JP2001316435A - Copolymer and cosmetic material containing it - Google Patents
Copolymer and cosmetic material containing itInfo
- Publication number
- JP2001316435A JP2001316435A JP2000135295A JP2000135295A JP2001316435A JP 2001316435 A JP2001316435 A JP 2001316435A JP 2000135295 A JP2000135295 A JP 2000135295A JP 2000135295 A JP2000135295 A JP 2000135295A JP 2001316435 A JP2001316435 A JP 2001316435A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- hair
- general formula
- salt
- group
- 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.)
- Withdrawn
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 104
- 239000002537 cosmetic Substances 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 68
- 150000003839 salts Chemical class 0.000 claims abstract description 33
- 239000000470 constituent Substances 0.000 claims abstract description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 125000002252 acyl group Chemical group 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 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
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000008365 aqueous carrier Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 48
- 230000002209 hydrophobic effect Effects 0.000 abstract description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 29
- 229910052757 nitrogen Inorganic materials 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- -1 polyoxyethylene group Polymers 0.000 description 27
- 238000003756 stirring Methods 0.000 description 26
- 239000000203 mixture Substances 0.000 description 23
- 235000019441 ethanol Nutrition 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 239000012046 mixed solvent Substances 0.000 description 14
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 9
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 9
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000008055 phosphate buffer solution Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 5
- 239000006210 lotion Substances 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 229940048053 acrylate Drugs 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- ULYIFEQRRINMJQ-UHFFFAOYSA-N 3-methylbutyl 2-methylprop-2-enoate Chemical compound CC(C)CCOC(=O)C(C)=C ULYIFEQRRINMJQ-UHFFFAOYSA-N 0.000 description 2
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 239000002552 dosage form Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 231100000507 endocrine disrupting Toxicity 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003676 hair preparation Substances 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 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
- 238000005191 phase separation Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 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
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- AQVRBCMAYYDFRP-UHFFFAOYSA-N 1-[1-(1-hydroxypropan-2-yloxy)propan-2-yloxy]-3-methoxypropan-2-ol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.COCC(O)COC(C)COC(C)CO AQVRBCMAYYDFRP-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-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
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- LEACJMVNYZDSKR-UHFFFAOYSA-N 2-octyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCCCC LEACJMVNYZDSKR-UHFFFAOYSA-N 0.000 description 1
- GECRRQVLQHRVNH-MRCUWXFGSA-N 2-octyldodecyl (z)-octadec-9-enoate Chemical compound CCCCCCCCCCC(CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC GECRRQVLQHRVNH-MRCUWXFGSA-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
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QXKHYNVANLEOEG-UHFFFAOYSA-N Methoxsalen Chemical group C1=CC(=O)OC2=C1C=C1C=COC1=C2OC QXKHYNVANLEOEG-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- BTFJIXJJCSYFAL-UHFFFAOYSA-N arachidyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 229940082483 carnauba wax Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005131 dialkylammonium group Chemical group 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000037308 hair color Effects 0.000 description 1
- 230000003699 hair surface Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229940119170 jojoba wax Drugs 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 229940114937 microcrystalline wax Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 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
- 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
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 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
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 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
- 239000008363 phosphate buffer Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 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
- 238000005507 spraying Methods 0.000 description 1
- 229940032094 squalane Drugs 0.000 description 1
- 239000008117 stearic acid 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
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000003760 tallow Substances 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
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Landscapes
- Cosmetics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は化粧料の原料として
有用なコポリマー及びその塩及び該コポリマー及び／又
は塩を含有してなる化粧料に関する。The present invention relates to a copolymer useful as a raw material for cosmetics, a salt thereof, and a cosmetic comprising the copolymer and / or salt.
【０００２】[0002]
【従来の技術】化粧料などの皮膚外用剤の分野におい
て、ホモポリマー或いはコポリマーなどのポリマー類
は、皮膜形成剤として、皮膚の水分散逸を防止する目的
或いは毛髪などの形を整え維持する目的で広く使用され
ている。前者に於いては主として、水性担体とともに透
明で一様な溶状を呈するものが使用され、後者に於いて
は主として、水には溶けずアルコール類に可溶溶状のも
のが使用される。後者においてこの様な溶状のものが私
用されるのは、前者のような水性担体と容易に混合する
ものでは、汗或いは雨などにより、整髪力が損なわれる
ことがままあるからである。後者のように水には容易に
混合しない形であれば、この様な汗や雨などによって整
髪特性が損なわれることが極めて少ないためである。し
かしながら、この様なポリマーに於いては、エタノール
などの様な低級アルコール或いは天然ガスやフロンのよ
うな液化ガスを使用することを必須とする。この為、環
境的な配慮から、この様な製剤は使用しにくくなってい
るのが現状である。加えて、この様な製剤で毛髪などを
処理した場合に於いては、その汚れは水のみでは容易に
は落とせず、溶剤として使用しているエタノールによる
めがねのフレームの変質など問題もあり、この様な問題
の解決が望まれていた。2. Description of the Related Art In the field of external preparations for skin such as cosmetics, polymers such as homopolymers or copolymers are used as film-forming agents for the purpose of preventing water from dispersing in the skin or for the purpose of shaping and maintaining the shape of hair. Widely used. In the former, those which exhibit a transparent and uniform solution together with an aqueous carrier are used, and in the latter, those which are insoluble in water but soluble in alcohols are mainly used. The reason why such a solution is used in the latter is that the hair which is easily mixed with the aqueous carrier as in the former may lose its hair styling ability due to sweat or rain. This is because if the form is not easily mixed with water as in the latter case, the hair styling properties are hardly impaired by such sweat or rain. However, in such a polymer, it is essential to use a lower alcohol such as ethanol or a liquefied gas such as natural gas or Freon. For this reason, it is presently difficult to use such preparations from environmental considerations. In addition, when hair and the like are treated with such a preparation, the stain cannot be easily removed only with water, and there is a problem such as deterioration of the frame of the glasses due to ethanol used as a solvent. It was desired to solve such problems.
【０００３】一方、曇点を有するコポリマー及び／又は
その塩については未だ全く知られておらず、この様なコ
ポリマー及び／又はその塩が水溶性であるにもかかわら
ず、使用後に於いては疎水性の皮膜を形成し、整髪など
に好適であることも知られていなかった。従って、この
様なコポリマー及び／又はその塩を整髪用の化粧料など
の化粧料に含有させることも行われていなかった。[0003] On the other hand, copolymers and / or salts thereof having a cloud point are not yet known at all, and even though such copolymers and / or salts are water-soluble, they are hydrophobic after use. It has not been known that it forms a water-resistant film and is suitable for hair styling and the like. Therefore, such copolymers and / or salts thereof have not been incorporated into cosmetics such as cosmetics for hair styling.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、この様な状
況下為されたものであり、水溶性であって、使用後は疎
水性の皮膜を形成するコポリマー及び／又はその塩及び
それを含有してなる、整髪などに有用な化粧料を提供す
ることを課題とする。DISCLOSURE OF THE INVENTION The present invention has been made under such a circumstance, and a copolymer and / or a salt thereof which is water-soluble and forms a hydrophobic film after use is disclosed. An object of the present invention is to provide a cosmetic that is useful for hairdressing and the like.
【０００５】[0005]
【課題の解決手段】本発明者らは、この様な状況に鑑
み、水溶性であって、使用後は疎水性の皮膜を形成する
コポリマー及び／又はその塩及びそれを含有してなる、
整髪などに有用な化粧料を求め、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
て含有するコポリマーにおいて、曇点を有することを特
徴とする、コポリマー及び／又はその塩に水溶性であっ
て、曇点以上に加熱することにより、コポリマーが遊離
し、疎水性の皮膜を形成することを見いだし、解決課題
の着想を得た。更に、詳細に検討を重ねた結果、該コポ
リマーを整髪料などの化粧料に含有させ、毛髪などを処
置後、ドライヤーで加熱乾燥させることにより、疎水性
に優れる皮膜を形成することを見いだし、発明を完成さ
せるに至った。即ち、本発明は、以下に示す技術に関す
るものである。 （１）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
て含有するコポリマーにおいて、曇点を有することを特
徴とする、コポリマー及び／又はその塩。 （２）化粧料用であることを特徴とする、（１）に記載
のコポリマー及び／又はその塩。 （３）一般式（Ｉ）に表されるモノマーの構成モノマー
としての含有量が総量で１〜４０重量％であり、一般式
（ＩＩ）に表されるモノマーの構成モノマーとしての含
有量が総量で３０〜７０重量％であることを特徴とす
る、（１）又は（２）に記載のコポリマー及び／又はそ
の塩。 （４）曇点が４０℃〜７０℃であることを特徴とする、
（１）〜（３）何れか１項に記載のコポリマー。 （５）（１）〜（４）何れか１項に記載のコポリマー及
びその塩から選ばれる１種乃至は２種以上を含有するこ
とを特徴とする、化粧料。 （６）整髪料であることを特徴とする、（５）に記載の
化粧料。 （７）水性担体とともに透明な形態を有していることを
特徴とする、（５）又は（６）に記載の化粧料。 （８）曇点を有するコポリマー及び／又はその塩を含む
化粧料で毛髪を処理し、しかる後、ヘアドライヤーによ
り、該曇点以上の温度に処理された毛髪を加熱し、毛髪
表面上にコポリマー及び／又はその塩を析出させること
を特徴とする、整髪方法。 （９）曇点が４０℃〜７０℃であることを特徴とする、
（８）に記載の整髪方法。 （１０）コポリマー及び／又はその塩による処理が、
（５）〜（７）何れか１項に記載の化粧料の使用による
ものであることを特徴とする、（８）又は（９）に記載
の方法。以下、本発明について、実施の形態を中心に詳
細に説明を加える。 （１１）前記一般式（Ｉ）に表されるモノマーから選ば
れる１種乃至は２種以上と前記一般式（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コポリマーにおいて、一般式
（Ｉ）に表されるモノマーの構成モノマーとしての含有
量が総量で１〜４０重量％であり、一般式（ＩＩ）に表
されるモノマーの構成モノマーとしての含有量が総量で
３０〜７０重量％であることを特徴とする、コポリマー
及び／又はその塩。 （１２）化粧料用であることを特徴とする、（１１）記
載のコポリマー及び／又はその塩。 （１３）頭髪用の化粧料用であることを特徴とする、
（１１）又は（１２）に記載のコポリマー及び／又はそ
の塩。SUMMARY OF THE INVENTION In view of such circumstances, the present inventors have found that a copolymer and / or a salt thereof which is water-soluble and forms a hydrophobic film after use is contained.
In pursuit of cosmetics useful for hair styling and the like, as a result of intensive research efforts, 1 is selected from the monomers represented by the general formula (I).
A copolymer comprising a kind or two or more kinds and one or more kinds selected from monomers represented by the general formula (II) as constituent monomers, having a cloud point; Alternatively, it has been found that the copolymer is liberated by heating to a temperature higher than the cloud point and is soluble in a salt thereof to form a hydrophobic film. Furthermore, as a result of detailed studies, it was found that the copolymer was contained in a cosmetic such as a hairdressing agent, and after treatment of the hair, etc., the film was heated and dried with a dryer to form a film having excellent hydrophobicity. Was completed. That is, the present invention relates to the following technology. (1) 1 selected from monomers represented by the general formula (I)
A copolymer comprising a kind or two or more kinds and one or more kinds selected from monomers represented by the general formula (II) as constituent monomers, having a cloud point; Or a salt thereof. (2) The copolymer according to (1) and / or a salt thereof, which is used for cosmetics. (3) The content of the monomer represented by the general formula (I) as a constituent monomer is 1 to 40% by weight in total, and the content of the monomer represented by the general formula (II) as a constituent monomer is a total amount. The copolymer according to (1) or (2), and / or a salt thereof, wherein the content is 30 to 70% by weight. (4) a cloud point of 40 ° C. to 70 ° C.
(1) The copolymer according to any one of (1) to (3). (5) A cosmetic, comprising one or more selected from the copolymers and salts thereof according to any one of (1) to (4). (6) The cosmetic according to (5), which is a hairdressing agent. (7) The cosmetic according to (5) or (6), which has a transparent form together with the aqueous carrier. (8) treating the hair with a cosmetic containing a copolymer having a cloud point and / or a salt thereof, and then heating the hair treated to a temperature equal to or higher than the cloud point with a hair dryer to form a copolymer on the hair surface; And / or precipitating a salt thereof. (9) The cloud point is 40 ° C to 70 ° C.
The hair styling method according to (8). (10) The treatment with a copolymer and / or a salt thereof
(5) The method according to (8) or (9), characterized by using the cosmetic according to any one of (7) to (7). Hereinafter, the present invention will be described in detail focusing on embodiments. (11) Monomers comprising one or more selected from the monomers represented by the general formula (I) and one or two or more selected from the monomers represented by the general formula (II) The total content of the monomer represented by the general formula (I) as the constituent monomer is 1 to 40% by weight, and the content of the monomer represented by the general formula (II) as the constituent monomer Copolymers and / or salts thereof, characterized in that the total amount is from 30 to 70% by weight. (12) The copolymer and / or salt thereof according to (11), which is used for cosmetics. (13) for hair cosmetics,
The copolymer according to (11) or (12) and / or a salt thereof.
【０００６】[0006]
【化３】 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は炭素数４〜３０の炭化水素基を表
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 a hydrocarbon group having 4 to 30 carbon atoms)
【０００７】[0007]
【化４】 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２〜４
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. R 5 represents a hydrogen atom, an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or an acyl group, and n represents 2 to 4
Represents a numerical value of 0. )
【０００８】[0008]
【発明の実施の形態】（１）本発明のコポリマー、その
塩に使用される一般式（Ｉ）に表されるモノマー 本発明のコポリマーは、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種以上を構成モノマーとし
て構成モノマー全量に対して、総量で１〜４０重量％、
更に好ましくは３〜３０重量％含有する。これは、この
部分にコポリマーの耐水性が起因しているため、一般式
（Ｉ）のモノマーに起因する部分が少なすぎたり、この
部分の疎水性が低すぎたりすると、コポリマーの被膜と
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。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は炭素数４〜３０の炭化水素基
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、コポリマーなどで汎用され
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、直鎖、分岐乃至は環状構造を有する
アルキル基乃至はアルケニル基が特に好ましい。炭素数
としては、５〜３０のもの、更に好ましくは６〜３０の
ものが特に好ましい。これは、本発明のコポリマーに於
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り、更には、この部分と後記一
般式（ＩＩ）に表されるモノマーに由来する部分との比
によって曇点の有無或いはその温度が決定されるからで
ある。特に好ましい形態としては、コポリマーに於ける
疎水部分を担う前記モノマーは炭素数１２〜３０の疎水
性の高いものを選択し、構成含有量として少量に抑える
のが、溶液では水溶性を示し、被膜では可塑性を有する
疎水性を示すなどの、機能的な物性を出す意味で好まし
い。この様な一般式（Ｉ）に表されるモノマーとして
は、ｎブチルアクリレート、ｎブチルメタアクリレー
ト、イソブチルアクリレート、イソブチルメタアクリレ
ート、tertブチルアクリレート、tertブチルメタアクリ
レート、イソアミルアクリレート、イソアミルメタアク
リレート、ｎヘキシルアクリレート、ｎヘキシルメタア
クリレート、シクロヘキシルアクリレート、シクロヘキ
シルメタアクリレート、ｎオクチルアクリレート、ｎオ
クチルメタアクリレート、２−エチルヘキシルアクリレ
ート、２−エチルヘキシルメタアクリレート、ベンジル
アクリレート、ベンジルメタアクリレート、ドデシルア
クリレート、ドデシルメタアクリレート、ステアリルア
クリレート、ステアリルメタアクリレート等が挙げられ
る。この様な、本発明のコポリマーの構成モノマーであ
る、一般式（Ｉ）に表されるモノマーは、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。BEST MODE FOR CARRYING OUT THE INVENTION (1) Monomers represented by the general formula (I) used for the copolymers of the present invention and salts thereof The copolymers of the present invention are selected from the monomers represented by the general formula (I) One or two or more kinds are used as constituent monomers, and the total amount of the constituent monomers is 1 to 40% by weight,
More preferably, the content is 3 to 30% by weight. This is because, due to the water resistance of the copolymer in this portion, if the portion due to the monomer of the general formula (I) is too small or if the hydrophobicity of this portion is too low, the water resistance as a film of the copolymer will be high. This is because the property is reduced. If the amount is too large, the solubility in water may be impaired. In the general formula (I), R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 represents a hydrocarbon group having 4 to 30 carbon atoms. R1 is particularly preferably a hydrogen atom or a methyl group. This is the structure of acrylic acid or methacrylic acid that is widely used in copolymers and the like.
This is because many commercial products are easily available as raw materials.
Further, as R2, an alkyl group or an alkenyl group having a linear, branched or cyclic structure is particularly preferred. The number of carbon atoms is particularly preferably 5 to 30, more preferably 6 to 30. This is because, in the copolymer of the present invention, the partial structure of R2 realizes the water resistance of the coating film after application, and furthermore, this portion and the monomer represented by the following general formula (II) This is because the presence or absence of the cloud point or the temperature thereof is determined by the ratio with the origin. In a particularly preferred embodiment, the monomer bearing the hydrophobic portion in the copolymer is selected from those having a high hydrophobicity having 12 to 30 carbon atoms, and the content of the monomer is controlled to a small value. Is preferred from the viewpoint of exhibiting functional physical properties such as exhibiting plasticity and hydrophobicity. Examples of such a monomer represented by the general formula (I) include n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, isoamyl acrylate, isoamyl methacrylate, and n-hexyl Acrylate, n-hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate And stearyl methacrylate. The monomer represented by the general formula (I), which is a constituent monomer of the copolymer 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 at a rate. Further, the corresponding alcohol is further treated with thionyl chloride, phosphorus oxychloride, etc., and converted to chloride,
It can also be obtained by reacting 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.
【０００９】（２）本発明のコポリマーに使用される一
般式（ＩＩ）に表されるモノマー 本発明のコポリマーは、一般式（ＩＩ）に表されるモノ
マー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２〜
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、コポリマーなど
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。（Ｒ４−Ｏ）ｎ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−Ｏ）
ｎ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（２３）基、エチルポリオキシ
エチレン（２）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
れるモノマーとしては、一般式（ＩＩＩ）に表されるも
のが特に好ましい。本発明のコポリマー中に構成モノマ
ーとして一般式（ＩＩ）に表されるモノマーが含有され
るされる割合は、１分子中の総量の平均重量百分率で、
３０〜７０重量％、更に好ましくは４０〜６０重量％で
ある。これは、本発明のコポリマーの水への溶解性と曇
点の有無とその温度とが、この一般式（ＩＩ）に表され
る構成部分によるため、少なすぎるとコポリマーの水へ
の溶解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) Monomer represented by the general formula (II) used in the copolymer of the present invention The copolymer of the present invention is characterized by containing a monomer represented by the general formula (II) as a constituent monomer. I do.
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 represents a hydrogen atom, an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or an acyl group;
Represents a numerical value of 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 copolymers and the like, and its safety has already been confirmed for many products, and many commercial products are easily available as raw materials. (R4-O) n can be exemplified by a polyoxyethylene group, a polyoxypropylene group, a polyoxybutene group, a polyoxy (hydroxypropylene) group, a part or all of its acylated product, 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. As such an acyl group, an acetyl group, a benzoyl group, an acryloyl group, a methacryloyl group and the like can be preferably exemplified.
4 are preferred. Preferred (R4-O)
Examples of n include methylpolyoxyethylene (9), methylpolyoxyethylene (23), ethylpolyoxyethylene (2), and phenylpolyoxyethylene (2).
Groups, methyl polyoxyethylene (3) groups, acryl polyoxyethylene (4) groups, acryl polyoxypropylene (3) groups, acryl polyoxypropylene (7) groups, and the like. As such a monomer represented by the general formula (II), a monomer represented by the general formula (III) is particularly preferable. The proportion of the monomer represented by the general formula (II) as a constituent monomer in the copolymer of the present invention is the average weight percentage of the total amount in one molecule,
The content is 30 to 70% by weight, more preferably 40 to 60% by weight. This is because the solubility of the copolymer of the present invention in water, the presence or absence of a cloud point and the temperature thereof depend on the component represented by the general formula (II). This is because they may be hindered, and if too much, the water resistance of the formed film may be impaired.
【００１０】[0010]
【化５】 一般式（ＩＩＩ） （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 (III) (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.)
【００１１】（３）本発明のコポリマー 本発明のコポリマーは上記一般式（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。本発明のコポリマーでは、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、アクリル酸メチル、アクリル酸エチル、アク
リル酸ｎプロピル、アクリル酸イソプロピル等のアクリ
ル酸の炭素数３以下のアルコールとのエステル類、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
プロピル、メタクリル酸イソプロピル等の炭素数３以下
のアルコールとメタクリル酸のエステル類、アクリル酸
２ヒドロキシエチル、アクリル酸ヒドロキシプロピル、
アクリル酸４ヒドロキシブチル等のアクリル酸のヒドロ
キシアルキルエステル類、メタクリル酸２ヒドロキシエ
チル、メタクリル酸ヒドロキシプロピル、メタクリル酸
４ヒドロキシブチル等のメタクリル酸のヒドロキシアル
キルエステル類、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
コポリマー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。本発明のコポリ
マー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
すれば水の方へとコポリマーは移行する。しかる後に水
相をとり、濃縮すれば本発明のコポリマーを得ることが
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、コポリマー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
明のコポリマー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。又、
これらのコポリマーにおいてアクリル酸乃至はメタクリ
ル酸を構成モノマーに含有する場合には、ナトリウムや
カリウムなどのアルカリ金属や、カルシウムやマグネシ
ウムなどのアルカリ土類金属、アンモニウム、有機アミ
ンとともに塩にして私用することも出来る。かくして得
られたコポリマーは、水溶性を有するばかりでなく、曇
点を有し、水溶液を毛髪などに塗布し、ドライヤーなど
で加熱した場合、該加熱によりコポリマーが曇点以上の
温度となり、析出し、可塑剤なしでも柔軟性のある疎水
性の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、エタノールなどの有機溶剤をかなり減量した剤形で
の組成物を作成することが出来る。従って、整髪料など
の頭髪用化粧料特に好ましく使用され、水を主成分と
し、多価アルコールやエタノールなどを１０重量％程度
含有する、水性担体とともに製剤化し、ドライヤーの使
用のもとに速やかに疎水性皮膜を形成する整髪剤として
好適に適用される他、皮膚表面に保護膜を形成する目的
で皮膚化粧料、爪用化粧料等の化粧料に配合できるほ
か、ヒートガンなどにより固定可能な水性ペイントや金
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、曇点以上の温度
で加熱乾燥・被膜形成後は疎水性と可塑性の被膜を形成
する物質は今のところ知られていない。この様な曇点の
好ましい範囲は４０℃〜７０℃であり、この様な曇点に
設定するには、一般式（Ｉ）に表されるモノマーと一般
式（ＩＩ）に表されるモノマーとを上記に示した含有量
で構成単位として含む場合に於いては、この数値範囲に
大凡入る。又、この様な本発明のコポリマーにおいて、
好ましい分子量は、ＧＰＣ（ゲルパーミエイションクロ
マトグラフィー）測定によるポリエチレン換算数平均分
子量が５０００〜３０００００であり、更に好ましくは
７０００〜２５００００である。(3) Copolymer of the Present Invention The copolymer of the present invention comprises one or two or more monomers selected from the monomers represented by the general formula (I) and the general formula (II)
Or one or more selected from monomers represented by the formula (1) as constituent monomers. That is, it is characterized by having the following partial structural formula 1 and partial structural formula 2 in one molecule. In the copolymer of the present invention, in addition to these essential constituent monomers, monomers commonly used in copolymers can be contained as constituent monomers as long as the effects of the present invention are not impaired. Examples of such an optional constituent monomer include esters of acrylic acid with an alcohol having 3 or less carbon atoms, such as acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, and isopropyl acrylate; Methyl, ethyl methacrylate, methacrylic acid n
Propyl, esters of methacrylic acid with an alcohol having 3 or less carbon atoms such as isopropyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate,
Hydroxyalkyl esters of acrylic acid such as 4-hydroxybutyl acrylate; hydroxyalkyl esters of methacrylic acid such as 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate; vinyl acetate, vinyl alcohol, and vinyl alcohol Examples thereof include alkyl ether, styrene, α-alkylstyrene, butadiene, isoprene, propene, vinyl chloride, and acrylonitrile. The copolymer 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 commonly used, for example, peroxides such as benzoyl peroxide,
The polymerization may be started using an azo compound such as azobisisobutyronitrile, a persulfate, a persulfate and a sulfite (redox initiator), or the like. Since the copolymer 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 and flushed. The copolymer migrates towards the water. Thereafter, the aqueous phase is removed and concentrated to obtain the copolymer of the present invention. As used herein, the term "water-soluble" refers to the solubility in water. Specifically, when a uniform system is prepared by adding 99 parts by weight of water to 1 part by weight of a copolymer, the transmittance of the liquid to visible light is determined. Is 90% or more. The copolymer of the present invention may be a random type copolymer, a graft type copolymer, a block type or a combination thereof. or,
When acrylic acid or methacrylic acid is contained as a constituent monomer in these copolymers, they are used as salts with alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, ammonium and organic amines. You can do it. The copolymer thus obtained not only has water solubility, but also has a cloud point.When an aqueous solution is applied to hair or the like and heated with a drier or the like, the temperature of the copolymer becomes higher than the cloud point due to the heating, and the copolymer precipitates. It has the property of forming a flexible hydrophobic film without a plasticizer, and it is not necessary to use a phthalate ester or the like as a plasticizer, which is concerned about endocrine disrupting effects. In addition, since it has water solubility as described above, water can be used as a solvent in formulating, and a composition can be prepared in a dosage form in which an organic solvent such as ethanol is considerably reduced. Therefore, it is particularly preferably used for hair cosmetics such as hair styling, and is formulated with an aqueous carrier containing water as a main component and containing about 10% by weight of a polyhydric alcohol, ethanol or the like, and is rapidly prepared under the use of a dryer. In addition to being suitably applied as a hair styling agent for forming a hydrophobic film, it can be added to cosmetics such as skin cosmetics and nail cosmetics for the purpose of forming a protective film on the skin surface, and can be fixed with a heat gun or the like. It can also be used as a surface treatment agent for paint, metal, glass, fiber and the like. At present, there is no known substance capable of forming a hydrophobic and plastic film after drying by heating at a temperature higher than the cloud point and forming a film. A preferred range of such a cloud point is 40 ° C. to 70 ° C. To set such a cloud point, a monomer represented by the general formula (I) and a monomer represented by the general formula (II) are used. In the case where is contained as a constituent unit with the above-mentioned content, it is roughly within this numerical range. In such a copolymer of the present invention,
The preferred molecular weight is such that the number average molecular weight in terms of polyethylene measured by GPC (gel permeation chromatography) is 5,000 to 300,000, and more preferably 7000 to 250,000.
【００１２】[0012]
【化６】 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は炭素数４〜３０の炭化水素基を表
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 a hydrocarbon group having 4 to 30 carbon atoms)
【００１３】[0013]
【化７】 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２〜４
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 2 to 4
Represents a numerical value of 0. )
【００１４】（４）本発明の化粧料 上記本発明のコポリマーは、特に好適に化粧料の分野に
適用される。これは、本発明のコポリマーの特徴が、曇
点を有するためドライヤーなどの処置により、疎水性の
皮膜を形成することであり、この様な処置が必要な用途
に好適だからである。更に、可塑剤無しであっても可塑
性を有する皮膜を形成し、且つ、該皮膜が疎水性を有す
る性質が、特に内分泌攪乱物質を避けなければならない
化粧料にとって好適であるからである。又、この事よ
り、化粧料に於いてもドライヤーを使用する頭髪用の化
粧料に適用するのが特に好ましい。本発明の化粧料にお
いて、上記コポリマーは、毛髪の形状を整える整髪料、
皮膚などから水分が散逸するのを防ぐ、皮膚などの保護
皮膜として、或いは、皮脂や風などの物理的な力によ
り、皮膚上に施したメークアップが崩れるのを防ぐ、メ
ークアップ化粧料などに於ける、色材などの固着媒体と
しての機能を有する。具体的に適用される例としては、
例えば、クリーム、乳液、化粧水、パック料など基礎化
粧料、ネールカラー、リップカラー、マスカラ、アイラ
イナー、ファンデーション、アンダーメークアップなど
のメークアップ化粧料、ヘアリクィッド、セットローシ
ョン、ヘアカラー、ヘアマスカラなどの頭髪用の化粧料
等が例示でき、頭髪用の化粧料としてはエタノールなど
の有機溶剤や天然ガスやフロンガスなどの液化ガスを含
まない剤形ののものが特に好適に例示できる。本発明の
化粧料に於いては、上記コポリマーは唯１種含有するこ
とも出来るし、２種以上を組み合わせて含有することも
出来る。本発明の化粧料に於ける、上記コポリマーの好
ましい含有量は、０．０１〜３０重量％であり、更に好
ましくは０．１〜１５重量％である。(4) Cosmetic of the Present Invention The copolymer of the present invention is particularly preferably applied to the field of cosmetics. This is because the feature of the copolymer of the present invention is that it has a cloud point and thus forms a hydrophobic film by a treatment such as a drier, which is suitable for an application requiring such a treatment. Furthermore, a plastic film is formed even without a plasticizer, and the hydrophobic property of the film is particularly suitable for cosmetics in which endocrine disrupting substances must be avoided. In view of this, it is particularly preferable to apply the present invention to cosmetics for hair using a dryer. In the cosmetic of the present invention, the copolymer is a hairdressing agent for shaping the shape of hair,
For make-up cosmetics, etc., to prevent moisture from escaping from the skin, etc., as a protective film for the skin, or to prevent the make-up applied on the skin from being destroyed by physical force such as sebum or wind. It has a function as a fixing medium such as a coloring material. As a specific example,
For example, basic cosmetics such as creams, emulsions, lotions, and packs, make-up cosmetics such as nail colors, lip colors, mascaras, eyeliners, foundations, and under makeups, hair liquids, set lotions, hair colors, and hair mascaras Examples of the cosmetics for the hair include, for example, cosmetics for the hair which do not contain an organic solvent such as ethanol or a liquefied gas such as natural gas or Freon gas. In the cosmetic of the present invention, the copolymer may contain only one kind or two or more kinds in combination. The preferred content of the copolymer in the cosmetic of the present invention is 0.01 to 30% by weight, and more preferably 0.1 to 15% by weight.
【００１５】本発明の化粧料に於いては、上記必須成分
であるコポリマー以外に、通常化粧料で使用される任意
成分を含有することが出来る。かかる任意の成分として
は、例えば、スクワラン、ワセリン、マイクロクリスタ
リンワックス等の炭化水素類、ホホバ油、カルナウバワ
ックス，オレイン酸オクチルドデシル等のエステル類、
オリーブ油、牛脂、椰子油等のトリグリセライド類、ス
テアリン酸、オレイン酸、リチノレイン酸等の脂肪酸、
オレイルアルコール、ステアリルアルコール、オクチル
ドデカノール等の高級アルコール、スルホコハク酸エス
テルやポリオキシエチレンアルキル硫酸ナトリウム等の
アニオン界面活性剤類、アルキルベタイン塩等の両性界
面活性剤類、ジアルキルアンモニウム塩等のカチオン界
面活性剤類、ソルビタン脂肪酸エステル、脂肪酸モノグ
リセライド、これらのポリオキシエチレン付加物、ポリ
オキシエチレンアルキルエーテル、ポリオキシエチレン
脂肪酸エステル等の非イオン界面活性剤類、ポリエチレ
ングリコール、グリセリン、１，３−ブタンジオール等
の多価アルコール類、増粘・ゲル化剤、酸化防止剤、紫
外線吸収剤、色材、防腐剤、粉体等を含有することがで
きる。これらの内、特に注目すべきは、通常この様な剤
形ではエタノールなどの有機溶剤を、コポリマーのベヒ
クルとして４０重量％用いなければならないが、本発明
のコポリマーは水溶性であるため、１０重量％程度まで
減量できることである。これら任意の成分と必須成分と
を常法に従って処理することにより、本発明の化粧料は
製造される。The cosmetic of the present invention may contain optional components usually used in cosmetics, in addition to the above-mentioned copolymer which is an essential component. Such optional components include, for example, hydrocarbons such as squalane, petrolatum, microcrystalline wax, jojoba oil, carnauba wax, esters such as octyldodecyl oleate,
Triglycerides such as olive oil, beef tallow, and coconut oil; fatty acids such as stearic acid, oleic acid, and ritinoleic acid;
Higher alcohols such as oleyl alcohol, stearyl alcohol and octyl dodecanol; anionic surfactants such as sulfosuccinates and sodium polyoxyethylene alkyl sulfate; amphoteric surfactants such as alkyl betaine salts; cationic interfaces such as dialkyl ammonium salts. Activators, sorbitan fatty acid esters, fatty acid monoglycerides, nonionic surfactants such as polyoxyethylene adducts, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, etc., polyethylene glycol, glycerin, 1,3-butanediol And the like, a thickening / gelling agent, an antioxidant, an ultraviolet absorber, a coloring material, a preservative, a powder, and the like. Of these, it should be particularly noted that in such a dosage form, an organic solvent such as ethanol must be used as a vehicle for the copolymer in an amount of 40% by weight. However, since the copolymer of the present invention is water-soluble, 10% by weight is required. %. The cosmetic of the present invention is produced by treating these optional components and essential components according to a conventional method.
【００１６】[0016]
【実施例】以下に、実施例を挙げて本発明について更に
詳細に説明を加えるが、本発明がこれら実施例にのみ限
定されないことは言うまでもない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to only these Examples.
【００１７】＜実施例１＞ 製造例１ 冷却器、攪拌機、窒素導入管付きフラスコにメトキシポ
リエチレングリコール（９）アクリレート２８．０ｇ、
ｎオクチルアクリレート１２．０ｇ及び酢酸エチル８０
ｍｌ、エタノール８０ｍｌ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を混合溶媒１０ｍ
ｌに溶解した溶液を添加した後攪拌を続けながら窒素気
流で充分置換を行った。溶媒の沸点で重合を８時間行っ
た。反応終了後混合溶媒から水にフラッシングをおこな
ってポリマーの水溶液を得た。これを凍結乾燥し本発明
のコポリマー１を得た。Example 1 Production Example 1 28.0 g of methoxypolyethylene glycol (9) acrylate was placed in a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube.
12.0 g of n-octyl acrylate and 80 ethyl acetate
A mixed solvent of 80 ml of ethanol and 80 ml of ethanol was taken and mixed with stirring. Then, 0.2 g of benzoyl peroxide was added to a mixed solvent of 10 m.
After adding the solution dissolved in 1 liter, 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 8 hours. After the completion of the reaction, the mixed solvent was flushed with water to obtain an aqueous solution of the polymer. This was freeze-dried to obtain Copolymer 1 of the present invention.
【００１８】＜実施例２＞ 製造例２ 冷却器、攪拌機、窒素導入管付きフラスコにメトキシポ
リエチレングリコール（２３）メタクリレート３０．０
ｇ、シクロヘキシルメタクリレート１２．０ｇ、２ヒド
ロキシエチルメタクリレート１８．０ｇ及びエタノール
８０ｍｌ、水６０ｍｌ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０．５ｇ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
置換を行った。８０℃に加熱して重合を１２時間行っ
た。反応終了後水酸化ナトリウム水溶液でｐＨを７．０
に調製した後、エタノールを除去してポリマーの水溶液
を得た。これを凍結乾燥し本発明のコポリマー２を得
た。Example 2 Production Example 2 A flask equipped with a condenser, a stirrer, and a nitrogen inlet tube was charged with methoxypolyethylene glycol (23) methacrylate 30.0.
g, 12.0 g of cyclohexyl methacrylate, 18.0 g of 2hydroxyethyl methacrylate, 80 ml of ethanol, and 60 ml of water were mixed with stirring.
A solution of 0.5 g of ammonium persulfate dissolved in 10 ml of water was added thereto, and 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 the completion of the reaction, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution.
Then, ethanol was removed to obtain an aqueous solution of a polymer. This was freeze-dried to obtain Copolymer 2 of the present invention.
【００１９】＜実施例３＞ 製造例３ 冷却器、攪拌機、窒素導入管付きフラスコにメトキシポ
リエチレングリコール（２３）メタクリレート２４．０
ｇ、２エチルヘキシルメタクリレート９．０ｇ、２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１５．０ｇ及びイソプロピルアルコール１８０
ｍｌ、市販標準中性リン酸緩衝溶液（ｐＨ６．８６）１
２０ｍｌ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１．０ｇ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っ
た。６５℃に加熱して重合を１６時間行った。反応終了
後水酸化カルシウム１．８ｇを反応系に添加し６５℃で
２時間攪拌した。濾過により粉末を除去した後、イソプ
ロピルアルコールを除去してポリマーの水溶液を得た。
これを凍結乾燥し本発明のコポリマー３を得た。Example 3 Production Example 3 Methoxypolyethylene glycol (23) methacrylate 24.0 was placed in a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube.
g, 2 ethylhexyl methacrylate 9.0 g, 2 hydroxyethyl methacrylate 12.0 g, methyl methacrylate 15.0 g and isopropyl alcohol 180
ml, commercially available standard neutral phosphate buffer solution (pH 6.86) 1
20 ml of the mixed solvent was taken and mixed with stirring. A solution of 1.0 g of ammonium persulfate dissolved in 10 ml of water was added thereto, and the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. The polymerization was carried out by heating to 65 ° C. for 16 hours. After completion of the reaction, 1.8 g of calcium hydroxide was added to the reaction system, and the mixture was stirred at 65 ° C for 2 hours. After removing the powder by filtration, isopropyl alcohol was removed to obtain an aqueous solution of the polymer.
This was freeze-dried to obtain Copolymer 3 of the present invention.
【００２０】＜実施例４＞ 製造例４ 冷却器、攪拌機、窒素導入管付きフラスコにポリエチレ
ングリコール（２３）モノアクリレート４８．０ｇ、ｎ
ヘキシルメタクリレート８．０ｇ、ｎブチルメタクリレ
ート８．０ｇ、２ヒドロキシエチルメタクリレート１
６．０ｇ、及びエチルアルコール１６０ｍｌ、水６０ｍ
ｌ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い、６５℃に加熱後に過硫酸カ
リウム１．５ｇを水１０ｍｌに溶解した溶液及び亜硫酸
水素ナトリウム１．５ｇを水１０ｍｌに溶解した溶液を
添加した。温度を６５℃に保ち重合を１０時間行った。
反応終了後水酸化ナトリウム水溶液でｐＨを７．０に調
製した後、エタノールを除去してポリマーの水溶液を得
た。これを凍結乾燥し本発明のコポリマー４を得た。Example 4 Production Example 4 48.0 g of polyethylene glycol (23) monoacrylate was placed in a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube, and
Hexyl methacrylate 8.0 g, n-butyl methacrylate 8.0 g, 2-hydroxyethyl methacrylate 1
6.0 g, ethyl alcohol 160 ml, water 60 m
1 mixed solvent was taken and mixed with stirring. Thereafter, the mixture was sufficiently replaced with a nitrogen stream while continuing stirring, and after heating to 65 ° C., a solution in which 1.5 g of potassium persulfate was dissolved in 10 ml of water and a solution in which 1.5 g of sodium bisulfite was dissolved in 10 ml of water were added. The polymerization was carried out for 10 hours while maintaining the temperature at 65 ° C.
After the completion of the reaction, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution, and then ethanol was removed to obtain an aqueous polymer solution. This was freeze-dried to obtain Copolymer 4 of the present invention.
【００２１】＜実施例５＞ 製造例５ 冷却器、攪拌機、窒素導入管付きフラスコにメトキシポ
リエチレングリコール（２３）モノメタクリレート４
０．０ｇ、ドデシルメタクリレート４．８ｇ、２ヒドロ
キシエチルメタクリレート２０．０ｇ、エチルメタクリ
レート１５．２ｇ及びイソプロピルアルコール１５０ｍ
ｌ、市販標準酸性フタル酸緩衝液（ｐＨ４．０１）１０
０ｍｌ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った。
８０℃に加熱して重合を１２時間行った。反応終了後水
酸化ナトリウム水溶液でｐＨを７．０に調製した後、エ
タノールを除去してポリマーの水溶液を得た。これを凍
結乾燥し本発明のコポリマー５を得た。Example 5 Production Example 5 Methoxy polyethylene glycol (23) monomethacrylate 4 was placed in a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube.
0.0 g, dodecyl methacrylate 4.8 g, 2hydroxyethyl methacrylate 20.0 g, ethyl methacrylate 15.2 g, and isopropyl alcohol 150 m
1, commercially available standard acid phthalate buffer (pH 4.01) 10
0 ml of the mixed solvent was taken and mixed with stirring. After a solution of 0.7 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 the completion of the reaction, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution, and then ethanol was removed to obtain an aqueous polymer solution. This was freeze-dried to obtain Copolymer 5 of the present invention.
【００２２】＜実施例６＞ 製造例６ 冷却器、攪拌機、窒素導入管付きフラスコにポリエチレ
ングリコール（９）モノメタクリレート３９．０ｇ、イ
ソアミルメタクリレート９．０ｇ、メチルメタクリレー
ト９．０ｇ、スチレン３．０ｇ及び酢酸エチル８０ｍ
ｌ、イソプロピルアルコール６０ｍｌ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を混合溶媒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っ
た。溶媒の沸点で重合を１６時間行った。反応終了後混
合溶媒を蒸発除去し本発明のコポリマー６を得た。Example 6 Production Example 6 39.0 g of polyethylene glycol (9) monomethacrylate, 9.0 g of isoamyl methacrylate, 9.0 g of methyl methacrylate, 3.0 g of styrene were placed in a flask equipped with a condenser, a stirrer and a nitrogen inlet tube. Ethyl acetate 80m
and a mixed solvent of 60 ml of isopropyl alcohol, and stirred and mixed. A solution prepared by dissolving 0.2 g of 2,2-azobis (isobutyronitrile) in 10 ml of a mixed solvent was added thereto, and the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. Polymerization was carried out for 16 hours at the boiling point of the solvent. After completion of the reaction, the mixed solvent was removed by evaporation to obtain Copolymer 6 of the present invention.
【００２３】＜実施例７＞ 製造例７ 冷却器、攪拌機、窒素導入管付きフラスコにポリエチレ
ングリコール（２３）モノメタクリレート２０．０ｇ、
メトキシトリプロピレングリコールメタクリレート１
０．０ｇ、ｎヘキシルメタクリレート５．０ｇ、メチル
メタクリレート１０．０ｇ、酢酸ビニル５．０ｇ及びメ
タノール１８０ｍｌ、水７０ｍｌの混合溶媒を採り攪拌
混合した。これに過硫酸カリウム０．５ｇ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
で充分置換を行った。８０℃に加熱して重合を６時間行
った。反応終了後水酸化ナトリウム水溶液でｐＨを７．
０に調製した後、メタノールを除去してポリマーの水溶
液を得た。これを凍結乾燥し本発明のコポリマー７を得
た。Example 7 Production Example 7 20.0 g of polyethylene glycol (23) monomethacrylate was placed in a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube.
Methoxytripropylene glycol methacrylate 1
A mixed solvent of 0.0 g, 5.0 g of n-hexyl methacrylate, 10.0 g of methyl methacrylate, 5.0 g of vinyl acetate, 180 ml of methanol and 70 ml of water was taken and mixed. 0.5 g of potassium persulfate and 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 polymerization was carried out by heating to 80 ° C. for 6 hours. After completion of the reaction, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution.
After adjusting to 0, methanol was removed to obtain an aqueous solution of the polymer. This was freeze-dried to obtain Copolymer 7 of the present invention.
【００２４】＜実施例８＞ 製造例８ 冷却器、攪拌機、窒素導入管付きフラスコにメトキシポ
リエチレングリコール（２３）アクリレート２０．０
ｇ、イソブチルアクリレート８．０ｇ、２ヒドロキシエ
チルアクリレート１２．０ｇ、及びイソプロピルアルコ
ール９０ｍｌ、市販標準中性リン酸緩衝溶液（ｐＨ６．
８６）６０ｍｌ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１．０ｇ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
行った。７０℃に加熱して重合を１６時間行った。反応
終了後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てポリマーの水
溶液を得た。これを凍結乾燥し本発明のコポリマー８を
得た。Example 8 Production Example 8 Methoxy polyethylene glycol (23) acrylate 20.0 was placed in a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube.
g, 8.0 g of isobutyl acrylate, 12.0 g of 2hydroxyethyl acrylate, and 90 ml of isopropyl alcohol, a commercially available standard neutral phosphate buffer solution (pH 6.0).
86) 60 ml of the mixed solvent was taken and mixed with stirring. A solution of 1.0 g of ammonium persulfate dissolved in 10 ml of water was added thereto, and the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. The polymerization was carried out by heating to 70 ° C. for 16 hours. After completion of the reaction, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution, and then isopropyl alcohol was removed to obtain an aqueous solution of a polymer. This was freeze-dried to obtain Copolymer 8 of the present invention.
【００２５】＜実施例９＞ 製造例９ 冷却器、攪拌機、窒素導入管付きフラスコにメトキシポ
リエチレングリコール（９）アクリレート２７．０ｇ、
２エチルヘキシルアクリレート３．０ｇ、４ヒドロキシ
ブチルメタクリレート１８．０ｇ、イソプロピルアクリ
レート１２．０ｇ及びイソプロピルアルコール２４０ｍ
ｌを採り攪拌混合した。これに過酸化ベンゾイル０．５
ｇ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っ
た。溶媒の沸点で重合を１６時間行った。反応終了後イ
ソプロピルアルコールを除去し本発明のコポリマー９を
得た。Example 9 Production Example 9 27.0 g of methoxypolyethylene glycol (9) acrylate was placed in a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube.
3.0 g of 2-ethylhexyl acrylate, 18.0 g of 4-hydroxybutyl methacrylate, 12.0 g of isopropyl acrylate and 240 m of isopropyl alcohol
1 and mixed with stirring. Add benzoyl peroxide 0.5
g was dissolved in 10 ml of isopropyl alcohol, and the mixture was sufficiently replaced with a nitrogen stream while stirring. Polymerization was carried out for 16 hours at the boiling point of the solvent. After completion of the reaction, isopropyl alcohol was removed to obtain Copolymer 9 of the present invention.
【００２６】＜実施例１０＞ 製造例１０ 冷却器、攪拌機、窒素導入管付きフラスコにメトキシポ
リエチレングリコール（９）メタクリレート３６．０
ｇ、ｎブチルアクリレート９．０ｇ、メチルメタクリレ
ート１５．０ｇ及びイソプロピルアルコール１８０ｍ
ｌ、市販標準中性リン酸緩衝溶液（ｐＨ６．８６）１２
０ｍｌ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１．０ｇ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った。
６５℃に加熱して重合を１４時間行った。反応終了後水
酸化カルシウム１．８ｇを反応系に添加し６５℃で２時
間攪拌した。濾過により粉末を除去した後、イソプロピ
ルアルコールを除去してポリマーの水溶液を得た。これ
を凍結乾燥し本発明のコポリマー１０を得た。Example 10 Production Example 10 Methoxypolyethylene glycol (9) methacrylate 36.0 was placed in a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube.
g, n-butyl acrylate 9.0 g, methyl methacrylate 15.0 g and isopropyl alcohol 180 m
1, commercially available standard neutral phosphate buffer solution (pH 6.86) 12
0 ml of the mixed solvent was taken and mixed with stirring. A solution of 1.0 g of ammonium persulfate dissolved in 10 ml of water was added thereto, and the mixture was sufficiently replaced with a nitrogen stream while stirring was continued.
The polymerization was carried out for 14 hours by heating to 65 ° C. After completion of the reaction, 1.8 g of calcium hydroxide was added to the reaction system, and the mixture was stirred at 65 ° C for 2 hours. After removing the powder by filtration, isopropyl alcohol was removed to obtain an aqueous solution of the polymer. This was freeze-dried to obtain the copolymer 10 of the present invention.
【００２７】＜実施例１１＞ 製造例１１ 冷却器、攪拌機、窒素導入管付きフラスコにメトキシポ
リエチレングリコール（２３）メタクリレート２４．０
ｇ、ｎヘキシルアクリレート６．０ｇ、２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及びイソプロピルアルコール１８０ｍｌ、市
販標準中性リン酸緩衝溶液（ｐＨ６．８６）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１．０ｇ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った。７０℃
に加熱して重合を１６時間行った。反応終了後水酸化ナ
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てポリマーの水溶液を得た。こ
れを凍結乾燥し本発明のコポリマー１１を得た。Example 11 Production Example 11 Methoxypolyethylene glycol (23) methacrylate 24.0 was placed in a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube.
g, n-hexyl acrylate 6.0 g, 2-hydroxyethyl methacrylate 12.0 g, methyl methacrylate 18.0 g and isopropyl alcohol 180 ml, commercially available standard neutral phosphate buffer solution (pH 6.86) 120 ml
And mixed with stirring. A solution of 1.0 g of ammonium persulfate dissolved in 10 ml of water was added thereto, and the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. 70 ° C
And the polymerization was carried out for 16 hours. After completion of the reaction, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution, and then isopropyl alcohol was removed to obtain an aqueous solution of a polymer. This was freeze-dried to obtain copolymer 11 of the present invention.
【００２８】＜実施例１２＞ 製造例１２ 冷却器、攪拌機、窒素導入管付きフラスコにメトキシポ
リエチレングリコール（２３）メタクリレート１５．０
ｇ、ｎヘキシルアクリレート２４．０ｇ、２ヒドロキシ
エチルメタクリレート２１．０ｇ、及びイソプロピルア
ルコール１８０ｍｌ、市販標準中性リン酸緩衝溶液（ｐ
Ｈ６．８６）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１．０ｇ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
充分置換を行った。７０℃に加熱して重合を１６時間行
った。反応終了後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てポ
リマーの水溶液を得た。これを凍結乾燥し実施例１２の
コポリマーを得た。Example 12 Production Example 12 Methoxypolyethylene glycol (23) methacrylate 15.0 was placed in a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube.
g, 24.0 g of n-hexyl acrylate, 21.0 g of 2-hydroxyethyl methacrylate, and 180 ml of isopropyl alcohol, a commercially available standard neutral phosphate buffer solution (p
H6.86) 120 ml of a mixed solvent was taken and mixed by stirring. A solution of 1.0 g of ammonium persulfate dissolved in 10 ml of water was added thereto, and the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. The polymerization was carried out by heating to 70 ° C. for 16 hours. After completion of the reaction, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution.
After adjusting to 0, isopropyl alcohol was removed to obtain an aqueous solution of the polymer. This was freeze-dried to obtain the copolymer of Example 12.
【００２９】＜実施例１３＞ 製造例１３ 冷却器、攪拌機、窒素導入管付きフラスコにメトキシポ
リエチレングリコール（２３）メタクリレート５１．０
ｇ、ｎヘキシルアクリレート９．０ｇ及びイソプロピル
アルコール１８０ｍｌ、市販標準中性リン酸緩衝溶液
（ｐＨ６．８６）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１．０ｇ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
で充分置換を行った。７０℃に加熱して重合を１６時間
行った。反応終了後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
てポリマーの水溶液を得た。これを凍結乾燥し実施例１
３のコポリマーを得た。Example 13 Production Example 13 Methoxy polyethylene glycol (23) methacrylate 51.0 was placed in a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube.
g, 9.0 g of n-hexyl acrylate, 180 ml of isopropyl alcohol, and 120 ml of a commercially available standard neutral phosphate buffer solution (pH 6.86) were mixed with stirring. 1.0 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 polymerization was carried out by heating to 70 ° C. for 16 hours. After completion of the reaction, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution, and then isopropyl alcohol was removed to obtain an aqueous solution of a polymer. This was freeze-dried and used in Example 1.
3 was obtained.
【００３０】＜実施例１４＞下記に示す比較例１のコポ
リマーを作成し、実施例１〜１３の本発明のコポリマー
１〜１１とその物性を比較した。曇点の確認は次の方法
に従って行った。即ち、コポリマーの５ｗｔ％水溶液を
所定の温度で３０分間加熱し、溶液からポリマーが相分
離するかを観察する。ポリマーが相分離により不溶化し
た温度を曇点とした。分子量の測定は次の方法に従って
行った。即ち、２０ｍＭの燐酸一水素カリウム水溶液に
アクリロニトリル３０ｖ％を添加した混合溶液を溶離液
とし、トーソー（株）TSK-GEL PWシリーズをカラムとし
て用いたＧＰＣによりポリエチレン換算分子量として測
定した。結果を表１に示す。是より、本発明のコポリマ
ーは曇点を有していることがわかる。即ち、本発明のコ
ポリマーの構成をとることにより、かかる物性を有する
こともわかる。Example 14 The copolymer of Comparative Example 1 shown below was prepared, and the physical properties of the copolymers 1 to 11 of Examples 1 to 13 were compared. The confirmation of the cloud point was performed according to the following method. That is, a 5 wt% aqueous solution of the copolymer is heated at a predetermined temperature for 30 minutes, and it is observed whether the polymer undergoes phase separation from the solution. The temperature at which the polymer was insolubilized by phase separation was taken as the cloud point. The molecular weight was measured according to the following method. That is, a mixed solution obtained by adding 30 v% of acrylonitrile to a 20 mM aqueous solution of potassium hydrogen phosphate was used as an eluent, and the molecular weight was measured in terms of polyethylene by GPC using a column of TSK-GEL PW series of Tosoh Corporation. Table 1 shows the results. Indeed, it can be seen that the copolymer of the present invention has a cloud point. That is, it is also understood that the copolymer of the present invention has such physical properties by adopting the constitution.
【００３１】比較例１ 冷却器、攪拌機、窒素導入管付きフラスコにメタクリル
酸４２．０ｇ、ｎヘキシルアクリレート９．０ｇ、２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１８０ｍｌ、市販標準中性リン酸緩衝溶
液（ｐＨ６．８６）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１．０ｇを水１０ｍ
ｌに溶解した溶液を添加した後攪拌を続けながら窒素気
流で充分置換を行った。７０℃に加熱して重合を１６時
間行った。反応終了後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
てポリマーの水溶液を得た。これを凍結乾燥し比較例１
のコポリマーを得た。Comparative Example 1 In a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube, 42.0 g of methacrylic acid, 9.0 g of n-hexyl acrylate, 9.0 g of 2-hydroxyethyl methacrylate, and 180 ml of isopropyl alcohol, a commercially available standard neutral phosphate buffer 120 ml of a mixed solvent of the solution (pH 6.86) was taken and mixed by stirring. 1.0 g of ammonium persulfate was added to 10 m of water.
After adding the solution dissolved in 1 liter, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. The polymerization was carried out by heating to 70 ° C. for 16 hours. After completion of the reaction, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution, and then isopropyl alcohol was removed to obtain an aqueous solution of a polymer. This was freeze-dried and Comparative Example 1
Was obtained.
【００３２】[0032]
【表１】 [Table 1]
【００３３】＜実施例１５＞ 耐水性試験 実施例１〜１３の本発明のコポリマー１〜１３と比較例
のコポリマー１について、１０重量％水溶液を作成し、
毛束に１０ｇに１ｍｌ均一に塗布した。塗布後、通常の
ドライヤー条件で熱風乾燥させ試料とした。各試料は、
流水で３分間流し、風乾して、その後ＡＴＲ−ＩＲによ
り流水処理の前後のメチレンの伸縮のピーク強度の差よ
り残存度を測定した。結果を表２に示す。これより、本
発明の曇点を有するコポリマーは何れも優れた耐水性を
有していることがわかる。更には、構成モノマーとし
て、一般式（Ｉ）に表されるモノマーを３〜３０重量％
含み、且つ、一般式（ＩＩ）にあわされるモノマーを４
０〜６０重量％含むコポリマーは何れも曇点が４０〜７
０℃に存在し、塗布時は一様な水性溶液で、ドライヤー
処置により疎水膜を生成して、毛髪に好適に固定される
ので、特に優れた特性を有することがわかる。Example 15 Water Resistance Test With respect to the copolymers 1 to 13 of the present invention of Examples 1 to 13 and the copolymer 1 of the comparative example, a 10% by weight aqueous solution was prepared.
1 ml was uniformly applied to 10 g of the hair bundle. After the application, the sample was dried with hot air under ordinary dryer conditions. Each sample is
After flowing for 3 minutes in running water and air-drying, the remaining degree was measured by ATR-IR based on the difference in peak intensity of expansion and contraction of methylene before and after the running water treatment. Table 2 shows the results. This shows that all of the copolymers having a cloud point of the present invention have excellent water resistance. Further, as a constituent monomer, 3 to 30% by weight of a monomer represented by the general formula (I)
And a monomer represented by the general formula (II):
All of the copolymers containing 0-60% by weight have a cloud point of 40-7.
It can be seen that it has particularly excellent properties because it is present at 0 ° C. and is a uniform aqueous solution at the time of application, forms a hydrophobic film by drier treatment and is suitably fixed to the hair.
【００３４】[0034]
【表２】 [Table 2]
【００３５】＜実施例１６＞実施例１〜１３の本発明の
コポリマー１〜１３と比較例１のコポリマーを用いて、
手に付いたコポリマーの洗浄性の試験を行った。即ち、
それぞれのコポリマーの１０重量％水溶液を作成し、
０．１ｍｌ手に付け、軽く擦り、流水で流した。その
後、軽く手をタオルで拭き取り、残り感を○：残り感無
し、△：やや残り感あり、×：明確な残り感の基準で判
定した。結果を表３に示す。これより、本発明のコポリ
マーは何れも、ドライヤー処理を行わなければ、容易に
水洗できることがわかる。Example 16 Using the copolymers 1 to 13 of the present invention of Examples 1 to 13 and the copolymer of Comparative Example 1,
The hand-held copolymer was tested for detergency. That is,
Make 10% by weight aqueous solution of each copolymer,
0.1 ml was attached to hands, gently rubbed, and flushed with running water. Thereafter, the hands were gently wiped with a towel, and the remaining feeling was evaluated according to the following criteria: ：: no remaining feeling, Δ: slight remaining feeling, ×: clear remaining feeling. Table 3 shows the results. This shows that any of the copolymers of the present invention can be easily washed with water without drying.
【００３６】[0036]
【表３】 [Table 3]
【００３７】＜実施例１７＞下記に示す処方に従って、
整髪用の化粧料を作成した。即ち、処方成分を８０℃で
加熱可溶化し、攪拌冷却して整髪料用の化粧料組成物を
得た。このものを噴霧用のノズルを有する容器に充填
し、整髪料とした。このものを専門パネラーにより評価
した。評価時点は整髪直後と整髪後４時間であった。評
価基準は○：良い、△：やや良い、×：悪いであった。
結果を表４に示す。本発明の整髪料は優れた整髪力を長
時間維持する作用に優れていることがわかる。又、本発
明により、有機溶剤であるエタノールの使用量を１０重
量％に低減できることもわかる。 コポリマー＊ １０ 重量部 エタノール １０ 重量部 ジメチコン ０．５重量部 ＰＯＥ（２０）セチルエーテル ０．３重量部 ＰＯＥ（９）ラウリルエーテル ０．７重量部 １，３−ブタンジオール ０．５重量部 水 ７８ 重量部 ＊詳細は表４に示す。Example 17 According to the following formulation,
A hairdressing cosmetic was created. That is, the prescription components were heated and solubilized at 80 ° C., and were stirred and cooled to obtain a cosmetic composition for hairdressing. This was filled into a container having a nozzle for spraying to prepare a hairdressing composition. This was evaluated by a specialized panel. The time points for evaluation were immediately after hair styling and 4 hours after hair styling. The evaluation criteria were ：: good, Δ: somewhat good, ×: bad.
Table 4 shows the results. It can be seen that the hairdressing composition of the present invention is excellent in the action of maintaining excellent hairdressing power for a long time. It is also found that the present invention can reduce the amount of ethanol used as an organic solvent to 10% by weight. Copolymer * 10 parts by weight Ethanol 10 parts by weight Dimethicone 0.5 parts by weight POE (20) cetyl ether 0.3 parts by weight POE (9) lauryl ether 0.7 parts by weight 0.5 parts by weight 1,3-butanediol Water 78 Parts by weight * Details are shown in Table 4.
【００３８】[0038]
【表４】 [Table 4]
【００３９】＜実施例１８＞下記に示す処方に従って、
本発明の化粧料である化粧水を作成した。これらの化粧
水について、散逸水分量を測定し、２０％以上抑制のも
のに○、１０％以上２０％未満のものに△、１０％未満
のものに×を付してクラス分けを行った。これらの結果
を表５に示す。これらの化粧水は何れも保水性に優れる
ものであった。 コポリマー＊＊ １ 重量部 １，３−ブタンジオール ５ 重量部 エタノール ５ 重量部 水 ８９ 重量部 ＊＊表５に詳細を記す。Example 18 According to the following formulation,
A lotion as the cosmetic of the present invention was prepared. With respect to these lotions, the amount of dissipated water was measured, and those classified as 20% or more suppressed were marked with ○, those with 10% or more but less than 20%, and those with less than 10% were marked with X. Table 5 shows the results. Each of these lotions was excellent in water retention. Copolymer ** 1 part by weight 1,3-butanediol 5 parts by weight Ethanol 5 parts by weight Water 89 parts by weight ** Details are shown in Table 5.
【００４０】[0040]
【表５】 [Table 5]
【００４１】[0041]
【発明の効果】本発明によれば、水溶性であって、使用
後は疎水性の皮膜を形成するコポリマー及び／又はその
塩及びそれを含有してなる、整髪などに有用な化粧料を
提供することが出来る。According to the present invention, there is provided a copolymer which is water-soluble and forms a hydrophobic film after use, and / or a salt thereof, and a cosmetic composition containing the same, which is useful for hair styling. You can do it.
フロントページの続き Ｆターム(参考） 4C083 AC102 AC112 AC182 AD091 AD092 AD152 BB53 CC04 CC32 DD08 DD23 EE06 EE07 EE28 4J027 AC02 AC03 AC04 AC06 AJ02 BA07 BA10 BA11 CB04 CC02 CD00 4J100 AL03Q AL04Q AL05Q AL08P AL08Q BA08P BC04Q BC43Q CA04 DA36 JA61 Continued on the front page F-term (reference) 4C083 AC102 AC112 AC182 AD091 AD092 AD152 BB53 CC04 CC32 DD08 DD23 EE06 EE07 EE28 4J027 AC02 AC03 AC04 AC06 AJ02 BA07 BA10 BA11 CB04 CC02 CD00 4J100 AL03Q AL04Q AL05Q AL08P AL04QJA08
Claims (13)
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コポリマーにおいて、曇点を有する
ことを特徴とする、コポリマー及び／又はその塩。 【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は炭素数４〜３０の炭化水素基を表
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２〜４
０の数値を表す。）1. A monomer comprising at least one kind selected from the monomers represented by the general formula (I) and at least one kind selected from the monomers represented by the general formula (II) A copolymer and / or a salt thereof, which has a cloud point. Embedded image Formula (I) (wherein, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 represents a hydrocarbon group having 4 to 30 carbon atoms). 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. R 5 represents a hydrogen atom, an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or an acyl group, and n represents 2 to 4
Represents a numerical value of 0. )
項１に記載のコポリマー及び／又はその塩。2. The copolymer and / or salt thereof according to claim 1, which is used for cosmetics.
モノマーとしての含有量が総量で１〜４０重量％であ
り、一般式（ＩＩ）に表されるモノマーの構成モノマー
としての含有量が総量で３０〜７０重量％であることを
特徴とする、請求項１又は２に記載のコポリマー及び／
又はその塩。3. The content of the monomer represented by the general formula (I) as a constituent monomer is 1 to 40% by weight in total, and the content of the monomer represented by the general formula (II) as a constituent monomer Is 30 to 70% by weight in total, and the copolymer according to claim 1 or 2 and / or
Or a salt thereof.
とする、請求項１〜３何れか１項に記載のコポリマー。4. The copolymer according to claim 1, wherein the cloud point is between 40 ° C. and 70 ° C.
マー及びその塩から選ばれる１種乃至は２種以上を含有
することを特徴とする、化粧料。5. A cosmetic comprising at least one selected from the copolymers according to claim 1 and salts thereof.
５に記載の化粧料。6. The cosmetic according to claim 5, which is a hairdressing agent.
ることを特徴とする、請求項５又は６に記載の化粧料。7. The cosmetic according to claim 5, which has a transparent form together with the aqueous carrier.
塩を含む化粧料で毛髪を処理し、しかる後、ヘアドライ
ヤーにより、該曇点以上の温度に処理された毛髪を加熱
し、毛髪表面上にコポリマー及び／又はその塩を析出さ
せることを特徴とする、整髪方法。8. The hair is treated with a cosmetic containing a copolymer having a cloud point and / or a salt thereof, and then the hair treated with a hair dryer is heated to a temperature higher than the cloud point to form a hair on the surface of the hair. A hair styling method comprising precipitating a copolymer and / or a salt thereof on the hair.
とする、請求項８に記載の整髪方法。9. The hair styling method according to claim 8, wherein the cloud point is 40 ° C. to 70 ° C.
理が、請求項５〜７何れか１項に記載の化粧料の使用に
よるものであることを特徴とする、請求項８又は９に記
載の方法。10. The method according to claim 8, wherein the treatment with the copolymer and / or a salt thereof is due to the use of the cosmetic according to claim 5. .
から選ばれる１種乃至は２種以上と前記一般式（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コポリマーにおいて、一
般式（Ｉ）に表されるモノマーの構成モノマーとしての
含有量が総量で１〜４０重量％であり、一般式（ＩＩ）
に表されるモノマーの構成モノマーとしての含有量が総
量で３０〜７０重量％であることを特徴とする、コポリ
マー及び／又はその塩。11. One or more kinds selected from the monomers represented by the general formula (I) and the general formula (II)
In a copolymer containing one or more selected from monomers represented by the following formula (I), the total content of the monomers represented by the general formula (I) as the constituent monomers is 1 to 40% by weight. And the general formula (II)
A copolymer and / or a salt thereof, characterized in that the total content of the monomers represented by the formula (1) is 30 to 70% by weight.
求項１１記載のコポリマー及び／又はその塩。12. The copolymer and / or salt thereof according to claim 11, which is used for cosmetics.
する、請求項１１又は１２に記載のコポリマー及び／又
はその塩。13. The copolymer and / or salt thereof according to claim 11, which is used for cosmetics for hair.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000135295A JP2001316435A (en) | 2000-05-09 | 2000-05-09 | Copolymer and cosmetic material containing it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000135295A JP2001316435A (en) | 2000-05-09 | 2000-05-09 | Copolymer and cosmetic material containing it |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001316435A true JP2001316435A (en) | 2001-11-13 |
Family
ID=18643397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000135295A Withdrawn JP2001316435A (en) | 2000-05-09 | 2000-05-09 | Copolymer and cosmetic material containing it |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001316435A (en) |
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