JPH04103510A - Cosmetic - Google Patents
CosmeticInfo
- Publication number
- JPH04103510A JPH04103510A JP22076090A JP22076090A JPH04103510A JP H04103510 A JPH04103510 A JP H04103510A JP 22076090 A JP22076090 A JP 22076090A JP 22076090 A JP22076090 A JP 22076090A JP H04103510 A JPH04103510 A JP H04103510A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- polymer
- water
- weight
- aqueous
- 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.)
- Granted
Links
- 239000002537 cosmetic Substances 0.000 title claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 88
- 239000000178 monomer Substances 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000839 emulsion Substances 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 30
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 30
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002932 luster Substances 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 7
- -1 N,N-dimethylaminoethyl Chemical group 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000003755 preservative agent Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 6
- 239000003205 fragrance Substances 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 3
- ZAWQXWZJKKICSZ-UHFFFAOYSA-N 3,3-dimethyl-2-methylidenebutanamide Chemical compound CC(C)(C)C(=C)C(N)=O ZAWQXWZJKKICSZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000003676 hair preparation Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 2
- 235000013871 bee wax Nutrition 0.000 description 2
- 239000012166 beeswax Substances 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000001587 sorbitan monostearate Substances 0.000 description 2
- 235000011076 sorbitan monostearate Nutrition 0.000 description 2
- 229940035048 sorbitan monostearate Drugs 0.000 description 2
- 239000000516 sunscreening agent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- NDAJNMAAXXIADY-UHFFFAOYSA-N 2-methylpropanimidamide Chemical compound CC(C)C(N)=N NDAJNMAAXXIADY-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 240000001417 Vigna umbellata Species 0.000 description 1
- 235000011453 Vigna umbellata Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- PUSKHXMZPOMNTQ-UHFFFAOYSA-N ethyl 2,1,3-benzoselenadiazole-5-carboxylate Chemical group CCOC(=O)C1=CC=C2N=[Se]=NC2=C1 PUSKHXMZPOMNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000000118 hair dye Substances 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 1
- SYUYXOYNRMMOGW-UHFFFAOYSA-N n,n-dimethyl-3-phenylprop-2-en-1-amine Chemical compound CN(C)CC=CC1=CC=CC=C1 SYUYXOYNRMMOGW-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Cosmetics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は化粧料に関するものであり、更に詳しくは、つ
や、耐水性、造膜性等に優れた水性複合ポリマーエマル
ジョンを含有する毛髪化粧料、皮膚化粧料等の化粧料に
関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to cosmetics, and more specifically, hair cosmetics containing an aqueous composite polymer emulsion with excellent shine, water resistance, film-forming properties, etc. , relates to cosmetics such as skin cosmetics.
〔従来の技術及び発明が解決しようとする課題〕従来か
ら毛髪化粧料、メークアップ化粧料、薬用化粧料等の化
粧料には各種の造膜性ポリマーが用いられてきた。この
造膜性ポリマーとしては、水溶性ポリマーや油溶性ポリ
マーが用いられてきたが、一般に前者では耐水性が悪く
汗や水でとれやすい、後者では耐油性が悪く、皮脂でと
れやすく、また溶剤として揮発性有機溶剤を使わざるを
得ないといった問題点があった。[Prior Art and Problems to be Solved by the Invention] Various film-forming polymers have been used in cosmetics such as hair cosmetics, makeup cosmetics, and medicated cosmetics. Water-soluble polymers and oil-soluble polymers have been used as film-forming polymers, but the former generally have poor water resistance and are easily removed by sweat or water, while the latter have poor oil resistance, are easily removed by sebum, and are solvent-resistant. There was a problem in that volatile organic solvents had to be used.
このため、両者の欠点を有しない造膜性物質として水性
のポリマーエマルジョン（ラテックス）が注目されてき
たが、つや、造膜性、耐水性等の特性に十分満足のいく
ポリマーエマルジョンは得られていないのが現状である
。For this reason, water-based polymer emulsions (latex) have been attracting attention as a film-forming material that does not have the drawbacks of both, but no polymer emulsion that is fully satisfactory in terms of gloss, film-forming properties, water resistance, etc. has yet to be obtained. The current situation is that there is no such thing.
係る状況に鑑み、本発明者らは、つや、耐水性、造膜性
に優れたポリマーエマルジョンを得るべく鋭意研究を重
ねた結果、特定の水性複合ポリマーエマルジョンが、本
目的達成に極めて有効である事を見出し、本発明に至っ
た。In view of this situation, the present inventors have conducted extensive research to obtain a polymer emulsion with excellent gloss, water resistance, and film-forming properties, and have found that a specific aqueous composite polymer emulsion is extremely effective in achieving this objective. This discovery led to the present invention.
すなわち、本発明は、ポリマーエマルジョンを構成する
ポリマー粒子が化学組成の異なる少なくとも二層からな
る多層構造を有し、かつ、最外層のポリマーが内層のポ
リマーよりも低い軟化温度を有する水性複合ポリマーエ
マルジョンを固形分換算で１〜６０重量％含有すること
を特徴とする化粧料を提供するものである。That is, the present invention provides an aqueous composite polymer emulsion in which the polymer particles constituting the polymer emulsion have a multilayer structure consisting of at least two layers with different chemical compositions, and the polymer in the outermost layer has a softening temperature lower than that of the polymer in the inner layer. The purpose of the present invention is to provide a cosmetic material containing from 1 to 60% by weight in terms of solid content.
本発明に用いられる多層構造を有する水性複合ポリマー
エマルジョンは、塗料分野においていくつか知られてお
り、例えば、英国特許第９２８．２５１号公報には、３
段階にわけて乳化重合することによって得られた多層構
造ポリマーラテックスが耐水性の良い塗膜性能の優れた
水性の光沢ペイント素材となることが、また米国特許第
３．２５６，２３３号公報には、重合を２〜３段階にわ
けて行い、生成した層構造をもったポリマーラテックス
とアルカリ可溶性のスチレン／無水マレイン酸系の交互
共重合体とからなる水性の光沢ペイントが、更に米国特
許第３，２３６，７９８号公報には、重合を段階的に行
ったアクリロニトリルとアクリル酸エチルの共重合体ラ
テックスが耐溶剤の優れたラテックスペイント素材とな
ることが記載されているが、化粧品分野への応用例は見
当たらない。Several aqueous composite polymer emulsions having a multilayer structure used in the present invention are known in the paint field; for example, British Patent No. 928.251 describes 3
U.S. Pat. No. 3,256,233 discloses that a multilayered polymer latex obtained by emulsion polymerization in stages can be used as a water-based glossy paint material with good water resistance and excellent coating performance. The polymerization is carried out in two to three stages, and a water-based glossy paint consisting of a polymer latex with a layered structure and an alkali-soluble styrene/maleic anhydride-based alternating copolymer is further developed in US Pat. , No. 236,798 describes that a copolymer latex of acrylonitrile and ethyl acrylate that is polymerized in stages can be used as a latex paint material with excellent solvent resistance, but it is difficult to apply it to the cosmetic field. No examples found.
多層構造をとることによって、ロールなどで混練する従
来技術のブレンド方法では困難であった、ガラス転移温
度が高く、かつ、相溶性の悪いポリマーどうしの組み合
わせや、ガラス相〜結晶相〜ゴム相の共存するポリマー
の生成などの種々の組み合わせが可能である。本発明者
らは、最外層のポリマーの軟化温度が内層のポリマーの
軟化温度に比べて低くなるように設計すれば、多層構造
をとらない均一組成の粒子からなるポリマーエマルジョ
ンに比べて、成膜性のよさと、塗膜硬度の高さを両立さ
せることが可能となり、化粧料として好適に用い得るこ
とを見出した。By adopting a multilayer structure, it is possible to combine polymers with high glass transition temperatures and poor compatibility, which is difficult with conventional blending methods that involve kneading with rolls, and to combine polymers that have a glass phase, crystalline phase, and rubber phase. Various combinations are possible, such as the generation of coexisting polymers. The present inventors believe that if the outermost polymer layer is designed to have a softening temperature lower than that of the inner layer, it will be easier to form a film than a polymer emulsion consisting of particles with a uniform composition that does not have a multilayer structure. It has been found that it is possible to achieve both good properties and high coating film hardness, and that it can be suitably used as a cosmetic.
このような多層構造を有する粒子がらなろ水性複合ポリ
マーエマルジョンの製造方法としては、一般的に、水媒
体中で段階的に乳化重合を行う方法等が知られている０
例えば、いわゆるシード乳化重合により内層と外層とを
異なる組成のモノマーを組み合わせて生成せしめる方法
がある（色材協会誌９皿（５）、 ２６７−２７５（１
９７７）等）。As a method for producing a water-free composite polymer emulsion consisting of particles having such a multilayer structure, a method of carrying out emulsion polymerization in stages in an aqueous medium is generally known.
For example, there is a method in which the inner layer and the outer layer are formed by combining monomers with different compositions by so-called seed emulsion polymerization (Color Materials Association Journal 9 Plate (5), 267-275 (1).
977) etc.).
その際に、組み合わせるモノマーの種類を選択すること
によりシード（種）ポリマーが内層を形成する場合と、
外層を形成する場合とがある。At that time, there are cases where the seed polymer forms an inner layer by selecting the type of monomers to be combined;
Sometimes it forms an outer layer.
またシード重合により層構造の明瞭でないポリマー粒子
が得られることもあるが、そのようなポリマーのエマル
ジョンは本発明には用いられない。Further, polymer particles with unclear layer structure may be obtained by seed polymerization, but emulsions of such polymers are not used in the present invention.
更に得られたポリマーエマルジョン粒子の内層と外層を
構成するポリマーが相異なる軟化温度を有するように設
計することも、用いるモノマーの種類を選択することに
より可能である。Furthermore, it is also possible to design the polymers constituting the inner and outer layers of the obtained polymer emulsion particles to have different softening temperatures by selecting the types of monomers used.
本発明においては特に、最外層を構成するポリマーが内
層を構成するポリマーよりも低い軟化温度を有すること
を特徴とする。このような構成をとることにより、皮膚
や毛髪に塗布した際により低い軟化温度を有する最外層
が連続相となって良好な成膜性を示し、より高い軟化温
度を有する内層が塗膜内部にあって適度な塗膜硬度を付
与できるものと思われる。最外層を構成するポリマーが
内層を構成するポリマーよりも高い軟化温度となるよう
にポリマーエマルジョンを設計しても、成膜性及び得ら
れた塗膜の物性は化粧料の用途には好適とは言えない。The present invention is particularly characterized in that the polymer constituting the outermost layer has a lower softening temperature than the polymer constituting the inner layer. By adopting this structure, when applied to the skin or hair, the outermost layer with a lower softening temperature becomes a continuous phase and exhibits good film forming properties, while the inner layer with a higher softening temperature forms inside the coating film. Therefore, it is thought that appropriate coating hardness can be imparted. Even if a polymer emulsion is designed so that the polymer constituting the outermost layer has a higher softening temperature than the polymer constituting the inner layer, the film-forming properties and physical properties of the resulting coating film may not be suitable for cosmetic applications. I can not say.
本発明において上記最外層のポリマーの軟化温度はでき
るだけ低い方が成膜性の面で有利であるが、低すぎると
塗膜がべとつき光沢保持性に欠けることから、−１０°
Ｃ以上が好ましく、より好ましくはＯ″Ｃ０以上る。ま
た、最外層のポリマーの軟化温度が高く（例えば室温以
上）成膜しにくい場合には成膜助剤、可塑剤を適宜併用
して成膜性を調整することができる。In the present invention, it is advantageous to have the softening temperature of the polymer in the outermost layer as low as possible in terms of film forming properties; however, if it is too low, the coating film becomes sticky and lacks gloss retention;
C or higher, more preferably O''C0 or higher. In addition, if the outermost layer polymer has a high softening temperature (e.g., room temperature or higher) and is difficult to form a film, a film-forming aid and a plasticizer may be appropriately used in combination. Film properties can be adjusted.
一方、内層のポリマーの軟化温度は、最外層のポリマー
のそれより１０°Ｃ以上高いことが好ましい。軟化温度
の差が１０″Ｃ未満の場合は、上記の良好な成膜性と適
度な塗膜硬度を両立させることが難しい。On the other hand, the softening temperature of the polymer in the inner layer is preferably 10° C. or more higher than that of the polymer in the outermost layer. If the difference in softening temperature is less than 10''C, it is difficult to achieve both the above-mentioned good film formability and appropriate coating hardness.
内層部と最外層部のポリマーの重量比について述べると
、最外層部のポリマーは内層部のポリマーに対して、０
．１〜２０重量倍が好ましく、より好ましくは０．５〜
５重量倍である。０．１重量倍未満及び２０重量倍を越
えた場合は、内層部もしくは最外層部のポリマーの性質
がより支配的になるため、上記のような複合ボリマーエ
マルジツンとしての効果は期待できない。Regarding the weight ratio of the polymers in the inner layer and the outermost layer, the polymer in the outermost layer has a weight ratio of 0 to the polymer in the inner layer.
．． 1 to 20 times by weight is preferable, more preferably 0.5 to 20 times by weight.
It is 5 times the weight. If the amount is less than 0.1 times by weight or more than 20 times by weight, the properties of the polymer in the inner layer or outermost layer become more dominant, and the above-mentioned effect as a composite polymer emulsion cannot be expected. .
尚、シード重合を１段階行えば内層と外層の二層からな
る複合ポリマーエマルジョンが得うれるが、更にシード
重合をくり返して行い、更に多層構造の複合ポリマーエ
マルジョンを得ることも可能である。その場合、最外層
を構成するポリマーの軟化温度が内層を構成するポリマ
ーの軟化温度よりも低く設計しておけば、本発明の目的
は達成され得る。Although a composite polymer emulsion consisting of two layers, an inner layer and an outer layer, can be obtained by carrying out one stage of seed polymerization, it is also possible to obtain a composite polymer emulsion having a multilayer structure by repeating the seed polymerization. In that case, the object of the present invention can be achieved if the softening temperature of the polymer constituting the outermost layer is designed to be lower than the softening temperature of the polymer constituting the inner layer.
本発明において、外層及び内層を構成するポリマーは、
重合可能な二重結合を有するモノマーを重合することに
よって得られる。用いられるモノマーとしては特に制限
はなく、例えば、アクリル酸メチル、アクリル酸エチル
、アクリル酸ｎ−ブチル、アクリル酸ラウリル、メタク
リル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−
ブチル等の（メタ）アクリル酸エステル類；スチレン、
クロルスチレンなどのスチレン系モノマー； ｔ−ブチ
ルアクリルアミドなとのＮ−置換（メタ）アクリルアミ
ド；並びにアクリロニトリル、メタクリロニトリルなど
が挙げられ、これらの一種または二種以上から選択する
ことができる。In the present invention, the polymers constituting the outer layer and the inner layer are:
It is obtained by polymerizing a monomer having a polymerizable double bond. There are no particular limitations on the monomers used, and examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, and n-methacrylate.
(Meth)acrylic acid esters such as butyl; styrene,
Examples include styrenic monomers such as chlorostyrene; N-substituted (meth)acrylamides such as t-butylacrylamide; and acrylonitrile, methacrylonitrile, etc., and one or more of these can be selected.
ここで内層を構成するポリマーは外層を構成するポリマ
ーに比べて疎水的であった方が、目的とする多層構造エ
マルジョンを得やすい。Here, it is easier to obtain the desired multilayer structure emulsion if the polymer constituting the inner layer is more hydrophobic than the polymer constituting the outer layer.
従って、重合して得られるポリマーの親水性／疎水性、
及び軟化温度の高／低を考慮して用いるモノマーを選択
すればよい。これらを適宜組み合わせて乳化剤を用いた
乳化重合、シード乳化重合、乳化剤を用いない水媒体不
均一重合等、公知の手法により多層構造を有する水性複
合ポリマーエマルジッンを作製することができる。Therefore, the hydrophilicity/hydrophobicity of the polymer obtained by polymerization,
The monomer to be used may be selected in consideration of the high/low softening temperature. By appropriately combining these, an aqueous composite polymer emulsion having a multilayer structure can be produced by known methods such as emulsion polymerization using an emulsifier, seed emulsion polymerization, and aqueous medium heterogeneous polymerization without using an emulsifier.
本発明において用いられる特に好ましい水性複合ボリマ
ーエマルジッンは、塩生成基を有し重合可能な二重結合
を有する単量体０．５〜１５重量％と、それと共重合し
得る重合可能な二重結合を有する単量体８５〜９９．５
重量％とを共重合して得られる共重合体の有機溶剤溶液
に水を加えた後、有機溶剤を留去して得られる水性ビニ
ル樹脂（Ａ）の存在下で、一種又は二種以上の重合可能
な二重結合を有する単量体（Ｂ）を重合して得られた水
性複合ポリマーエマルジョンである。A particularly preferred aqueous composite polymer emulsion used in the present invention contains 0.5 to 15% by weight of a monomer having a salt-forming group and a polymerizable double bond, and a polymerizable polymer copolymerizable therewith. Monomer with double bond 85-99.5
After adding water to an organic solvent solution of a copolymer obtained by copolymerizing % by weight, in the presence of an aqueous vinyl resin (A) obtained by distilling off the organic solvent, one or more types of This is an aqueous composite polymer emulsion obtained by polymerizing a monomer (B) having a polymerizable double bond.
本発明において、水性ビニル樹脂（Ａ）の製造に用いら
れる塩生成基を有し重合可能な二重結合を有する単量体
としては、アニオン性単量体、カチオン性単量体、両性
単量体等が挙げられる。In the present invention, monomers having a salt-forming group and a polymerizable double bond used in the production of the aqueous vinyl resin (A) include anionic monomers, cationic monomers, and amphoteric monomers. Examples include the body.
アニオン性単量体としては、アクリル酸、メタクリル酸
、マレイン酸等の不飽和カルボン酸モノマー又はそれら
の無水物あるいは塩；スチレンスルホン酸、２−アクリ
ルアミド−２−メチルプロパンスルホン酸等の不飽和ス
ルホン酸モノマー又はそれらの塩：ビニルホスホン酸、
アシッドホスホキシエチル（メタ）アクリレート等の不
飽和リン酸モノマー等が挙げられる。Examples of anionic monomers include unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, and maleic acid, or their anhydrides or salts; unsaturated sulfones such as styrene sulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid. Acid monomers or their salts: vinylphosphonic acid,
Examples include unsaturated phosphoric acid monomers such as acid phosphoxyethyl (meth)acrylate.
カチオン性単量体としては、Ｎ、Ｎ−ジメチルアミノエ
チル（メタ）アクリレート、Ｎ、Ｎ−ジメチルアミノプ
ロピルアクリルアミド等のジアルキルアミノ基を有する
（メタ）アクリル酸エステル又は（メタ）アクリルアミ
ドｌ［；Ｎ、Ｎ−ジメチルアミノスチレン、Ｎ、Ｎ−ジ
メチルアミノメチルスチレンの如きジアルキルアミノ基
を有するスチレン類；４−ビニルピリジン、２−ビニル
ピリジンの如きビニルピリジン類；或いはこれらをハロ
ゲン化アルキル、ハロゲン化ベンジル、アルキル又はア
リールスルホン酸、又は硫酸ジアルキルの如き公知の四
級化剤で四級化したもの等が挙げられる。Examples of the cationic monomer include (meth)acrylic acid esters or (meth)acrylamide having a dialkylamino group such as N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropylacrylamide, etc. , N-dimethylaminostyrene and N,N-dimethylaminomethylstyrene; vinylpyridines such as 4-vinylpyridine and 2-vinylpyridine; or these can be combined with halogenated alkyl or halogenated benzyl , alkyl or aryl sulfonic acids, or those quaternized with known quaternizing agents such as dialkyl sulfate.
両性単量体としては、Ｎ−（３−スルホプロピル）−Ｎ
−メタクリロイルオキシエチル−Ｎ。As an amphoteric monomer, N-(3-sulfopropyl)-N
-methacryloyloxyethyl-N.
Ｎ−ジメチルアンモニウムベタイン、Ｎ−カルボキシメ
チル−Ｎ−メタクリロイルオキシエチル−Ｎ、Ｎ−ジメ
チルアンモニウムベタイン等が挙げられる。Examples include N-dimethylammonium betaine, N-carboxymethyl-N-methacryloyloxyethyl-N, and N-dimethylammonium betaine.
これら塩生成基を有し重合可能な二重結合を有する単量
体と共重合し得る重合可能な二重結合を有する単量体と
しては、アクリル酸メチル、アクリル酸エチル、アクリ
ル酸ｎ−ブチル、アクリル酸ラウリル、メタクリル酸メ
チル、メタクリル酸エチル、メタクリル酸ｎ−ブチル等
の（メタ）アクリル酸エステル類；スチレン、クロルス
チレンなどのスチレン系モノマー； ｔ−ブチルアクリ
ルアミドなとのＮ−Ｊｊ換（メタ）アクリルアミド；並
びにアクリロニトリル、メタクリロニトリルなどが挙げ
られ、これらの−種又は二種以上から選択することがで
きる。Examples of monomers having a polymerizable double bond that can be copolymerized with these salt-forming group-containing monomers having a polymerizable double bond include methyl acrylate, ethyl acrylate, and n-butyl acrylate. , (meth)acrylic acid esters such as lauryl acrylate, methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate; styrenic monomers such as styrene and chlorostyrene; N-Jj conversion with t-butylacrylamide ( (meth)acrylamide; as well as acrylonitrile, methacrylonitrile, etc., and can be selected from one or more of these.
本発明において、塩生成基を有し重合可能な二重結合を
有する単量体と、それと共重合し得る重合可能な二重結
合を有する単量体の配合割合は、前者０．５〜１５重量
％、後者８５〜９９．５重量％であり、より好ましくは
前者２〜１０重量％、後者９０〜９８重量％である。塩
生成基を有し重合可能な二重結合を有する単量体の量が
０．５重量％未満では安定な水性ビニル樹脂は得られず
、１５重量％を趨えると、実用性のある耐水性を有する
樹脂は得られない。In the present invention, the blending ratio of a monomer having a salt-forming group and a polymerizable double bond to a monomer having a polymerizable double bond that can be copolymerized with the monomer is 0.5 to 15 The latter is 85 to 99.5% by weight, more preferably the former is 2 to 10% by weight, and the latter is 90 to 98% by weight. If the amount of the monomer having a salt-forming group and a polymerizable double bond is less than 0.5% by weight, a stable aqueous vinyl resin cannot be obtained, and if it exceeds 15% by weight, it will not have practical water resistance. A resin with properties cannot be obtained.
上記の塩生成基を有し重合可能な二重結合を有する単量
体と、それと共重合し得る重合可能な二重結合を有する
単量体とを共重合させるには、公知のラジカル開始剤を
用い、溶液重合法、バルク重合法、沈殿重合法等の公知
の重合法により共重合させればよい、後に水系に転相す
ることから、溶液重合法を用い重合後直ちに次の工程に
移るのが好ましい、又、重合の後、水系に転相させる前
に得られた共重合体を公知の方法で精製することも可能
である。得られた共重合体の重量平均分子量は１０．０
００〜５００．０００が好適であり、ｓｏ、ｏｏｏ〜２
００．０００がより好ましい。In order to copolymerize the above monomer having a salt-forming group and a polymerizable double bond with a monomer having a polymerizable double bond that can be copolymerized with the monomer, a known radical initiator is used. Copolymerization can be carried out using known polymerization methods such as solution polymerization, bulk polymerization, and precipitation polymerization.Since the phase is later inverted to an aqueous system, use solution polymerization and proceed to the next step immediately after polymerization. It is also possible to purify the obtained copolymer by a known method after polymerization and before phase inversion to an aqueous system. The weight average molecular weight of the obtained copolymer was 10.0
00~500.000 is suitable, so, ooo~2
00.000 is more preferred.
重量平均分子量がｉｏ、ｏｏｏ未満では塗膜の物性が劣
り、また５００，０００を超えると転相が困難となり、
水性ビニル樹脂が得られなくなる。If the weight average molecular weight is less than io or ooo, the physical properties of the coating film will be poor, and if it exceeds 500,000, phase inversion will be difficult.
Water-based vinyl resin cannot be obtained.
共重合体の塩生成基がイオン化されていない場合は必要
に応じて中和剤によりイオン化を行う、塩生成基を有し
重合可能な二重結合を有する単量体として、既に塩とな
っている単量体を用いる場合は、中和剤によるイオン化
は不要であるが、そうでない場合は、中和剤によりイオ
ン化した方が皮膚や毛髪に対する刺激性が少ないため好
ましい。If the salt-forming group of the copolymer is not ionized, ionize it with a neutralizing agent as necessary. If a monomer is used, ionization with a neutralizing agent is not necessary, but in other cases, ionization with a neutralizing agent is preferable because it is less irritating to the skin and hair.
中和剤としては塩生成基の種類に応じてそれぞれ公知の
酸、塩基を用いればよい。酸としては、例えば塩酸、硫
酸等の無機酸；酢酸、プロピオン酸、乳酸、コハク酸、
グリコール酸等の有機酸が挙げられる。また塩基として
は例えばトリメチルアミン、トリエチルアミン等の３級
アミン類、アンモニア、水酸化ナトリウム等が挙げられ
る。中和度に特に制限はないが、得られた水性ビニル樹
脂のｐＨが中性付近になるように中和するのが望ましい
。As the neutralizing agent, known acids and bases may be used depending on the type of salt-forming group. Examples of acids include inorganic acids such as hydrochloric acid and sulfuric acid; acetic acid, propionic acid, lactic acid, succinic acid,
Examples include organic acids such as glycolic acid. Examples of the base include tertiary amines such as trimethylamine and triethylamine, ammonia, and sodium hydroxide. Although there are no particular limitations on the degree of neutralization, it is desirable to neutralize the resulting aqueous vinyl resin so that its pH is near neutral.
こうして得られた共重合体を水系に転相し、水性樹脂と
するには、共重合体をアルコール系、ケトン系、エステ
ル系、エーテル系等の有機溶剤の溶液とし、これに水を
加え、上記有機溶剤を留去すればよい。In order to phase-invert the copolymer thus obtained into an aqueous system and make it into an aqueous resin, the copolymer is made into a solution of an organic solvent such as an alcohol-based, ketone-based, ester-based, or ether-based solvent, and water is added to the solution. The organic solvent may be distilled off.
上記有機溶剤溶液の濃度は共重合体の組成及び分子量に
よって適宜決定されるが、通常１０〜８０重量％であり
、好ましくは２０〜７０重量％である。The concentration of the organic solvent solution is appropriately determined depending on the composition and molecular weight of the copolymer, but is usually 10 to 80% by weight, preferably 20 to 70% by weight.
有機溶剤としては上記のものの中でも、アルコール系及
び／又はケトン系の有機溶剤で沸点が水より低く、水と
混和し得るものが転相と溶剤の留去がうま（行なえるの
で好ましい。尚、溶液重合法による場合、重合の溶剤と
しては任意に選ぶことができるが、上記のような有機溶
剤を用いれば、重合から転相までの工程が簡略化される
ので好ましい。Among the organic solvents mentioned above, alcohol-based and/or ketone-based organic solvents that have a boiling point lower than that of water and are miscible with water are preferred because they facilitate phase inversion and solvent distillation. When using the solution polymerization method, the polymerization solvent can be arbitrarily selected, but it is preferable to use the organic solvents mentioned above because the steps from polymerization to phase inversion can be simplified.
本発明に用いられるアルコール系溶削としては、例えば
メタノール、エタノール、ｎ−プロパツール、イソプロ
パツール等が挙げられ、好ましくはイソプロパツールで
ある。ケトン系溶剤としては、例えばアセトン、メチル
エチルケトン、ジエチルケトン等が挙げられ、好ましく
はメチルエチルケトンである。これらは１種又は２種以
上混合して用いられる。Examples of the alcohol-based melt cutting used in the present invention include methanol, ethanol, n-propatool, isopropatool, etc., and isopropatool is preferable. Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, etc., with methyl ethyl ketone being preferred. These may be used alone or in a mixture of two or more.
上記のような有機溶剤溶液から水系への転相は従来公知
の手法により行うことができ、有機溶剤溶液を攪拌下、
室温〜８０℃、好ましくは室温〜６０°Ｃの温度で水を
加えればよい。このように、水系に転相した後、常圧下
もしくは減圧下で有機溶剤を留去することにより、水性
ビニル樹脂（Ａ）が得られる。The phase inversion from an organic solvent solution to an aqueous system as described above can be performed by a conventionally known method.
Water may be added at a temperature of room temperature to 80°C, preferably room temperature to 60°C. After phase inversion to an aqueous system in this manner, the organic solvent is distilled off under normal pressure or reduced pressure to obtain the aqueous vinyl resin (A).
上記水性ビニル樹脂（１）の存在下で重合させる一種又
は二種以上の重合可能な二重結合を有する単量体（Ｂ）
としては、アクリル酸メチル、アクリル酸エチル、アク
リル酸ｎ−ブチル、アクリル酸ラウリル、メタクリル酸
メチル、メタクリル酸エチル、メタクリル酸ｎ−ブチル
、メタクリル酸イソブチル、メタクリル酸ｔ−ブチル等
の（メタ）アクリル酸エステル類；スチレン、クロルス
チレンなどのスチレン系モノマー；ｔ−ブチルアクリル
アミドなとのＮ−置換（メタ）アクリルアミド；並びに
アクリロニトリル、メタクリロニトリルなどが挙げられ
、これらの一種又は二種以上から選択することができる
。Monomer (B) having one or more polymerizable double bonds that is polymerized in the presence of the above water-based vinyl resin (1)
Examples include (meth)acrylics such as methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. Acid esters; Styrenic monomers such as styrene and chlorostyrene; N-substituted (meth)acrylamides such as t-butylacrylamide; and acrylonitrile, methacrylonitrile, etc., selected from one or more of these. be able to.
重合方法としては、水性ビニル樹脂（Ａ）に上記単量体
（Ｂ）及び公知のラジカル開始剤を加えて重合させれば
よい、ラジカル開始剤は過硫酸カリウム、過硫酸ナトリ
ウム、２，２゛−アゾビス（２−アミジノプロパン）ジ
クロライドなどの水溶性ラジカル開始剤、２．２゛−ア
ゾビス（２，４−ジメチルバレロニトリル） 、２．２
°−アゾビスイソブチロニトリルなどの油溶性ラジカル
開始剤のどちらか一方もしくは両方併用して使用するこ
とができる。水溶性の開始剤を使用するときには通常の
乳化重合の手法で重合することができ、油溶性の開始剤
を使用するときには単量体溶液に溶解して水性ビニル樹
脂（Ａ）に加えればよい。The polymerization method may be carried out by adding the above monomer (B) and a known radical initiator to the aqueous vinyl resin (A). The radical initiator may be potassium persulfate, sodium persulfate, 2,2゛-Water-soluble radical initiator such as azobis(2-amidinopropane) dichloride, 2.2'-azobis(2,4-dimethylvaleronitrile), 2.2
Either one or both oil-soluble radical initiators such as °-azobisisobutyronitrile can be used in combination. When using a water-soluble initiator, polymerization can be carried out by a normal emulsion polymerization method, and when using an oil-soluble initiator, it can be dissolved in a monomer solution and added to the aqueous vinyl resin (A).
重合温度は開始剤の分解速度を考慮して自由に設定でき
る。単量体（Ｂ）の使用量は、水性ビニル樹脂（Ａ）中
の樹脂分と単量体（Ｂ）の合計量が全系の５０重量％以
下となる範囲が好ましい。５０重量％を超えると、安定
な水性複合ポリマーエマルジョンは得られにくい、又、
単量体（Ｂ）の使用量は水性ビニル樹脂（Ａ）中の樹脂
分の０．０５〜１０重量倍が好ましく、更に好ましくは
０．２〜２重量倍である。 ０．０５重量倍未満では新
たに生じた単量体（Ｂ）の（共）重合体の割合が低すぎ
るため所期の目的は達し得ない、１０重量倍を超えると
安定な水性複合ボリマーエマルジ５ンが得られにくい、
このようにして、水性ビニル樹脂（Ａ）の存在下で乳化
剤を用いずに一種又は二種以上の単量体（Ｂ）を重合す
ることができるが、もし安定な水性複合ポリマーエマル
ジョンが得られにくい場合は系にメタノール、エタノー
ルなどのアルコール系溶媒、アセトン、メチルエチルケ
トンなどのケトン系溶媒といった水溶性溶媒を加えて重
合を行い、重合終了後留去することにより安定な水性複
合ポリマーエマルジジンが得られやすい、この場合は、
例えば、単量体（Ｂ）と上記水溶性溶媒とを予め混合し
、これを水性ビニル樹脂（Ａ）に添加すればよい。The polymerization temperature can be freely set in consideration of the decomposition rate of the initiator. The amount of monomer (B) to be used is preferably such that the total amount of the resin content and monomer (B) in the aqueous vinyl resin (A) is 50% by weight or less of the entire system. If it exceeds 50% by weight, it is difficult to obtain a stable aqueous composite polymer emulsion;
The amount of monomer (B) used is preferably 0.05 to 10 times the weight of the resin in the aqueous vinyl resin (A), more preferably 0.2 to 2 times the weight of the resin. If it is less than 0.05 times the weight, the ratio of the (co)polymer of the newly formed monomer (B) is too low and the desired purpose cannot be achieved; if it exceeds 10 times the weight, the aqueous composite polymer emulsion 5 becomes stable. It is difficult to obtain
In this way, one or more monomers (B) can be polymerized in the presence of an aqueous vinyl resin (A) without using an emulsifier, but if a stable aqueous composite polymer emulsion cannot be obtained. If the polymerization is difficult, add a water-soluble solvent such as an alcohol solvent such as methanol or ethanol, or a ketone solvent such as acetone or methyl ethyl ketone to the system, and then distill it off after the polymerization is complete to obtain a stable aqueous composite polymer emulzidine. In this case,
For example, the monomer (B) and the water-soluble solvent may be mixed in advance and added to the aqueous vinyl resin (A).
こうして得られる水性複合ボリマーエマルジッンは、化
粧料として使用した場合、好適な成膜性と塗膜強度を有
するものである。また、界面活性剤等の乳化剤成分を含
まないため、得られた塗膜の耐水性も優れている。The aqueous composite polymer emulsion thus obtained has suitable film-forming properties and film strength when used as a cosmetic. Furthermore, since it does not contain emulsifier components such as surfactants, the resulting coating film also has excellent water resistance.
得られた水性複合ポリマーエマルジョン粒子の微細構造
は未だ明らかではないが、第二段階の重合、即ち、水系
に転相して得られた水性ビニル樹脂（Ａ）の存在下で単
量体（Ｂ）の重合を行う際に、水性ビニル樹脂（Ａ）が
単量体（Ｂ）の液滴及び生成ポリマー粒子の分散安定剤
として働いているのか、あるいは水性ビニル樹脂（Ａ）
がシードとして働き、単量体（Ｂ）を吸収して重合が行
われるかのいずれかと思われる。いずれにせよ、出来上
がったポリマーエマルジョンにおいて水性ビニル樹脂（
Ａ）はイオン基を有し、比較晦親水性であるので粒子の
表面近傍もしくは外層部に存在し、単量体（Ｂ）の（共
）重合体は粒子の中心部もしくは内層を形成すると思わ
れる。Although the microstructure of the obtained aqueous composite polymer emulsion particles is not yet clear, the monomer (B ), does the aqueous vinyl resin (A) act as a dispersion stabilizer for the droplets of the monomer (B) and the resulting polymer particles?
It is thought that the monomer (B) acts as a seed and absorbs the monomer (B) to cause polymerization. In any case, in the finished polymer emulsion, water-based vinyl resin (
Since A) has an ionic group and is relatively hydrophilic, it exists near the surface or in the outer layer of the particle, and the (co)polymer of monomer (B) is thought to form the center or inner layer of the particle. It will be done.
水性ビニル樹脂（Ａ）、及び単量体（Ｂ）の（共）重合
体の物性はモノマーを適宜選択することにより任意に設
計可能であるが、本発明においては、とりわけ、水性ビ
ニル樹脂（Ａ）の軟化温度が、単量体（Ｂ）の（共）重
合体の軟化温度よりも低くなるように設計した場合によ
り好ましい結果が得られる。特に、水性ビニル樹脂（Ａ
）中の樹脂分の軟化温度は一１０°Ｃ以上が好ましく、
より好ましくは０℃以上である。軟化温度が一１０℃未
満では塗膜がべとつき、光沢保持性に欠ける。又、上記
のような効果、即ち、成膜性と塗膜硬度の両立を発現さ
せるためには、水性ビニル樹脂（Ａ）の共存下で重合し
た単量体（Ｂ）の（共）重合体の軟化温度は水性ビニル
樹脂（Ａ）中の樹脂分の軟化温度より１０℃以上高いこ
とが好ましい。The physical properties of the aqueous vinyl resin (A) and the (co)polymer of the monomer (B) can be arbitrarily designed by appropriately selecting the monomers. ) is designed to be lower than the softening temperature of the (co)polymer of monomer (B), more favorable results can be obtained. In particular, water-based vinyl resin (A
) The softening temperature of the resin component in ) is preferably -10°C or higher,
More preferably, the temperature is 0°C or higher. When the softening temperature is less than 110°C, the coating film becomes sticky and lacks gloss retention. In addition, in order to achieve the above effects, that is, both film formability and coating hardness, a (co)polymer of the monomer (B) polymerized in the coexistence of the aqueous vinyl resin (A) is required. The softening temperature of is preferably 10°C or more higher than the softening temperature of the resin component in the aqueous vinyl resin (A).
尚、本発明において、軟化温度は熱応力歪測定装置（Ｔ
ＭＡ）を用いて０．１〜０．２ｍＸ ３ ｍ＋Ｘ２０■
の試料片の熱変形開始点の温度を測定した値である（昇
温速度５℃／ａｋｉｎ）。In the present invention, the softening temperature is measured using a thermal stress strain measuring device (T
MA) using 0.1~0.2mX 3m+X20■
This is the measured value of the temperature at the starting point of thermal deformation of the sample piece (heating rate: 5° C./akin).
本発明の化粧料において、上記水性複合ポリマーエマル
ジョンは塗膜形成基剤として用いられ、その含有量は１
〜６０重量％（固形分として）である。１重量％より少
ない場合には実用上十分な塗膜が得に＜＜、６０重量％
を趙える場合には化粧料の粘度が高くなり、製剤化や皮
膚、毛髪への適用が困難となる。In the cosmetic of the present invention, the aqueous composite polymer emulsion is used as a coating film-forming base, and its content is 1
~60% by weight (as solids). If it is less than 1% by weight, a practically sufficient coating film can be obtained <<, 60% by weight.
If this occurs, the viscosity of the cosmetic becomes high, making it difficult to formulate it or apply it to the skin or hair.
本発明の化粧料には、本発明の効果を損なわない範囲で
、上記必須成分の他に化粧料成分として一般に使用され
ている油分、界面活性剤、保湿剤、紫外線吸収剤、キレ
ート剤、ｐＨ調整剤、防腐剤、増粘剤、染料、顔料、香
料等の通常化粧料に用いられる成分を適宜配合すること
ができる。また本発明の化粧料は毛髪用、皮膚用の他、
サンスクリーン剤等の薬用に水性、乳化型、エアゾール
等の剤型で用いられるが、特にアイシャドウ、マスカラ
等のアイメイクアップ化粧料として用いるのが好ましい
。In addition to the above-mentioned essential ingredients, the cosmetics of the present invention include oils, surfactants, humectants, ultraviolet absorbers, chelating agents, pH Components commonly used in cosmetics, such as regulators, preservatives, thickeners, dyes, pigments, and fragrances, can be appropriately blended. In addition, the cosmetics of the present invention can be used for hair, skin, etc.
It is used in aqueous, emulsified, aerosol, and other forms for medicinal purposes such as sunscreens, and is particularly preferably used as eye makeup cosmetics such as eye shadows and mascara.
次に水性複合ポリマーエマルジョンの合成例、化粧料の
実施例を掲げて本発明を具体的に説明するが、本発明が
これらに限定されないことは言うまでもない。Next, the present invention will be specifically explained with reference to synthesis examples of aqueous composite polymer emulsions and examples of cosmetics, but it goes without saying that the present invention is not limited thereto.
なお、例中の部及び％は特記しない限り全て重量基準で
ある。In addition, all parts and percentages in the examples are based on weight unless otherwise specified.
合成例１
撹拌機、還流冷却器、滴下ロート、温度針、窒素導入管
のついた反応器にメチルエチルケトン５０部を仕込み、
窒素ガスを流し溶存酸素を除去した。Synthesis Example 1 50 parts of methyl ethyl ketone was charged into a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature needle, and a nitrogen introduction tube.
Dissolved oxygen was removed by flowing nitrogen gas.
一方、滴下ロートにメチルエチルケトン３５凱、メチル
メタクリレート５６部、ｎ−ブチルアクリレート４０部
、アクリル酸４部及びアゾビスイソブチロニトリル０．
２部を仕込んだ。Meanwhile, in a dropping funnel, 35 ml of methyl ethyl ketone, 56 parts of methyl methacrylate, 40 parts of n-butyl acrylate, 4 parts of acrylic acid, and 0.0 ml of azobisisobutyronitrile were added.
I prepared the second part.
攪拌下、反応器内を８０℃まで昇温し、滴下ロートより
上記モノマー及びラジカル開始剤のメチルエチルケトン
溶液を２．５時間かけて滴下した。七ツマ−を滴下終了
２時間後、アゾビスイソブチロニトリル０．２部をメチ
ルエチルケトン１０部に溶解した溶液を加えた。３時間
同じ温度で熟成後、再びアゾビスイソブチロニトリル０
．１部をメチルエチルケトン５部に溶解したものを加え
、更に５時間反応を続け、共重合体を得た。While stirring, the temperature inside the reactor was raised to 80° C., and a solution of the monomer and radical initiator in methyl ethyl ketone was added dropwise from the dropping funnel over 2.5 hours. Two hours after the completion of the dropwise addition, a solution of 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone was added. After aging at the same temperature for 3 hours, azobisisobutyronitrile 0
．． A solution of 1 part dissolved in 5 parts of methyl ethyl ketone was added, and the reaction was continued for an additional 5 hours to obtain a copolymer.
得られた共重合体の一部を単離し、分子量をゲルパーミ
ェーションクロマトグラフィーによって測定したところ
、その重量平均分子量は７５．０００であった。尚、ゲ
ルバーミニ−シランクロマトクラフィーの検量線はポリ
スチレンを標準物質として作成した（溶媒：テトラヒド
ロフラン）。When a part of the obtained copolymer was isolated and its molecular weight was measured by gel permeation chromatography, its weight average molecular weight was 75,000. Note that a calibration curve for gel vermini-silane chromatography was prepared using polystyrene as a standard substance (solvent: tetrahydrofuran).
反応終了後の共重合体溶液を室温まで冷却し、トリエチ
ルアミン５．６部を加えて中和し、更に３００ ｒｐｍ
で攪拌下イオン交換水４００部を加えた後、減圧下４０
°Ｃでメチルエチルケトンを留去し、更に５０℃で水を
留去することにより濃縮し、固形分２５％の水性ビニル
樹脂を得た。After the reaction, the copolymer solution was cooled to room temperature, neutralized by adding 5.6 parts of triethylamine, and further heated at 300 rpm.
After adding 400 parts of ion-exchanged water with stirring, 40 parts of ion-exchanged water was added under reduced pressure.
Methyl ethyl ketone was distilled off at °C, and water was further distilled off at 50 °C to obtain a water-based vinyl resin with a solid content of 25%.
撹拌機、還流冷却器、滴下ロート、温度計、窒素導入管
のついた反応器に上記水性ビニル樹脂を２００部、水１
００部を仕込み、窒素ガスを流し溶存酸素を除去した。In a reactor equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen introduction tube, add 200 parts of the above aqueous vinyl resin and 1 part of water.
00 parts were charged, and dissolved oxygen was removed by flowing nitrogen gas.
一方、滴下ロートにイソブチルメタクリレート５０部、
メタノール７５部を仕込んだ。Meanwhile, 50 parts of isobutyl methacrylate was added to the dropping funnel.
75 parts of methanol was charged.
攪拌下、滴下ロートにより上記モノマーのメタノール溶
液を１時間かけて上記反応器内に滴下した０反応器内を
７０°Ｃまで昇温した後、過硫酸カリウム０．２部を水
１０部に溶解した溶液を加えた。６時間同じ温度で熟成
して、重合反応を終了した。反応器内を５０℃まで冷却
後、減圧下５０°Ｃでメタノール及び水を留去すること
より濃縮し、固形分３５％の水性複合ポリマーエマルジ
ョンを得た。While stirring, a methanol solution of the above monomer was dropped into the above reactor using a dropping funnel over 1 hour. After heating the inside of the reactor to 70°C, 0.2 parts of potassium persulfate was dissolved in 10 parts of water. solution was added. The polymerization reaction was completed by aging at the same temperature for 6 hours. After cooling the inside of the reactor to 50°C, the mixture was concentrated by distilling off methanol and water at 50°C under reduced pressure to obtain an aqueous composite polymer emulsion with a solid content of 35%.
得られた水性複合ポリマーエマルジョンの一部を乾燥し
て樹脂を取り出し、樹脂の軟化温度を熱応力歪測定装置
（セイコー電子工業■製ＴＭＡ／５Ｓ−１０）で測定し
たところ、２３°Ｃと５１゛Ｃに２つの軟化温度が観察
された。尚、上記水性ビニル樹脂のみの樹脂分の軟化温
度を別途測定したところ２２°Ｃであった。A portion of the obtained aqueous composite polymer emulsion was dried to take out the resin, and the softening temperature of the resin was measured using a thermal stress strain measuring device (TMA/5S-10 manufactured by Seiko Electronics Co., Ltd.), and it was found to be 23°C and 51°C. Two softening temperatures were observed at °C. The softening temperature of the water-based vinyl resin alone was separately measured and found to be 22°C.
合成例２
合成例１と同様な方法でメチルメタクリレート４０部、
エチルアクリレート５２部、Ｎ、Ｎ−ジメチルアミノエ
チルメタクリレート８部をメチルエチルケトン中で重合
し、共重合体を得た。この共重合体の重量平均分子量は
、８２．０００であった。Synthesis Example 2 In the same manner as in Synthesis Example 1, 40 parts of methyl methacrylate,
52 parts of ethyl acrylate and 8 parts of N,N-dimethylaminoethyl methacrylate were polymerized in methyl ethyl ketone to obtain a copolymer. The weight average molecular weight of this copolymer was 82.000.
次にこの共重合体に乳酸４．５部を加え中和し、合成例
１と同様な方法で水に転相し、固形分２５％の水性ビニ
ル樹脂を得た。Next, 4.5 parts of lactic acid was added to this copolymer to neutralize it, and the phase was inverted to water in the same manner as in Synthesis Example 1 to obtain an aqueous vinyl resin with a solid content of 25%.
合成例１と同様な反応器に上記水性ビニル樹脂を２００
部、水１００部を仕込み、窒素ガスを流し、溶存酸素を
除去した。200% of the above aqueous vinyl resin was placed in a reactor similar to Synthesis Example 1.
100 parts of water were charged, and nitrogen gas was passed through the flask to remove dissolved oxygen.
一方、滴下ロートにメチルメタクリレート４０部を仕込
み、攪拌下、滴下ロートよりモノマーを１時間かけて上
記反応器内に滴下した。反応器内を７０°Ｃまで昇温し
た後、過硫酸カリウム０．２部を水１０部に溶解した溶
液を加えた。６時間同じ温度で熟成して、重合反応を終
了した０合成例１と同様な方法で水を留去し、固形分３
５％の水性複合ポリマーエマルジョンを得た
得られた水性複合ポリマーエマルジョン中の樹脂の軟化
温度は２１°Ｃと９８°Ｃであった。尚、上記水性ビニ
ル樹脂のみの樹脂分の軟化温度は２０℃であった。On the other hand, 40 parts of methyl methacrylate was charged into the dropping funnel, and the monomer was dropped into the reactor from the dropping funnel over 1 hour while stirring. After raising the temperature inside the reactor to 70°C, a solution of 0.2 parts of potassium persulfate dissolved in 10 parts of water was added. The polymerization reaction was completed by aging at the same temperature for 6 hours.Water was distilled off in the same manner as in Synthesis Example 1, and the solid content was reduced to 3.
A 5% aqueous composite polymer emulsion was obtained. The softening temperature of the resin in the resulting aqueous composite polymer emulsion was 21°C and 98°C. The softening temperature of the water-based vinyl resin alone was 20°C.
合成例３
撹拌機、還流冷却器、滴下ロート、温度針、窒素導入管
のついた反応器に合成例２で合成した水性ビニル樹脂を
２００部、水１００部を仕込み、窒素ガスを流し、溶存
酸素を除去した。Synthesis Example 3 200 parts of the aqueous vinyl resin synthesized in Synthesis Example 2 and 100 parts of water were placed in a reactor equipped with a stirrer, reflux condenser, dropping funnel, temperature needle, and nitrogen introduction tube, and nitrogen gas was passed through the reactor to dissolve the Oxygen was removed.
一方、滴下ロートにスチレン４０部、エタノール８０部
、２，２゛−アゾビス（２，４−ジメチルバレロニトリ
ル）０．２部を仕込んだ。Meanwhile, 40 parts of styrene, 80 parts of ethanol, and 0.2 part of 2,2'-azobis(2,4-dimethylvaleronitrile) were charged into the dropping funnel.
攪拌下、滴下ロートより上記モノマー及びラジカル開始
剤のエタノール溶液を１時間かけて上記反応器内に滴下
した０反応器内を６０°Ｃまで昇温し、６時間同じ温度
で熟成して、重合反応を終了した。合成例１と同様な方
法でエタノール及び水を留去し、固形分３５％の水性複
合ポリマーエマルジョンを得た。While stirring, an ethanol solution of the above monomer and radical initiator was dropped into the above reactor from the dropping funnel over 1 hour. The temperature inside the reactor was raised to 60°C, and the temperature was aged at the same temperature for 6 hours to initiate polymerization. The reaction has ended. Ethanol and water were distilled off in the same manner as in Synthesis Example 1 to obtain an aqueous composite polymer emulsion with a solid content of 35%.
得られた水性複合ポリマーエマルジョン中の樹脂の軟化
温度は１９℃と９２°Ｃであった。The softening temperatures of the resin in the resulting aqueous composite polymer emulsion were 19°C and 92°C.
実施例１
下記に示す製法で下記組成のクリームタイプのアイシャ
ドウを製造した。Example 1 A cream-type eyeshadow having the following composition was manufactured by the manufacturing method shown below.
く組 成〉
ミツロウ ２．５％ステア
リン酸 ２．５流動パラフイン
１０．０ラノリン
１．０ソルビタンモノステアレート
１．５グリセリン ４，０
％トリエタノールアミン １．５イオン
交換水 ５０．５メチルヒドロキ
シプロピルセルロース０．５フタル酸ジブチル
２．０水性複合ボリマーエマルジジン
１２．０（合成例１） （固形分）バー
ル顔料 １０．０群青
２．０
香 料 適量防腐剤
適量〈製 法〉
イオン交換水にメチルヒドロキシプロピルセルロース、
グリセリン、トリエタノールアミンを溶解し、その後、
加温してバール顔料及び群青を均一に分散する０次いで
、ミツロウ等の油相成分を加熱溶解し、前記水相中に攪
拌しながら添加し乳化を行う、冷却後、水性複合ボリマ
ーエマルジッン、フタル酸ジプチル及び香料、防腐剤を
加えて青色のクリームタイプアイシャドウとする。Composition> Beeswax 2.5% Stearic acid 2.5 Liquid paraffin 10.0 Lanolin
1.0 Sorbitan Monostearate
1.5 Glycerin 4.0
% triethanolamine 1.5 ion exchange water 50.5 methyl hydroxypropyl cellulose 0.5 dibutyl phthalate
2.0 Aqueous composite polymer emulsion
12.0 (Synthesis Example 1) (Solid content) Var pigment 10.0 Ultramarine
2.0 Flavorings Appropriate amount of preservatives
Appropriate amount <Manufacturing method> Methyl hydroxypropyl cellulose in ion exchange water,
Dissolve the glycerin and triethanolamine, then
Disperse the Burl pigment and ultramarine uniformly by heating.Next, heat and dissolve oil phase components such as beeswax, and add to the aqueous phase with stirring to emulsify.After cooling, form an aqueous composite polymer emulsion. A blue cream-type eye shadow is made by adding diptyl phthalate, fragrance, and preservatives.
実施例２ 下記に示す製法で下記組成のマスカラを製造した。Example 2 A mascara having the following composition was manufactured by the manufacturing method shown below.
く組 成〉
黒色酸化鉄 １５．０タルク
１０．０ヒドロキシエチル
セルロース ２．０ポリオキシエチレン
ソルビタンモノオレート１．５
フタル酸ジエチル ４．０グリセリン
５．０イオン交換水
１２．５香 料
適量防腐剤 適量〈製
法〉
イオン交換水にヒドロキシエチルセルロース、タルク、
フタル酸ジエチル及び水性複合ポリマーエマルジョンを
添加し、均一に攪拌混合した後に、黒色酸化鉄、グリセ
リン、ポリオキシエチレンソルビタンモノオレートから
なる着色ペーストを添加して均一に混合し、香料及び防
腐剤を加えて黒色のマスカラとする。Composition〉 Black iron oxide 15.0 talc
10.0 Hydroxyethyl cellulose 2.0 Polyoxyethylene sorbitan monooleate 1.5 Diethyl phthalate 4.0 Glycerin 5.0 Ion exchange water
12.5 fragrance
Appropriate amount of preservatives Appropriate amount
Method> Hydroxyethylcellulose, talc, ion-exchanged water,
After adding diethyl phthalate and the aqueous composite polymer emulsion and stirring and mixing them uniformly, a coloring paste consisting of black iron oxide, glycerin, and polyoxyethylene sorbitan monooleate is added and mixed uniformly, and fragrance and preservatives are added. Apply black mascara.
実施例３
下記に示す製法で下記組成の液状皮膜タイプのアイライ
ナーを製造した。Example 3 A liquid film type eyeliner having the following composition was manufactured by the manufacturing method shown below.
く組 成〉
水性複合ポリマーエマルジョン ６８．０％（合成
例３） （固形分）カーボンブラック
５．０二酸化チタン
２．０ポリオキシエチレン
ソルビタンモノステアレート
１．０
２．０
４．０
１．０
１７．０
適量
適量
グリセリン
フタル酸ジエチル
ヒドロキシエチルセルロース
イオン交換水
香料
防腐剤
〈製 法〉
イオン交換水にポリオキシエチレンソルビタンモノステ
アレートを溶解し、それにカーボンブラック及び二酸化
チタンを混合し、コロイドミルを用いて均一に分散させ
る。これにグリセリン、ヒドロキシエチルセルロース、
フタル酸ジエチル及び水性複合ポリマーエマルジョンを
添加し、均一に混合し、最後に香料、防腐剤を添加して
黒色の皮膜タイプアイライナーとする。Composition> Aqueous composite polymer emulsion 68.0% (Synthesis Example 3) (Solid content) Carbon black
5.0 titanium dioxide
2.0 Polyoxyethylene sorbitan monostearate 1.0 2.0 4.0 1.0 17.0 Appropriate amount Appropriate amount Glycerin Diethyl hydroxyethyl phthalate Cellulose Ion-exchanged water Fragrance preservative <Manufacturing method> Polyoxyethylene in ion-exchanged water Sorbitan monostearate is dissolved, carbon black and titanium dioxide are mixed therein, and uniformly dispersed using a colloid mill. This includes glycerin, hydroxyethyl cellulose,
Add diethyl phthalate and the aqueous composite polymer emulsion, mix uniformly, and finally add fragrance and preservative to form a black film-type eyeliner.
本発明はその他のファンデーション類、アイシャドウ、
アイライナー、アイフロラ、マスカラ等のアイメイクア
ップ化粧料類、パック、口紅、はぼ紅、毛髪用着色料、
サンスクリーン剤等の皮膚化粧料や毛髪化粧料、薬用化
粧料に広く応用されるものである。The present invention applies to other foundations, eye shadows,
Eye make-up cosmetics such as eyeliner, eye flora, mascara, packs, lipsticks, red bean paste, hair colorants,
It is widely applied to skin cosmetics such as sunscreen agents, hair cosmetics, and medicinal cosmetics.
Claims (1)
学組成の異なる少なくとも二層からなる多層構造を有し
、かつ、最外層のポリマーが内層のポリマーよりも低い
軟化温度を有する水性複合ポリマーエマルジョンを固形
分換算で１〜６０重量％含有することを特徴とする化粧
料。 ２、塩生成基を有し重合可能な二重結合を有する単量体
０．５〜１５重量％と、それと共重合し得る重合可能な
二重結合を有する単量体８５〜９９．５重量％とを共重
合して得られる共重合体の有機溶剤溶液に水を加えた後
、有機溶剤を留去して得られる水性ビニル樹脂（Ａ）の
存在下で、一種又は二種以上の重合可能な二重結合を有
する単量体（Ｂ）を重合して得られた水性複合ポリマー
エマルジョンを固形分換算で１〜６０重量％含有するこ
とを特徴とする化粧料。 ３、水性ビニル樹脂（Ａ）の樹脂分の軟化温度が、一種
又は二種以上の重合可能な二重結合を有する単量体（Ｂ
）の（共）重合体の軟化温度よりも低いものである請求
項２記載の化粧料。[Claims] 1. An aqueous composite in which the polymer particles constituting the polymer emulsion have a multilayer structure consisting of at least two layers with different chemical compositions, and the outermost layer polymer has a lower softening temperature than the inner layer polymer. A cosmetic comprising 1 to 60% by weight of a polymer emulsion in terms of solid content. 2. 0.5 to 15% by weight of a monomer having a salt-forming group and a polymerizable double bond, and 85 to 99.5% by weight of a monomer having a polymerizable double bond that can be copolymerized therewith. Polymerization of one or more types in the presence of an aqueous vinyl resin (A) obtained by adding water to an organic solvent solution of a copolymer obtained by copolymerizing with 1. A cosmetic containing 1 to 60% by weight, calculated as solid content, of an aqueous composite polymer emulsion obtained by polymerizing a monomer (B) having a possible double bond. 3. The softening temperature of the resin component of the aqueous vinyl resin (A) is higher than that of the monomer (B) having one or more types of polymerizable double bonds.
3. The cosmetic composition according to claim 2, which has a softening temperature lower than the softening temperature of the (co)polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22076090A JP2857238B2 (en) | 1990-08-21 | 1990-08-21 | Cosmetics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22076090A JP2857238B2 (en) | 1990-08-21 | 1990-08-21 | Cosmetics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04103510A true JPH04103510A (en) | 1992-04-06 |
| JP2857238B2 JP2857238B2 (en) | 1999-02-17 |
Family
ID=16756118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22076090A Expired - Fee Related JP2857238B2 (en) | 1990-08-21 | 1990-08-21 | Cosmetics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2857238B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6113890A (en) * | 1995-09-01 | 2000-09-05 | The Procter & Gamble Company | Hair styling shampoos containing organic oil |
| US6268431B1 (en) | 1995-09-01 | 2001-07-31 | The Procter & Gamble Company | Hair styling shampoos containing low Tg latex polymer particles |
| FR2827164A1 (en) * | 2001-07-16 | 2003-01-17 | Oreal | Composition for coating keratinic fibers, especially eyelashes, comprises a dispersion of particles with a rigid core of functionalized (semi)crystalline material and a shell of a flexible polymer |
| FR2827160A1 (en) * | 2001-07-16 | 2003-01-17 | Oreal | Cosmetic composition for make-up and/or care of the skin and lips comprises a dispersion of particles with a rigid core of functionalized (semi)crystalline material and a shell of a flexible polymer |
| FR2827163A1 (en) * | 2001-07-16 | 2003-01-17 | Oreal | Cosmetic composition useful for coating keratinic fibers comprises a dispersion of particles with a rigid core and a flexible polymer shell |
| WO2003007897A1 (en) * | 2001-07-16 | 2003-01-30 | L'oreal | Cosmetic composition comprising a dispersion of particles |
| WO2003007895A3 (en) * | 2001-07-16 | 2003-11-06 | Oreal | Cosmetic composition comprising a dispersion of particles |
| JP2007161600A (en) * | 2005-12-09 | 2007-06-28 | Kao Corp | Polymer emulsion for cosmetic |
| JP2010105936A (en) * | 2008-10-29 | 2010-05-13 | Pola Chem Ind Inc | Makeup cosmetic |
| CN111867682A (en) * | 2018-03-29 | 2020-10-30 | 可泰克斯公司 | Water-repellent cosmetic composition |
-
1990
- 1990-08-21 JP JP22076090A patent/JP2857238B2/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6113890A (en) * | 1995-09-01 | 2000-09-05 | The Procter & Gamble Company | Hair styling shampoos containing organic oil |
| US6248315B1 (en) | 1995-09-01 | 2001-06-19 | The Procter & Gamble Company | Hair styling shampoos containing organic oil |
| US6268431B1 (en) | 1995-09-01 | 2001-07-31 | The Procter & Gamble Company | Hair styling shampoos containing low Tg latex polymer particles |
| WO2003007898A1 (en) * | 2001-07-16 | 2003-01-30 | L'oreal | Mascara comprising a dispersion of particles |
| US6793913B2 (en) | 2001-07-16 | 2004-09-21 | L'oreal S.A. | Cosmetic composition comprising a particle dispersion |
| FR2827163A1 (en) * | 2001-07-16 | 2003-01-17 | Oreal | Cosmetic composition useful for coating keratinic fibers comprises a dispersion of particles with a rigid core and a flexible polymer shell |
| WO2003007897A1 (en) * | 2001-07-16 | 2003-01-30 | L'oreal | Cosmetic composition comprising a dispersion of particles |
| WO2003007899A1 (en) * | 2001-07-16 | 2003-01-30 | L'oreal | Mascara comprising a dispersion of particles |
| FR2827164A1 (en) * | 2001-07-16 | 2003-01-17 | Oreal | Composition for coating keratinic fibers, especially eyelashes, comprises a dispersion of particles with a rigid core of functionalized (semi)crystalline material and a shell of a flexible polymer |
| WO2003007895A3 (en) * | 2001-07-16 | 2003-11-06 | Oreal | Cosmetic composition comprising a dispersion of particles |
| FR2827160A1 (en) * | 2001-07-16 | 2003-01-17 | Oreal | Cosmetic composition for make-up and/or care of the skin and lips comprises a dispersion of particles with a rigid core of functionalized (semi)crystalline material and a shell of a flexible polymer |
| JP2005508303A (en) * | 2001-07-16 | 2005-03-31 | ロレアル | Cosmetic composition comprising a particle dispersion |
| JP2005523234A (en) * | 2001-07-16 | 2005-08-04 | ロレアル | Mascara with particle dispersion |
| JP2007161600A (en) * | 2005-12-09 | 2007-06-28 | Kao Corp | Polymer emulsion for cosmetic |
| JP4629566B2 (en) * | 2005-12-09 | 2011-02-09 | 花王株式会社 | Polymer emulsion for cosmetics |
| JP2010105936A (en) * | 2008-10-29 | 2010-05-13 | Pola Chem Ind Inc | Makeup cosmetic |
| CN111867682A (en) * | 2018-03-29 | 2020-10-30 | 可泰克斯公司 | Water-repellent cosmetic composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2857238B2 (en) | 1999-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100844610B1 (en) | Acrylic-based copolymer compositions for cosmetic and personal care | |
| US20100040572A1 (en) | Block ethylenic copolymers comprising a vinyllactam block, cosmetic compositions containing them and cosmetic use of these copolymers | |
| US20070003506A1 (en) | Adhesive block ethylenic copolymers, cosmetic compositions containing them and cosmetic use of these copolymers | |
| JP2003534264A (en) | Use of block ethylene-based copolymers having elastic properties in cosmetics and compositions containing the same | |
| JP3362784B2 (en) | COMPOSITIONS CONTAINING POLYMER HAVING STAR STRUCTURE, THE POLYMERS AND THEIR USE | |
| JP2000319327A (en) | Composition containing polymer of star-structure, the polymer and use thereof | |
| AU2001293038B9 (en) | Acrylic-based copolymer compositions for cosmetic and personal care | |
| US20050238594A1 (en) | Block ethylenic copolymers comprising a vinyllactam block, cosmetic or pharmaceutical compositions comprising them and cosmetic use of these copolymers | |
| JP2857238B2 (en) | Cosmetics | |
| JPH03133916A (en) | Water-based manicure | |
| AU2001293038A1 (en) | Acrylic-based copolymer compositions for cosmetic and personal care | |
| JP4382398B2 (en) | Cosmetic resin | |
| DE602004003530T2 (en) | Ethylenic sequence copolymers containing a vinyl lactam sequence, cosmetic compositions containing them, and use of these copolymers in cosmetics #### | |
| JPH04103512A (en) | Water-based manicure cosmetic | |
| JP3362782B2 (en) | COMPOSITIONS CONTAINING POLYMER HAVING STAR STRUCTURE, THE POLYMERS AND THEIR USE | |
| JPH05310531A (en) | Cosmetic | |
| JPH05148122A (en) | Water-based manicure | |
| US20060088487A1 (en) | Block ethylenic copolymers comprising a vinyllactam block, cosmetic or pharmaceutical compositions containing them and cosmetic use of these copolymers | |
| JP3229651B2 (en) | Cosmetics | |
| JPH0517320A (en) | Cosmetic | |
| JP2918660B2 (en) | Cosmetics | |
| DE10256148A1 (en) | The present invention relates to compositions comprising at least one copolymer (A) and at least one copolymer (B) and their use in cosmetic preparations | |
| JPH02258709A (en) | Oil-in-water type emulsified cosmetic | |
| JPH04297409A (en) | Water-based manicure | |
| JPH08239308A (en) | Cosmetic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071127 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081127 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091127 Year of fee payment: 11 |
|
| LAPS | Cancellation because of no payment of annual fees |