR100898444B1|2009-05-21|

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KR20090029313A|2009-03-20|

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EP1424365A4|2004-10-13|

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US8828410B2|2014-09-09|

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EP1424365B1|2006-05-17|

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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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JP2001267608||2001-09-04||

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JP2001267608||2001-09-04||

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PCT/JP2002/008955|WO2003020828A1|2001-09-04|2002-09-03|Pasty composition and cosmetics containing the same|

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