JP2000234042A - Copolymer-containing composition for surface modification - Google Patents
Copolymer-containing composition for surface modificationInfo
- Publication number
- JP2000234042A JP2000234042A JP11289352A JP28935299A JP2000234042A JP 2000234042 A JP2000234042 A JP 2000234042A JP 11289352 A JP11289352 A JP 11289352A JP 28935299 A JP28935299 A JP 28935299A JP 2000234042 A JP2000234042 A JP 2000234042A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- weight
- general formula
- group
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 86
- 229920001577 copolymer Polymers 0.000 title abstract description 19
- 230000004048 modification Effects 0.000 title 1
- 238000012986 modification Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000002537 cosmetic Substances 0.000 claims abstract description 39
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 25
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 11
- 125000002252 acyl group Chemical group 0.000 claims abstract description 8
- 239000000835 fiber Substances 0.000 claims abstract description 8
- 238000004381 surface treatment Methods 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 125000004423 acyloxy group Chemical group 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 96
- 150000001875 compounds Chemical class 0.000 claims description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 239000004014 plasticizer Substances 0.000 claims description 15
- 239000000470 constituent Substances 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000003699 hair surface Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- 238000000576 coating method Methods 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 12
- 239000008365 aqueous carrier Substances 0.000 abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract 3
- 239000001257 hydrogen Substances 0.000 abstract 3
- 239000012530 fluid Substances 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 66
- -1 phthalate ester Chemical class 0.000 description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 238000003756 stirring Methods 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 230000000694 effects Effects 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 19
- 210000003491 skin Anatomy 0.000 description 19
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 17
- 238000009472 formulation Methods 0.000 description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- 239000012046 mixed solvent Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 11
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 235000011187 glycerol Nutrition 0.000 description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 10
- 239000003973 paint Substances 0.000 description 9
- 239000006071 cream Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 229920006254 polymer film Polymers 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 7
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000006210 lotion Substances 0.000 description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 229940048053 acrylate Drugs 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 229940057995 liquid paraffin Drugs 0.000 description 4
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 4
- 239000004200 microcrystalline wax Substances 0.000 description 4
- 235000019808 microcrystalline wax Nutrition 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 3
- VHJHZYSXJKREEE-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropyl prop-2-enoate Chemical compound FC(F)C(F)(F)COC(=O)C=C VHJHZYSXJKREEE-UHFFFAOYSA-N 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KJYGRYJZFWOECQ-UHFFFAOYSA-N [2-hydroxy-3-[2-hydroxy-3-[2-hydroxy-3-(16-methylheptadecanoyloxy)propoxy]propoxy]propyl] 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OCC(O)COCC(O)COCC(O)COC(=O)CCCCCCCCCCCCCCC(C)C KJYGRYJZFWOECQ-UHFFFAOYSA-N 0.000 description 3
- 230000000843 anti-fungal effect Effects 0.000 description 3
- 239000004203 carnauba wax Substances 0.000 description 3
- 235000013869 carnauba wax Nutrition 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000003676 hair preparation Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003431 steroids Chemical class 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940067596 butylparaben Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000003766 combability Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 2
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 2
- 229960002216 methylparaben Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000004006 olive oil Substances 0.000 description 2
- 235000008390 olive oil Nutrition 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000008194 pharmaceutical composition Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- GHBFNMLVSPCDGN-UHFFFAOYSA-N rac-1-monooctanoylglycerol Chemical compound CCCCCCCC(=O)OCC(O)CO GHBFNMLVSPCDGN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- JPPRXACMNPYJNK-UHFFFAOYSA-N 1-docosoxydocosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCCCCCC JPPRXACMNPYJNK-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- ZNJXRXXJPIFFAO-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoropentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)F ZNJXRXXJPIFFAO-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010012438 Dermatitis atopic Diseases 0.000 description 1
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- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 231100000507 endocrine disrupting Toxicity 0.000 description 1
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- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007951 isotonicity adjuster Substances 0.000 description 1
- 229940119170 jojoba wax Drugs 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000002811 oleoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- OIGNJSKKLXVSLS-VWUMJDOOSA-N prednisolone Chemical compound O=C1C=C[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OIGNJSKKLXVSLS-VWUMJDOOSA-N 0.000 description 1
- 229960005205 prednisolone Drugs 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 229940010747 sodium hyaluronate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 210000000434 stratum corneum Anatomy 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000009495 sugar coating Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229960002722 terbinafine Drugs 0.000 description 1
- DOMXUEMWDBAQBQ-WEVVVXLNSA-N terbinafine Chemical compound C1=CC=C2C(CN(C\C=C\C#CC(C)(C)C)C)=CC=CC2=C1 DOMXUEMWDBAQBQ-WEVVVXLNSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000015961 tonic Nutrition 0.000 description 1
- 230000001256 tonic effect Effects 0.000 description 1
- 229960000716 tonics Drugs 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Medicinal Preparation (AREA)
- Cosmetics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、表面処理などに好
適な、水に対する溶解度を改善された、フタル酸エステ
ルなどの可塑剤を必要としない、可塑性を有する高分子
を含有する、化粧料などの組成物に関する。TECHNICAL FIELD The present invention relates to cosmetics and the like, which are suitable for surface treatment and the like, have improved solubility in water, do not require a plasticizer such as a phthalate ester, and contain a polymer having plasticity. The composition of
【０００２】[0002]
【従来の技術】様々な材料を加工する上で、その表面を
処理することは、各部材の材質保持のために重要な要素
となっている。この為、建設材料に於いては、各種ワニ
ス類やペイントなどが開発されてきたし、保水性の被膜
を形成する化粧料もこの様な観点に立てば一種の表面処
理剤と認識できる。この様な表面処理で通常使用される
材料としては、通常高分子が多く、しかも非水溶性のも
のが多い。これは、被膜によって、多くの場合水性成分
との遮断が意図されるからである。この為、この様な処
理に際しては、通常高分子は水性担体等に分散させて用
いたり、有機溶剤などに溶解させて用いていた。しかし
ながら、水性担体への分散などに於いては凝集などによ
り組成物の使用性が著しく低下することがあり、有機溶
剤系では、有機溶剤の使用そのものが制限を受けている
という問題があった。特に、皮膚、毛髪、爪を対象とす
る化粧料の分野に於いては水性担体を使用して塗布でき
ることは必須の条件であった。即ち、水性担体中で一様
に溶解していて、塗布後は優れた耐水性のある被膜を形
成する、高分子の登場が望まれていた。更に、従来の高
分子は被膜特性としては硬い膜であるため、可塑剤を必
要としていたが、この様な可塑剤の中にはフタル酸エス
テルのように、内分泌物質撹乱物質の作用が疑われるも
のがあった。可塑性を有し、この様な可塑剤を使用しな
くても良い高分子の開発のニーズも近年高まってきてい
る。2. Description of the Related Art In processing various materials, surface treatment is an important factor for maintaining the material of each member. For this reason, various varnishes, paints, and the like have been developed as construction materials, and cosmetics that form a water-retaining film can be recognized as a kind of surface treatment agent from such a viewpoint. As materials usually used in such surface treatment, there are usually many polymers and many water-insoluble materials. This is because the coating is often intended to block off aqueous components. Therefore, in such a treatment, the polymer is usually used by dispersing it in an aqueous carrier or the like, or by dissolving it in an organic solvent or the like. However, in the case of dispersion in an aqueous carrier or the like, the usability of the composition may be significantly reduced due to agglomeration or the like, and the organic solvent system has a problem that the use of the organic solvent itself is restricted. In particular, in the field of cosmetics for the skin, hair, and nails, it was an essential condition to be able to apply using an aqueous carrier. That is, there has been a demand for a polymer which is uniformly dissolved in an aqueous carrier and forms a film having excellent water resistance after coating. Furthermore, conventional polymers require a plasticizer because of their hard film properties, but some of these plasticizers are suspected of acting as endocrine disruptors, such as phthalates. There was something. In recent years, the need for the development of polymers having plasticity and not requiring the use of such plasticizers has been increasing in recent years.
【０００３】一方、後記一般式（Ｉ）に表される化合物
も、後記一般式（ＩＩ）に表される化合物も既に文献公
知の化合物であり、高分子製造用のモノマーとして市販
されているが、これらを組み合わせて、水性担体に溶解
して、塗布後は耐水性と可塑性に優れる被膜を形成する
高分子をつくることは全く行われていなかった。又、一
般式（Ｉ）に表される化合物と一般式（ＩＩ）に表され
る化合物とを構成モノマーとして含有する水溶性と可塑
性を有する高分子も全く知られていなかった。従って、
これらの高分子を含有する化粧料やペイントなどの組成
物も、該組成物が表面処理に適していることも全く知ら
れていなかった。On the other hand, the compound represented by the following general formula (I) and the compound represented by the following general formula (II) are already known in the literature, and are commercially available as monomers for producing polymers. These have not been combined to form a polymer that forms a film having excellent water resistance and plasticity after application by dissolving in an aqueous carrier. Further, a water-soluble and plastic polymer containing the compound represented by the general formula (I) and the compound represented by the general formula (II) as constituent monomers has not been known at all. Therefore,
Compositions containing these polymers, such as cosmetics and paints, have never been known to be suitable for surface treatment.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、化粧料や塗
料、繊維処理剤として有用な、水性担体中で一様に溶解
していて、塗布後は優れた耐水性と可塑性のある被膜を
形成する高分子を含有する、表面処理などに好適な化粧
料などの組成物を提供することを課題とする。DISCLOSURE OF THE INVENTION The present invention provides a coating film having excellent water resistance and plasticity after application, which is useful as a cosmetic, paint, or fiber treatment agent and is uniformly dissolved in an aqueous carrier. An object of the present invention is to provide a composition such as a cosmetic suitable for surface treatment or the like, which contains a polymer to be formed.
【０００５】[0005]
【課題の解決手段】この様な状況に鑑みて、本発明者ら
は、化粧料や塗料、繊維処理剤として有用な、水性担体
中で一様に溶解していて、塗布後は優れた耐水性のある
被膜を形成する、高分子を求めて鋭意研究努力を重ねた
結果、一般式（Ｉ）に表されるモノマーから選ばれる１
種乃至は２種以上、好ましくは一般式（ＩＩＩ）に表さ
れる化合物と一般式（ＩＩ）に表されるモノマーから選
ばれる１種乃至は２種以上、好ましくは一般式（ＩＶ）
に表される化合物とを構成モノマーとして含有する高分
子にその様な特質があることを見出し、これを化粧料な
どの組成物に含有させることにより、被膜形成に好適な
化粧料が提供しうることを見出し発明を完成させた。例
えば、この様な組成物の内、基礎化粧料に於いては、優
れた保護被膜形成作用を有し、毛髪用化粧料では毛髪に
於いては、優れたトリートメント効果を有し、ファンデ
ーションにおいては化粧くずれしにくい特性を有し、マ
ニキュア等に配合すると水性担体中で一様に溶解してい
て、塗布後は優れた耐水性のある被膜を形成する。以
下、実施の形態を中心に、本発明について詳細に説明を
加える。In view of such circumstances, the present inventors have found that the present inventors have found that water-soluble carriers, which are useful as cosmetics, paints and fiber treatment agents, are uniformly dissolved and have excellent water resistance after application. As a result of diligent research efforts for a polymer that forms a functional film, 1 is selected from monomers represented by the general formula (I).
One or more kinds, preferably one or more kinds selected from the compound represented by the general formula (III) and the monomer represented by the general formula (II), preferably the general formula (IV)
It has been found that a polymer containing the compound represented by the formula (1) as a constituent monomer has such characteristics, and by including this in a composition such as a cosmetic, a cosmetic suitable for forming a film can be provided. This led to the completion of the invention. For example, among such compositions, basic cosmetics have an excellent protective film forming action, hair cosmetics have an excellent treatment effect on hair, and foundations have an excellent treatment effect. It has properties that make it hard to lose makeup, and when it is mixed with nail polish, it is uniformly dissolved in an aqueous carrier, and after coating, it forms a film with excellent water resistance. Hereinafter, the present invention will be described in detail focusing on embodiments.
【０００６】[0006]
【化５】 一般式（Ｉ） （但し、式中Ｒ１は水素原子又は炭素数１〜４のアルキ
ル基を表し、Ｒ２はフッ素原子を有していても良い炭素
数１〜２０のアルキル基を表す。）Embedded image General formula (I) (wherein, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 represents an alkyl group having 1 to 20 carbon atoms which may have a fluorine atom.)
【０００７】[0007]
【化６】 一般式（ＩＩ） （但し、式中Ｒ３は水素原子又は炭素数１〜４のアルキ
ル基を表し、Ｒ４はアルキルオキシ基、アシロキシ基又
は水酸基を有していても良い、炭素数２〜４のアルキル
基を表し、Ｒ５は水素原子、芳香族乃至は脂肪族の炭素
数１〜８の炭化水素基又はアシル基を表し、ｎは１〜４
０の数値を表す。）Embedded image Formula (II) (wherein, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 may have an alkyloxy group, an acyloxy group, or a hydroxyl group, and has 2 to 4 carbon atoms. R5 represents a hydrogen atom, an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or an acyl group, and n represents 1 to 4
Represents a numerical value of 0. )
【０００８】[0008]
【化７】 一般式（ＩＩＩ） （但し、式中Ｒ６は水素原子又は炭素数１〜４のアルキ
ル基を表し、Ｏ、Ｐはそれぞれ独立に１〜１０の数値を
表し、Ｒ７はフッ素原子又は水素原子を表す。）Embedded image General formula (III) (wherein, R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, O and P each independently represent a numerical value of 1 to 10, and R7 represents a fluorine atom or a hydrogen atom. .)
【０００９】[0009]
【化８】 一般式（ＩＶ） （但し、式中Ｒ８は水素原子又は炭素数１〜４のアルキ
ル基を表し、Ｒ９は炭素数１〜８の芳香族乃至は脂肪族
の炭化水素基又は水素原子を表し、Ｑは５〜３０の数値
を表す。）Embedded image General formula (IV) (wherein, R8 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R9 represents an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or a hydrogen atom, Q represents a numerical value of 5 to 30.)
【００１０】[0010]
【発明の実施の形態】（１）本発明の高分子に使用され
る一般式（Ｉ）に表される化合物 本発明の高分子は、一般式（Ｉ）に表される化合物から
選ばれる１種乃至は２種以上を構成モノマーとして含有
する。一般式（Ｉ）において、Ｒ１は水素原子又は炭素
数１〜４のアルキル基を表し、Ｒ２はフッ素原子を有し
ていても良い炭素数１〜２０のアルキル基を表す。Ｒ１
としては、水素原子又はメチル基であることが特に好ま
しい。これは、高分子などで汎用されているアクリル酸
或いはメタクリル酸の構造であり、安全性などが多くの
ものについて既に確認されているし、原料として、市販
品も多く入手がた易いためである。又、Ｒ２としては、
フッ素原子を含有することが好ましく、しかも炭素との
結合以外はフッ素原子で置換されている構造のメチレン
基を部分構造として含むものが特に好ましい。これは、
本発明の高分子に於いて、このＲ２の部分構造によっ
て、塗布後の被膜の耐水性を具現するからである。フッ
素原子を含まない場合では、それに代わる耐水性の具現
が必要であり、長鎖で分岐或いは環状構造を有するアル
キル基であることが必要である。ここで言う長鎖とは、
炭素数が１２以上のものを言う。これらの内でも一般式
（ＩＩＩ）に示される化合物を、一般式（Ｉ）から選ば
れる１種乃至は２種以上として含有することが好まし
い。この様な一般式（Ｉ）のＲ２に表されるアルキル基
として好ましいものを具体的に例示するならば、２，
２，２−トリフルオロエチル基、２，２，３，３，４．
４，５，５−オクタフルオロペンチル基、３．３，４，
４，５，５，６，６，７，７，８，８，９，９，１０，
１０，１０−ヘプタデカフルオロデカニル基、２，２，
２，２’，２’，２’−ヘキサフルオロイソプロピル
基、２，２，３，３−テトラフルオロプロピル基、イソ
パルミチル基、イソステアリル基、３−シクロヘキシル
ペンチル基等が例示できる。これらの内特に好ましいも
のは、２，２，３，３，４．４，５，５−オクタフルオ
ロペンチル基と３．３，４，４，５，５，６，６，７，
７，８，８，９，９，１０，１０，１０−ヘプタデカフ
ルオロデカニル基である。中でも、３．３，４，４，
５，５，６，６，７，７，８，８，９，９，１０，１
０，１０−ヘプタデカフルオロデカニル基が特に好まし
い。これは、溶液に於いては水溶性を示し、皮膜として
は疎水性を示すためには、分子内に疎水性の大きい基を
必要最小限度に導入することが好ましいためである。こ
の様な、本発明の高分子の構成モノマーである、一般式
（Ｉ）に表される化合物は、アクリル酸乃至はメタクリ
ル酸の酸クロリドと対応するアルカリ金属のアルコラー
トとを反応させることにより高収率で得ることが出来
る。又、更には対応するアルコールを塩化チオニルやオ
キシ塩化リン等で処理し、クロリドと為し、アクリル酸
ナトリウムやメタクリル酸ナトリウムと反応させても得
ることが出来る。既にこの様な化合物の市販品も多数あ
るので、この様な市販品を利用することもできる。本発
明の高分子に於いて、一般式（Ｉ）に表される化合物の
構成モノマーとしての含有量は、総量で５〜９．９重量
％、更に好ましくは、７〜９．５重量％１分子中に含有
するのが好ましい。これは、この部分に高分子の耐水性
が起因しているため、一般式（Ｉ）の化合物に起因する
部分が少なすぎると、高分子の被膜としての耐水性が低
下してしまうためである。又、多すぎると水への溶解性
が阻害されてしまうことがある。BEST MODE FOR CARRYING OUT THE INVENTION (1) The compound represented by the general formula (I) used in the polymer of the present invention The polymer of the present invention is a compound selected from the compounds represented by the general formula (I) One or more species are contained as constituent monomers. In the general formula (I), R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 represents an alkyl group having 1 to 20 carbon atoms which may have a fluorine atom. R1
Is particularly preferably a hydrogen atom or a methyl group. This is the structure of acrylic acid or methacrylic acid, which is widely used in polymers and the like, because many things such as safety have already been confirmed, and many commercial products are easily available as raw materials. . Also, as R2,
It preferably contains a fluorine atom, and particularly preferably contains, as a partial structure, a methylene group having a structure substituted with a fluorine atom except for a bond to carbon. this is,
This is because, in the polymer of the present invention, the partial structure of R2 realizes the water resistance of the coating film after application. In the case where a fluorine atom is not contained, it is necessary to embody water resistance instead, and it is necessary that the alkyl group has a long-chain, branched or cyclic structure. The long chain here means
A compound having 12 or more carbon atoms. Among these, it is preferable that the compound represented by the general formula (III) is contained as one kind or two or more kinds selected from the general formula (I). Specific examples of preferred alkyl groups represented by R2 in the general formula (I) include 2,2.
2,2-trifluoroethyl group, 2,2,3,3,4.
4,5,5-octafluoropentyl group, 3.3,4,
4,5,5,6,6,7,7,8,8,9,9,10,
10,10-heptadecafluorodecanyl group, 2,2,
Examples thereof include a 2,2 ′, 2 ′, 2′-hexafluoroisopropyl group, a 2,2,3,3-tetrafluoropropyl group, an isopalmityl group, an isostearyl group, and a 3-cyclohexylpentyl group. Of these, particularly preferred are 2,2,3,3,4.4,5,5-octafluoropentyl and 3.3,4,4,5,5,6,6,7,
7,8,8,9,9,10,10,10-heptadecafluorodecanyl group. Among them, 3.3, 4, 4,
5,5,6,6,7,7,8,8,9,9,10,1
A 0,10-heptadecafluorodecanyl group is particularly preferred. This is because, in order to exhibit water solubility in a solution and hydrophobicity as a film, it is preferable to introduce a group having high hydrophobicity into the molecule to a minimum necessary. Such a compound represented by the general formula (I), which is a constituent monomer of the polymer of the present invention, is obtained by reacting an acid chloride of acrylic acid or methacrylic acid with a corresponding alkali metal alcoholate. It can be obtained in yield. Further, it can also be obtained by treating the corresponding alcohol with thionyl chloride, phosphorus oxychloride or the like, converting it to chloride, and reacting it with sodium acrylate or sodium methacrylate. Since there are already many commercially available products of such compounds, such commercially available products can also be used. In the polymer of the present invention, the content of the compound represented by the general formula (I) as a constituent monomer is 5 to 9.9% by weight in total, more preferably 7 to 9.5% by weight. It is preferably contained in the molecule. This is because the water resistance of the polymer is caused by this portion, and if the portion caused by the compound of the general formula (I) is too small, the water resistance of the polymer film is reduced. . If the amount is too large, the solubility in water may be impaired.
【００１１】（２）本発明の高分子に使用される一般式
（ＩＩ）に表される化合物 本発明の高分子は、一般式（ＩＩ）に表される化合物を
構成モノマーとして含有することを特徴とする。 ここ
で、式中Ｒ３は水素原子又は炭素数１〜４のアルキル基
を表し、Ｒ４はアルキルオキシ基、アシロキシ基又は水
酸基を有していても良い、炭素数２〜４のアルキル基を
表し、Ｒ５は水素原子、芳香族乃至は脂肪族の炭素数１
〜８の炭化水素基又はアシル基を表し、ｎは１〜４０の
数値を表す。Ｒ３としては、水素原子又はメチル基であ
ることが特に好ましい。これは、高分子などで汎用され
ているアクリル酸或いはメタクリル酸の構造であり、安
全性などが多くのものについて既に確認されているし、
原料として、市販品も多く入手がた易いためである。Ｒ
４はポリオキシエチレン基、ポリオキシプロピレン基、
ポリオキシブテン基、ポリオキシ（ヒドロキシプロピレ
ン）基、その１部又は全部のアシル化物、アルキルエー
テル等が例示できる。アシル基としてはアセチル基、ベ
ンゾイル基、ステアロイル基、オレオイル基等の炭素数
１〜２０のものが好ましく例示でき、アルキル基として
は炭素数１〜４のアルキル基が好ましく例示できる。こ
れらの中では、ポリオキシエチレン基であることが好ま
しい。この末端の水酸基はフリーのままでも良いし、ア
シル基やアルキル基で封鎖することも可能である。この
様なアシル基としては、アセチル基、ベンゾイル基、ア
クリロイル基、メタクリロイル基等が好ましく例示で
き、アルキル基としては炭素数１〜４のものが好ましく
例示できる。好ましいＲ４の基としてはメチルポリオキ
シエチレン（９）基、メチルポリオキシエチレン（２
３）基、メトキシエチル基、３−メトキシブチル基、エ
チルポリオキシエチレン（２）基、フェノキシチル基、
フェニルポリオキシエチレン（２）基、メチルポリオキ
シエチレン（３）基、アクリルポリオキシエチレン
（４）基、アクリルポリオキシプロピレン（３）基、ア
クリルポリオキシプロピレン（７）基等が好ましく例示
できる。この様な一般式（ＩＩ）に表される化合物とし
ては、一般式（ＩＶ）に表されるものが特に好ましい。
本発明の高分子中に構成モノマーとして一般式（ＩＩ）
に表される化合物が含有されるされる割合は、１分子中
の総量の平均重量百分率で、３０〜９０。１重量％、更
に好ましくは４０〜７０重量％である。これは、本発明
の高分子の水への溶解性が、この一般式（ＩＩ）に表さ
れる構成部分によるため、少なすぎると高分子の水への
溶解性や被膜形成時の可塑性が阻害されることがあり、
多すぎると形成された被膜の耐水性が損なわれることが
あるためである。(2) Compound represented by the general formula (II) used in the polymer of the present invention The polymer of the present invention contains a compound represented by the general formula (II) as a constituent monomer. Features. Here, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 represents an alkyl group having 2 to 4 carbon atoms, which may have an alkyloxy group, an acyloxy group or a hydroxyl group, R5 is a hydrogen atom, aromatic or aliphatic carbon number 1
Represents a hydrocarbon group or an acyl group of 8 to 8, and n represents a numerical value of 1 to 40. R3 is particularly preferably a hydrogen atom or a methyl group. This is the structure of acrylic acid or methacrylic acid, which is widely used in polymers, etc., and safety and many others have already been confirmed.
This is because many commercial products are easily available as raw materials. R
4 is a polyoxyethylene group, a polyoxypropylene group,
Examples thereof include a polyoxybutene group, a polyoxy (hydroxypropylene) group, a part or all of an acylated product thereof, and an alkyl ether. The acyl group preferably has 1 to 20 carbon atoms such as an acetyl group, a benzoyl group, a stearoyl group and an oleoyl group, and the alkyl group preferably has 1 to 4 carbon atoms. Among these, a polyoxyethylene group is preferable. This terminal hydroxyl group may be left free, or it may be blocked with an acyl group or an alkyl group. Preferred examples of such an acyl group include an acetyl group, a benzoyl group, an acryloyl group and a methacryloyl group, and preferred examples of the alkyl group include those having 1 to 4 carbon atoms. Preferred R4 groups are methylpolyoxyethylene (9) group and methylpolyoxyethylene (2
3) group, methoxyethyl group, 3-methoxybutyl group, ethylpolyoxyethylene (2) group, phenoxytyl group,
Preferable examples include a phenyl polyoxyethylene (2) group, a methyl polyoxyethylene (3) group, an acryl polyoxyethylene (4) group, an acryl polyoxypropylene (3) group, and an acryl polyoxypropylene (7) group. As the compound represented by the general formula (II), a compound represented by the general formula (IV) is particularly preferable.
In the polymer of the present invention, a monomer represented by the general formula (II):
Is 30 to 90.1% by weight, more preferably 40 to 70% by weight, as the average weight percentage of the total amount in one molecule. This is because the solubility of the polymer of the present invention in water depends on the component represented by the general formula (II). If the amount is too small, the solubility of the polymer in water and the plasticity during film formation are impaired. May be
If the amount is too large, the water resistance of the formed film may be impaired.
【００１２】（３）本発明の組成物の必須成分である高
分子 本発明の組成物の必須成分である高分子は上記一般式
（Ｉ）に表される化合物から選ばれる１種乃至は２種以
上と一般式（ＩＩ）に表される化合物から選ばれる１種
乃至は２種以上とを構成モノマーとして含有することを
特徴とする。即ち、下記部分構造式１と部分構造式２と
を１分子中に有することを特徴とする。本発明の高分子
では、これら必須の構成モノマー以外に、通常共重合体
で使用されるモノマーを構成モノマーとして、本発明の
効果を損なわない範囲に於いて、含有することが出来
る。かかる任意の構成モノマーとしては、例えば、アク
リル酸、メタクリル酸、酢酸ビニル、ビニルアルコー
ル、ビニルアルコールのアルキルエーテル、スチレン、
αーアルキルスチレン、ブタジエン、イソプレン、プロ
ペン、塩化ビニル、アクリロニトリル等が例示できる。
本発明の高分子はこれらのモノマーを常法に従って処理
することにより製造することが出来る。即ち、溶媒など
にモノマーを溶かし、重合開始剤などを加えた後、加熱
などすればよい。重合開始剤としては、通常使用されて
いるものであれば、特段の限定なく使用することが可能
であり、例えば、過酸化ベンゾイルなどのような過酸化
物、アゾビスイソブチロニトリル等のようなアゾ系の化
合物、過硫酸塩、過硫酸塩と亜硫酸塩（レドックス系開
始剤）等を用いて重合を開始すればよい。本発明の高分
子は水溶性を有する為、溶媒が水と混和するものであれ
ばそのまま濃縮し得ることもできるし、溶媒が水と混和
しないものであれば、反応後水を加えてフラッシングす
れば水の方へと高分子は移行する。しかる後に水相をと
り、濃縮すれば本発明の高分子を得ることが出来る。こ
こで本発明で言う水溶性とは、水に対する溶状をいい、
具体的には、高分子１重量部に水９９重量部を加え一様
な系を作成した場合、その液の可視光に対する透過度が
９０％以上であることを意味する。本発明の高分子はラ
ンダムタイプの共重合体であっても良いし、グラフトタ
イプの共重合体でも、ブロックタイプでもこれらの組合
せでも何れも使用可能である。かくして得られた高分子
は、水溶性を有するばかりでなく、被膜を形成させた場
合、可塑剤なしでも柔軟性のある被膜を形成する特性が
あり、内分泌物質撹乱作用が懸念されている、フタル酸
エステルなどを可塑剤として用いる必要もない。又、前
記の如く水溶性を有するため、製剤化にあたっては水を
溶媒として用いることが出来、有機溶剤無しの組成物を
作成することが出来る。従って、頭髪用化粧料、皮膚化
粧料、爪用化粧料等の化粧料に配合できるほか、水性ペ
イントや金属、ガラス、繊維などの表面処理剤として使
用することも可能である。この様な水溶性にして、乾燥
・被膜形成後は疎水性の被膜を形成する物質は今のとこ
ろ知られていない。本発明の組成物では、これらのただ
一種を含有させて使用することもできるし、二種以上を
組み合わせて使用させることもできる。本発明の組成物
に於ける、該高分子の好ましい含有量は、総量で０．１
〜４０重量％であり、その含有させる方法としては、予
め水溶液を作成しておき、これを利用して含有させるの
が好ましい。以下に、これらの本発明の組成物の必須成
分である、高分子について、製造例を挙げて更に詳細に
説明を加える。(3) Polymer which is an essential component of the composition of the present invention The polymer which is an essential component of the composition of the present invention is one or two selected from the compounds represented by the above general formula (I). It is characterized by containing, as constituent monomers, at least one kind and at least one kind selected from the compounds represented by the general formula (II). That is, it is characterized by having the following partial structural formula 1 and partial structural formula 2 in one molecule. The polymer of the present invention may contain, in addition to these essential constituent monomers, monomers commonly used in copolymers as constituent monomers as long as the effects of the present invention are not impaired. Such optional monomers include, for example, acrylic acid, methacrylic acid, vinyl acetate, vinyl alcohol, alkyl ether of vinyl alcohol, styrene,
Examples include α-alkylstyrene, butadiene, isoprene, propene, vinyl chloride, acrylonitrile and the like.
The polymer of the present invention can be produced by treating these monomers according to a conventional method. That is, the monomers may be dissolved in a solvent or the like, a polymerization initiator or the like may be added, and heating may be performed. The polymerization initiator can be used without any particular limitation as long as it is generally used.For example, peroxides such as benzoyl peroxide, azobisisobutyronitrile, etc. The polymerization may be started using a suitable azo compound, a persulfate, a persulfate and a sulfite (redox-based initiator), or the like. Since the polymer of the present invention has water solubility, if the solvent is miscible with water, it can be concentrated as it is, or if the solvent is immiscible with water, after the reaction, water can be added to flush. The macromolecules migrate toward the water. Thereafter, the aqueous phase is taken and concentrated to obtain the polymer of the present invention. Here, the water-soluble referred to in the present invention means a solution state in water,
Specifically, when a uniform system is prepared by adding 99 parts by weight of water to 1 part by weight of a polymer, this means that the liquid has a transmittance of 90% or more to visible light. The polymer of the present invention may be a random type copolymer, a graft type copolymer, a block type or a combination thereof. The polymer thus obtained is not only water-soluble, but also has the property of forming a flexible film without a plasticizer when a film is formed. It is not necessary to use an acid ester or the like as a plasticizer. Further, since it has water solubility as described above, water can be used as a solvent in formulating, and a composition without an organic solvent can be prepared. Therefore, it can be used in cosmetics such as hair cosmetics, skin cosmetics, nail cosmetics, and the like, and can also be used as a surface treatment agent for aqueous paints, metals, glass, fibers, and the like. At present, there is no known substance capable of forming such a water-soluble, hydrophobic film after drying and film formation. In the composition of the present invention, only one of these can be used, or two or more can be used in combination. The preferred content of the polymer in the composition of the present invention is 0.1% in total.
It is preferable to prepare an aqueous solution in advance and use the aqueous solution to contain it. Hereinafter, the polymer, which is an essential component of the composition of the present invention, will be described in more detail with reference to production examples.
【００１３】[0013]
【化９】 部分構造式１ （但し、式中Ｒ１は水素原子又は炭素数１〜４のアルキ
ル基を表し、Ｒ２はフッ素原子を有していても良い炭素
数１〜２０のアルキル基を表す。）Embedded image Partial structural formula 1 (wherein, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 represents an alkyl group having 1 to 20 carbon atoms which may have a fluorine atom.)
【００１４】[0014]
【化１０】 部分構造式２ （但し、式中Ｒ３は水素原子又は炭素数１〜４のアルキ
ル基を表し、Ｒ４はアルキルオキシ基、アシロキシ基又
は水酸基を有していても良い、炭素数２〜４のアルキル
基を表し、Ｒ５は水素原子、芳香族乃至は脂肪族の炭素
数１〜８の炭化水素基又はアシル基を表し、ｎは１〜４
０の数値を表す。）Embedded image Partial structural formula 2 (wherein, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 is an alkyl having 2 to 4 carbon atoms which may have an alkyloxy group, an acyloxy group or a hydroxyl group. R5 represents a hydrogen atom, an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or an acyl group, and n represents 1 to 4
Represents a numerical value of 0. )
【００１５】＜製造例１＞冷却器、攪拌機、窒素導入管
付きフラスコにメチルポリオキシエチレン（９）メタク
リレート２６．６ｇ、メタクリル酸１１．４ｇ、１０，
１０，１０，９，９，８，８，７，７，６，６，５，
５，４，４，３，３−ヘプタデカフルオロデカニルアク
リレート２．０ｇ、及びイソプロピルアルコール１００
ｍｌ，水１００ｍｌの混合溶媒を採り攪拌混合した。こ
れに、過硫酸アンモニウム０．１ｇを水１０ｍｌに溶解
した溶液を添加したのち攪拌を続けながら窒素気流で充
分置換をおこなった。８０℃に加熱して１２時間重合を
行なった。水酸化ナトリウム５．２ｇを溶解した水溶液
を添加混合した後イソプロピルアルコールを除去し目的
の共重合体の水溶液を得た。このものを凍結乾燥し、高
分子１を得た。Production Example 1 26.6 g of methyl polyoxyethylene (9) methacrylate, 11.4 g of methacrylic acid,
10, 10, 9, 9, 8, 8, 7, 7, 6, 6, 6, 5,
5,4,4,3,3-heptadecafluorodecanyl acrylate 2.0 g and isopropyl alcohol 100
A mixed solvent of 100 ml of water and 100 ml of water was taken and mixed by stirring. After a solution of 0.1 g of ammonium persulfate dissolved in 10 ml of water was added thereto, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. The polymerization was carried out by heating to 80 ° C. for 12 hours. After adding and mixing an aqueous solution in which 5.2 g of sodium hydroxide was dissolved, isopropyl alcohol was removed to obtain an aqueous solution of a desired copolymer. This was freeze-dried to obtain polymer 1.
【００１６】[0016]
【化１１】 メチルポリオキシエチレン（９）メタクリレートEmbedded image Methyl polyoxyethylene (9) methacrylate
【００１７】[0017]
【化１２】 １０，１０，１０，９，９，８，８，７，７，６，６，
５，５，４，４，３，３−ヘプタデカフルオロデカニル
アクリレートEmbedded image 10, 10, 10, 9, 9, 8, 8, 7, 7, 6, 6, 6,
5,5,4,4,3,3-heptadecafluorodecanyl acrylate
【００１８】＜製造例２＞冷却器、攪拌機、窒素導入管
付きフラスコにメチルポリオキシエチレン（２３）メタ
クリレート１９．６ｇ、ヒドロキシエチルメタクリレー
ト８．４ｇ、２，２，３，３−テトラフルオロプロピル
アクリレート１２．０ｇ、及びイソプロピルアルコール
１２０ｍｌ，水８０ｍｌの混合溶媒を採り攪拌混合し
た。攪拌を続けながら窒素気流で充分置換をおこなった
後６０℃に加熱し、過硫酸アンモニウム０．１ｇ、亜硫
酸ナトリウム０．１ｇを夫々水１０ｍｌに溶解した溶液
を添加し６時間加熱を続け重合を行なった。水酸化ナト
リウム水溶液でｐHを７．０に調製した後、イソプロピ
ルアルコールを除去し、目的の共重合体の水溶液を得
た。これを凍結乾燥し、高分子２を得た。<Production Example 2> 19.6 g of methyl polyoxyethylene (23) methacrylate, 8.4 g of hydroxyethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate were placed in a flask equipped with a condenser, a stirrer and a nitrogen inlet tube. A mixed solvent of 12.0 g, 120 ml of isopropyl alcohol and 80 ml of water was taken and mixed with stirring. After sufficient replacement with a nitrogen stream while continuing to stir, the mixture was heated to 60 ° C., a solution of 0.1 g of ammonium persulfate and 0.1 g of sodium sulfite dissolved in 10 ml of water was added, and heating was continued for 6 hours to carry out polymerization. . After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, isopropyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain polymer 2.
【００１９】[0019]
【化１３】 メチルポリオキシエチレン（２３）メタクリレートEmbedded image Methyl polyoxyethylene (23) methacrylate
【００２０】[0020]
【化１４】 ヒドロキシエチルメタクリレートEmbedded image Hydroxyethyl methacrylate
【００２１】[0021]
【化１５】 ２，２，３，３−テトラフルオロプロピルアクリレートEmbedded image 2,2,3,3-tetrafluoropropyl acrylate
【００２２】＜製造例３＞冷却器、攪拌機、窒素導入管
付きフラスコにメチルポリオキシエチレン（２３）メタ
クリレート６０．０ｇ、２，２，２−トリフルオロエチ
ルメタクリレート４０．０ｇ、及びイソプロピルアルコ
ール１００ｍｌ，酢酸エチル１００ｍｌの混合溶媒をと
り攪拌混合した。これに、過酸化ベンゾイル０．１ｇを
イソプロピルアルコール１０ｍｌに溶解した溶液を添加
したのち攪拌を続けながら窒素気流で充分置換をおこな
った。溶媒の沸点で１０時間重合を行なった。混合溶媒
から水にフラッシングをおこなって、共重合体の水溶液
を得た。これを凍結乾燥し、高分子３を得た。<Production Example 3> 60.0 g of methyl polyoxyethylene (23) methacrylate, 40.0 g of 2,2,2-trifluoroethyl methacrylate, and 100 ml of isopropyl alcohol were placed in a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube. A mixed solvent of 100 ml of ethyl acetate was taken and mixed with stirring. After adding a solution of 0.1 g of benzoyl peroxide dissolved in 10 ml of isopropyl alcohol, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. Polymerization was carried out at the boiling point of the solvent for 10 hours. The mixed solvent was flushed with water to obtain an aqueous solution of the copolymer. This was freeze-dried to obtain polymer 3.
【００２３】[0023]
【化１６】 ２，２，２−トリフルオロエチルメタクリレートEmbedded image 2,2,2-trifluoroethyl methacrylate
【００２４】＜製造例４＞冷却器、攪拌機、窒素導入管
付きフラスコにメチルポリオキシエチレン（９）メタク
リレート２１．０ｇ、２，２，２−トリフルオロエチル
メタクリレート８．０ｇ、１０，１０，１０，９，９，
８，８，７，７，６，６，５，５，４，４，３，３−ヘ
プタデカフルオロデカニルアクリレート２．０ｇ、ヒド
ロキシエチルメタクリレート９．０ｇ、及びイソプロピ
ルアルコール１２０ｍｌ，水８０ｍｌの混合溶媒を採り
攪拌混合した。これに、過硫酸アンモニウム０．１ｇを
水１０ｍｌに溶解した溶液を添加したのち攪拌を続けな
がら窒素気流で充分置換をおこなった。８０℃に加熱し
て１２時間重合を行なった。水酸化ナトリウム水溶液で
ｐHを７．０に調製した後、イソプロピルアルコールを
除去し、共重合体の水溶液を得た。これを凍結乾燥し、
高分子４を得た。<Production Example 4> 21.0 g of methyl polyoxyethylene (9) methacrylate, 8.0 g of 2,2,2-trifluoroethyl methacrylate were placed in a flask equipped with a condenser, a stirrer and a nitrogen inlet tube. , 9,9,
Mixing of 8,8,7,7,6,6,5,5,4,4,3,3-heptadecafluorodecanyl acrylate 2.0 g, hydroxyethyl methacrylate 9.0 g, isopropyl alcohol 120 ml, and water 80 ml The solvent was taken and mixed with stirring. After a solution of 0.1 g of ammonium persulfate dissolved in 10 ml of water was added thereto, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. The polymerization was carried out by heating to 80 ° C. for 12 hours. After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, isopropyl alcohol was removed to obtain an aqueous solution of a copolymer. This is freeze-dried,
Polymer 4 was obtained.
【００２５】＜製造例５＞冷却器、攪拌機、窒素導入管
付きフラスコに２−ヒドロキシ−３−フェノキシプロピ
ルアクリレート１０ｇ、メチルポリオキシエチレン（２
３）メタクリレート５０．０ｇ、スチレン４ｇ、２，
２，２−トリフルオロエチルメタクリレート３５．０
ｇ、及びイソプロピルアルコール１００ｍｌ，酢酸エチ
ル１００ｍｌの混合溶媒を採り攪拌混合した。これに、
過酸化ベンゾイル０．１ｇをイソプロピルアルコール１
０ｍｌに溶解した溶液を添加したのち攪拌を続けながら
窒素気流で充分置換をおこなった。溶媒の沸点で１０時
間重合を行なった。混合溶媒から水にフラッシングをお
こなって、共重合体の水溶液を得た。これを凍結乾燥し
本発明の高分子５を得た。<Production Example 5> 10 g of 2-hydroxy-3-phenoxypropyl acrylate and methylpolyoxyethylene (2
3) Methacrylate 50.0 g, styrene 4 g, 2,
2,2-trifluoroethyl methacrylate 35.0
g, and a mixed solvent of 100 ml of isopropyl alcohol and 100 ml of ethyl acetate were taken and mixed with stirring. to this,
0.1 g of benzoyl peroxide in isopropyl alcohol 1
After adding a solution dissolved in 0 ml, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. Polymerization was carried out at the boiling point of the solvent for 10 hours. The mixed solvent was flushed with water to obtain an aqueous solution of the copolymer. This was freeze-dried to obtain Polymer 5 of the present invention.
【００２６】[0026]
【化１７】 ２−ヒドロキシ−３−フェノキシプロピルアクリレートEmbedded image 2-hydroxy-3-phenoxypropyl acrylate
【００２７】＜製造例６＞冷却器、攪拌機、窒素導入管
付きフラスコにポリオキシプロピレン（２）アクリレー
ト５ｇ、ビニルアルコール５ｇ、メチルポリオキシエチ
レン（２３）メタクリレート５０．０ｇ、α−メチルス
チレン４ｇ、２，２，２−トリフルオロエチルメタクリ
レート３５．０ｇ、及びイソプロピルアルコール１００
ｍｌ，酢酸エチル１００ｍｌの混合溶媒を採り攪拌混合
した。これに、過酸化ベンゾイル０．１ｇをイソプロピ
ルアルコール１０ｍｌに溶解した溶液を添加したのち攪
拌を続けながら窒素気流で充分置換をおこなった。溶媒
の沸点で１０時間重合を行なった。混合溶媒から水にフ
ラッシングをおこなって、共重合体の水溶液を得た。こ
れを凍結乾燥し、高分子６を得た。<Production Example 6> 5 g of polyoxypropylene (2) acrylate, 5 g of vinyl alcohol, 50.0 g of methyl polyoxyethylene (23) methacrylate, 4 g of α-methylstyrene were placed in a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube. 35.0 g of 2,2,2-trifluoroethyl methacrylate and isopropyl alcohol 100
and a mixed solvent of 100 ml of ethyl acetate. After adding a solution of 0.1 g of benzoyl peroxide dissolved in 10 ml of isopropyl alcohol, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. Polymerization was carried out at the boiling point of the solvent for 10 hours. The mixed solvent was flushed with water to obtain an aqueous solution of the copolymer. This was freeze-dried to obtain polymer 6.
【００２８】[0028]
【化１８】 ポリオキシプロピレン（２）アクリレートEmbedded image Polyoxypropylene (2) acrylate
【００２９】＜製造例７＞冷却器、攪拌機、窒素導入管
付きフラスコにメチルポリオキシエチレン（２３）メタ
クリレート１９．６ｇ、ヒドロキシエチルメタクリレー
ト８．４ｇ、アクリル酸ステアリル１２．０ｇ、及びイ
ソプロピルアルコール１２０ｍｌ，水８０ｍｌの混合溶
媒を採り攪拌混合した。攪拌を続けながら窒素気流で充
分置換をおこなった後６０℃に加熱し、過硫酸アンモニ
ウム０．１ｇ、亜硫酸ナトリウム０．１ｇを夫々水１０
ｍｌに溶解した溶液を添加し6時間加熱を続け重合を行
なった。水酸化ナトリウム水溶液でｐHを７．０に調製
した後、イソプロピルアルコールを除去し、目的の共重
合体の水溶液を得た。これを凍結乾燥し、高分子７を得
た。Production Example 7 19.6 g of methyl polyoxyethylene (23) methacrylate, 8.4 g of hydroxyethyl methacrylate, 12.0 g of stearyl acrylate, and 120 ml of isopropyl alcohol were placed in a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube. A mixed solvent of 80 ml of water was taken and mixed with stirring. After performing sufficient replacement with a nitrogen stream while continuing stirring, the mixture was heated to 60 ° C., and 0.1 g of ammonium persulfate and 0.1 g of sodium sulfite were added to each of 10 parts of water.
A solution dissolved in ml was added, and heating was continued for 6 hours to carry out polymerization. After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, isopropyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain polymer 7.
【００３０】[0030]
【化１９】 アクリル酸ステアリルEmbedded image Stearyl acrylate
【００３１】＜製造例８＞冷却器、攪拌機、窒素導入管
付きフラスコにメチルポリオキシエチレン（２３）メタ
クリレート２０．０g、ヒドロキシエチルメタクリレー
ト１６．４ｇ、２，２，２，２’，２’，２’−ヘキサ
フルオロイソプロピルアクリレート３．６ｇ、及びエチ
ルアルコール１２０ｍｌ，水８０ｍｌの混合溶媒を採り
攪拌混合した。後攪拌を続けながら窒素気流で充分置換
を行なった後６０℃に加熱し、過硫酸アンモニウム０．
１ｇ、亜硫酸水素ナトリウム０．１ｇを夫々水１０ｍｌ
に溶解した溶液を添加し６時間加熱を続け重合を行なっ
た。水酸化ナトリウム水溶液でｐHを７．０に調節した
後エチルアルコールを除去して目的の共重合体の水溶液
を得た。このものを凍結乾燥し、本発明の高分子８を得
た。Production Example 8 20.0 g of methyl polyoxyethylene (23) methacrylate, 16.4 g of hydroxyethyl methacrylate, 2,2,2,2 ', 2', A mixed solvent of 3.6 g of 2'-hexafluoroisopropyl acrylate, 120 ml of ethyl alcohol and 80 ml of water was taken and mixed with stirring. Thereafter, the mixture was sufficiently replaced with a nitrogen stream while continuing to stir, and then heated to 60 ° C. to form ammonium persulfate 0.1 ml.
1 g, sodium bisulfite 0.1 g and water 10 ml each
Was added thereto, and heating was continued for 6 hours to carry out polymerization. After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, ethyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain Polymer 8 of the present invention.
【００３２】＜製造例９＞冷却器、攪拌機、窒素導入管
付きフラスコにメチルポリオキシエチレン（２３）メタ
クリレート２４．３g、ヒドロキシエチルメタクリレー
ト１２．０ｇ、メチルメタクリレート１８．０ｇ、１
０，１０，１０，９，９，８，８，７，７，６，６，
５，５，４，４，３，３−ヘプタデカフルオロデカニル
アクリレート５．７ｇ、及びイソプロピルアルコール１
８０ｍｌ，水１２０ｍｌの混合溶媒を採り攪拌混合し
た。これに、過硫酸アンモニウム０．７ｇを水１０ｍｌ
に溶解した溶液を添加した後攪拌を続けながら窒素気流
で充分置換を行なった。80℃に加熱し12時間重合を行な
った。水酸化ナトリウム水溶液でｐHを７．０に調節し
た後イソプロピルアルコールを除去して目的の共重合体
の水溶液を得た。このものを凍結乾燥し、本発明の高分
子９を得た。<Production Example 9> In a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube, 24.3 g of methyl polyoxyethylene (23) methacrylate, 12.0 g of hydroxyethyl methacrylate, 18.0 g of methyl methacrylate, 1
0,10,10,9,9,8,8,7,7,6,6
5.7 g of 5,5,4,4,3,3-heptadecafluorodecanyl acrylate and isopropyl alcohol 1
A mixed solvent of 80 ml and 120 ml of water was taken and mixed with stirring. 0.7 g of ammonium persulfate was added to 10 ml of water.
After the addition of the solution dissolved in, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. The mixture was heated to 80 ° C. and polymerized for 12 hours. After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, isopropyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain Polymer 9 of the present invention.
【００３３】＜製造例１０＞冷却器、攪拌機、窒素導入
管付きフラスコにメチルポリオキシエチレン（９）メタ
クリレート２０．０g、２−ヒドロキシ−３−フェノキ
シプロピルアクリレート１２．８ｇ、ｎ−ブチルアクリ
レート４．０ｇ、５，５，４，４，３，３，２，２−オ
クタフルオロペンチルメタクリレート３．４ｇ、及びイ
ソプロピルアルコール１００ｍｌ，酢酸エチル１００ｍ
ｌの混合溶媒を採り攪拌混合した。これに、過酸化ベン
ゾイル０．２ｇをイソプロピルアルコール１０ｍｌに溶
解した溶液を添加した後攪拌を続けながら窒素気流で充
分置換を行なった。溶媒の沸点で１０時間重合を行なっ
た。混合溶媒から水へのフラッシングを行なって目的の
共重合体の水溶液を得た。このものを凍結乾燥し、本発
明の高分子１０を得た。<Production Example 10> In a flask equipped with a condenser, a stirrer, and a nitrogen introducing tube, 20.0 g of methyl polyoxyethylene (9) methacrylate, 12.8 g of 2-hydroxy-3-phenoxypropyl acrylate, and n-butyl acrylate 4. 0 g, 5,5,4,4,3,3,2,2-octafluoropentyl methacrylate 3.4 g, isopropyl alcohol 100 ml, ethyl acetate 100 m
1 mixed solvent was taken and mixed with stirring. A solution of 0.2 g of benzoyl peroxide dissolved in 10 ml of isopropyl alcohol was added thereto, and the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. Polymerization was carried out at the boiling point of the solvent for 10 hours. Flushing from the mixed solvent to water was performed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain Polymer 10 of the present invention.
【００３４】＜製造例１１＞冷却器、攪拌機、窒素導入
管付きフラスコにメチルポリオキシエチレン（２３）メ
タクリレート２４．０g、メチルメタクリレート１２．
１ｇ、２，２，３，３−テトラフロオロプロピルアクリ
レート３．９ｇ、及びイソプロピルアルコール１５０ｍ
ｌ，水５０ｍｌの混合溶媒を採り攪拌混合した。これ
に、過硫酸アンモニウム０．３ｇを水１０ｍｌに溶解し
た溶液を添加した後攪拌を続けながら窒素気流で充分置
換を行なった。80℃に加熱し８時間重合を行なった。水
酸化ナトリウム水溶液でｐHを７．０に調節した後イソ
プロピルアルコールを除去して目的の共重合体の水溶液
を得た。このものを凍結乾燥し、本発明の高分子１１を
得た。<Production Example 11> 24.0 g of methyl polyoxyethylene (23) methacrylate and methyl methacrylate were placed in a flask equipped with a cooler, a stirrer and a nitrogen inlet tube.
1 g, 3.9 g of 2,2,3,3-tetrafluoropropyl acrylate, and 150 m of isopropyl alcohol
A mixed solvent of 50 ml of water was taken and mixed with stirring. After a solution of 0.3 g of ammonium persulfate dissolved in 10 ml of water was added thereto, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. The mixture was heated to 80 ° C. and polymerized for 8 hours. After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, isopropyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain the polymer 11 of the present invention.
【００３５】＜製造例１２＞冷却器、攪拌機、窒素導入
管付きフラスコにメチルポリオキシエチレン（９）メタ
クリレート１６．０g、メタクリル酸１２．０ｇ、メチ
ルメタクリレート８．４ｇ、２，２，２，２’，２’，
２’−ヘキサフルオロイソプロピルアクリレート３．６
ｇ、及びイソプロピルアルコール１００ｍｌ，酢酸エチ
ル１００ｍｌの混合溶媒を採り攪拌混合した。これに、
２，２−アゾビス（イソブチロニトリル）０．２ｇをイ
ソプロピルアルコール１０ｍｌに溶解した溶液を添加し
た後攪拌を続けながら窒素気流で充分置換を行なった。
溶媒の沸点で６時間重合を行なった。混合溶媒から水へ
のフラッシングを行なって目的の共重合体の水溶液を得
た。このものを凍結乾燥し、本発明の高分子６を得た。<Production Example 12> In a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube, 16.0 g of methyl polyoxyethylene (9) methacrylate, 12.0 g of methacrylic acid, 8.4 g of methyl methacrylate, 2, 2, 2, and 2 ', 2',
2'-hexafluoroisopropyl acrylate 3.6
g, and a mixed solvent of 100 ml of isopropyl alcohol and 100 ml of ethyl acetate were taken and mixed with stirring. to this,
After a solution of 0.2 g of 2,2-azobis (isobutyronitrile) dissolved in 10 ml of isopropyl alcohol was added, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued.
Polymerization was carried out at the boiling point of the solvent for 6 hours. Flushing from the mixed solvent to water was performed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain Polymer 6 of the present invention.
【００３６】本発明の高分子の物性（溌水・溌油性）を
例を示して説明する。高分子１〜１２の５％水溶液をろ
紙上に滴下し乾燥してろ紙にポリマー膜をキャストす
る。このろ紙にキャストしたポリマー膜状に水および油
（オリーブ油）を滴下し接触角を測定した。高分子１〜
６、８〜１２の測定値は水に対しても油に対しても６０
度から７０度で４８時間全く変化しなかった。高分子７
は油の滴下後１時間には、油が濾紙に吸収されていた。
又、水に対しても４時間までは変化がなかったが、２４
時間以内に濾紙に吸収されていた。これより、本発明の
組成物の必須成分の高分子の分子内にはフッ素原子を含
有するのが好ましいことがわかる。The physical properties (water repellency and oil repellency) of the polymer of the present invention will be described with reference to examples. A 5% aqueous solution of polymers 1 to 12 is dropped on filter paper and dried, and a polymer film is cast on the filter paper. Water and oil (olive oil) were dropped on the polymer film cast on the filter paper, and the contact angle was measured. Polymer 1
6, 8 to 12 measured values are 60 for water and oil
The temperature did not change at all from 70 degrees to 48 degrees for 48 hours. Polymer 7
One hour after the oil was dropped, the oil was absorbed by the filter paper.
Also, there was no change in water up to 4 hours.
Within hours the filter paper had absorbed it. This indicates that it is preferable that a fluorine atom be contained in the molecule of the polymer, which is an essential component of the composition of the present invention.
【００３７】高分子１〜１２について、上記と同様の方
法でポリマー膜をろ紙にキャストする。このろ紙をフリ
ッツ拡散セルにセットし、下部を水（ポリアクリル酸ソ
ーダ０．５％水溶液）及びグリセリルトリイソオクタネ
ートで満たした。上部に色素（Ｒ１０２）水溶液（ポリ
アクリル酸ソーダ０．５％水溶液）、色素（Ｒ５０２）
グリセリルトリイソオクタネート溶液を添加し下部を攪
拌しながら３０分放置した。下部の溶液をとり吸光度を
測定したが色素の透過はほとんど認められなかった。こ
れより、本発明の組成物の必須成分である高分子の被膜
は溌水・溌油性に優れ、水や油の透過を抑制することが
わかる。これより、この様な膜が保護被膜として有用で
あることもわかる。For the polymers 1 to 12, polymer films are cast on filter paper in the same manner as described above. The filter paper was set in a Fritz diffusion cell, and the lower portion was filled with water (aqueous solution of 0.5% sodium polyacrylate) and glyceryl triisooctanoate. Dye (R102) aqueous solution (sodium polyacrylate 0.5% aqueous solution), dye (R502)
A glyceryl triisooctate solution was added, and the mixture was left for 30 minutes while stirring the lower part. The lower solution was taken and the absorbance was measured, but almost no permeation of the dye was observed. This indicates that the polymer film, which is an essential component of the composition of the present invention, has excellent water repellency and oil repellency and suppresses water and oil permeation. This shows that such a film is useful as a protective film.
【００３８】 上記と同様にキャスト膜を作成し、これ
を２回軽くもんで、同様に試験したが同様の結果であっ
た。これより、本発明の組成物の必須成分である高分子
の被膜が、可塑剤なしでも十分に可塑性を有しているこ
とが明白である。即ち、本発明の組成物に於いては内分
泌撹乱物質の可能性のある可塑剤の使用が必要ないこと
がわかる。A cast film was prepared in the same manner as described above, gently squeezed twice, and tested in the same manner. It is apparent from the above that the polymer film, which is an essential component of the composition of the present invention, has sufficient plasticity without a plasticizer. That is, it is understood that the composition of the present invention does not require the use of a plasticizer that may be an endocrine disrupting substance.
【００３９】濾紙を布（テトロン）に変えて、上記と同
様の試験を行ったが、同様の結果が得られた。The same test as above was performed with the filter paper replaced with a cloth (Tetron), but similar results were obtained.
【００４０】金属表面に高分子１〜１２の被膜を作成
し、水、油を滴下し接触角を測定したが、結果は上記と
同様であった。Films of polymers 1 to 12 were formed on the metal surface, and water and oil were dropped to measure the contact angle. The results were the same as above.
【００４１】（４）本発明の組成物 本発明の組成物は、上記一般式（Ｉ）に表されるモノマ
ーから選ばれる１種乃至は２種以上と一般式（ＩＩ）に
表されるモノマーから選ばれる１種乃至は２種以上とを
構成モノマーとして含有する高分子構造を有する高分子
を含有することを特徴とする。本発明の組成物として
は、表面の処理に使用されるものが好適であり、処理さ
れる表面としては、皮膚表面、爪表面、毛髪表面、繊維
表面、ガラス表面乃至は金属表面が好適に例示できる。
即ち、本発明の組成物としては、具体的には、皮膚外用
剤、繊維処理剤、ペイントなどが好適に例示でき、中で
も皮膚外用剤に適用するのが特に好ましい。皮膚外用剤
としては、例えば、化粧料、皮膚外用医薬、外用殺菌剤
などが例示でき、これらの内では化粧料が特に好まし
い。これは、本発明の組成物の必須成分である高分子の
機能が、化粧料の求めている品質と良く一致するからで
ある。ここで、化粧料とは、一般的に言われる化粧料で
あり、例えば、クリーム、乳液、化粧水、パック等の肌
の手入れを旨とする基礎化粧料、アンダーメークアッ
プ、ファンデーション、リップカラー、チークカラー、
ネイルカラー等の装いの機能を旨とするメークアップ化
粧料、ヘアトニック、ヘアリキッド、ヘアクリーム等の
毛髪の手入れと保全を旨とする毛髪化粧料、洗顔料、シ
ャンプー、リンス、石鹸などの洗浄作用を旨とする洗浄
化粧料等が例示できる。本発明の化粧料ではこれらの何
れもが適用可能であり、基礎化粧料であれば、優れた皮
膚保護効果を発現し、メークアップ化粧料であれば、化
粧のりが良く、もちも良いメークアップ効果を発現し、
毛髪用化粧料であれば、優れた毛髪保護作用と同時に櫛
通りの良さなどの優れた機能を発現する。本発明の組成
物に於いては特徴としては、可塑剤を必要としないこと
であり、皮膜形成剤に従来より使用されていた、フタル
酸ジエステル、クエン酸トリエチル、モノカプリル酸グ
リセリル、炭酸プロピル等の可塑剤は含まなくてもかま
わないし、環境問題等を勘案すると、前記可塑剤成分を
含まないことが特に好ましい。(4) Composition of the Present Invention The composition of the present invention comprises one or more monomers selected from the monomers represented by the above general formula (I) and a monomer represented by the general formula (II) And a polymer having a polymer structure containing at least one selected from the group consisting of: As the composition of the present invention, those used for surface treatment are preferable, and the surface to be treated is preferably skin surface, nail surface, hair surface, fiber surface, glass surface or metal surface. it can.
That is, as the composition of the present invention, specifically, an external preparation for skin, a fiber treatment agent, a paint and the like can be suitably exemplified, and it is particularly preferable to apply the composition to an external preparation for skin. Examples of the skin external preparation include cosmetics, skin external medicines, and external bactericides, among which cosmetics are particularly preferred. This is because the function of the polymer, which is an essential component of the composition of the present invention, matches well with the quality required of the cosmetic. Here, the cosmetics are cosmetics generally referred to as, for example, creams, emulsions, lotions, basic cosmetics for purifying the skin such as packs, under makeup, foundation, lip color, Teak color,
Make-up cosmetics with the function of clothes such as nail colors, hair tonics, hair liquids, hair creams, etc. Examples thereof include cleaning cosmetics having an effect. Any of these can be applied to the cosmetic of the present invention. If it is a basic cosmetic, it exhibits an excellent skin protection effect, and if it is a make-up cosmetic, it has good make-up and good make-up. Express the effect,
Hair cosmetics exhibit excellent functions such as excellent comb protection and good combability at the same time. A feature of the composition of the present invention is that it does not require a plasticizer, and has conventionally been used as a film-forming agent, such as diester phthalate, triethyl citrate, glyceryl monocaprylate, and propyl carbonate. The plasticizer may not be contained, and it is particularly preferable not to contain the plasticizer component in consideration of environmental problems and the like.
【００４２】本発明の組成物では、上記必須成分である
高分子以外に、通常この様な組成物で使用される任意成
分を、本発明の効果を損ねない範囲に於いて、含有する
ことが出来る。この様な任意成分としては、例えば、化
粧料であれば、ワセリンやマイクロクリスタリンワック
ス等のような炭化水素類、ホホバ油やゲイロウ等のエス
テル類、牛脂、オリーブ油等のトリグリセライド類、セ
タノール、オレイルアルコール等の高級アルコール類、
ステアリン酸、オレイン酸等の脂肪酸、グリセリンや
１，３−ブタンジオール等の多価アルコール類、非イオ
ン界面活性剤、アニオン界面活性剤、カチオン界面活性
剤、両性界面活性剤、エタノール、カーボポール等の増
粘剤、防腐剤、紫外線吸収剤、抗酸化剤、色素、粉体類
等が例示でき、医薬であれば、賦形剤、結合剤、被覆
剤、滑沢剤、糖衣剤、崩壊剤、増量剤、矯味矯臭剤、乳
化・可溶化・分散剤、安定剤、ｐＨ調整剤、等張剤等が
例示でき、ペイントであれば、顔料類、分散剤としての
界面活性剤、分散溶媒等が例示でき、繊維処理剤であれ
ば、溶媒や界面活性剤などの浸透促進成分等が例示でき
る。本発明の組成物は、これらの成分を常法に従って処
理することにより、製造することが出来る。The composition of the present invention may contain, in addition to the above-mentioned essential component, a polymer, optional components usually used in such a composition as long as the effects of the present invention are not impaired. I can do it. Such optional components include, for example, in the case of cosmetics, hydrocarbons such as petrolatum and microcrystalline wax, esters such as jojoba oil and gay wax, triglycerides such as tallow, olive oil, cetanol, and oleyl alcohol. Higher alcohols such as
Fatty acids such as stearic acid and oleic acid, polyhydric alcohols such as glycerin and 1,3-butanediol, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, ethanol, carbopol, etc. Thickeners, preservatives, ultraviolet absorbers, antioxidants, dyes, powders, etc. can be exemplified. In the case of medicines, excipients, binders, coating agents, lubricants, sugar coatings, disintegrants , Extenders, flavoring agents, emulsifying / solubilizing / dispersing agents, stabilizers, pH adjusters, isotonic agents, etc., and in the case of paints, pigments, surfactants as dispersing agents, dispersing solvents, etc. In the case of a fiber treatment agent, examples thereof include a penetration promoting component such as a solvent and a surfactant. The composition of the present invention can be produced by treating these components according to a conventional method.
【００４３】＜実施例１〜８＞下記処方に基づいてネイ
ルカラーを作成した。即ち、処方成分をよく撹拌混合
し、ロール掛けを行い、ネイルカラーを得た。塗布後
は、全ての処方系で優れた耐水性のある被膜を形成し
た。この効果を本発明の化粧料である実施例１の高分子
１と水の一部を乾燥残分が等しくなるように、通常水系
で使用されるアクリル樹脂エマルジョンに置換した比較
例１と比べて、硬度Ｈの鉛筆による引っかき試験の結果
が良いものに○、同等に△、劣るもの×を付し評価し
た。この結果も表にあわせて示す。これは、本発明の必
須成分である、高分子が可塑剤無しでも柔軟性を有する
被膜を形成するからである。<Examples 1 to 8> Nail colors were prepared based on the following formulations. That is, the prescription components were well stirred and mixed and rolled to obtain a nail color. After coating, excellent water-resistant coatings were formed in all the formulation systems. This effect is compared with that of Comparative Example 1 in which the polymer 1 of Example 1, which is the cosmetic of the present invention, and a part of water are replaced with an acrylic resin emulsion which is usually used in an aqueous system so that the dry residue is equal. The results of the scratch test with a pencil having a hardness of H were evaluated as good (○), equivalently Δ and poor (×). The results are also shown in the table. This is because the polymer, which is an essential component of the present invention, forms a flexible film even without a plasticizer.
【００４４】[0044]
【表１】 [Table 1]
【００４５】＜実施例９〜１６＞下記処方に基づいて塗
料を作成した。即ち、処方成分をよく撹拌混合し、ロー
ル掛けし、塗料を得た。塗布後は、全ての処方系で、可
塑剤がないにもかかわらず、優れた耐水性のある被膜を
形成した。<Examples 9 to 16> Paints were prepared based on the following formulations. That is, the prescription components were well mixed with stirring and rolled to obtain a paint. After application, excellent water-resistant coatings were formed in all formulation systems despite the absence of plasticizer.
【００４６】[0046]
【表２】 [Table 2]
【００４７】＜実施例１７〜２４＞下記処方に基づいて
防水用スプレーを作成した。即ち、処方成分をよく撹拌
混合し、防水用スプレーを得た。スプレー後は、全ての
処方系で、水系であるにもかかわらず優れた耐水性のあ
る被膜を形成した。Examples 17 to 24 Waterproofing sprays were prepared based on the following formulations. That is, the prescription components were well stirred and mixed to obtain a waterproof spray. After spraying, in all the formulation systems, excellent water-resistant coatings were formed despite being water-based.
【００４８】[0048]
【表３】 [Table 3]
【００４９】＜実施例２５〜３２＞下記処方に基づいて
頭髪用の化粧料を作成した。即ち、即ち、イ、ロをそれ
ぞれ８０℃で撹拌可溶化した後、良く撹拌しながらイに
ロを加え、撹拌冷却し頭髪用化粧料を得た。噴霧後は、
全ての処方系で優れた耐水性のある被膜を形成した。こ
れは、櫛通りの良さと整髪力について、本発明の化粧料
である、実施例２５の高分子１と水の一部を、乾燥残分
が高分子１の含有量と同じになるように、通常のアクリ
ル樹脂エマルジョンに置換した、比較例２と専門パネラ
ーにより比較して評価したところ、表４、５に示す如く
に、何れも優れた評価を得たことより明らかである。こ
こで、評価の基準は、○：比較例２よりも良い、△：比
較例２と同程度、×：比較例２より劣るを用いた。<Examples 25 to 32> Cosmetics for hair were prepared based on the following prescription. That is, after each of (a) and (b) was stirred and solubilized at 80 ° C., (b) was added to (a) while stirring well, and the mixture was stirred and cooled to obtain a hair cosmetic. After spraying,
Excellent water-resistant coatings were formed in all formulations. This is because the cosmetic 1 of Example 25 and a part of water, which is the cosmetic of the present invention, have the same dry residue as the content of the polymer 1 in terms of good combability and hair styling. The results were compared with Comparative Example 2 in which a normal acrylic resin emulsion was substituted and evaluated by a specialized panelist, and as shown in Tables 4 and 5, it is clear from the fact that all were obtained with excellent evaluations. Here, the evaluation criteria were: ：: better than Comparative Example 2, Δ: comparable to Comparative Example 2, ×: inferior to Comparative Example 2.
【００５０】[0050]
【表４】 [Table 4]
【００５１】[0051]
【表５】 [Table 5]
【００５２】＜実施例３３〜４０＞以下に示す処方に従
って、本発明の組成物である水中油クリーム（化粧料）
を作成した。即ち、イ、ロの成分をそれぞれ８０℃に加
熱し、イにロを徐々に加え、乳化し、ホモジナイザーで
粒子を均一化した後、撹拌冷却してクリームを得た。こ
のものについて、高分子を保水性が高いことで知られて
いるヒアルロン酸ナトリウムに置換した比較例３を作成
し、肌荒れに悩む人１群１０名、計９０名のパネラーを
用いて、３週間の連続使用に於ける肌荒れ改善の評価を
行った。結果を出現例数として、表６に示す。これよ
り、本発明の化粧料に於いては、その優れた被膜によ
り、損傷した角層機能を補い、肌荒れを改善するする作
用に優れることがわかる。ここで肌荒れ改善作用の評価
基準は、＋＋：著しく改善、＋：明らかに改善、±：や
や改善、−：改善せずであった。又、化粧料などにアク
リル系の高分子成分を含有させ、可塑剤を含有させない
場合、その被膜特性により、突っ張った感触を発現する
ことがしばしばあるが、本発明の化粧料に於いてはこの
様な突っ張り感は全くなかった。これは、本発明の化粧
料の必須成分である高分子化合物が優れた可塑性を有し
ているためである。 イ 蔗糖脂肪酸エステル ０．５ 重量部 ワセリン １ 重量部 ラノリン ３ 重量部 流動パラフィン ８ 重量部 低粘度シリコーン １０ 重量部 ステアリルアルコール ０．５ 重量部 ステアリン酸 ０．５５重量部 ウンデシレン酸モノグリセリド ２ 重量部 ポリオキシエチレン（２０）ベヘニルエーテル ２ 重量部 ロ １，３−ブタンジオール ５ 重量部 グリセリン ５ 重量部 高分子＊ １ 重量部 水酸化カリウム ０．０５重量部 水 ６１．４ 重量部 ＊詳細は表６に記す。<Examples 33 to 40> Oil-in-water cream (cosmetics) which is a composition of the present invention according to the following formulation:
It was created. That is, the components (a) and (b) were each heated to 80 ° C., (b) was gradually added to (a), emulsified, and the particles were homogenized with a homogenizer, followed by stirring and cooling to obtain a cream. A comparative example 3 was prepared by replacing the polymer with sodium hyaluronate, which is known to have a high water retention, and a group of 10 people suffering from rough skin, using a total of 90 panelists, for 3 weeks The evaluation of the improvement of the rough skin in the continuous use of was evaluated. Table 6 shows the results as the number of appearance cases. From this, it can be seen that the cosmetic of the present invention is excellent in the effect of supplementing the damaged stratum corneum function and improving the rough skin due to the excellent coating. Here, the evaluation criteria for the skin roughness improving effect were ++: markedly improved, +: clearly improved, ±: slightly improved,-: not improved. In addition, when an acrylic polymer component is contained in a cosmetic or the like, and a plasticizer is not contained, a tactile feeling is often exhibited due to the film properties thereof. There was no such feeling of tension. This is because the polymer compound, which is an essential component of the cosmetic of the present invention, has excellent plasticity. A Sucrose fatty acid ester 0.5 parts by weight Vaseline 1 part by weight Lanolin 3 parts by weight Liquid paraffin 8 parts by weight Low viscosity silicone 10 parts by weight Stearyl alcohol 0.5 parts by weight Stearic acid 0.55 parts by weight Undecylenic acid monoglyceride 2 parts by weight Polyoxy Ethylene (20) behenyl ether 2 parts by weight b 1,3-butanediol 5 parts by weight Glycerin 5 parts by weight Polymer * 1 part by weight Potassium hydroxide 0.05 parts by weight Water 61.4 parts by weight * Details are shown in Table 6. .
【００５３】[0053]
【表６】 [Table 6]
【００５４】＜実施例４１〜４８＞下記に示す処方に従
って、本発明の組成物であるファンデーション（化粧
料）を作成した。即ち、イ、ロ、ハ、ニをそれぞれ８０
℃に加熱し、イとロとを良く混練りし、これにハを加え
て希釈し、ホを分散させて、これに徐々にニを加えて乳
化し、撹拌冷却し、ファンデーションを得た。これらの
ものについて、サウナ３０分の条件での化粧もちを、高
分子を水に置換した対照例１と比較して、専門パネラー
により評価した。評価基準は、＋＋：対照例１より著し
く良い、＋：対照例１より明らかに良い、±：対照例１
よりやや良い、−：対照例１と同程度を用いた。結果を
表７に示す。これより、本発明の化粧料のもちが極めて
良いことがわかる。 イ ７０％マルチトール水溶液 ５ 重量部 グリセリン ２ 重量部 １，３−ブタンジオール ５ 重量部 ロ トリグリセリンジイソステアレート ５ 重量部 ハ 流動パラフィン １５ 重量部 カルナウバワックス ２ 重量部 マイクロクリスタリンワックス ３ 重量部 パラメトキシ桂皮酸イソオクチル ２ 重量部 ニ 水 ４２．５重量部 高分子＊＊ ３．５重量部 ホ 鉄ドープ二酸化チタン ８ 重量部 酸化亜鉛 １ 重量部 二酸化チタン １ 重量部 タルク ３ 重量部 ベンガラ １ 重量部 黄色酸化鉄 １ 重量部<Examples 41 to 48> According to the following formulation, a foundation (cosmetic) as a composition of the present invention was prepared. That is, a, b, c and d are 80
The mixture was heated to 0 ° C., kneaded well with the mixture (a) and (b), and diluted by adding c to the mixture. E was dispersed therein, and the mixture was gradually added and emulsified, followed by stirring and cooling to obtain a foundation. With respect to these, the cosmetic moistness under the condition of the sauna for 30 minutes was evaluated by a specialized panelist in comparison with Control Example 1 in which the polymer was replaced with water. Evaluation criteria: ++: significantly better than control example 1, +: clearly better than control example 1, ±: control example 1
Slightly better,-: The same degree as that of Comparative Example 1 was used. Table 7 shows the results. From this, it is understood that the cosmetic of the present invention has extremely good stickiness. A 70% aqueous maltitol solution 5 parts by weight glycerin 2 parts by weight 1,3-butanediol 5 parts by weight b triglycerin diisostearate 5 parts by weight c liquid paraffin 15 parts by weight carnauba wax 2 parts by weight microcrystalline wax 3 parts by weight Isooctyl paramethoxycinnamate 2 parts by weight D 42.5 parts by weight Polymer ** 3.5 parts by weight E Iron-doped titanium dioxide 8 parts by weight Zinc oxide 1 part by weight Titanium dioxide 1 part by weight Talc 3 parts by weight Bengala 1 part by weight Yellow Iron oxide 1 part by weight
【００５５】[0055]
【表７】 [Table 7]
【００５６】＜実施例４９＞以下に示す処方に従って、
本発明の皮膚外用医薬組成物であるステロイドクリーム
を作成した。即ち、イ、ロ、ハ、ニをそれぞれ８０℃に
加熱し、イとロを良く混練りし、これにハを加え希釈
し、更にニを徐々に加え乳化した。これを撹拌冷却し
て、ステロイドクリームを得た。このものをアトピー性
皮膚炎に悩む患者に１カ月使用してもらったところ、症
状が著しく改善した。この患者は、ステロイドクリーム
が効果を奏さないことが度々あったが、本発明の皮膚外
用医薬組成物では著しい効果を発揮した。 イ ７０％マルビトール水溶液 ５ 重量部 グリセリン ３ 重量部 １，３−ブタンジオール ５ 重量部 メチルパラベン ０．３重量部 ブチルパラベン ０．１重量部 ロ トリグリセリンジイソステアレート ５ 重量部 ハ 固形パラフィン ２ 重量部 マイクロクリスタリンワックス ３ 重量部 流動パラフィン １０ 重量部 カルナウバワックス ２ 重量部 軽質イソパラフィン ５ 重量部 プレドニゾロン １ 重量部 ニ 水 ５８ 重量部 高分子１ ０．６重量部<Example 49> According to the following formulation,
A steroid cream which is a pharmaceutical composition for external use on the skin of the present invention was prepared. That is, A, B, C, and D were each heated to 80 ° C., and A and B were well kneaded, C was added and diluted, and D was gradually added and emulsified. This was stirred and cooled to obtain a steroid cream. When this product was used for one month by a patient suffering from atopic dermatitis, the symptoms were remarkably improved. This patient often did not respond to the steroid cream, but the dermatological composition of the present invention exerted a remarkable effect. A 70% aqueous malbitol solution 5 parts by weight glycerin 3 parts by weight 1,3-butanediol 5 parts by weight methyl paraben 0.3 parts by weight butyl paraben 0.1 parts by weight b triglycerin diisostearate 5 parts by weight c solid paraffin 2 parts by weight Microcrystalline wax 3 parts by weight Liquid paraffin 10 parts by weight Carnauba wax 2 parts by weight Light isoparaffin 5 parts by weight Prednisolone 1 part by weight D 58 parts by weight Polymer 1 0.6 parts by weight
【００５７】＜実施例５０＞以下に示す処方に従って、
本発明の皮膚外用医薬組成物である抗真菌クリームを作
成した。即ち、イ、ロ、ハ、ニをそれぞれ８０℃に加熱
し、イとロを良く混練りし、これにハを加え希釈し、更
にニを徐々に加え乳化した。これを撹拌冷却して、抗真
菌クリームを得た。このものは優れた抗真菌作用を示し
た。これは、本発明の組成物の必須成分である一般式
（Ｉ）の化合物と一般式（ＩＩ）の化合物を構成モノマ
ーに含む高分子の被膜による閉塞性と該高分子被膜の可
塑性に起因する被膜維持性によるものであることがわか
る。 イ ７０％マルビトール水溶液 ５ 重量部 グリセリン ３ 重量部 １，３−ブタンジオール ５ 重量部 メチルパラベン ０．３重量部 ブチルパラベン ０．１重量部 ロ トリグリセリンジイソステアレート ５ 重量部 ハ 固形パラフィン ２ 重量部 マイクロクリスタリンワックス ３ 重量部 流動パラフィン １０ 重量部 カルナウバワックス ２ 重量部 軽質イソパラフィン ５ 重量部 テルビナフィン １ 重量部 ニ 水 ５８ 重量部 高分子２ ０．６重量部<Example 50> According to the following formulation,
An antifungal cream which is a pharmaceutical composition for external use on the skin of the present invention was prepared. That is, A, B, C, and D were each heated to 80 ° C., and A and B were well kneaded, C was added and diluted, and D was gradually added and emulsified. This was stirred and cooled to obtain an antifungal cream. It exhibited excellent antifungal activity. This is due to the obstruction by the polymer film containing the compound of the general formula (I) and the compound of the general formula (II), which are essential components of the composition of the present invention, and the plasticity of the polymer film. It can be seen that this is due to the film maintenance. A 70% aqueous malbitol solution 5 parts by weight glycerin 3 parts by weight 1,3-butanediol 5 parts by weight methyl paraben 0.3 parts by weight butyl paraben 0.1 parts by weight b triglycerin diisostearate 5 parts by weight c solid paraffin 2 parts by weight Microcrystalline wax 3 parts by weight Liquid paraffin 10 parts by weight Carnauba wax 2 parts by weight Light isoparaffin 5 parts by weight Terbinafine 1 part by weight D Water 58 parts by weight Polymer 2 0.6 parts by weight
【００５８】＜実施例５１＞下記に示す処方に従って、
本発明の組成物である化粧水を作成した。このものは優
れた保水性による肌改善効果を有すると共に、４０℃１
ヶ月及び５℃１ヶ月の過酷な保存条件において安定であ
り、これは本発明の高分子の優れた水溶性に起因するも
のであることがわかる。又、前記肌改善効果は、該高分
子の可塑性を有する保水性皮膜形成作用によるものであ
ることがわかる。 グリセリン ３ 重量部 １，２−ペンタンジオール ５ 重量部 エタノール ５ 重量部 本発明の高分子９ ０．１重量部 水 ８６．９重量部<Example 51> According to the following formulation,
A lotion, a composition of the present invention, was prepared. It has a skin-improving effect due to excellent water retention,
It is stable under severe storage conditions of 1 month and 5 ° C. for 1 month, which indicates that this is due to the excellent water solubility of the polymer of the present invention. Further, it can be seen that the skin improving effect is due to the action of forming a water-retaining film having plasticity of the polymer. Glycerin 3 parts by weight 1,2-pentanediol 5 parts by weight Ethanol 5 parts by weight Polymer of the present invention 9 0.1 parts by weight Water 86.9 parts by weight
【００５９】＜実施例５２＞下記に示す処方に従って、
本発明の組成物である化粧水を作成した。このものは優
れた保水性による肌改善効果を有すると共に、４０℃１
ヶ月及び５℃１ヶ月の過酷な保存条件において安定であ
り、これは本発明の高分子の優れた水溶性に起因するも
のであることがわかる。又、前記肌改善効果は、該高分
子の可塑性を有する保水性皮膜形成作用によるものであ
ることがわかる。 グリセリン ３ 重量部 １，２−ペンタンジオール ５ 重量部 エタノール ５ 重量部 本発明の高分子１０ ０．１重量部 水 ８６．９重量部<Example 52> According to the following formulation,
A lotion, a composition of the present invention, was prepared. It has a skin-improving effect due to excellent water retention,
It is stable under severe storage conditions of 1 month and 5 ° C. for 1 month, which indicates that this is due to the excellent water solubility of the polymer of the present invention. Further, it can be seen that the skin improving effect is due to the action of forming a water-retaining film having plasticity of the polymer. Glycerin 3 parts by weight 1,2-pentanediol 5 parts by weight Ethanol 5 parts by weight Polymer 10 of the present invention 10 parts by weight Water 86.9 parts by weight
【００６０】＜実施例５３＞下記に示す処方に従って、
本発明の組成物である化粧水を作成した。このものは優
れた保水性による肌改善効果を有すると共に、４０℃１
ヶ月及び５℃１ヶ月の過酷な保存条件において安定であ
り、これは本発明の高分子の優れた水溶性に起因するも
のであることがわかる。又、前記肌改善効果は、該高分
子の可塑性を有する保水性皮膜形成作用によるものであ
ることがわかる。 グリセリン ３ 重量部 １，２−ペンタンジオール ５ 重量部 エタノール ５ 重量部 本発明の高分子１１ ０．１重量部 水 ８６．９重量部<Example 53> According to the following formulation,
A lotion, a composition of the present invention, was prepared. It has a skin-improving effect due to excellent water retention,
It is stable under severe storage conditions of 1 month and 5 ° C. for 1 month, which indicates that this is due to the excellent water solubility of the polymer of the present invention. Further, it can be seen that the skin improving effect is due to the action of forming a water-retaining film having plasticity of the polymer. Glycerin 3 parts by weight 1,2-pentanediol 5 parts by weight Ethanol 5 parts by weight Polymer 11 of the present invention 0.1 parts by weight Water 86.9 parts by weight
【００６１】＜実施例５４＞下記に示す処方に従って、
本発明の組成物である化粧水を作成した。このものは優
れた保水性による肌改善効果を有すると共に、４０℃１
ヶ月及び５℃１ヶ月の過酷な保存条件において安定であ
り、これは本発明の高分子の優れた水溶性に起因するも
のであることがわかる。又、前記肌改善効果は、該高分
子の可塑性を有する保水性皮膜形成作用によるものであ
ることがわかる。 グリセリン ３ 重量部 １，２−ペンタンジオール ５ 重量部 エタノール ５ 重量部 本発明の高分子１２ ０．１重量部 水 ８６．９重量部<Example 54> According to the following formulation,
A lotion, a composition of the present invention, was prepared. It has a skin-improving effect due to excellent water retention,
It is stable under severe storage conditions of 1 month and 5 ° C. for 1 month, which indicates that this is due to the excellent water solubility of the polymer of the present invention. Further, it can be seen that the skin improving effect is due to the action of forming a water-retaining film having plasticity of the polymer. Glycerin 3 parts by weight 1,2-pentanediol 5 parts by weight Ethanol 5 parts by weight Polymer of the present invention 12 0.1 part by weight Water 86.9 parts by weight
【００６２】＜実施例５５＞下記に示す処方に従って、
本発明の組成物である化粧水を作成した。このものは優
れた保水性による肌改善効果を有すると共に、４０℃１
ヶ月及び５℃１ヶ月の過酷な保存条件において、実施例
５１〜５４の化粧水に比べれば、やや濁りは認められる
ものの、ほぼ安定であり、これは本発明の高分子の優れ
た水溶性に起因するものであることがわかる。又、この
僅かな曇化から考察するに、一般式（Ｉ）に表される化
合物の高分子に於ける構成比は、５〜９．９重量％、更
に好ましくは、７〜９．５重量％が特に好ましい範囲で
あることがわかる。又、前記肌改善効果は、該高分子の
可塑性を有する保水性皮膜形成作用によるものであるこ
とがわかる。 グリセリン ３ 重量部 １，２−ペンタンジオール ５ 重量部 エタノール ５ 重量部 本発明の高分子２ ０．１重量部 水 ８６．９重量部Example 55 According to the following formulation,
A lotion, a composition of the present invention, was prepared. It has a skin-improving effect due to excellent water retention,
Under harsh storage conditions of 5 months and 5 ° C. for 1 month, compared to the lotions of Examples 51 to 54, although a little turbidity was observed, it was almost stable, which was due to the excellent water solubility of the polymer of the present invention. It can be seen that this is the cause. Considering the slight clouding, the composition ratio of the compound represented by the general formula (I) in the polymer is 5 to 9.9% by weight, more preferably 7 to 9.5% by weight. % Is a particularly preferred range. Further, it can be seen that the skin improving effect is due to the action of forming a water-retaining film having plasticity of the polymer. Glycerin 3 parts by weight 1,2-pentanediol 5 parts by weight Ethanol 5 parts by weight Polymer 2 of the present invention 0.1 part by weight Water 86.9 parts by weight
【００６３】[0063]
【発明の効果】本発明によれば、化粧料や塗料、繊維処
理剤として有用な、水性担体中で一様に溶解していて、
塗布後は優れた耐水性のある被膜を形成する高分子含有
組成物を提供することができる。According to the present invention, it is useful that it is uniformly dissolved in an aqueous carrier,
It is possible to provide a polymer-containing composition that forms a coating having excellent water resistance after application.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｄ 133/06 Ｃ０９Ｄ 133/06 133/14 133/14 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C09D 133/06 C09D 133/06 133/14 133/14 133/14
Claims (9)
選ばれる１種乃至は２種以上と一般式（ＩＩ）に表され
るモノマーから選ばれる１種乃至は２種以上とを構成モ
ノマーとして含有する、可塑性を有する高分子を含有す
る組成物。 【化１】 一般式（Ｉ） （但し、式中Ｒ１は水素原子又は炭素数１〜４のアルキ
ル基を表し、Ｒ２はフッ素原子を有していても良い炭素
数１〜２０のアルキル基を表す。） 【化２】 一般式（ＩＩ） （但し、式中Ｒ３は水素原子又は炭素数１〜４のアルキ
ル基を表し、Ｒ４はアルキルオキシ基、アシロキシ基又
は水酸基を有していても良い、炭素数２〜４のアルキル
基を表し、Ｒ５は水素原子、芳香族乃至は脂肪族の炭素
数１〜８の炭化水素基又はアシル基を表し、ｎは１〜４
０の数値を表す。）(1) one or more kinds selected from the monomers represented by the following general formula (I) and one or more kinds selected from the monomers represented by the general formula (II) A composition containing a polymer having plasticity, which is contained as a monomer. Embedded image General formula (I) (wherein, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 represents an alkyl group having 1 to 20 carbon atoms which may have a fluorine atom.) Formula 2 Formula (II) (wherein, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 may have an alkyloxy group, an acyloxy group, or a hydroxyl group, and has 2 to 4 carbon atoms. R5 represents a hydrogen atom, an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or an acyl group, and n represents 1 to 4
Represents a numerical value of 0. )
一般式（ＩＩＩ）に表される化合物を含有することを特
徴とする、請求項１に記載の組成物。 【化３】 一般式（ＩＩＩ） （但し、式中Ｒ６は水素原子又は炭素数１〜４のアルキ
ル基を表し、Ｏ、Ｐはそれぞれ独立に１〜１０の数値を
表し、Ｒ７はフッ素原子又は水素原子を表す。）2. A compound represented by the general formula (I):
The composition according to claim 1, comprising a compound represented by the general formula (III). Embedded image General formula (III) (wherein, R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, O and P each independently represent a numerical value of 1 to 10, and R7 represents a fluorine atom or a hydrogen atom. .)
て、一般式（ＩＶ）に表される化合物を含有することを
特徴とする、請求項１記載の組成物。 【化４】 一般式（ＩＶ） （但し、式中Ｒ８は水素原子又は炭素数１〜４のアルキ
ル基を表し、Ｒ９は炭素数１〜８の芳香族乃至は脂肪族
の炭化水素基又は水素原子を表し、Ｑは５〜３０の数値
を表す。）3. The composition according to claim 1, wherein the compound represented by the general formula (II) contains a compound represented by the general formula (IV). Embedded image General formula (IV) (wherein, R8 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R9 represents an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or a hydrogen atom, Q represents a numerical value of 5 to 30.)
れる１種乃至は２種以上を５〜９．９重量％、一般式
（ＩＩ）に表される化合物から選ばれる１種乃至は２種
以上を３０〜９０．１重量％構成モノマーとして含有す
ることを特徴とする、請求項１〜３の何れか一項に記載
の高分子含有組成物。4. One or more compounds selected from the compounds represented by the general formula (I), 5 to 9.9% by weight, and one or more compounds selected from the compounds represented by the general formula (II) The polymer-containing composition according to any one of claims 1 to 3, wherein the polymer contains two or more kinds as constituent monomers in an amount of 30 to 90.1% by weight.
一様な系を作成した場合、その液の可視光に対する透過
度が９０％以上であることを特徴とする、請求項１〜４
の何れか一項に記載の高分子含有組成物。5. The method according to claim 1, wherein when a uniform system is prepared by adding 99 parts by weight of water to 1 part by weight of the polymer, the transmittance of the liquid to visible light is 90% or more. ~ 4
The polymer-containing composition according to any one of the above.
求項１〜５の何れか一項に記載の高分子含有組成物。6. The polymer-containing composition according to claim 1, which is for surface treatment.
繊維表面、ガラス表面乃至は金属表面であることを特徴
とする、請求項１〜６の何れか一項に記載の高分子含有
組成物。7. The method according to claim 1, wherein the surface is a skin surface, a nail surface, a hair surface,
The polymer-containing composition according to any one of claims 1 to 6, wherein the composition is a fiber surface, a glass surface, or a metal surface.
請求項１〜７何れか１項に記載の高分子含有組成物。8. It does not contain a plasticizer,
The polymer-containing composition according to claim 1.
１〜８の何れか一項に記載の高分子含有組成物。9. The polymer-containing composition according to claim 1, which is a cosmetic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11289352A JP2000234042A (en) | 1998-12-16 | 1999-10-12 | Copolymer-containing composition for surface modification |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10-375653 | 1998-12-16 | ||
| JP37565398 | 1998-12-16 | ||
| JP11289352A JP2000234042A (en) | 1998-12-16 | 1999-10-12 | Copolymer-containing composition for surface modification |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000234042A true JP2000234042A (en) | 2000-08-29 |
Family
ID=26557570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11289352A Pending JP2000234042A (en) | 1998-12-16 | 1999-10-12 | Copolymer-containing composition for surface modification |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000234042A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005120443A1 (en) * | 2004-06-14 | 2005-12-22 | Yoshikazu Shimizu | Method of hair restoration, method of fixation and stabilization of hair foundation agent, and hair restoration setting agent used in the methods |
| JP2008019219A (en) * | 2006-07-14 | 2008-01-31 | Kao Corp | Oil-in-water emulsion composition |
| JP2009137914A (en) * | 2007-12-10 | 2009-06-25 | Kao Corp | Oil-in-water type emulsion cosmetic |
| JP2012031087A (en) * | 2010-07-30 | 2012-02-16 | Fancl Corp | Polymer emulsifier and emulsified composition |
| CN102415955A (en) * | 2010-09-27 | 2012-04-18 | 株式会社芳珂 | Emulsified compound |
| JP2017072397A (en) * | 2015-10-05 | 2017-04-13 | 株式会社 資生堂 | Functionality evaluation method for cosmetic using hair keratin film |
-
1999
- 1999-10-12 JP JP11289352A patent/JP2000234042A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005120443A1 (en) * | 2004-06-14 | 2005-12-22 | Yoshikazu Shimizu | Method of hair restoration, method of fixation and stabilization of hair foundation agent, and hair restoration setting agent used in the methods |
| JP2008019219A (en) * | 2006-07-14 | 2008-01-31 | Kao Corp | Oil-in-water emulsion composition |
| JP2009137914A (en) * | 2007-12-10 | 2009-06-25 | Kao Corp | Oil-in-water type emulsion cosmetic |
| JP2012031087A (en) * | 2010-07-30 | 2012-02-16 | Fancl Corp | Polymer emulsifier and emulsified composition |
| CN102415955A (en) * | 2010-09-27 | 2012-04-18 | 株式会社芳珂 | Emulsified compound |
| JP2017072397A (en) * | 2015-10-05 | 2017-04-13 | 株式会社 資生堂 | Functionality evaluation method for cosmetic using hair keratin film |
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