JP2020164474A - Agent for inhibiting discoloration of dyed hair and hair washing agent containing the same - Google Patents
Agent for inhibiting discoloration of dyed hair and hair washing agent containing the same Download PDFInfo
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- JP2020164474A JP2020164474A JP2019067673A JP2019067673A JP2020164474A JP 2020164474 A JP2020164474 A JP 2020164474A JP 2019067673 A JP2019067673 A JP 2019067673A JP 2019067673 A JP2019067673 A JP 2019067673A JP 2020164474 A JP2020164474 A JP 2020164474A
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- group
- meth
- hair
- carbon atoms
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- Granted
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- 230000002401 inhibitory effect Effects 0.000 title abstract description 8
- 238000002845 discoloration Methods 0.000 title abstract description 6
- 238000005406 washing Methods 0.000 title description 6
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000004480 active ingredient Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims description 38
- 238000005562 fading Methods 0.000 claims description 37
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 9
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 5
- 239000003599 detergent Substances 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 239000002453 shampoo Substances 0.000 abstract description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 118
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 55
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 50
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 50
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 43
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 41
- 239000000243 solution Substances 0.000 description 33
- 230000000694 effects Effects 0.000 description 31
- -1 T-butyl group Chemical group 0.000 description 29
- 239000004205 dimethyl polysiloxane Substances 0.000 description 28
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 28
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 28
- 238000000862 absorption spectrum Methods 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 26
- 239000000047 product Substances 0.000 description 25
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 25
- 238000011156 evaluation Methods 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000000126 substance Substances 0.000 description 20
- 239000008213 purified water Substances 0.000 description 18
- 238000001914 filtration Methods 0.000 description 16
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- 239000002244 precipitate Substances 0.000 description 16
- 239000003921 oil Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000007877 V-601 Substances 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000011282 treatment Methods 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 230000002633 protecting effect Effects 0.000 description 6
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 239000002537 cosmetic Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 3
- 239000002552 dosage form Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 229940008099 dimethicone Drugs 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 2
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 2
- 229940093471 ethyl oleate Drugs 0.000 description 2
- 230000037308 hair color Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 125000002960 margaryl group Chemical group [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])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 2
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 2
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 229960002216 methylparaben Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001421 myristyl group Chemical group [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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [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])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 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004079 stearyl group Chemical group [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])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 2
- 230000002459 sustained effect Effects 0.000 description 2
- 125000002889 tridecyl group Chemical group [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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- JDCBWJCUHSVVMN-SCSAIBSYSA-N (2r)-but-3-en-2-amine Chemical compound C[C@@H](N)C=C JDCBWJCUHSVVMN-SCSAIBSYSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- NDWVRLFFXDNHQF-UHFFFAOYSA-N 1-ethyl-2-prop-2-enoyloxycyclohexane-1,2-dicarboxylic acid Chemical compound CCC1(C(O)=O)CCCCC1(OC(=O)C=C)C(O)=O NDWVRLFFXDNHQF-UHFFFAOYSA-N 0.000 description 1
- WAYINTBTZWQNSN-UHFFFAOYSA-N 11-methyldodecyl 3,5,5-trimethylhexanoate Chemical compound CC(C)CCCCCCCCCCOC(=O)CC(C)CC(C)(C)C WAYINTBTZWQNSN-UHFFFAOYSA-N 0.000 description 1
- YDRQKFSCVSLQKI-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1(CCOC(=O)C=C)C(O)=O YDRQKFSCVSLQKI-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 1
- UIVPNOBLHXUKDX-UHFFFAOYSA-N 3,5,5-trimethylhexyl 3,5,5-trimethylhexanoate Chemical compound CC(C)(C)CC(C)CCOC(=O)CC(C)CC(C)(C)C UIVPNOBLHXUKDX-UHFFFAOYSA-N 0.000 description 1
- UXTGJIIBLZIQPK-UHFFFAOYSA-N 3-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCOC(=O)C=C)=C1C(O)=O UXTGJIIBLZIQPK-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 1
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000195940 Bryophyta Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、特定の(メタ)アクリルシリコーン系グラフト共重合体を有効成分とする染色された毛髪の褪色抑制剤に関するものであり、更に詳しくは、褪色抑制効果が持続し、毛髪のハリコシをも改善する褪色抑制剤に関するものである。 The present invention relates to an agent for suppressing fading of dyed hair containing a specific (meth) acrylic silicone-based graft copolymer as an active ingredient, and more specifically, the effect of suppressing fading is sustained and the hair is also firm. It relates to an improving fading inhibitor.
近年、毛髪を様々な色に変化させるカラーリングが男女問わず幅広い年代で行われているが、日光により染色毛髪の色素が消失したり、洗髪により染色毛髪から色素が溶出したりするなどの褪色に関する問題がある。 In recent years, coloring that changes hair to various colors has been performed in a wide range of ages regardless of gender, but fading such as the pigment disappearing from dyed hair due to sunlight and the pigment elution from dyed hair due to washing the hair. I have a problem with.
従来より、カラーリング後の染色毛髪の色を維持するための技術として、特定のシリコーンと固形油分を組合せて染色毛髪の退色を抑制する技術(例えば、特許文献1参照)や、両性界面活性剤とキレート剤を用いて洗髪による退色を抑制する技術(例えば、特許文献2参照)が開示されている。 Conventionally, as a technique for maintaining the color of dyed hair after coloring, a technique for suppressing fading of dyed hair by combining a specific silicone and a solid oil (see, for example, Patent Document 1) and an amphoteric surfactant And a technique for suppressing discoloration due to hair washing using a chelating agent (see, for example, Patent Document 2) are disclosed.
しかしながら、特許文献1のような技術では、シャンプーなどの配合可能な油剤量が少ない剤型への配合は難しく、適用可能な剤型が限られている。また、特許文献2のような技術は、洗髪処理において染色毛髪の褪色を十分に抑制することができない点や退色抑制効果が持続しないという点において不十分であった。したがって、毛髪洗浄料への配合性に優れ、洗い流し後も褪色抑制効果が持続する染色毛髪に対する褪色抑制剤の開発が望まれていた。 However, with a technique such as Patent Document 1, it is difficult to formulate a dosage form such as shampoo in which the amount of oil that can be blended is small, and the applicable dosage form is limited. Further, the technique as in Patent Document 2 is insufficient in that the fading of dyed hair cannot be sufficiently suppressed in the hair washing treatment and the fading suppressing effect is not maintained. Therefore, it has been desired to develop a fading inhibitor for dyed hair, which is excellent in blendability with a hair cleaning agent and the fading suppressing effect is maintained even after rinsing.
かかる実情に鑑み、本発明者らは褪色抑制剤について鋭意検討した結果、(メタ)アクリルシリコーン系グラフト共重合体が、顕著に褪色抑制効果を示し、褪色抑制効果が持続すること、加えて毛髪保護効果、ハリコシ改善効果に優れていることを見出し、本発明を完成するに至った。 In view of this situation, the present inventors have diligently studied a fading inhibitor, and as a result, the (meth) acrylic silicone-based graft copolymer shows a remarkable fading inhibitory effect, the fading inhibitory effect is sustained, and in addition, the hair They have found that they are excellent in protective effect and elasticity improving effect, and have completed the present invention.
すなわち、本発明は、次の成分(A)を有効成分とする、染色された毛髪の褪色抑制剤を提供するものである。
(A)下記(a)、(b)、(c)及び(d)のラジカル重合性モノマーを反応させて得られ、(a)、(b)、(c)及び(d)のラジカル重合性モノマー全体に対して、(a)=20〜50質量%、(b)=0.5〜4質量%、(c)及び(d)=46〜79.5質量%である、(メタ)アクリルシリコーン系グラフト共重合体
(a)下記一般式(I)
(b)下記一般式(II)
(c)下記一般式(IV)
(d)下記一般式(V)
(A) Obtained by reacting the following radically polymerizable monomers (a), (b), (c) and (d), and the radically polymerizable of (a), (b), (c) and (d). (A) = 20-50% by mass, (b) = 0.5-4% by mass, (c) and (d) = 46-79.5% by mass, based on the total monomer, (meth) acrylic. Silicone-based graft copolymer (a) The following general formula (I)
また、前記成分(A)を有効成分とする、毛髪保護剤を提供するものである。 Further, the present invention provides a hair protective agent containing the component (A) as an active ingredient.
また、前記成分(A)を有効成分とする、毛髪のハリコシ改善剤を提供するものである。 Further, the present invention provides a hair elasticity improving agent containing the above component (A) as an active ingredient.
また、25℃におけるpHが7以下である、前記成分(A)を有効成分とする、染色された毛髪の褪色抑制剤を提供するものである。 Further, the present invention provides an agent for suppressing fading of dyed hair, which has a pH of 7 or less at 25 ° C. and contains the component (A) as an active ingredient.
また、成分(B)分子量400以下の極性油を含有する、前記成分を有効成分とする、染色された毛髪の褪色抑制剤を提供するものである。 Further, the present invention provides an agent for suppressing fading of dyed hair, which contains a polar oil having a molecular weight of component (B) of 400 or less and contains the component as an active ingredient.
また、上記記載の剤を含む毛髪洗浄料を提供するものである。 In addition, a hair cleansing agent containing the above-mentioned agent is provided.
また、前記成分(A)を染色された毛髪の褪色抑制剤として用いる、染色された毛髪の褪色抑制方法を提供するものである。 Further, the present invention provides a method for suppressing fading of dyed hair, which uses the component (A) as a fading inhibitor for dyed hair.
本発明の染色された毛髪の褪色抑制剤及びこれを含有する毛髪洗浄料は、染色された毛髪に対する優れた褪色抑制を有し、洗い流し後の褪色抑制効果の持続性、ハリコシ改善効果、毛髪保護効果も併せて提供することができる。 The dyed hair fading inhibitor of the present invention and a hair cleaning agent containing the same have excellent fading inhibitory effect on dyed hair, and have a long-lasting fading inhibitory effect after rinsing, an effect of improving elasticity, and a hair protection. The effect can also be provided.
以下、本発明について詳細に説明する。なお、本明細書において、「〜」はその前後の数値を含む範囲を意味するものとする。
本発明に用いられる成分(A)の(メタ)アクリルシリコーン系グラフト共重合体は、少なくとも、下記(a)、(b)、(c)及び(d)のラジカル重合性モノマーを反応させて得られる重合体であり、その他、(a)〜(d)以外の共重合可能なモノマーを加えて反応させて得られる重合体を包含する。
本発明において(メタ)アクリルとは、アクリル及びメタアクリルを包含することを意味する。
各モノマーの仕込割合は、(a)〜(d)のモノマーの全体に対して、(a)=20〜50質量%、(b)=0.5〜4質量%、(c)及び(d)=46〜79.5質量%であり、(a)〜(d)以外の共重合可能なモノマーを使用する場合は、(a)〜(d)のモノマーの合計は、全体の66.5質量%以上であることが好ましい。
なお、本発明において、モノマーの仕込割合とは共重合体中のそれらの組成割合と略同義である。
本発明の(メタ)アクリルシリコーン系グラフト共重合体は、共重合体を20質量%となるように99.5%エタノールに溶解させたときのエタノール溶液の、25℃においてB型回転粘度計を用いて測定した粘度(単位mPa・s=CS)は、50〜250、好ましくは、70〜150である。
さらに、本発明の(メタ)アクリルシリコーン系グラフト共重合体は、ランダム共重合体、ブロック共重合体等の種々の形態を包含する。
Hereinafter, the present invention will be described in detail. In addition, in this specification, "~" means the range including the numerical values before and after it.
The (meth) acrylic silicone-based graft copolymer of the component (A) used in the present invention is obtained by reacting at least the following radically polymerizable monomers (a), (b), (c) and (d). In addition, the polymer obtained by adding and reacting a copolymerizable monomer other than (a) to (d) is included.
In the present invention, (meth) acrylic means to include acrylic and methacrylic.
The charging ratio of each monomer is (a) = 20 to 50% by mass, (b) = 0.5 to 4% by mass, (c) and (d) with respect to the total of the monomers of (a) to (d). ) = 46 to 79.5% by mass, and when copolymerizable monomers other than (a) to (d) are used, the total of the monomers of (a) to (d) is 66.5 as a whole. It is preferably mass% or more.
In the present invention, the charging ratio of the monomers is substantially synonymous with the composition ratio thereof in the copolymer.
The (meth) acrylic silicone-based graft copolymer of the present invention is a B-type rotational viscometer at 25 ° C. of an ethanol solution obtained by dissolving the copolymer in 99.5% ethanol so as to have a content of 20% by mass. The viscosity measured in use (unit: mPa · s = CS) is 50 to 250, preferably 70 to 150.
Furthermore, the (meth) acrylic silicone-based graft copolymer of the present invention includes various forms such as a random copolymer and a block copolymer.
以下に、共重合体の原料であるモノマーについて説明する。
(a)一般式(I)で表されるラジカル重合性モノマー
The monomer that is the raw material of the copolymer will be described below.
(A) Radical polymerizable monomer represented by the general formula (I)
式中、Meはメチル基、R1は水素原子又はメチル基を表す。
R2は直鎖状又は分岐鎖状の炭素数1〜10の2価の飽和炭化水素基を表し、1又は2個のエーテル結合を含んでいてもよい。具体的には、−CH2−,−(CH2)2,−(CH2)5−,−(CH2)10−、−CH2−CH(CH3)−CH2−,−CH2CH2OCH2CH2CH2−,−CH2CH2OCH2(CH3)CH2−,−CH2CH2OCH2CH2CH2OCH2CH2CH2−などが例示される。
R3は炭素数1〜10の飽和炭化水素基を表し、具体的には、メチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、s−ブチル基、i−ブチル基、t−ブチル基、n−ペンチル基、n−ヘキシル基、n−ノニル基、イソノニル基、n−デシル基等の炭素数1〜10のアルキル基;シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基、シクロヘプチル基、シクロオクチル基、シクロドデシル基等の炭素数1〜10のシクロアルキル基;シクロプロピルメチル基、2−シクロプロピルエチル基、シクロブチルメチル基、シクロペンチルメチル基、3−シクロペンチルプロピル基、シクロへキシルメチル基、2−シクロヘキシルエチル基、シクロヘプチルメチル基、シクロオクチルメチル基等の炭素数1〜10のシクロアルキルアルキル基が挙げられる。
mは5〜100の整数を表す。
In the formula, Me represents a methyl group and R1 represents a hydrogen atom or a methyl group.
R2 represents a linear or branched chain of divalent saturated hydrocarbon groups having 1 to 10 carbon atoms, and may contain 1 or 2 ether bonds. Specifically, −CH 2 −, − (CH 2 ) 2 , − (CH 2 ) 5 −, − (CH 2 ) 10 −, −CH 2 −CH (CH 3 ) −CH 2 −, −CH 2 CH 2 OCH 2 CH 2 CH 2 −, −CH 2 CH 2 OCH 2 (CH 3 ) CH 2 −, −CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 −, etc. are exemplified.
R3 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, and an i-butyl group. , T-butyl group, n-pentyl group, n-hexyl group, n-nonyl group, isononyl group, n-decyl group and other alkyl groups having 1 to 10 carbon atoms; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclo Cycloalkyl groups having 1 to 10 carbon atoms such as hexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group; cyclopropylmethyl group, 2-cyclopropylethyl group, cyclobutylmethyl group, cyclopentylmethyl group, 3- Examples thereof include cycloalkylalkyl groups having 1 to 10 carbon atoms such as cyclopentylpropyl group, cyclohexylmethyl group, 2-cyclohexylethyl group, cycloheptylmethyl group and cyclooctylmethyl group.
m represents an integer of 5 to 100.
この式(I)で表わされるモノマーは、たとえば、式(1−a) The monomer represented by the formula (I) is, for example, the formula (1-a).
で表わされる(メタ)アクリレート置換クロロシラン化合物と式(1−b) (Meta) acrylate-substituted chlorosilane compound represented by and formula (1-b)
で表わされる片末端水酸基置換ポリシロキサンとを常法に従い、脱塩酸反応させることにより得ることができるが、合成方法は、これに限定されるものではない。 It can be obtained by subjecting a single-terminal hydroxyl group-substituted polysiloxane represented by (1) to a dehydrochloric acid reaction according to a conventional method, but the synthesis method is not limited to this.
式(I)で表されるモノマーとしては、具体例には以下のものが挙げられる。なお以下の式中、Meはメチル基を、n−Buはn−ブチル基を示す。 Specific examples of the monomer represented by the formula (I) include the following. In the following formula, Me represents a methyl group and n-Bu represents an n-butyl group.
(b)式(II)又は式(III)で表されるラジカル重合性モノマー
(b)成分は、下記式(II)又は式(III)で表されるカチオン性化合物から選ばれる少なくとも1種である。
The radically polymerizable monomer (b) component represented by the formula (II) or the formula (III) is at least one selected from the cationic compounds represented by the following formula (II) or the formula (III). is there.
式(II)中、R4は水素原子又はメチル基を表す。
R5、R6、R7は同一又は異なっていてもよく、水素原子又は炭素数1〜4のアルキル基を表し、炭素数1〜4のアルキル基としては、メチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、s−ブチル基、i−ブチル基、t−ブチル基が例示される。
Xは−O−、−NH−、−O−CH2−又は−O−CH2CH(OH)−を表す。
Yは直鎖状又は分岐鎖状の炭素数1〜4の2価の飽和炭化水素基を表し、−CH2−,−(CH2)2,−(CH2)3−,−(CH2)4−,−CH2−CH(CH3)−CH2−等が例示される。
Z−は対アニオンであり、例えば、塩素イオン、臭素イオン、硫酸水素イオン、硝酸イオン、過塩素酸イオン、四フッ化ホウ素イオン、六フッ化リンイオン等が例示される。
In formula (II), R4 represents a hydrogen atom or a methyl group.
R5, R6, and R7 may be the same or different, and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, and an n-propyl group. Examples thereof include i-propyl group, n-butyl group, s-butyl group, i-butyl group and t-butyl group.
X is -O -, - NH -, - O-CH 2 - or -O-CH 2 CH (OH) - represents a.
Y represents a linear or branched chain of divalent saturated hydrocarbon groups having 1 to 4 carbon atoms, −CH 2 −, − (CH 2 ) 2 , − (CH 2 ) 3 −, − (CH 2). ) 4 -, - CH 2 -CH (CH 3) -CH 2 - and the like.
Z- is a counter anion, and examples thereof include chlorine ion, bromine ion, hydrogen sulfate ion, nitrate ion, perchlorate ion, boron tetrafluoride ion, and phosphorus hexafluoride ion.
式(III)中、R8、R9は同一又は異なっていてもよく、水素原子又は炭素数1〜4のアルキル基を表し、炭素数1〜4のアルキル基としてはメチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、s−ブチル基、i−ブチル基、t−ブチル基が例示される。
R10、R11は同一又は異なっていてもよく、水素原子又は炭素数1〜18のアルキル基を表し、炭素数1〜18のアルキル基としては、 メチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、s−ブチル基、i−ブチル基、t−ブチル基、n−ペンチル基、n−ヘキシル基、n−ノニル基、イソノニル基、n−デシル基、ラウリル基、トリデシル基、ミリスチル基、n−ペンタデシル基、パルミチル基、ヘプタデシル基、ステアリル基等が例示される。
In formula (III), R8 and R9 may be the same or different, and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, and n−. Examples thereof include propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group and t-butyl group.
R10 and R11 may be the same or different, and represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, an n-propyl group and i-. Propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-nonyl group, isononyl group, n-decyl group, lauryl group, tridecyl Examples thereof include a group, a myristyl group, an n-pentadecyl group, a palmityl group, a heptadecyl group, and a stearyl group.
(c)式(IV)で表されるラジカル重合性モノマー (C) Radical polymerizable monomer represented by formula (IV)
式中、R12は水素原子又はメチル基を表す。
R13は水素原子又は直鎖状又は分岐鎖状の炭素数1〜3のアルキル基を表し、直鎖状又は分岐鎖状の炭素数1〜3のアルキル基としては、メチル基、エチル基、n−プロピル基、i−プロピル基が例示される。
In the formula, R12 represents a hydrogen atom or a methyl group.
R13 represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and the linear or branched alkyl group having 1 to 3 carbon atoms includes a methyl group, an ethyl group and n. -Propyl group and i-propyl group are exemplified.
(d)式(V)で表されるラジカル重合性モノマー (D) Radical polymerizable monomer represented by the formula (V)
式中、R14は水素原子又はメチル基を表す。
R15は炭素数1〜4のヒドロキシアルキル基を表し、ヒドロキシメチル基、2−ヒドロキシエチル基、3−ヒドロキシ−n−プロピル基、4−ヒドロキシ−n−ブチル基等が例示される。
In the formula, R14 represents a hydrogen atom or a methyl group.
R15 represents a hydroxyalkyl group having 1 to 4 carbon atoms, and examples thereof include a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group.
その他の共重合可能なモノマーとしては、以下の物が例示される。
((メタ)アクリル系モノマー)
(メタ)アクリル酸n−ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t−ブチル、(メタ)アクリル酸2−エチルへキシル、(メタ)アクリル酸n−へキシル、(メタ)アクリル酸n−オクチル、(メタ)アクリル酸シクロへキシル、(メタ)アクリル酸デシル、(メタ)アクリル酸ウンデシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸トリデシル、(メタ)アクリル酸ミリスチル、(メタ)アクリル酸ペンタデシル、(メタ)アクリル酸パルミチル、(メタ)アクリル酸へプタデシル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸イソステアリル、(メタ)アクリル酸オレイル、(メタ)アクリル酸ベヘニル、直鎖状、分岐鎖状又は脂環式の炭化水素基を有する(メタ)アクリル酸エステル;アクリロニトリル;アクリルアミド、ジアセトンアクリルアミド、N,N−ジメチルアクリルアミド、N−t−ブチルアクリルアミド、N−オクチルアクリルアミド、N−t−オクチルアクリルアミド等の(メタ)アクリルアミド;2−(メタ)アクリルアミド−2−メチルプロパンスルホン酸等のスルホン酸基含有(メタ)アクリルアミド;アミノエチル(メタ)アクリレート、t−ブチルアミノエチルメタクリレート、メチルアミノエチル(メタ)アクリレート等のアルキルアミノアルキル(メタ)アクリレート;ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート等のジアルキルアミノアルキル(メタ)アクリレート;ジメチルアミノエチル(メタ)アクリルアミド、ジエチルアミノエチル(メタ)アクリルアミド等のジアルキルアミノアルキル(メタ)メタアクリルアミド;(メタ)アクリル酸テトラヒドロフルフリル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸グリシジル等の、環式化合物とメタ)アクリル酸のエステル類;(メタ)アクリル酸エトキシエチル、(メタ)アクリル酸メトキシエチル等の(メタ)アクリル酸アルコキシアルキルエステル;ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート等のポリアルキレングリコールと(メタ)アクリル酸とのモノエステル類;スルホン酸基含有(メタ)アクリルエステル;(メタ)アクリロイルオキシエチルホスフェート等のメタアクリロイルオキシアルキルリン酸モノエステル;(メタ)アクリル酸グリセリル、2−メタアクリロイルオキシエチルコハク酸、2−(メタ)アクリロイルオキシエチルフタル酸、β−カルボキシエチルアクリレート、アクリロイルオキシエチルサクシネート、2−(メタ)アクリロイルオキシエチルテトラヒドロフタル酸、2−(メタ)アクリロイルオキシエチルヘキサヒドロフタル酸;1,4−ブタンジオールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ポリエチレン(n=2〜50)グリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ポリプロピレン(n=2〜50)グリコールジ(メタ)アクリレート、ブチレングリコールジ(メタ)アクリレート、ジペンチルグリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、メチレンビスアクリルアミド、ビスフェノールF EO変性(n=2〜50)ジ(メタ)アクリレート、ビスフェノールA EO変性(n=2〜50)ジアクリレート、ビスフェノールS EO変性(n=2〜50)ジ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールプロパントリカプロラクトネートトリ(メタ)アクリレート、トリメチロールヘキサントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジグリセリンテトラ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、ジトリメチロールプロパンテトラカプロラクトネート、テトラ(メタ)アクリレート、ジトリメチロールエタンテトラ(メタ)アクリレート、ジトリメチロールブタンテトラ(メタ)アクリレート、ジトリメチロールヘキサンテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリペンタエリスリトールヘキサ(メタ)アクリレート、トリペンタエリスリトールヘプタ(メタ)アクリレート、トリペンタエリスリトールオクタ(メタ)アクリレート等のエチレン性不飽和二重結合を2個以上有する(メタ)アクリレート等が例示される。
Examples of other copolymerizable monomers include the following.
((Meta) acrylic monomer)
N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylic N-octyl acid, cyclohexyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, ( Pentadecyl acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, oleyl (meth) acrylate, behenyl (meth) acrylate, (Meta) acrylic acid ester having a linear, branched or alicyclic hydrocarbon group; acrylonitrile; acrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, Nt-butylacrylamide, N-octylacrylamide (Meta) acrylamide such as Nt-octylacrylamide; sulfonic acid group-containing (meth) acrylamide such as 2- (meth) acrylamide-2-methylpropanesulfonic acid; aminoethyl (meth) acrylate, t-butylaminoethyl Alkylaminoalkyl (meth) acrylates such as methacrylate and methylaminoethyl (meth) acrylate; Dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; dimethylaminoethyl (meth) acrylamide , Dialkylaminoalkyl (meth) metaacrylamide such as diethylaminoethyl (meth) acrylamide; cyclic compounds such as tetrahydrofurfurfryl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate and (meth) acrylic Acid esters; (meth) acrylic acid alkoxyalkyl esters such as (meth) ethoxyethyl acrylate, (meth) methoxyethyl acrylate; polyalkylenes such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. Monoesters of glycol and (meth) acrylic acid; (meth) acrylic ester containing sulfonic acid group; metaacryloyloxyalkyl phosphate monoester such as (meth) acryloyloxyethyl phosphate; glyceryl (meth) acrylic acid, 2 -Metaacryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, β-carboxyethyl acrylate, acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid, 2- (meth) acryloyloxy Ethylhexahydrophthalic acid; 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene (n = 2-50) glycol di (meth) ) Acrylate, propylene glycol di (meth) acrylate, polypropylene (n = 2 to 50) glycol di (meth) acrylate, butylene glycol di (meth) acrylate, dipentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate , Trimethylolpropane di (meth) acrylate, methylenebisacrylamide, bisphenol F EO modified (n = 2 to 50) di (meth) acrylate, bisphenol A EO modified (n = 2 to 50) diacrylate, bisphenol S EO modified (n = 2 to 50) n = 2-50) Di (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tricaprolactonate tri (meth) acrylate, trimethylolhexanetri (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diglycerin tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane tetracaprolactonate, tetra (meth) acrylate, Ditrimethylolethanetetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dimethylolhexanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa ( Examples thereof include (meth) acrylates having two or more ethylenically unsaturated double bonds such as meth) acrylate, trimethylolpropane hepta (meth) acrylate, and trypentaerythritol octa (meth) acrylate.
((メタ)アクリル系以外のモノマー)
クロトン酸等の不飽和モノカルボン酸;スチレン等の芳香族ビニル化合物;イタコン酸、マレイン酸、フマル酸、無水マレイン酸、シトラコン酸等の不飽和ジカルボン酸;マレイン酸モノアルキルエステル、フマル酸モノアルキルエステル、イタコン酸モノアルキルエステル等の不飽和ジカルボン酸のモノアルキルエステル;スルホン酸基含有単量体としては、例えばビニルスルホン酸、(メタ)アリルスルホン酸等のアルケンスルホン酸;α−メチルスチレンスルホン酸等の芳香族ビニル基含有スルホン酸;(メタ)アリルアミン等の1〜3級アミノ基含有不飽和化合物;N,N−ジメチルアミノスチレン等のアミノ基含有芳香族ビニル系化合物;ジビニルベンゼン、ジイソプロペニルベンゼン、トリビニルベンゼン等のエチレン性不飽和二重結合を2個以上有する化合物;エチレン性不飽和二重結合を2個以上有するウレタンオリゴマー;エチレン性不飽和二重結合を2個以上有するシリコーン化合物;酢酸ビニル、ビニルピロリドン等が例示される。
(Monomers other than (meth) acrylic)
Unsaturated monocarboxylic acids such as crotonic acid; aromatic vinyl compounds such as styrene; unsaturated dicarboxylic acids such as itaconic acid, maleic acid, fumaric acid, maleic anhydride, citraconic acid; monoalkyl maleic acid ester, monoalkyl fumarate Monoalkyl esters of unsaturated dicarboxylic acids such as esters and monoalkyl esters of itaconic acid; sulfonic acid group-containing monomers include, for example, vinyl sulfonic acid, alkene sulfonic acid such as (meth) allyl sulfonic acid; α-methylstyrene sulfone. Aromatic vinyl group-containing sulfonic acid such as acid; 1-3-amino group-containing unsaturated compound such as (meth) allylamine; amino group-containing aromatic vinyl compound such as N, N-dimethylaminostyrene; divinylbenzene, di Compounds having two or more ethylenically unsaturated double bonds such as isopropenylbenzene and trivinylbenzene; urethane oligomers having two or more ethylenically unsaturated double bonds; having two or more ethylenically unsaturated double bonds Silicone compounds; vinyl acetate, vinylpyrrolidone and the like are exemplified.
本発明における成分(A)は、一種又は二種以上組み合わせて用いることができ、その含有量は、特に限定されないが、1質量%以下(以下、「質量%」を単に「%」と略す)が好ましく、0.01〜0.1%がより好ましく、0.01〜0.05%が特に好ましい。成分(A)をこの範囲で含有すると、染色された毛髪の褪色抑制効果、ハリコシ改善効果、毛髪保護効果が得られると同時に、製剤への安定配合が可能であるため、より好ましい。
より詳細に説明すると、成分(A)の共重合体はカチオン性を有することから、毛髪に吸着されやすい性質を持つ。このことにより成分(A)の共重合体が毛髪上に均一に密着することができる。さらに本共重合体自体が弾力性を有し、毛髪上に付着した際にその効果が発揮され、ハリコシ感のある毛髪に仕上がる。
前記成分(A)のINCI(International Nomenclature of Cosmetic Ingredients)名としては、例えばポリクオタニウム−104が挙げられる。
The component (A) in the present invention can be used alone or in combination of two or more, and the content thereof is not particularly limited, but is 1% by mass or less (hereinafter, "mass%" is simply abbreviated as "%"). Is preferable, 0.01 to 0.1% is more preferable, and 0.01 to 0.05% is particularly preferable. It is more preferable that the component (A) is contained in this range because it is possible to obtain an effect of suppressing fading of dyed hair, an effect of improving elasticity, and an effect of protecting hair, and at the same time, a stable blending into the preparation is possible.
More specifically, since the copolymer of the component (A) has a cationic property, it has a property of being easily adsorbed on hair. As a result, the copolymer of the component (A) can be uniformly adhered to the hair. Furthermore, the copolymer itself has elasticity, and when it adheres to the hair, the effect is exhibited, and the hair is finished with a feeling of elasticity.
Examples of the INCI (International Nomenclature of Cosmetic Ingredients) name of the component (A) include polyquaternium-104.
さらに、本発明には分子量400以下の極性油(成分(B))を含有することも可能である。本発明に用いられる分子量400以下の極性油は、分子量400以下で、有機概念図における有機性値(OV)に対する無機性値(IV)の比(IOB値)が0.1以上のものを指し、化粧料一般に用いられるものであれば特に限定されるものではない。例えば、ミリスチン酸イソプロピル(Mw:270.45)、イソステアリン酸(Mw:284.48)、イソノナン酸イソノニル(Mw:284.48)、パルミチン酸イソプロピル(Mw:298.5)、オレイン酸エチル(Mw:310.51)、イソノナン酸イソトリデシル(Mw:340.58)、エチルヘキサン酸セチル(Mw:368.64)、などが挙げられる。また、一種または二種以上を組み合わせて配合することも可能である。 Further, the present invention can also contain a polar oil (component (B)) having a molecular weight of 400 or less. The polar oil having a molecular weight of 400 or less used in the present invention refers to an oil having a molecular weight of 400 or less and a ratio (IOB value) of an inorganic value (IV) to an organic value (OV) in the organic conceptual diagram of 0.1 or more. , Cosmetics are not particularly limited as long as they are generally used. For example, isopropyl myristate (Mw: 270.45), isostearic acid (Mw: 284.48), isononyl isononanoate (Mw: 284.48), isopropyl palmitate (Mw: 298.5), ethyl oleate (Mw). : 310.51), isotridecyl isononanoate (Mw: 340.58), cetyl ethylhexanoate (Mw: 368.64), and the like. It is also possible to mix one kind or a combination of two or more kinds.
本発明に用いられる分子量400以下の極性油の含有量は特に限定されないが、成分(A)の共重合体に対して質量比0.5以上が好ましく、1以上がより好ましい。分子量400以下の極性油をこの範囲で含有すると、成分(A)の共重合体の配合性と褪色抑制効果がより優れたものとなる。 The content of the polar oil having a molecular weight of 400 or less used in the present invention is not particularly limited, but the mass ratio to the copolymer of the component (A) is preferably 0.5 or more, and more preferably 1 or more. When a polar oil having a molecular weight of 400 or less is contained in this range, the compoundability of the copolymer of the component (A) and the effect of suppressing fading become more excellent.
本発明品の25℃におけるpHは特に限定されないが、7以下が好ましく、3〜7がより好ましい。この範囲であると、褪色抑制効果がより優れたものとなる。 The pH of the product of the present invention at 25 ° C. is not particularly limited, but is preferably 7 or less, and more preferably 3 to 7. Within this range, the fading suppressing effect becomes more excellent.
pHは最終的な化粧料のpHが前記範囲になるよう、適宜pH調整剤を添加して調整する。pH調整剤としては、特に限定されず、例えば乳酸、クエン酸、グリコール酸、コハク酸、酒石酸、dl−リンゴ酸などの酸物質、炭酸カリウム、炭酸水素ナトリウム、炭酸水素アンモニウム、水酸化ナトリウム、水酸化カリウム、トリエタノールアミン、モノエタノールアミン等のアルカリ物質が挙げられ、1種または2種以上を用いることができる。また、調整方法も特に限定されず、化粧料を調製した後に、pHを確認しながら添加してもよい。 The pH is adjusted by appropriately adding a pH adjuster so that the pH of the final cosmetic is within the above range. The pH adjuster is not particularly limited, and is, for example, an acid substance such as lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-apple acid, potassium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate, sodium hydroxide, water. Examples thereof include alkaline substances such as potassium oxide, triethanolamine and monoethanolamine, and one or more of them can be used. Further, the adjustment method is not particularly limited, and after preparing the cosmetic, it may be added while checking the pH.
本発明品には、上記成分以外に、化粧料に通常使用される成分、カチオン性界面活性剤、ノニオン性界面活性剤、アニオン性界面活性剤、両性界面活性剤等の界面活性剤、紫外線吸収剤、水溶性高分子、多価アルコール、糖類等の水性成分、抗菌剤、防腐剤、清涼剤、粉体、ビタミン類、美容成分、香料等を本発明の効果を損なわない範囲で適宜含有することができる。 In addition to the above components, the product of the present invention includes components usually used in cosmetics, cationic surfactants, nonionic surfactants, anionic surfactants, surfactants such as amphoteric surfactants, and ultraviolet absorption. Aqueous ingredients such as agents, water-soluble polymers, polyhydric alcohols, sugars, antibacterial agents, preservatives, refreshing agents, powders, vitamins, beauty ingredients, fragrances, etc. are appropriately contained within a range that does not impair the effects of the present invention. be able to.
本発明品の製造方法は、特に限定されず、常法により調製される。例えば、成分(A)の共重合体、さらに必要に応じて分子量400以下の極性油や上記任意成分を加え、これを混合することにより調製する方法が挙げられる。 The method for producing the product of the present invention is not particularly limited, and is prepared by a conventional method. For example, a method of preparing by adding a copolymer of the component (A), a polar oil having a molecular weight of 400 or less or the above optional component as needed, and mixing them.
また、本発明品は、液状、乳液状、クリーム状、ジェル状、ムース状、ミスト状等の種々の形態で実施することが可能である。 本発明品の用途については特に制限はなく、剤型に応じて、洗髪時に使用する毛髪洗浄料、洗髪後に使用するインバストリートメント料、アウトバストリートメント料、ドライヤー使用前後、整髪時、日中のトリートメント料等、通常毛髪化粧料が使用される状況において用いることができる。特に、顕著な褪色抑制効果が得られることから、毛髪洗浄料に適用されることが好ましい。さらに、成分(A)の共重合体の良好な配合性を発揮できることから、透明毛髪洗浄料への適用が特に好ましい。 In addition, the product of the present invention can be implemented in various forms such as liquid, milky, creamy, gel, mousse, and mist. The use of the product of the present invention is not particularly limited, and depending on the dosage form, a hair cleaning agent used when washing hair, an in-bath treatment charge used after washing hair, an out-bath treatment charge, before and after using a dryer, during hair styling, and during the daytime treatment. It can be used in situations where hair cosmetics are usually used. In particular, it is preferably applied to a hair cleansing agent because it has a remarkable effect of suppressing fading. Further, it is particularly preferable to apply it to a transparent hair cleansing agent because it can exhibit a good blendability of the copolymer of the component (A).
以下に実施例を挙げて、本発明を更に詳細に説明する。尚、これらは本発明を何ら限定するものではない。
<(メタ)アクリルシリコーン系グラフト共重合体の製造>
Hereinafter, the present invention will be described in more detail with reference to examples. It should be noted that these do not limit the present invention in any way.
<Manufacturing of (meth) acrylic silicone-based graft copolymer>
[参考製造例1]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(IPA)(注1)100gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(V−601)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−24−8201)(注3)40g、エチルアクリレート(EA)(注4)31g、2−ヒドロキシエチルメタクリレート(HEMA)(注5)27g、3−トリメチルアンモニウムプロピルメタクリルアミドクロライド(MAPTAC)(注6)4g、イソプロパノール(注1)50gを3〜4時間かけて添加した。次いで、イソプロパノールに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を87g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した(この生成物は、赤外吸収スペクトルによりジメチルポリシロキサン、アミド結合、エステル結合、アルキル基、水酸基を有するポリマーであることが確認された)。
モノマーの仕込割合は以下のとおりである。
MAPTAC:EA:HEMA:X−24−8201=2:31:27:40
(注1)IPA 関東化学株式会社製
(注2)V−601 和光純薬工業株式会社製
(注3)X−24−8201 信越化学工業社製
(注4)EA 関東化学株式会社社製
(注5)HEMA 関東化学株式会社社製
(注6)MAPTAC エボニック・デグサ・ジャパン株式会社製,50%水溶液
[Reference manufacturing example 1]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask under a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 40 g, ethyl acrylate (EA) (Note 4) 31 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 27 g , 3-trimethylammonium propyl methacrylamide chloride (MAPTAC) (Note 6) 4 g, and isopropanol (Note 1) 50 g were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 87 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane and amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 2: 31: 27: 40
(Note 1) IPA manufactured by Kanto Chemical Co., Ltd. (Note 2) V-601 manufactured by Wako Pure Chemical Industries, Ltd. (Note 3) X-24-8201 manufactured by Shin-Etsu Chemical Co., Ltd.
(Note 4) EA Kanto Chemical Co., Ltd. (Note 5) HEMA Kanto Chemical Co., Ltd. (Note 6) MAPTAC Evonik Degussa Japan Co., Ltd., 50% aqueous solution
[参考製造例2]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(注1)50gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−22−174DX)(注7)40g、エチルアクリレート(注4)31g、2−ヒドロキシエチルメタクリレート(注5)27g、3−トリメチルアンモニウムプロピルメタクリルアミドクロライド(注6)4g、イソプロパノール(注1)170gを3〜4時間かけて添加した。次いで、イソプロパノールに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を90g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した。
モノマーの仕込割合は以下のとおりである。
MAPTAC:EA:HEMA:X−22−174DX=2:31:27:40
(注7)X−22−174DX 信越化学工業社製
[Reference manufacturing example 2]
In a three-necked flask, under a nitrogen atmosphere, 50 g of isopropanol (Note 1) was stirred, and at 70 to 80 ° C., 4 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2), one end. Methacrylate-substituted dimethylpolysiloxane (X-22-174DX) (Note 7) 40 g, ethyl acrylate (Note 4) 31 g, 2-hydroxyethyl methacrylate (Note 5) 27 g, 3-trimethylammonium propyl methacrylamide chloride (Note 6) 4 g , 170 g of isopropanol (Note 1) was added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 90 g of a transparent rubber-like substance.
Infrared absorption spectra confirmed that the obtained rubber-like material was the target (meth) acrylic silicone-based graft copolymer.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-22-174DX = 2: 31: 27: 40
(Note 7) X-22-174DX manufactured by Shin-Etsu Chemical Co., Ltd.
[参考製造例3]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(注1)100gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−22−174ASX)(注8)40g、エチルアクリレート(注4)31g、2−ヒドロキシエチルメタクリレート(注5)27g、3−トリメチルアンモニウムプロピルメタクリルアミドクロライド(注6)4g、イソプロパノール(注1)50gを3〜4時間かけて添加した。次いで、イソプロパノールに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を83g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した。
モノマーの仕込割合は以下のとおりである。
MAPTAC:EA:HEMA:X−22−174ASX=2:31:27:40
(注8)X−22−174ASX 信越化学工業社製
[Reference manufacturing example 3]
In a three-necked flask, under a nitrogen atmosphere, 100 g of isopropanol (Note 1) was stirred, and at 70 to 80 ° C., 4 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2), one end. Methacrylate-substituted dimethylpolysiloxane (X-22-174ASX) (Note 8) 40 g, ethyl acrylate (Note 4) 31 g, 2-hydroxyethyl methacrylate (Note 5) 27 g, 3-trimethylammonium propyl methacrylamide chloride (Note 6) 4 g , Isopropanol (Note 1) 50 g was added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 83 g of a transparent rubber-like substance.
Infrared absorption spectra confirmed that the obtained rubber-like material was the target (meth) acrylic silicone-based graft copolymer.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-22-174ASX = 2: 31: 27: 40
(Note 8) X-22-174ASX manufactured by Shin-Etsu Chemical Co., Ltd.
[参考製造例4]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(注1)100gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−24−8201)(注3)40.4g、エチルアクリレート(注4)27.3g、2−ヒドロキシエチルメタクリレート(注5)31.3g、3−トリメチルアンモニウムプロピルメタクリルアミドクロライド(注6)2g、イソプロパノール(注1)50gを3〜4時間かけて添加した。次いで、イソプロパノールに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を86g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した。
モノマーの仕込割合は以下のとおりである。
MAPTAC:EA:HEMA:X−24−8201=1:27.3:31.3:40.4
[Reference manufacturing example 4]
In a three-necked flask, under a nitrogen atmosphere, 100 g of isopropanol (Note 1) was stirred, and at 70 to 80 ° C., 4 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2), one end. Methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 40.4 g, ethyl acrylate (Note 4) 27.3 g, 2-hydroxyethyl methacrylate (Note 5) 31.3 g, 3-trimethylammonium propyl methacrylamide 2 g of chloride (Note 6) and 50 g of isopropanol (Note 1) were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 86 g of a transparent rubber-like substance.
Infrared absorption spectra confirmed that the obtained rubber-like material was the target (meth) acrylic silicone-based graft copolymer.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 1: 27.3: 31.3: 40.4
[参考製造例5]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(注1)50gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−24−8201)(注3)40g、エチルアクリレート(注4)26g、2−ヒドロキシエチルメタクリレート(注5)30g、3−トリメチルアンモニウムプロピルメタクリルアミドクロライド(注6)8g、イソプロパノール(注1)120gを3〜4時間かけて添加した。次いで、イソプロパノールに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を83g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した。
モノマーの仕込割合は以下のとおりである。
MAPTAC:EA:HEMA:X−24−8201=4:26:30:40
[Reference manufacturing example 5]
In a three-necked flask, under a nitrogen atmosphere, 50 g of isopropanol (Note 1) was stirred, and at 70 to 80 ° C., 4 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2), one end. Methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 40 g, ethyl acrylate (Note 4) 26 g, 2-hydroxyethyl methacrylate (Note 5) 30 g, 3-trimethylammonium propylmethacrylamide chloride (Note 6) 8 g , 120 g of isopropanol (Note 1) was added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 83 g of a transparent rubber-like substance.
Infrared absorption spectra confirmed that the obtained rubber-like material was the target (meth) acrylic silicone-based graft copolymer.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 4:26:30:40
[参考製造例6]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(注1)100gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−24−8201)(注3)20g、エチルアクリレート(注4)41.5g、2−ヒドロキシエチルメタクリレート(注5)36.5g、3−トリメチルアンモニウムプロピルメタクリルアミドクロライド(注6)4g、イソプロパノール(注1)50gを3〜4時間かけて添加した。次いで、イソプロパノールに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を86g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した。
モノマーの仕込割合は以下のとおりである。
MAPTAC:EA:HEMA:X−24−8201=2:41.5:36.5:20
[Reference manufacturing example 6]
In a three-necked flask, under a nitrogen atmosphere, 100 g of isopropanol (Note 1) was stirred, and at 70 to 80 ° C., 4 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2), one end. Methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 20 g, ethyl acrylate (Note 4) 41.5 g, 2-hydroxyethyl methacrylate (Note 5) 36.5 g, 3-trimethylammonium propyl methacrylamide chloride (Note 5) Note 6) 4 g and 50 g of isopropanol (Note 1) were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 86 g of a transparent rubber-like substance.
Infrared absorption spectra confirmed that the obtained rubber-like material was the target (meth) acrylic silicone-based graft copolymer.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 2: 41.5: 36.5: 20
[参考製造例7]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(注1)50gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−24−8201)(注3)50g、エチルアクリレート(注4)23g、2−ヒドロキシエチルメタクリレート(注5)25g、3−トリメチルアンモニウムプロピルメタクリルアミドクロライド(注6)4g、イソプロパノール(注1)100gを3〜4時間かけて添加した。次いで、IPAに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を96g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した。
モノマーの仕込割合は以下のとおりである。
MAPTAC:EA:HEMA:X−24−8201=2:23:25:50
[Reference manufacturing example 7]
In a three-necked flask, under a nitrogen atmosphere, 50 g of isopropanol (Note 1) was stirred, and at 70 to 80 ° C., 4 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2), one end. Methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 50 g, ethyl acrylate (Note 4) 23 g, 2-hydroxyethyl methacrylate (Note 5) 25 g, 3-trimethylammonium propyl methacrylamide chloride (Note 6) 4 g , 100 g of isopropanol (Note 1) was added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in IPA was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 96 g of a transparent rubber-like substance.
Infrared absorption spectra confirmed that the obtained rubber-like material was the target (meth) acrylic silicone-based graft copolymer.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 2: 23: 25: 50
[参考製造例8]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(IPA)(注1)100gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(V−601)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−24−8201)(注3)40g、エチルアクリレート(EA)(注4)31g、2−ヒドロキシエチルメタクリレート(HEMA)(注5)27g、ジメチルジアリルアンモニウムクロライド(DADMAC)(注9)3.34g、イソプロパノール(注1)50gを3〜4時間かけて添加した。次いで、イソプロパノールに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を87g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した(この生成物は、赤外吸収スペクトルによりジメチルポリシロキサン、アミド結合、エステル結合、アルキル基、水酸基を有するポリマーであることが確認された)。
モノマーの仕込割合は以下のとおりである。
DADMAC:EA:HEMA:X−24−8201=2:31:27:40
(注9)DADMAC 東京化成工業株式会社製,60%水溶液
[Reference manufacturing example 8]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask in a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 40 g, ethyl acrylate (EA) (Note 4) 31 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 27 g , DADMAC (Note 9) 3.34 g and Isopropanol (Note 1) 50 g were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 87 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane and amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The charging ratio of the monomer is as follows.
DADMAC: EA: HEMA: X-24-8201 = 2: 31: 27: 40
(Note 9) DADMAC Tokyo Chemical Industry Co., Ltd., 60% aqueous solution
[参考製造例9]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(IPA)(注1)100gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(V−601)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−24−8201)(注3)40g、エチルアクリレート(EA)(注4)30g、2−ヒドロキシエチルメタクリレート(HEMA)(注5)27g、3−トリメチルアンモニウムプロピルメタクリルアミドクロライド(MAPTAC)(注6)6g、イソプロパノール(注1)50gを3〜4時間かけて添加した。次いで、イソプロパノールに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を89g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した(この生成物は、赤外吸収スペクトルによりジメチルポリシロキサン、アミド結合、エステル結合、アルキル基、水酸基を有するポリマーであることが確認された)。
また、EA、HEMAから理論的に計算されるガラス転移温度(Tg)は、11℃である。
モノマーの仕込割合は以下のとおりである。
MAPTAC:EA:HEMA:X−24−8201=3:30:27:40
[Reference manufacturing example 9]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask under a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 40 g, ethyl acrylate (EA) (Note 4) 30 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 27 g , 3-trimethylammonium propyl methacrylamide chloride (MAPTAC) (Note 6) 6 g and isopropanol (Note 1) 50 g were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 89 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane and amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is 11 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 3:30:27:40
[参考製造例10]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(IPA)(注1)100gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(V−601)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−24−8201)(注3)30g、エチルアクリレート(EA)(注4)35g、2−ヒドロキシエチルメタクリレート(HEMA)(注5)32g、3−トリメチルアンモニウムプロピルメタクリルアミドクロライド(MAPTAC)(注6)6g、イソプロパノール(注1)50gを3〜4時間かけて添加した。次いで、イソプロパノールに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を88g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した(この生成物は、赤外吸収スペクトルによりジメチルポリシロキサン、アミド結合、エステル結合、アルキル基、水酸基を有するポリマーであることが確認された)。
また、EA、HEMAから理論的に計算されるガラス転移温度(Tg)は、11℃である。
モノマーの仕込割合は以下のとおりである。
MAPTAC:EA:HEMA:X−24−8201=3:35:32:30
[Reference Manufacturing Example 10]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask under a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 30 g, ethyl acrylate (EA) (Note 4) 35 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 32 g , 3-trimethylammonium propyl methacrylamide chloride (MAPTAC) (Note 6) 6 g and isopropanol (Note 1) 50 g were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 88 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane and amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is 11 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 3:35:32:30
[参考製造例11]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(IPA)(注1)100gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(V−601)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−24−8201)(注3)30g、エチルアクリレート(EA)(注4)36g、2−ヒドロキシエチルメタクリレート(HEMA)(注5)32g、3−トリメチルアンモニウムプロピルメタクリルアミドクロライド(MAPTAC)(注6)4g、イソプロパノール(注1)50gを3〜4時間かけて添加した。次いで、イソプロパノールに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を88g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した(この生成物は、赤外吸収スペクトルによりジメチルポリシロキサン、アミド結合、エステル結合、アルキル基、水酸基を有するポリマーであることが確認された)。
また、EA、HEMAから理論的に計算されるガラス転移温度(Tg)は、11℃である。
モノマーの仕込割合は以下のとおりである。
MAPTAC:EA:HEMA:X−24−8201=2:36:32:30
[Reference Manufacturing Example 11]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask under a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 30 g, ethyl acrylate (EA) (Note 4) 36 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 32 g , 3-trimethylammonium propyl methacrylamide chloride (MAPTAC) (Note 6) 4 g, and isopropanol (Note 1) 50 g were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 88 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane and amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is 11 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 2:36:32:30
[参考製造例12]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(IPA)(注1)100gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(V−601)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−24−8201)(注3)30g、エチルアクリレート(EA)(注4)37g、2−ヒドロキシエチルメタクリレート(HEMA)(注5)32g、3−トリメチルアンモニウムプロピルメタクリルアミドクロライド(MAPTAC)(注6)2g、イソプロパノール(注1)50gを3〜4時間かけて添加した。次いで、イソプロパノールに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を90g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した(この生成物は、赤外吸収スペクトルによりジメチルポリシロキサン、アミド結合、エステル結合、アルキル基、水酸基を有するポリマーであることが確認された)。
また、EA、HEMAから理論的に計算されるガラス転移温度(Tg)は、10℃である。
モノマーの仕込割合は以下のとおりである。
MAPTAC:EA:HEMA:X−24−8201=1:37:32:30
[Reference Manufacturing Example 12]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask under a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 30 g, ethyl acrylate (EA) (Note 4) 37 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 32 g , 3-trimethylammonium propyl methacrylamide chloride (MAPTAC) (Note 6) 2 g and isopropanol (Note 1) 50 g were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 90 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane and amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is 10 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 1:37:32:30
[参考製造例13]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(IPA)(注1)100gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(V−601)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−22−174DX)(注7)30g、エチルアクリレート(EA)(注4)36g、2−ヒドロキシエチルメタクリレート(HEMA)(注5)32g、3−トリメチルアンモニウムプロピルメタクリルアミドクロライド(MAPTAC)(注6)4g、イソプロパノール(注1)50gを3〜4時間かけて添加した。次いで、イソプロパノールに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を86g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した(この生成物は、赤外吸収スペクトルによりジメチルポリシロキサン、アミド結合、エステル結合、アルキル基、水酸基を有するポリマーであることが確認された)。
また、EA、HEMAから理論的に計算されるガラス転移温度(Tg)は、11℃である。
モノマーの仕込割合は以下のとおりである。
MAPTAC:EA:HEMA:X−22−174DX=2:36:32:30
[Reference Manufacturing Example 13]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask under a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-22-174DX) (Note 7) 30 g, ethyl acrylate (EA) (Note 4) 36 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 32 g , 3-trimethylammonium propyl methacrylamide chloride (MAPTAC) (Note 6) 4 g, and isopropanol (Note 1) 50 g were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 86 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane and amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is 11 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-22-174DX = 2: 36: 32: 30
[参考製造例14]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(IPA)(注1)100gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(V−601)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−24−8201)(注3)40g、エチルアクリレート(EA)(注4)16g、2−ヒドロキシエチルメタクリレート(HEMA)(注5)42g、3−トリメチルアンモニウムプロピルメタクリルアミドクロライド(MAPTAC)(注6)2g、イソプロパノール(注1)50gを3〜4時間かけて添加した。次いで、イソプロパノールに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を91g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した(この生成物は、赤外吸収スペクトルによりジメチルポリシロキサン、アミド結合、エステル結合、アルキル基、水酸基を有するポリマーであることが確認された)。
また、EA、HEMAから理論的に計算されるガラス転移温度(Tg)は、30℃である。
モノマーの仕込割合は以下のとおりである。
MAPTAC:EA:HEMA:X−24−8201=1:16.2:42.4:40.4
[Reference Manufacturing Example 14]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask under a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 40 g, ethyl acrylate (EA) (Note 4) 16 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 42 g , 3-trimethylammonium propyl methacrylamide chloride (MAPTAC) (Note 6) 2 g and isopropanol (Note 1) 50 g were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 91 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane and amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is 30 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 1: 16.2: 42.4: 40.4
[参考製造例15]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(IPA)(注1)100gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(V−601)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−24−8201)(注3)40g、エチルアクリレート(EA)(注4)27g、2−ヒドロキシエチルメタクリレート(HEMA)(注5)31g、3−トリメチルアンモニウムプロピルメタクリルアミドクロライド(MAPTAC)(注6)2g、イソプロパノール(注1)50gを3〜4時間かけて添加した。次いで、イソプロパノールに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を88g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した(この生成物は、赤外吸収スペクトルによりジメチルポリシロキサン、アミド結合、エステル結合、アルキル基、水酸基を有するポリマーであることが確認された)。
また、EA、HEMAから理論的に計算されるガラス転移温度(Tg)は、15℃である。
モノマーの仕込割合は以下のとおりである。
MAPTAC:EA:HEMA:X−24−8201=1:27.3:31.3:40.4
[Reference Manufacturing Example 15]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask under a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 40 g, ethyl acrylate (EA) (Note 4) 27 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 31 g , 3-trimethylammonium propyl methacrylamide chloride (MAPTAC) (Note 6) 2 g and isopropanol (Note 1) 50 g were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 88 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane and amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is 15 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 1: 27.3: 31.3: 40.4
[参考製造例16]
3つ口フラスコ内、窒素雰囲気下で、イソプロパノール(IPA)(注1)100gを攪拌下、70〜80℃にて、ジメチル2,2−アゾビス(2−メチルプロピオネート)(V−601)(注2)4g、片末端メタクリレート置換ジメチルポリシロキサン(X−24−8201)(注3)20.2g、エチルアクリレート(EA)(注4)65.7g、2−ヒドロキシエチルメタクリレート(HEMA)(注5)13.1g、3−トリメチルアンモニウムプロピルメタクリルアミドクロライド(MAPTAC)(注6)2g、イソプロパノール(注1)50gを3〜4時間かけて添加した。次いで、イソプロパノールに溶解したジメチル2,2−アゾビス(2−メチルプロピオネート)(注2)1gを添加し、70〜80℃の温度範囲内で5時間反応させ、粘稠な溶液を得た。この溶液を精製水に注ぎ込み、グラフトポリマーを沈殿析出させた後、沈殿物を濾別し、80℃にて減圧乾燥させて透明ゴム状物を87g得た。
赤外吸収スペクトルにて、得られたゴム状物が目的とする(メタ)アクリルシリコーン系グラフト共重合体であることを確認した(この生成物は、赤外吸収スペクトルによりジメチルポリシロキサン、アミド結合、エステル結合、アルキル基、水酸基を有するポリマーであることが確認された)。
また、EA、HEMAから理論的に計算されるガラス転移温度(Tg)は、−10℃である。
モノマーの仕込割合は以下のとおりである。
MAPTAC:EA:HEMA:X−24−8201=1:65.7:13.1:20.2
[Reference Manufacturing Example 16]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask under a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 20.2 g, ethyl acrylate (EA) (Note 4) 65.7 g, 2-hydroxyethyl methacrylate (HEMA) ( Note 5) 13.1 g, 2 g of 3-trimethylammonium propylmethacrylamide chloride (MAPTAC) (Note 6), and 50 g of isopropanol (Note 1) were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 87 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane and amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is −10 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 1: 65.7: 13.1: 20.2
実施例1〜5及び比較例1〜3:シャンプー
下記表1に示すシャンプーを下記製造方法により調製し、(イ)褪色抑制効果、(ロ)ハリコシ改善効果、(ハ)毛髪保護効果、(ニ)成分(A)の配合性、の各項目について、以下に示す評価方法及び判定基準により評価判定し、結果を合わせて表1に示した。
Examples 1 to 5 and Comparative Examples 1 to 3: Shampoos The shampoos shown in Table 1 below are prepared by the following production methods, and (a) fading suppressing effect, (b) elasticity improving effect, (c) hair protection effect, (d) ) Each item of the compoundability of the component (A) was evaluated and judged by the evaluation method and the judgment criteria shown below, and the results are also shown in Table 1.
(製造方法)
A:成分1〜3、15、16を均一に混合し、75℃に加熱する。
B:Aに5を添加し、均一に混合する。
C:Bに6〜12を添加し、均一に混合する。
D:Cを45℃まで冷却し、4、13、14を添加し、均一に混合し、シャンプーを得た。
(Production method)
A: Ingredients 1-3, 15 and 16 are uniformly mixed and heated to 75 ° C.
B: Add 5 to A and mix uniformly.
C: Add 6 to 12 to B and mix uniformly.
D: C was cooled to 45 ° C., 4, 13 and 14 were added and mixed uniformly to obtain a shampoo.
〔評価項目(イ)の評価方法〕
スタッフス社製毛束(人毛黒、10cm、1g)を市販のブリーチ剤にて処理した後、染毛剤(スティーブンノル カラークチュール ヘアカラー ライトブラウン)にて処理し、染色毛束を作製した。作製した染色毛束をシャンプー1gで洗髪し、イオン交換水ですすいだ。(以下、シャンプー処理と記載)シャンプー処理1回の後、100mLのイオン交換水(40℃)に24時間浸漬し、波長600nmにおける溶出液の透過率を紫外可視分光光度計UV−2600(島津製作所社製)にて測定した。この際、ポリスチレン製ディスポセル(ニッコー・ハンセン社製)を使用した。また、これにより褪色抑制効果の認められたサンプルに関して、シャンプー処理20回後における測定も同様の方法で実施した。
[Evaluation method of evaluation item (a)]
Stuffs hair bundles (human hair black, 10 cm, 1 g) were treated with a commercially available bleaching agent and then treated with a hair dye (Stephen Norcolor Couture Hair Color Light Brown) to prepare dyed hair bundles. .. The prepared dyed hair bundle was washed with 1 g of shampoo and rinsed with ion-exchanged water. (Hereinafter referred to as shampoo treatment) After one shampoo treatment, the mixture is immersed in 100 mL of ion-exchanged water (40 ° C.) for 24 hours, and the transmittance of the eluate at a wavelength of 600 nm is measured by the ultraviolet visible spectrophotometer UV-2600 (Shimadzu Corporation). Measured by the company). At this time, a polystyrene disposable cell (manufactured by Nikko Hansen) was used. Further, for the sample in which the fading suppressing effect was confirmed, the measurement after 20 times of shampoo treatment was also carried out by the same method.
評価基準
[評価結果] :[判定]
効果が持続(シャンプー処理20回後の溶出液の透過率90%以上) : ◎
効果あり(シャンプー処理1回後の溶出液の透過率80%以上) : ○
効果なし : ×
Evaluation Criteria [Evaluation Result]: [Judgment]
Lasting effect (90% or more permeability of eluate after 20 shampoo treatments): ◎
Effective (80% or more permeability of eluate after one shampoo treatment): ○
No effect: ×
〔評価項目(ロ)の評価方法〕
化粧品評価専門パネル10名に、実施例及び比較例のシャンプーを髪に使用してもらい、その後ドライヤーで十分に乾燥させ、(ロ)ハリコシ改善効果について、各自が以下の評価基準(I)に従って3段階に官能評価し、更に全パネルの評点の平均点を以下の判定基準(II)に従って判定した。
[Evaluation method of evaluation item (b)]
We asked 10 cosmetics evaluation panel to use the shampoos of Examples and Comparative Examples on their hair, and then dried them sufficiently with a dryer. (B) Regarding the effect of improving elasticity, each person according to the following evaluation criteria (I) 3 Sensory evaluation was performed in stages, and the average score of all panels was judged according to the following criterion (II).
評価基準(I)
[評価結果] :[評点]
非常に良好 : 3点
良好 : 2点
不良 : 1点
評価基準(II)
[評点の平均点] :[判定]
2.5以上 : ◎
1.5以上2.5未満 : ○
1.5未満 : ×
Evaluation Criteria (I)
[Evaluation result]: [Score]
Very good: 3 points Good: 2 points Bad: 1 point Evaluation criteria (II)
[Average score]: [Judgment]
2.5 or more: ◎
1.5 or more and less than 2.5: ○
Less than 1.5: ×
〔評価項目(ハ)の評価方法〕
スタッフス社製毛束(人毛黒、10cm、1g)を市販のブリーチ剤にて処理した後、ヘアアイロンによる物理処理を100回行い、ダメージ毛束を作製した。作製した毛束をシャンプー処理1回の後、専門評価者2名で、SEM観察(倍率:1000倍)にて1視野あたりのキューティクルのめくれ箇所をカウントした。
[Evaluation method of evaluation item (c)]
A hair bundle manufactured by Stuffs (human hair black, 10 cm, 1 g) was treated with a commercially available bleaching agent, and then physically treated with a curling iron 100 times to prepare a damaged hair bundle. After one shampoo treatment on the prepared hair bundles, two expert evaluators counted the cuticle turning points per visual field by SEM observation (magnification: 1000 times).
評価基準
[評価結果] :[判定]
保護効果あり(1視野あたりのめくれが10箇所以下) :○
保護効果なし(1視野あたりのめくれが11箇所以上) :×
Evaluation Criteria [Evaluation Result]: [Judgment]
Protective effect (10 or less turns per field of view): ○
No protective effect (11 or more turns per field of view): ×
〔評価項目(ニ)の評価方法〕
シャンプー作成後、外観の目視評価を行った。
[Evaluation method of evaluation item (d)]
After making the shampoo, the appearance was visually evaluated.
評価基準
[評価結果] :[判定]
透明 : ◎
半透明〜濁りあり : ○
Evaluation Criteria [Evaluation Result]: [Judgment]
Transparent: ◎
Translucent to turbid: ○
表1の結果から明らかなように、実施例1〜5のシャンプーは、比較例1〜3と比べ、全ての評価項目において優れた結果であった。
一方、成分(A)を含有しなかった比較例1は、褪色抑制効果、毛髪保護効果、ハリコシ改善効果ともに得ることはできなかった。成分(A)の代わりに、毛髪に固いフィルムを形成することで知られる(ビニルピロリドン/VA)コポリマーを配合した比較例2は、ある程度のハリコシ感を得ることはできたが、褪色抑制効果に劣るものであった。成分(A)の代わりに、ヘアカラーの色落ち防止効果があることで知られるポリクオタニウム―47を配合した比較例3は、ある程度の褪色抑制効果は得られたものの、毛髪保護効果や、ハリコシ改善効果に劣るものであった。
As is clear from the results in Table 1, the shampoos of Examples 1 to 5 were superior in all the evaluation items as compared with Comparative Examples 1 to 3.
On the other hand, Comparative Example 1 which did not contain the component (A) could not obtain any of the fading suppressing effect, the hair protecting effect, and the firmness improving effect. Comparative Example 2 in which a (vinylpyrrolidone / VA) copolymer known to form a hard film on the hair was blended instead of the component (A) was able to obtain a certain degree of elasticity, but it was effective in suppressing fading. It was inferior. In Comparative Example 3 in which polyquaternium-47, which is known to have an effect of preventing discoloration of hair color, was blended instead of the component (A), a certain degree of fading suppressing effect was obtained, but a hair protecting effect and an improvement in elasticity were obtained. It was inferior in effect.
[実施例6]シャンプー
以下に示す組成のシャンプーを下記の方法により製造した。
(成分) (%)
1.オレフィンスルホン酸ナトリウム 10.0
2.ラウレス硫酸ナトリウム 5.0
3.コカミドプロピルベタイン 5.0
4.PPG−2コカミド(注11) 4.0
5.ジステアリン酸グリコール 1.0
6.塩化ナトリウム 0.5
7.精製水 残量
8.ポリクオタニウム−10 0.5
9.参考製造例2の(メタ)アクリルシリコーン系グラフト共重合体 0.05
10.エタノール 0.5
11.メチルパラベン 0.1
12.イソステアリン酸PEG−50水添ヒマシ油(注15) 0.5
13.香料 適量
(製法)
A:成分1〜7を均一に混合し、75℃に加熱する。
B:Aに8、9を添加し、均一に混合する。
C:Bを45℃まで冷却し、10〜13を添加し、均一に混合し、シャンプーを得た。
実施例6のシャンプーは、褪色抑制効果、毛髪保護効果、ハリコシ改善効果に優れていた。
[Example 6] Shampoo A shampoo having the composition shown below was produced by the following method.
(Ingredient) (%)
1. 1. Sodium Olefin Sulfonate 10.0
2. Sodium Laureth Sulfate 5.0
3. 3. Cocamidopropyl Betaine 5.0
4. PPG-2 cocamide (Note 11) 4.0
5. Glycol distearate 1.0
6. Sodium chloride 0.5
7. Remaining amount of purified water 8. Polyquaternium-10 0.5
9. Reference Production Example 2 (Meta) Acrylic Silicone Graft Copolymer 0.05
10. Ethanol 0.5
11. Methylparaben 0.1
12. PEG-50 hydrogenated castor oil isostearate (Note 15) 0.5
13. Appropriate amount of fragrance (manufacturing method)
A: Ingredients 1 to 7 are uniformly mixed and heated to 75 ° C.
B: Add 8 and 9 to A and mix uniformly.
C: B was cooled to 45 ° C., 10 to 13 were added and mixed uniformly to obtain a shampoo.
The shampoo of Example 6 was excellent in fading suppressing effect, hair protecting effect, and firmness improving effect.
[実施例7]コンディショナー
以下に示す組成のコンディショナーを下記の方法により製造した。
(成分) (%)
1.ベヘニルアルコール 2.0
2.セトステアリルアルコール 1.0
3.ジメチコン 3.0
4.オレイン酸エチル 0.5
5.塩化アルキルトリメチルアンモニウム 1.0
6.精製水 残量
7.参考製造例2の(メタ)アクリルシリコーン系グラフト共重合体 0.5
8.エタノール 0.5
9.メチルパラベン 0.1
10.香料 適量
(製法)
A:成分1〜5、7を80℃にて均一に混合する。
B:成分6を80℃にて均一に混合する。
C:BにAを添加し、乳化する。
D:Cを45℃まで冷却し、8〜10を添加し、均一に混合し、コンディショナーを得た。
実施例7のコンディショナーは、褪色抑制効果、毛髪保護効果、ハリコシ改善効果に優れていた。
[Example 7] Conditioner A conditioner having the composition shown below was produced by the following method.
(Ingredient) (%)
1. 1. Behenyl alcohol 2.0
2. Setostearyl alcohol 1.0
3. 3. Dimethicone 3.0
4. Ethyl oleate 0.5
5. Alkyltrimethylammonium chloride 1.0
6. Remaining amount of purified water 7. Reference Production Example 2 (Meta) Acrylic Silicone Graft Copolymer 0.5
8. Ethanol 0.5
9. Methylparaben 0.1
10. Appropriate amount of fragrance (manufacturing method)
A: Ingredients 1 to 5 and 7 are uniformly mixed at 80 ° C.
B: Component 6 is uniformly mixed at 80 ° C.
C: Add A to B and emulsify.
D: C was cooled to 45 ° C., 8-10 was added and mixed uniformly to obtain a conditioner.
The conditioner of Example 7 was excellent in fading suppressing effect, hair protecting effect, and firmness improving effect.
[実施例8]ヘアオイル
以下に示す組成のヘアオイルを下記の方法により製造した。
(成分) (%)
1.水添ポリイソブテン 20.0
2.ジメチコン 残量
3.ジメチコノール 10.0
4.参考製造例2の(メタ)アクリルシリコーン系グラフト共重合体 1.0
5.イソステアリン酸 0.5
6.エタノール 1.0
7.香料 適量
(製法)
A:成分1〜7を常温にて均一に混合し、ヘアオイルを得た。
実施例8のヘアオイルは、褪色抑制効果、毛髪保護効果、ハリコシ改善効果に優れていた。
[Example 8] Hair oil A hair oil having the composition shown below was produced by the following method.
(Ingredient) (%)
1. 1. Hydrogenated polyisobutene 20.0
2. Dimethicone Remaining amount 3. Dimethiconol 10.0
4. Reference Production Example 2 (Meta) Acrylic Silicone Graft Copolymer 1.0
5. Isostearic acid 0.5
6. Ethanol 1.0
7. Appropriate amount of fragrance (manufacturing method)
A: Ingredients 1 to 7 were uniformly mixed at room temperature to obtain hair oil.
The hair oil of Example 8 was excellent in a fading suppressing effect, a hair protecting effect, and a firmness improving effect.
Claims (7)
(A)下記(a)、(b)、(c)及び(d)のラジカル重合性モノマーを反応させて得られ、(a)、(b)、(c)及び(d)のラジカル重合性モノマー全体に対して、(a)=20〜50質量%、(b)=0.5〜4質量%、(c)及び(d)=46〜79.5質量%である、(メタ)アクリルシリコーン系グラフト共重合体
(a)下記一般式(I)
(b)下記一般式(II)
(c)下記一般式(IV)
(d)下記一般式(V)
(A) Obtained by reacting the following radically polymerizable monomers (a), (b), (c) and (d), and the radically polymerizable of (a), (b), (c) and (d). (A) = 20-50% by mass, (b) = 0.5-4% by mass, (c) and (d) = 46-79.5% by mass, based on the total monomer, (meth) acrylic. Silicone-based graft copolymer (a) The following general formula (I)
A method for suppressing fading of dyed hair, which uses the component (A) as a fading inhibitor for dyed hair.
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