JP2022046324A - Adhesive for skin application, and sheet for skin application - Google Patents
Adhesive for skin application, and sheet for skin application Download PDFInfo
- Publication number
- JP2022046324A JP2022046324A JP2020152303A JP2020152303A JP2022046324A JP 2022046324 A JP2022046324 A JP 2022046324A JP 2020152303 A JP2020152303 A JP 2020152303A JP 2020152303 A JP2020152303 A JP 2020152303A JP 2022046324 A JP2022046324 A JP 2022046324A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylic acid
- adhesive
- alkyl ester
- skin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 54
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 53
- 239000000178 monomer Substances 0.000 claims abstract description 54
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- 239000002537 cosmetic Substances 0.000 claims abstract description 8
- 239000012790 adhesive layer Substances 0.000 claims abstract description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 58
- -1 n-octyl Chemical group 0.000 description 43
- 239000003505 polymerization initiator Substances 0.000 description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000003945 anionic surfactant Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 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
- 239000011248 coating agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- PGRHXDWITVMQBC-UHFFFAOYSA-N dehydroacetic acid Chemical compound CC(=O)C1C(=O)OC(C)=CC1=O PGRHXDWITVMQBC-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-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
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 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
- 239000003755 preservative agent Substances 0.000 description 2
- 229940071139 pyrrolidone carboxylate Drugs 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 230000037303 wrinkles Effects 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
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- MQFDMZNZEHTLND-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]benzoic acid Chemical compound CC(C)(C)OC1=CC=CC=C1C(O)=O MQFDMZNZEHTLND-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UDWIZRDPCQAYRF-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C=C UDWIZRDPCQAYRF-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- SDZPCJUYLXUAGL-UHFFFAOYSA-N 4-ethyl-2-(sulfanylmethyl)octanoic acid Chemical compound CCCCC(CC)CC(CS)C(O)=O SDZPCJUYLXUAGL-UHFFFAOYSA-N 0.000 description 1
- 229940073735 4-hydroxy acetophenone Drugs 0.000 description 1
- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 description 1
- ODHCTXKNWHHXJC-VKHMYHEASA-M 5-oxo-L-prolinate Chemical compound [O-]C(=O)[C@@H]1CCC(=O)N1 ODHCTXKNWHHXJC-VKHMYHEASA-M 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- AAOISIQFPPAFQO-UHFFFAOYSA-N 7:0(6Me,6Me) Chemical compound CC(C)(C)CCCCC(O)=O AAOISIQFPPAFQO-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、皮膚に直接的に貼付する粘着剤および粘着剤から形成されてなる粘着層を有する粘着シートに関する。 The present invention relates to a pressure-sensitive adhesive that is directly attached to the skin and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive.
近年、医療分野において、医薬品の経皮投与のためのパップ剤、プラスター剤等の医療用貼付剤や、ガーゼ、生体パッド等の医療用具を皮膚に固定するためのテープに粘着剤が幅広く使用されている。一方、化粧品分野においてもアイメイク用やウィッグのずれ防止用、特殊メイクにおけるしわの作製等、皮膚に直接触れる部分に粘着剤が用いられる。これらの皮膚貼付用粘着剤は、使用時には十分な粘着力が得られ、剥離時には皮膚側に糊残りしないことが求められる。 In recent years, adhesives have been widely used in the medical field for medical patches such as paps and plasters for transdermal administration of pharmaceuticals, and tapes for fixing medical devices such as gauze and biological pads to the skin. ing. On the other hand, in the field of cosmetics as well, adhesives are used for parts that come into direct contact with the skin, such as for eye makeup, for preventing wig slippage, and for creating wrinkles in special makeup. It is required that these adhesives for skin application have sufficient adhesive strength at the time of use and do not leave adhesive on the skin side at the time of peeling.
特許文献１には、アクリル酸メチル、炭素数４～１２のアルキル基を有する（メタ）アクリル酸エステル、並びにアクリル酸及び／又はメタクリル酸を含有してなる単量体混合物を乳化共重合して得られる共重合体を含有してなる人体貼付用粘着剤用エマルションが開示されている。 In Patent Document 1, a monomer mixture containing methyl acrylate, a (meth) acrylic acid ester having an alkyl group having 4 to 12 carbon atoms, and acrylic acid and / or methacrylic acid is emulsified and copolymerized. An emulsion for a pressure-sensitive adhesive for attaching to a human body containing the obtained copolymer is disclosed.
しかし、特許文献１に記載の発明は、皮膚に対する接着性と剥離性が低水準であり、粘着剤の剥離時の糊残りの問題も十分ではなかった。 However, the invention described in Patent Document 1 has a low level of adhesiveness and peelability to the skin, and the problem of adhesive residue at the time of peeling of the pressure-sensitive adhesive is not sufficient.
本発明は、皮膚に対する接着性および剥離性を高水準で両立し、とくに剥離時の皮膚への糊残りが抑制され、化粧料用としても好ましく使用できる皮膚貼付用粘着剤および前記粘着剤から形成されてなる粘着層を有する皮膚貼付用シートを提供することを目的とする。 INDUSTRIAL APPLICABILITY The present invention has a high level of adhesiveness and peelability to the skin, and is formed from a skin-adhesive adhesive and the above-mentioned adhesive, which suppresses adhesive residue on the skin at the time of peeling and can be preferably used for cosmetics. It is an object of the present invention to provide a skin-sticking sheet having an adhesive layer made of.
本発明は、炭素数１～３のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ａ）、炭素数４～６のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ｂ－１）、炭素数７～１２のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ｂ－２）およびエチレン性不飽和カルボン酸を含む単量体混合物の共重合体（１）を含有する皮膚貼付用粘着剤に関する。 The present invention comprises a (meth) acrylic acid alkyl ester (A) having an alkyl group having 1 to 3 carbon atoms, a (meth) acrylic acid alkyl ester (B-1) having an alkyl group having 4 to 6 carbon atoms, and a carbon number of carbon atoms. The present invention relates to a pressure-sensitive adhesive for skin application, which comprises a (meth) acrylic acid alkyl ester (B-2) having an alkyl group of 7 to 12 and a copolymer (1) of a monomer mixture containing an ethylenically unsaturated carboxylic acid.
また、本発明は、前記（メタ）アクリル酸アルキルエステル（Ａ）と、前記（メタ）アクリル酸アルキルエステル（Ｂ－１）および前記（メタ）アクリル酸アルキルエステル（Ｂ－２）との質量比が、（Ａ）／〔（Ｂ－１）＋（Ｂ－２）〕＝１０／９０～３０／７０である、前記皮膚貼付用粘着剤に関する。 Further, in the present invention, the mass ratio of the (meth) acrylic acid alkyl ester (A) to the (meth) acrylic acid alkyl ester (B-1) and the (meth) acrylic acid alkyl ester (B-2). The present invention relates to the above-mentioned adhesive for skin application, wherein (A) / [(B-1) + (B-2)] = 10/90 to 30/70.
また、本発明は、前記（メタ）アクリル酸アルキルエステル（Ｂ－１）と前記（メタ）アクリル酸アルキルエステル（Ｂ－２）との質量比が、（Ｂ－１）／（Ｂ－２）＝５／９５～５０／５０である、前記皮膚貼付用粘着剤に関する。 Further, in the present invention, the mass ratio of the (meth) acrylic acid alkyl ester (B-1) to the (meth) acrylic acid alkyl ester (B-2) is (B-1) / (B-2). The present invention relates to the pressure-sensitive adhesive for skin application, which is 5/95 to 50/50.
また、本発明は、単量体混合物の合計１００質量％中、エチレン性不飽和カルボン酸を０．５～５質量％含む、前記皮膚貼付用粘着剤に関する。 The present invention also relates to the pressure-sensitive adhesive for skin application, which contains 0.5 to 5% by mass of ethylenically unsaturated carboxylic acid in a total of 100% by mass of the monomer mixture.
さらに、本発明は、単量体混合物の合計１００質量％中、エチレン性不飽和カルボン酸を０．５～５質量％含む、前記皮膚貼付用粘着剤に関する。 Furthermore, the present invention relates to the pressure-sensitive adhesive for skin application, which contains 0.5 to 5% by mass of ethylenically unsaturated carboxylic acid in a total of 100% by mass of the monomer mixture.
さらにまた、本発明は、化粧料用である、前記皮膚貼付用粘着剤に関する。 Furthermore, the present invention relates to the above-mentioned adhesive for skin application, which is for cosmetics.
さらにまた、本発明は、基材と、前記皮膚貼付用粘着剤から形成されてなる粘着層を備えた皮膚貼付用シートに関する。 Furthermore, the present invention relates to a skin-sticking sheet provided with a base material and an adhesive layer formed of the skin-sticking pressure-sensitive adhesive.
本発明により、皮膚に対する接着性および剥離性を高水準で両立し、剥離時の皮膚への糊残りが抑制され、化粧料用としても好ましく使用できる皮膚貼付用粘着剤ならびに皮膚貼付用シートを提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, there is provided a skin-sticking adhesive and a skin-sticking sheet that have both adhesiveness and peelability to the skin at a high level, suppress the adhesive residue on the skin at the time of peeling, and can be preferably used for cosmetics. can do.
以下、本発明の実施形態について説明する。
尚、本明細書では、炭素数１～３のアルキル基を有する（メタ）アクリル酸アルキルエステル（Ａ）、炭素数４～６のアルキル基を有する（メタ）アクリル酸アルキルエステル（Ｂ－１）および炭素数７～１２のアルキル基を有する（メタ）アクリル酸アルキルエステル（Ｂ－２）をそれぞれ、（メタ）アクリル酸アルキルエステル（Ａ）、（メタ）アクリル酸アルキルエステル（Ｂ－１）および（メタ）アクリル酸アルキルエステル（Ｂ－２）と略記することがある。
なお、単量体とは、エチレン性不飽和基含有モノマーを意味する。
また、「アクリル酸アルキルエステル」と「メタクリル酸アルキルエステル」とを併せて「(メタ)アクリル酸アルキルエステル」と表記する。
本明細書中に出てくる各種成分はかかる例示のみに限定されるものではなく、特に注釈しない限り、それぞれ独立に一種単独でも二種以上を併用してもよい。
Hereinafter, embodiments of the present invention will be described.
In the present specification, the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 3 carbon atoms (A) and the (meth) acrylic acid alkyl ester having an alkyl group having 4 to 6 carbon atoms (B-1). And the (meth) acrylic acid alkyl ester (B-2) having an alkyl group having 7 to 12 carbon atoms is the (meth) acrylic acid alkyl ester (A), the (meth) acrylic acid alkyl ester (B-1) and It may be abbreviated as (meth) acrylic acid alkyl ester (B-2).
The monomer means an ethylenically unsaturated group-containing monomer.
Further, the "acrylic acid alkyl ester" and the "methacrylic acid alkyl ester" are collectively referred to as "(meth) acrylic acid alkyl ester".
The various components mentioned in the present specification are not limited to these examples only, and unless otherwise specified, they may be used independently or in combination of two or more.
≪皮膚貼付用粘着剤≫
炭素数１～３のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ａ）、炭素数４～６のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ｂ－１）、炭素数７～１２のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ｂ－２）およびエチレン性不飽和カルボン酸を含む単量体混合物の共重合体（１）を含有することを特徴とする。
≪Adhesive for skin application≫
A (meth) acrylic acid alkyl ester having an alkyl group having 1 to 3 carbon atoms (A), a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 6 carbon atoms (B-1), and having 7 to 12 carbon atoms. It is characterized by containing a copolymer (1) of a monomer mixture containing a (meth) acrylic acid alkyl ester having an alkyl group (B-2) and an ethylenically unsaturated carboxylic acid.
本発明の皮膚貼付用粘着剤は、共重合体（１）に、ｐＨ調整剤、増粘剤、消泡剤などの任意成分を加え、混合撹拌することで得られる。 The pressure-sensitive adhesive for skin application of the present invention can be obtained by adding an optional component such as a pH adjuster, a thickener, and an antifoaming agent to the copolymer (1), and mixing and stirring the mixture.
＜共重合体（１）＞
共重合体（１）は、炭素数１～３のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ａ）、炭素数４～６のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ｂ－１）、炭素数７～１２のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ｂ－２）およびエチレン性不飽和カルボン酸を含む単量体混合物の共重合体である。
<Copolymer (1)>
The copolymer (1) is a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 3 carbon atoms (A) and a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 6 carbon atoms (B-1). ), A copolymer of a monomer mixture containing a (meth) acrylic acid alkyl ester (B-2) having an alkyl group having 7 to 12 carbon atoms and an ethylenically unsaturated carboxylic acid.
［（メタ）アクリル酸アルキルエステル（Ａ）］
炭素数１～３のアルキル基を有する（メタ）アクリル酸アルキルエステル（Ａ）としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレートなどが挙げられるが、本発明は、かかる例示のみに限定されるものではない。これらの中でも、接着性と剥離性を高水準で両立した皮膚貼付用粘着剤を得る観点から、メチル（メタ）アクリレートが好ましく、メチルメタクリレートがより好ましい。
[(Meta) Acrylic Acid Alkyl Ester (A)]
Examples of the (meth) acrylic acid alkyl ester (A) having an alkyl group having 1 to 3 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. However, the present invention is not limited to such an example. Among these, methyl (meth) acrylate is preferable, and methyl methacrylate is more preferable, from the viewpoint of obtaining a pressure-sensitive adhesive for skin application having both adhesiveness and peelability at a high level.
本発明において、（メタ）アクリル酸アルキルエステル（Ａ）の含有率は、単量体混合物の合計１００質量％中、５～３５質量％であることが好ましく、１０～３０質量％であることがより好ましい。（メタ）アクリル酸アルキルエステル（Ａ）の含有率が、５質量％以上であることにより粘着剤の凝集力が高くなり、剥離性がより良くなる。また、３５質量％以下であることにより、皮膚に対する粘着剤の追従性がよくなり、接着性をより良化できる。 In the present invention, the content of the (meth) acrylic acid alkyl ester (A) is preferably 5 to 35% by mass, preferably 10 to 30% by mass, based on 100% by mass of the total monomer mixture. More preferred. When the content of the (meth) acrylic acid alkyl ester (A) is 5% by mass or more, the cohesive force of the pressure-sensitive adhesive is increased and the peelability is further improved. Further, when it is 35% by mass or less, the followability of the adhesive to the skin is improved, and the adhesiveness can be further improved.
［（メタ）アクリル酸アルキルエステル（Ｂ－１）］
炭素数４～６のアルキル基を有する（メタ）アクリル酸アルキルエステル（Ｂ－１）としては、例えば、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、イソアミル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、２－エチルブチル（メタ）アクリレート、２－メチルペンチル（メタ）アクリレートなどが挙げられる。
なかでもアクリル酸アルキルエステルであることが、接着性と剥離性のバランスの点で好ましい。
また、接着性と剥離性を高水準で両立した皮膚貼付用粘着剤を得る観点から、ｎ－ブチル（メタ）アクリレートが好ましく、ｎ－ブチルアクリレートがより好ましい。
[(Meta) Acrylic Acid Alkyl Ester (B-1)]
Examples of the (meth) acrylic acid alkyl ester (B-1) having an alkyl group having 4 to 6 carbon atoms include n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, and tert. -Butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, 2-methylpentyl (meth) acrylate and the like can be mentioned.
Of these, acrylic acid alkyl esters are preferable in terms of the balance between adhesiveness and peelability.
Further, from the viewpoint of obtaining a pressure-sensitive adhesive for skin application having both adhesiveness and peelability at a high level, n-butyl (meth) acrylate is preferable, and n-butyl acrylate is more preferable.
本発明において、（メタ）アクリル酸アルキルエステル（Ｂ－１）の含有率は、単量体混合物の合計１００質量％中、１～４５質量％であることが好ましく、５～４０質量％であることがより好ましい。（メタ）アクリル酸アルキルエステル（Ｂ－１）の含有率が、１質量％以上であると、皮膚に対する粘着剤の濡れ性が上がり、接着性がより良くなる。また、４５質量％以下であることにより、粘着剤が硬くなり、剥離性をより良化できる。 In the present invention, the content of the (meth) acrylic acid alkyl ester (B-1) is preferably 1 to 45% by mass, preferably 5 to 40% by mass, based on 100% by mass of the total monomer mixture. Is more preferable. When the content of the (meth) acrylic acid alkyl ester (B-1) is 1% by mass or more, the wettability of the adhesive to the skin is increased and the adhesiveness is further improved. Further, when it is 45% by mass or less, the pressure-sensitive adhesive becomes hard and the peelability can be further improved.
［（メタ）アクリル酸アルキルエステル（Ｂ－２）］
炭素数７～１２のアルキル基を有する（メタ）アクリル酸アルキルエステル（Ｂ－２）としては、例えば、ｎ－ヘプチル（メタ）アクリレート、ｎ－オクチル（メタ）アクレート、イソオクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－ノニル（メタ）アクリレート、イソノニル（メタ）アクレート、ｎ－デシル（メタ）アクリレート、ラウリル（メタ）アクリレートなどが挙げられるが、本発明は、かかる例示のみに限定されるものではない。これらの中でも、接着性と剥離性を高水準で両立した皮膚貼付用粘着剤を得る観点から、ｎ－オクチルアクリレート、２－エチルヘキシルアクリレートが好ましく、２－エチルヘキシルアクリレートがより好ましい。
[(Meta) Acrylic Acid Alkyl Ester (B-2)]
Examples of the (meth) acrylic acid alkyl ester (B-2) having an alkyl group having 7 to 12 carbon atoms include n-heptyl (meth) acrylate, n-octyl (meth) acrylate, and isooctyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate and the like can be mentioned, but the present invention is limited to such examples. It's not something. Among these, n-octyl acrylate and 2-ethylhexyl acrylate are preferable, and 2-ethylhexyl acrylate is more preferable, from the viewpoint of obtaining a pressure-sensitive adhesive for skin application having both adhesiveness and peelability at a high level.
本発明において、（メタ）アクリル酸アルキルエステル（Ｂ－２）の含有率は、単量体混合物の合計１００質量％中、３０～８５質量％であることが好ましく、３５～７５％質量％であることがより好ましい。（メタ）アクリル酸アルキルエステル（Ｂ－２）の含有率が、３０質量％以上であると、皮膚に対する粘着剤の追従性が向上し、接着性がより良くなる。また、８５質量％以下であることにより、粘着剤が硬くなり、剥離性をより良化できる。 In the present invention, the content of the (meth) acrylic acid alkyl ester (B-2) is preferably 30 to 85% by mass, preferably 35 to 75% by mass, based on 100% by mass of the total monomer mixture. It is more preferable to have. When the content of the (meth) acrylic acid alkyl ester (B-2) is 30% by mass or more, the followability of the pressure-sensitive adhesive to the skin is improved and the adhesiveness is further improved. Further, when it is 85% by mass or less, the pressure-sensitive adhesive becomes hard and the peelability can be further improved.
炭素数４～６のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ｂ－１）、炭素数７～１２のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ｂ－２）は、長鎖アルキル基を有する（メタ）アクリル酸アルキルエステルであり、なかでも（メタ）アクリル酸アルキルエステル（Ｂ－１）は、（メタ）アクリル酸アルキルエステル（Ｂ－２）よりも親水性が高いため、皮膚への濡れ性をより良くすることができる。一方、（メタ）アクリル酸アルキルエステル（Ｂ－２）は、（メタ）アクリル酸アルキルエステル（Ｂ－１）よりも長鎖アルキル基を有するため、共重合体のガラス転移温度を低下させ、皮膚への追従性をより良くすることができる。そのため、（メタ）アクリル酸アルキルエステル（Ｂ－１）と（メタ）アクリル酸アルキルエステル（Ｂ－２）を含む単量体混合物から得られる共重合体（１）を含有する皮膚貼付用粘着剤は、良好な皮膚への濡れ性と追従性を示すことが可能となり、より良い接着性と剥離性を示す。 The (meth) acrylic acid alkyl ester having an alkyl group having 4 to 6 carbon atoms (B-1) and the (meth) acrylic acid alkyl ester having an alkyl group having 7 to 12 carbon atoms (B-2) are long-chain alkyls. It is a (meth) acrylic acid alkyl ester having a group, and among them, the (meth) acrylic acid alkyl ester (B-1) is more hydrophilic than the (meth) acrylic acid alkyl ester (B-2), and therefore the skin. It is possible to improve the wettability to ester. On the other hand, the (meth) acrylic acid alkyl ester (B-2) has a longer chain alkyl group than the (meth) acrylic acid alkyl ester (B-1), so that the glass transition temperature of the copolymer is lowered and the skin is affected. It is possible to improve the followability to. Therefore, a pressure-sensitive adhesive for skin application containing a copolymer (1) obtained from a monomer mixture containing a (meth) acrylic acid alkyl ester (B-1) and a (meth) acrylic acid alkyl ester (B-2). Can show good wettability and followability to the skin, and show better adhesiveness and peelability.
(メタ)アクリル酸アルキルエステル（Ａ）と、(メタ)アクリル酸アルキルエステル（Ｂ－１）および(メタ)アクリル酸アルキルエステル（Ｂ－２）との質量比は、（Ａ）／〔（Ｂ－１）＋（Ｂ－２）〕＝１０／９０～３０／７０であることが好ましく、１０／９０～１５／８５であることがより好ましい。これらの長鎖アルキル基を有する単量体が単量体混合物中に上記の質量範囲にあることで、皮膚に対する良好な濡れ性と追従性を示すことが可能となり、接着性と剥離性が良好な皮膚貼付用粘着剤が、より得やすくなる。 The mass ratio of the (meth) acrylic acid alkyl ester (A) to the (meth) acrylic acid alkyl ester (B-1) and the (meth) acrylic acid alkyl ester (B-2) is (A) / [(B-2). -1) + (B-2)] = 10/90 to 30/70, more preferably 10/90 to 15/85. When these long-chain alkyl group-containing monomers are in the above-mentioned mass range in the monomer mixture, it is possible to exhibit good wettability and followability to the skin, and good adhesiveness and peelability. It becomes easier to obtain a sticky adhesive for skin application.
（メタ）アクリル酸アルキルエステル（Ｂ－１）と（メタ）アクリル酸アルキルエステル（Ｂ－２）との質量比は、（Ｂ－１）／（Ｂ－２）＝５／９５～５０／５０であることが好ましく、５／９５～３０／７０であることがより好ましい。これらの長鎖アルキル基を有する単量体が単量体混合物中に上記の質量範囲にあることで、皮膚に対する良好な濡れ性と追従性を示すことが可能となり、接着性と剥離性が良好な皮膚貼付用粘着剤が、より得やすくなる。 The mass ratio of the (meth) acrylic acid alkyl ester (B-1) to the (meth) acrylic acid alkyl ester (B-2) is (B-1) / (B-2) = 5/95 to 50/50. It is preferably 5/95 to 30/70, and more preferably 5/95 to 30/70. When these long-chain alkyl group-containing monomers are in the above-mentioned mass range in the monomer mixture, it is possible to exhibit good wettability and followability to the skin, and good adhesiveness and peelability. It becomes easier to obtain a sticky adhesive for skin application.
なかでも、（メタ）アクリル酸アルキルエステル（Ａ）と、（メタ）アクリル酸アルキルエステル（Ｂ－１）および（メタ）アクリル酸アルキルエステル（Ｂ－２）との質量比が（Ａ）／〔（Ｂ－１）＋（Ｂ－２）〕＝１０／９０～３０／７０であり、さらに (メタ)アクリル酸アルキルエステル（Ｂ－１）と(メタ)アクリル酸アルキルエステル（Ｂ－２）との質量比が、（Ｂ－１）／（Ｂ－２）＝５／９５～５０／５０であることがより好ましい。これらの長鎖アルキル基を有する単量体が単量体混合物中に上記の質量範囲にあることで、皮膚に対する良好な濡れ性と追従性を示すことが可能となり、接着性と剥離性を高水準で両立した皮膚貼付用粘着剤が、より得やすくなる。 Among them, the mass ratio of the (meth) acrylic acid alkyl ester (A) to the (meth) acrylic acid alkyl ester (B-1) and the (meth) acrylic acid alkyl ester (B-2) is (A) / [. (B-1) + (B-2)] = 10/90 to 30/70, and further, (meth) acrylic acid alkyl ester (B-1) and (meth) acrylic acid alkyl ester (B-2). The mass ratio of (B-1) / (B-2) = 5/95 to 50/50 is more preferable. When these long-chain alkyl group-containing monomers are in the above-mentioned mass range in the monomer mixture, it is possible to exhibit good wettability and followability to the skin, and high adhesiveness and peelability. It becomes easier to obtain an adhesive for skin application that is compatible with the standard.
［エチレン性不飽和カルボン酸］
エチレン性不飽和カルボン酸としては、本発明においては酸無水物も該当し、例えば、（メタ）アクリル酸、マレイン酸、フマル酸、クロトン酸、イタコン酸、無水マレイン酸などが挙げられるが、本発明は、かかる例示のみに限定されるものではない。これらの中でも、接着性と剥離性を高水準で両立した皮膚貼付用粘着剤を得る観点から、（メタ）アクリル酸が好ましい。
[Ethylene unsaturated carboxylic acid]
The ethylenically unsaturated carboxylic acid also corresponds to an acid anhydride in the present invention, and examples thereof include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, and maleic anhydride. The invention is not limited to such embodiments. Among these, (meth) acrylic acid is preferable from the viewpoint of obtaining a pressure-sensitive adhesive for skin application that has both adhesiveness and peelability at a high level.
本発明において、エチレン性不飽和カルボン酸は、単量体混合物の合計１００質量％中、０．５～５質量％含まれることが好ましく、１～４質量％含まれることがより好ましい。
エチレン性不飽和カルボン酸の含有率が、０．５質量％以上であると、共重合体（１）の重合安定性および粘着剤の機械安定性が向上し、接着性がより良くなる。また、５質量％以下であると、粘着剤が軟らかくなり、接着性がより良化する。
In the present invention, the ethylenically unsaturated carboxylic acid is preferably contained in an amount of 0.5 to 5% by mass, more preferably 1 to 4% by mass, based on 100% by mass of the total monomer mixture.
When the content of the ethylenically unsaturated carboxylic acid is 0.5% by mass or more, the polymerization stability of the copolymer (1) and the mechanical stability of the pressure-sensitive adhesive are improved, and the adhesiveness is further improved. Further, when it is 5% by mass or less, the adhesive becomes soft and the adhesiveness is further improved.
共重合体（１）を構成する単量体として、炭素数１～３のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ａ）、炭素数４～６のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ｂ－１）、炭素数７～１２のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ｂ－２）、エチレン性不飽和カルボン酸以外の単量体を含んでもよい。
それらの例としては、例えば、脂肪族環または芳香族環を有する単量体、スルホン酸基含有単量体、水酸基含有単量体、窒素含有単量体、アルコキシ基含有単量体、オキシアルキレン基含有単量体、グリシジル基含有単量体、シラン基含有単量体、架橋性単量体などが挙げられる。
As the monomer constituting the copolymer (1), a (meth) acrylic acid alkyl ester (A) having an alkyl group having 1 to 3 carbon atoms and a (meth) acrylic acid having an alkyl group having 4 to 6 carbon atoms. It may contain a monomer other than the alkyl ester (B-1), the (meth) acrylic acid alkyl ester (B-2) having an alkyl group having 7 to 12 carbon atoms, and the ethylenically unsaturated carboxylic acid.
Examples of these are, for example, a monomer having an aliphatic ring or an aromatic ring, a sulfonic acid group-containing monomer, a hydroxyl group-containing monomer, a nitrogen-containing monomer, an alkoxy group-containing monomer, and an oxyalkylene. Examples thereof include a group-containing monomer, a glycidyl group-containing monomer, a silane group-containing monomer, and a crosslinkable monomer.
脂肪族環または芳香族環を有する単量体としては、例えば、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、スチレン、α－メチルスチレン、ビニルナフタレン、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレートなどが挙げられるが、本発明は、かかる例示のみに限定されるものではない。 Examples of the monomer having an aliphatic ring or an aromatic ring include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, styrene, α-methylstyrene, vinylnaphthalene, phenyl (meth) acrylate, and benzyl (meth) acrylate. , Phenoxyethyl (meth) acrylate and the like, but the present invention is not limited to such examples.
スルホン酸基含有単量体としては、ｐ－ビニルベンゼンスルホン酸、２－アクリルアミド－２－メチルプロパンスルホン酸、アクリルアミドｔｅｒｔ－ブチルスルホン酸などが挙げられるが、本発明は、かかる例示のみに限定されるものではない。 Examples of the sulfonic acid group-containing monomer include p-vinylbenzenesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, acrylamidetert-butylsulfonic acid and the like, but the present invention is limited to such examples. It's not something.
水酸基含有単量体としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、グリセロール（メタ）アクリレート、アリルアルコールなどが挙げられるが、本発明は、かかる例示のみに限定されるものではない。 Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, and allyl alcohol. , The present invention is not limited to such an example.
窒素含有単量体としては、例えば（メタ）アクリルアミド、ダイアセトン（メタ）アクリルアミド、Ｎ－メチル（メタ）アクリルアミド、Ｎ－エチル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－ブトキシメチル（メタ）アクリルアミド、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、Ｎ－ビニルピロリドン、（メタ）アクリロニトリルなどが挙げられるが、本発明は、かかる例示のみに限定されるものではない。 Examples of the nitrogen-containing monomer include (meth) acrylamide, diacetone (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N, N-dimethyl. Examples thereof include (meth) acrylamide, N-butoxymethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N-vinylpyrrolidone, and (meth) acrylonitrile. It is not limited to only.
アルコキシ基含有単量体としては、例えば、２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレートなどが挙げられるが、本発明は、かかる例示のみに限定されるものではない。 Examples of the alkoxy group-containing monomer include 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate, but the present invention is not limited to these examples.
オキシアルキレン基含有単量体としては、例えば、エチレングリコール（メタ）アクリレート、エチレングリコールメトキシ（メタ）アクリレート、ジエチレングリコール（メタ）アクリレート、ジエチレングリコールメトキシ（メタ）アクリレートなどが挙げられるが、本発明は、かかる例示のみに限定されるものではない。 Examples of the oxyalkylene group-containing monomer include ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and diethylene glycol methoxy (meth) acrylate. It is not limited to illustrations only.
グリシジル基含有単量体としては、例えば、グリシジル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートグリシジルエーテルなどが挙げられるが、本発明は、かかる例示のみに限定されるものではない。 Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether, but the present invention is not limited to these examples.
シラン基含有単量体としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、３－アクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルメチルジメトキシシラン、３－アクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、パラスチリルトリメトキシシラン、パラスチリルトリエトキシシランなどが挙げられるが、本発明は、かかる例示のみに限定されるものではない。 Examples of the silane group-containing monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxysilane. 3-Acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxy Examples thereof include propylmethyldiethoxysilane, parastilyltrimethoxysilane, and parastilyltriethoxysilane, but the present invention is not limited to these examples.
架橋性単量体は、２個以上のエチレン性不飽和基を有する単量体である。架橋性単量体としては、例えば、アリル（メタ）アクリレート、ビニル（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、ジエチレングリコールジ（メタ） アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、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、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（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、グリセリンジ（メタ）アクリレート、ジメチロールトリシクロデカンジ（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、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、ジビニルベンゼン、アジピン酸ジビニル、イソフタル酸ジアリル、フタル酸ジアリル、及びマレイン酸ジアリル等が挙げられるが、本発明は、かかる例示のみに限定されるものではない。 The crosslinkable monomer is a monomer having two or more ethylenically unsaturated groups. Examples of the crosslinkable monomer include allyl (meth) acrylate, vinyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and polyethylene glycol di ( Meta) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) Acrylate, Neopentylglycoldi (meth) acrylate, Glycerindi (meth) acrylate, Dimethyloltricyclodecandi (meth) acrylate, Trimethylolpropanetri (meth) acrylate, Pentaerythritol tri (meth) acrylate, Pentaerythritol tetra ( Examples thereof include acrylate, divinylbenzene, divinyl adipate, diallyl isophthalate, diallyl phthalate, and diallyl maleate, but the present invention is not limited to these examples.
［共重合体（１）の合成方法］
共重合体（１）の合成方法としては、溶液重合、乳化重合、塊状重合などが挙げられるが、反応熱の制御性や、皮膚刺激の可能性がある有機溶剤を使用しないという観点から乳化重合が好ましい。
[Method for synthesizing copolymer (1)]
Examples of the method for synthesizing the copolymer (1) include solution polymerization, emulsion polymerization, bulk polymerization, etc., but emulsion polymerization is performed from the viewpoint of controlling the heat of reaction and not using an organic solvent that may irritate the skin. Is preferable.
乳化重合は、少なくとも界面活性剤の存在下で実施することが好ましい。界面活性剤としては、例えば、アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤などが挙げられる。この中でも、アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤が好ましく、アニオン性界面活性剤およびノニオン性界面活性剤がより好ましい。界面活性剤は、反応性界面活性剤であってもよく、非反応性界面活性剤であってもよい。 The emulsion polymerization is preferably carried out at least in the presence of a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants and the like. Among these, anionic surfactants, cationic surfactants and nonionic surfactants are preferable, and anionic surfactants and nonionic surfactants are more preferable. The surfactant may be a reactive surfactant or a non-reactive surfactant.
非反応性アニオン性界面活性剤としては、例えば、オレイン酸ナトリウムなどの高級脂肪酸塩、ドデシルベンゼンスルホン酸などのアルキルアリールスルホン酸塩、ラウリル硫酸ナトリウムなどのアルキル硫酸エステル塩、ポリオキシエチレンラウリルエーテル硫酸ナトリウムなどのポリオキシエチレンアルキルエーテル硫酸エステル塩、モノオクチルスルホコハク酸ナトリウム、ジオクチルスルホコハク酸ナトリウム、ポリオキシエチレンラウリルスルホコハク酸ナトリウムなどのアルキルスルホコハク酸エステル塩およびその誘導体、ポリオキシエチレンジスチレン化フェニルエーテル硫酸エステル塩などが挙げられる。 Examples of the non-reactive anionic surfactant include higher fatty acid salts such as sodium oleate, alkylaryl sulfonates such as dodecylbenzene sulfonic acid, alkyl sulfate ester salts such as sodium lauryl sulfate, and polyoxyethylene lauryl ether sulfate. Polyoxyethylene alkyl ether sulfate ester salts such as sodium, alkyl sulfosuccinic acid ester salts such as sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate and derivatives thereof, polyoxyethylene distyrene phenyl ether sulfate Ester salts and the like can be mentioned.
非反応性ノニオン性界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテルなどの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オクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテルなどのポリオキシエチレンアルキルフェニルエーテル、ソルビタンモノラウレート、ソルビタンモノステアレート、ソルビタントリオレエートなどのソルビタン高級脂肪酸エステル、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノステアレートなどのポリオキシエチレンソルビタン高級脂肪酸エステル、ポリオキシエチレンモノラウレート、ポリオキシエチレンモノステアレートなどのポリオキシエチレン高級脂肪酸エステル、オレイン酸モノグリセライド、ステアリン酸モノグリセライドなどのグリセリン高級脂肪酸エステル、ポリオキシエチレン・ポリオキシプロピレン・ブロックコポリマー、ポリオキシエチレンジスチレン化フェニルエーテルなどが挙げられる。 Examples of the non-reactive nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, and polyoxyethylene such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether. Solbitan higher fatty acid esters such as alkylphenyl ether, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, poly Polyoxyethylene higher fatty acid esters such as oxyethylene monolaurate and polyoxyethylene monostearate, glycerin higher fatty acid esters such as oleic acid monoglyceride and monoglyceride stearate, polyoxyethylene polyoxypropylene block copolymers, polyoxyethylene di Examples include styrene phenyl ether.
また、反応性界面活性剤は、ラジカル重合が可能な不飽和二重結合を１個以上有するアニオン性界面活性剤またはノニオン性界面活性剤である。
反応性アニオン性界面活性剤は、例えば、主骨格がスルホコハク酸エステル、アルキルエーテル、アルキルフェニルエーテル、アルキルフェニルエステル、（メタ）アクリレート硫酸エステル、リン酸エステルなどであるものが好ましい。
反応性ノニオン性界面活性剤は、例えば、主骨格がアルキルエーテル、アルキルフェニルエーテル、アルキルフェニルエステルなどであるものが好ましい。
The reactive surfactant is an anionic surfactant or a nonionic surfactant having one or more unsaturated double bonds capable of radical polymerization.
The reactive anionic surfactant is preferably one having a main skeleton of, for example, a sulfosuccinic acid ester, an alkyl ether, an alkyl phenyl ether, an alkyl phenyl ester, a (meth) acrylate sulfate ester, a phosphoric acid ester or the like.
The reactive nonionic surfactant is preferably, for example, one having a main skeleton of an alkyl ether, an alkyl phenyl ether, an alkyl phenyl ester or the like.
界面活性剤は、単量体混合物１００質量部に対して、０．１～１０質量部を使用することが好ましく、０．５～５質量部がより好ましい。界面活性剤を適量使用することで重合安定性が向上し、皮膚に対して悪影響を与えにくい。 The surfactant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the monomer mixture. By using an appropriate amount of surfactant, the polymerization stability is improved and it is less likely to have an adverse effect on the skin.
乳化重合には、ラジカル重合開始剤（ 以下、単に「重合開始剤」ともいう） を使用することが好ましい。前記重合開始剤は、公知の油溶性重合開始剤や水溶性重合開始剤を使用することができる。
油溶性開始剤としては、例えば、ベンゾイルパーオキサイド、ｔｅｒｔ－ブチルオキシベンゾエート、ｔｅｒｔ－ブチルハイドロパーオキサイド、ｔｅｒｔ－ブチルパーオキシ－２ －エチルヘキサノエート、ｔｅｒｔ－ブチルパーオキシ－３，５，５－トリメチルヘキサノエート、ジ－ｔｅｒｔ－ブチルパーオキサイド、キュメンハイドロパーオキサイド、ｐ－メンタンハイドロパーオキサイドなどの有機過酸化物、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス－２，４－ジメチルバレロニトリル、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）、１，１’－アゾビス－シクロヘキサン－１－カルボニトリルなどのアゾ化合物が挙げられる。
水溶性重合開始剤としては、例えば、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム、過酸化水素、２，２’－アゾビス（２－メチルプロピオンアミジン）ジハイドロクロライドなどが挙げられる。
For emulsion polymerization, it is preferable to use a radical polymerization initiator (hereinafter, also simply referred to as “polymerization initiator”). As the polymerization initiator, a known oil-soluble polymerization initiator or water-soluble polymerization initiator can be used.
Examples of the oil-soluble initiator include benzoyl peroxide, tert-butyloxybenzoate, tert-butyl hydroperoxide, tert-butylperoxy-2-ethylhexanoate, and tert-butylperoxy-3,5,5. -Organic peroxides such as trimethylhexanoate, di-tert-butyl peroxide, cumenhydroperoxide, p-menthan hydroperoxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis Examples thereof include azo compounds such as -2,4-dimethylvaleronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), and 1,1'-azobis-cyclohexane-1-carbonitrile.
Examples of the water-soluble polymerization initiator include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, 2,2'-azobis (2-methylpropionamidine) dihydrochloride and the like.
重合を実施する際に、重合開始剤とともに還元剤や遷移金属塩を併用することができる。これらを併用することで重合開始剤の分解が促進される。
還元剤としては、例えば、アスコルビン酸、エリソルビン酸、酒石酸、クエン酸、ブドウ糖、ホルムアルデヒドスルホキシラートなどの金属塩などの還元剤有機化合物、亜硫酸ナトリウム、重亜硫酸ナトリウム、メタ重亜硫酸ナトリウム、次亜硫酸ナトリウムなどの還元性無機化合物などが挙げられる。
遷移金属塩としては、例えば、塩化第一鉄、硫酸第一鉄、硫酸銅などが挙げられる。
When carrying out the polymerization, a reducing agent or a transition metal salt can be used in combination with the polymerization initiator. The combined use of these promotes the decomposition of the polymerization initiator.
Examples of the reducing agent include reducing agent organic compounds such as ascorbic acid, erythorbic acid, tartrate acid, citric acid, glucose, and metal salts such as formaldehyde sulfoxylate, sodium sulfite, sodium bisulfite, sodium metabisulfate, and sodium hyposulfate. Examples thereof include reducing inorganic compounds such as.
Examples of the transition metal salt include ferrous chloride, ferrous sulfate, copper sulfate and the like.
本発明における乳化重合には、水溶性重合開始剤を使用することが好ましい。重合開始剤は、単量体混合物１００質量部に対して、０．０３～５質量部を使用することが好ましい。還元剤は、単量体混合物１００質量部に対して、０．０１～２．５質量部を使用することが好ましい。遷移金属塩は、単量体混合物１００質量部に対して、０．０００１～０．００２質量部を使用することが好ましい。重合開始剤の添加方法は、例えば、初期一括仕込み、分割仕込み、連続滴下などが挙げられるが、特に限定されない。また、重合反応の終点を早める観点では、反応系内に単量体を添加する終了前または終了後に、重合開始剤の一部を反応系内に添加しても良い。 It is preferable to use a water-soluble polymerization initiator for the emulsion polymerization in the present invention. It is preferable to use 0.03 to 5 parts by mass of the polymerization initiator with respect to 100 parts by mass of the monomer mixture. It is preferable to use 0.01 to 2.5 parts by mass of the reducing agent with respect to 100 parts by mass of the monomer mixture. It is preferable to use 0.0001 to 0.002 parts by mass of the transition metal salt with respect to 100 parts by mass of the monomer mixture. The method of adding the polymerization initiator includes, for example, initial batch charging, split charging, continuous dropping, and the like, but is not particularly limited. Further, from the viewpoint of accelerating the end point of the polymerization reaction, a part of the polymerization initiator may be added to the reaction system before or after the completion of adding the monomer to the reaction system.
乳化重合の際、必要に応じて、緩衝剤、連鎖移動剤、塩基性化合物などを使用することができる。
緩衝剤としては、例えば、酢酸ナトリウム、クエン酸ナトリウム、重炭酸ナトリウムなどが挙げられる。
連鎖移動剤としては、例えば、ｎ－オクチルメルカプタン、ｎ－ドデシルメルカプタン、ｔｅｒｔ－ドデシルメルカプタン、ラウリルメルカプタン、ステアリルメルカプタン、３－メルカプトプロピオン酸、３－メルカプトプロピオン酸ｎ－オクチル、３－メルカプトプロピオン酸２－エチルヘキシル、チオグリコール酸ｎ－オクチル、チオグリコール酸２－エチルヘキシルなどが挙げられる。これらの中でも、３－メルカプトプロピオン酸２－エチルヘキシル、チオグリコール酸２－エチルヘキシルが好ましく、チオグリコール酸２－エチルヘキシルがより好ましい。
連鎖移動剤は、単量体混合物１００質量部に対して、０．０１～０．１質量部を使用することが好ましい。
塩基性化合物は、中和に使用し、例えば、トリメチルアミン、トリエチルアミン、ｎ－ブチルアミンなどのアルキルアミン、２－ジメチルアミノエタノール、ジエチルアミノエタノール、ジエタノールアミン、トリエタノールアミン、アミノメチルプロパノールなどのアルコールアミン、モルホリン、アンモニアなどが挙げられる。
塩基性化合物は、粘着剤を乾燥させる際の揮発性の観点からアンモニアが好ましい。
At the time of emulsion polymerization, a buffer, a chain transfer agent, a basic compound and the like can be used, if necessary.
Examples of the buffer include sodium acetate, sodium citrate, sodium bicarbonate and the like.
Examples of the chain transfer agent include n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, lauryl mercaptan, stearyl mercaptan, 3-mercaptopropionic acid, 3-mercaptopropionic acid n-octyl, and 3-mercaptopropionic acid 2. -Ethylhexyl, n-octyl thioglycolate, 2-ethylhexyl thioglycolate and the like can be mentioned. Among these, 2-ethylhexyl 3-mercaptopropionic acid and 2-ethylhexyl thioglycolate are preferable, and 2-ethylhexyl thioglycolate is more preferable.
It is preferable to use 0.01 to 0.1 parts by mass of the chain transfer agent with respect to 100 parts by mass of the monomer mixture.
Basic compounds are used for neutralization, for example, alkylamines such as trimethylamine, triethylamine, n-butylamine, alcoholamines such as 2-dimethylaminoethanol, diethylaminoethanol, diethanolamine, triethanolamine, aminomethylpropanol, morpholine, etc. Examples include ammonia.
The basic compound is preferably ammonia from the viewpoint of volatility when the pressure-sensitive adhesive is dried.
乳化重合の方法は、例えば、反応槽に単量体、界面活性剤、水を全て仕込み、反応させるバッチ反応、単量体を徐々に反応槽に滴下して反応させる滴下反応などが挙げられる。これらの中でも、重合反応の発熱を制御しやすい観点で滴下反応が好ましい。また、滴下反応は、重合安定性をより向上させるために、単量体、水、界面活性剤を混合撹拌し、乳化状態にしたプレエマルジョンを形成してから滴下することが好ましい。 Examples of the method of emulsion polymerization include a batch reaction in which a monomer, a surfactant, and water are all charged into a reaction vessel and reacted, and a dropping reaction in which the monomer is gradually dropped into a reaction vessel and reacted. Among these, the dropping reaction is preferable from the viewpoint of easily controlling the heat generation of the polymerization reaction. Further, in the dropping reaction, in order to further improve the polymerization stability, it is preferable that the monomer, water and the surfactant are mixed and stirred to form an emulsified pre-emulsion and then dropped.
乳化重合によって得られる場合の共重合体（１）の平均粒子径は、粘着剤の機械安定性を向上させる観点から、好ましくは５０ｎｍ以上、より好ましくは８０ｎｍ以上、さらに好ましくは１００ｎｍ以上であり、接着力の優れた粘着剤を得る観点から、好ましくは４００ｎｍ以下、より好ましくは３５０ｎｍ以下、さらに好ましくは３００ｎｍ以下である。
なお、平均粒子径は、動的光散乱測定法を使用したＤ５０平均粒子径であり、測定方法の例としては、ポリマー粒子の水分散体を水で５００倍に希釈した希釈液を作成し、当該希釈液を約５ｍＬ使用してナノトラック（日機装社製）で測定できる。
The average particle size of the copolymer (1) obtained by emulsion polymerization is preferably 50 nm or more, more preferably 80 nm or more, still more preferably 100 nm or more, from the viewpoint of improving the mechanical stability of the pressure-sensitive adhesive. From the viewpoint of obtaining a pressure-sensitive adhesive having excellent adhesive strength, it is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less.
The average particle size is the D50 average particle size using the dynamic light scattering measurement method. As an example of the measurement method, a diluted solution obtained by diluting an aqueous dispersion of polymer particles with water 500 times was prepared. It can be measured with Nanotrack (manufactured by Nikkiso Co., Ltd.) using about 5 mL of the diluted solution.
共重合体（１）のゲル分率は、優れた接着力を有する粘着剤を得る観点から、４５質量％以下が好ましく、１～３０質量％がより好ましい。
ゲル分率の調整は、単量体の組成、重合開始剤の種類およびその量、連鎖移動剤の種類およびその量、重合温度等により制御することができる。
なお、ゲル分率は、共重合体（１）をＴＨＦ（テトラヒドロフラン）に５０℃で７２時間浸漬させた場合の不溶分の比率である。
The gel fraction of the copolymer (1) is preferably 45% by mass or less, more preferably 1 to 30% by mass, from the viewpoint of obtaining a pressure-sensitive adhesive having excellent adhesive strength.
The adjustment of the gel fraction can be controlled by the composition of the monomer, the type and amount of the polymerization initiator, the type and amount of the chain transfer agent, the polymerization temperature and the like.
The gel fraction is the ratio of the insoluble fraction when the copolymer (1) is immersed in THF (tetrahydrofuran) at 50 ° C. for 72 hours.
＜任意成分＞
本発明の皮膚貼付用粘着剤は、課題が解決できる範囲であれば、任意成分として体質顔料、増粘剤、保湿剤、防腐剤、溶剤、消泡剤などの添加剤を含むことができる。
体質顔料としては、例えば、タルク、シリカ、炭酸カルシウム、硫酸バリウム、酸化チタン、珪藻土などが挙げられる。
増粘剤としては、例えば、アルカリ膨潤型増粘剤、会合性ポリウレタン、カルボキシビニルポリマー、増粘性多糖類、粘土鉱物などが挙げられる。
保湿剤としては、例えば、ソルビトール、キシリトール、プロピレングリコール、ジプロピレングリコール、１，３－ブチレングリコール、グリセリン、ジグリセリン、ポリエチレングリコール、ヒアルロン酸、コンドロイチン硫酸、ピロリドンカルボン酸塩、ＤＬ－ピロリドンカルボン酸塩などが挙げられる。
防腐剤としては、例えば、パラオキシ安息香酸メチル、パラオキシ安息香酸エチル、パラオキシ安息香酸プロピル、パラオキシ安息香酸ブチル、安息香酸、安息香酸ナトリウム、ソルビン酸、ソルビン酸カリウム、フェノキシエタノール、４－ヒドロキシアセトフェノン、デヒドロ酢酸、カプリリルグリコール、ペンチレングリコールなどが挙げられる。
消泡剤としては、例えば、シリコーン系消泡剤、鉱物油系消泡剤などが挙げられる。
<Arbitrary ingredient>
The pressure-sensitive adhesive for skin application of the present invention may contain additives such as extender pigments, thickeners, moisturizers, preservatives, solvents, and defoamers as optional components as long as the problems can be solved.
Examples of the extender pigment include talc, silica, calcium carbonate, barium sulfate, titanium oxide, diatomaceous earth and the like.
Examples of the thickener include alkaline swelling type thickeners, associative polyurethanes, carboxyvinyl polymers, thickening polysaccharides, clay minerals and the like.
Examples of the moisturizing agent include sorbitol, xylitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glycerin, diglycerin, polyethylene glycol, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, and DL-pyrrolidone carboxylate. And so on.
Examples of preservatives include methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, 4-hydroxyacetophenone, and dehydroacetic acid. , Caprylyl glycol, pentylene glycol and the like.
Examples of the defoaming agent include silicone-based defoaming agents and mineral oil-based defoaming agents.
≪皮膚貼付用シート≫
本発明の皮膚貼付用シートは、基材と、皮膚貼付用粘着剤から形成されてなる粘着層を備える。
基材は、例えば、プラスチックフィルム（ポリエチレン、ポリプロピレン、エチレン／酢酸ビニル共重合体、ポリスチレン、ポリエステル、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリウレタン、ポリアミドなどが挙げられる。
基材の厚さは、特に限定されないが通常２０～１０００μｍであり、柔軟性と強度を兼ね備えるという観点からは２５～５００μｍが好ましい。
≪Skin sticking sheet≫
The skin-sticking sheet of the present invention comprises a base material and an adhesive layer formed of a skin-sticking pressure-sensitive adhesive.
Examples of the base material include plastic films (polyethylene, polypropylene, ethylene / vinyl acetate copolymer, polystyrene, polyester, polyvinyl chloride, polyvinylidene chloride, polyurethane, polyamide and the like.
The thickness of the base material is not particularly limited, but is usually 20 to 1000 μm, and is preferably 25 to 500 μm from the viewpoint of having both flexibility and strength.
粘着層の形成は、基材上に粘着剤を塗工して形成する方法や、剥離シート上に粘着剤を塗工して形成した粘着層を基材に転写する方法が一般的である。なお、粘着層の基材と接しない面には剥離シートを貼り合わせて保管するのが通常である。 Generally, the pressure-sensitive adhesive layer is formed by applying an adhesive on the base material or transferring the pressure-sensitive adhesive layer formed by applying the pressure-sensitive adhesive on a release sheet to the base material. In addition, it is usual to attach a release sheet to the surface of the adhesive layer that does not come into contact with the base material and store it.
粘着剤の塗工方法は、例えば、スピンコート法、スプレーコート法、バーコート法、ナイフコート法、ロールコート法、ロールナイフコート法、ブレードコート法、ダイコート法、グラビアコート法などの公知の塗工方法を使用できる。また、塗工に際して、乾燥工程を行うことも好ましい。乾燥工程は、熱風オーブン、電気オーブン、赤外線ヒーターなどの装置を使用することができる。また、常温静置で乾燥させてもよい。
粘着層の厚さは、接着性と剥離性の両立という観点から通常１０～１００ｇ／ｍ２程度であり、２０～５０ｇ／ｍ２がより好ましい。
As a method for applying the adhesive, known coating methods such as spin coating method, spray coating method, bar coating method, knife coating method, roll coating method, roll knife coating method, blade coating method, die coating method, and gravure coating method are used. The construction method can be used. It is also preferable to perform a drying step at the time of coating. In the drying process, devices such as a hot air oven, an electric oven, and an infrared heater can be used. Further, it may be dried by allowing it to stand at room temperature.
The thickness of the adhesive layer is usually about 10 to 100 g / m 2 from the viewpoint of achieving both adhesiveness and peelability, and more preferably 20 to 50 g / m 2 .
本発明の皮膚貼付用粘着剤および皮膚貼付用シートは、例えば、電極貼付粘着剤、パップ剤、プラスター剤などの医療用粘着剤、アイメイク用、かつらやウィッグのずれ防止用、特殊メイクにおけるしわの作製用などの化粧料用粘着剤など、様々な用途に適用できる。 The skin-sticking adhesive and the skin-sticking sheet of the present invention are, for example, medical adhesives such as electrode-sticking adhesives, poultices, and plasters, for eye makeup, for preventing wigs and wigs from slipping, and for wrinkles in special makeup. It can be applied to various uses such as adhesives for cosmetics such as those for making wigs.
以下の実施例により、本発明をさらに詳細に説明するが、本発明は、かかる実施例のみに限定されるものではない。なお、特に断りのない限り、「部」は「質量部」、「％」は「質量％」を意味する。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to such examples. Unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".
＜実施例１＞
還流冷却管、滴下ロート、攪拌機、温度計、窒素ガス導入管、原料投入口を具備するフラスコ内に、イオン交換水１６部を仕込み、窒素ガス導入下で撹拌しながら、液温を８０℃に加熱した。
炭素数１～３のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ａ）として、メチルメタクリレート１０部、炭素数４～６のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ｂ－１）として、ｎ－ブチルアクリレート３部、炭素数７～１２のアルキル基を有する(メタ)アクリル酸アルキルエステル（Ｂ－２）として、２－エチルヘキシルアクリレート８５部、エチレン性不飽和カルボン酸として、メタクリル酸２部、界面活性剤として、エマール０（花王社製、ラウリル硫酸ナトリウム）の１０％水溶液１１．９部、連鎖移動剤として、チオグリコール酸２－エチルヘキシル０．０６部、イオン交換水１６部を混合してプレエマルジョンを調製し、滴下ロートに仕込んだ。
フラスコ内に、エマール０の１０％水溶液０．１部、プレエマルジョンの５％である６．４部を添加した。そして、重合開始剤として、過硫酸カリウムの５％水溶液１０部をフラスコ内に添加後、滴下ロートからプレエマルジョンの残部を１８０分かけて連続的に滴下し、８０℃に保ちながら乳化重合を行った。滴下終了後、８０℃を維持しながら、２１０分間撹拌を継続することで共重合体（１）を得た。
その後、５０℃まで冷却し、２５％アンモニア水で中和した後、１８０メッシュのポリエステル製の濾布で濾過することで、皮膚貼付用粘着剤を得た。
<Example 1>
16 parts of ion-exchanged water is placed in a flask equipped with a reflux condenser, a dropping funnel, a stirrer, a thermometer, a nitrogen gas introduction tube, and a raw material input port, and the liquid temperature is raised to 80 ° C. while stirring under the introduction of nitrogen gas. Heated.
As the (meth) acrylic acid alkyl ester (A) having an alkyl group having 1 to 3 carbon atoms, as the (meth) acrylic acid alkyl ester (B-1) having 10 parts of methyl methacrylate and an alkyl group having 4 to 6 carbon atoms. , N-butyl acrylate 3 parts, 2-ethylhexyl acrylate 85 parts as a (meth) acrylic acid alkyl ester (B-2) having an alkyl group having 7 to 12 carbon atoms, methacrylic acid 2 as an ethylenically unsaturated carboxylic acid. 11.9 parts of a 10% aqueous solution of Emar 0 (manufactured by Kao, sodium lauryl sulfate) as a surfactant, 0.06 parts of 2-ethylhexyl thioglycolate as a chain transfer agent, and 16 parts of ion-exchanged water are mixed. Then, a pre-emulsion was prepared and charged into a dropping funnel.
To the flask, 0.1 part of a 10% aqueous solution of Emar 0 and 6.4 parts of 5% of the pre-emulsion were added. Then, as a polymerization initiator, 10 parts of a 5% aqueous solution of potassium persulfate is added into the flask, and then the rest of the preemulsion is continuously dropped from the dropping funnel over 180 minutes to carry out emulsion polymerization while keeping the temperature at 80 ° C. rice field. After completion of the dropping, the copolymer (1) was obtained by continuing stirring for 210 minutes while maintaining 80 ° C.
Then, the mixture was cooled to 50 ° C., neutralized with 25% aqueous ammonia, and filtered through a 180 mesh polyester filter cloth to obtain a skin-adhesive adhesive.
＜実施例２～１８、比較例１～２＞
表１、表２に示す配合組成および配合量（質量部）に変更した以外は、実施例１と同様の方法で行うことで、実施例２～１８、比較例１～２の皮膚貼付用粘着剤を得た。
<Examples 2 to 18, Comparative Examples 1 to 2>
Adhesive for skin application of Examples 2 to 18 and Comparative Examples 1 to 2 by the same method as in Example 1 except that the composition and the amount (parts by mass) shown in Tables 1 and 2 were changed. I got the agent.
得られた皮膚貼付用粘着剤について、以下の方法でゲル分率、皮膚貼付した際の接着性および剥離性を評価した。 The obtained adhesive for skin application was evaluated for gel fraction, adhesiveness and peelability when applied to the skin by the following method.
＜ゲル分率＞
得られた皮膚貼付用粘着剤をシリコン容器の枠型に流し込み、４０℃で９６時間乾燥させた（片面４８時間）。得られた乾燥塗膜の一部を使用し、ＴＨＦ（テトラヒドロフラン）に５０℃で７２時間浸漬させ、不溶分を測定した。なお、不溶分は以下の式より算出した。
ゲル分率（％）＝（ＴＨＦ浸漬後の不溶分の乾燥質量／乾燥塗膜の質量）×１００
<Gel fraction>
The obtained adhesive for skin application was poured into a frame of a silicon container and dried at 40 ° C. for 96 hours (48 hours on one side). A part of the obtained dry coating film was used and immersed in THF (tetrahydrofuran) at 50 ° C. for 72 hours, and the insoluble content was measured. The insoluble matter was calculated from the following formula.
Gel fraction (%) = (dry mass of insoluble matter after THF immersion / mass of dry coating film) x 100
得られた粘着剤を２５μｍＰＥＴフィルム（東レ社製、ルミラーＳ１０）にアプリケーターにて乾燥質量が２５ｇ／ｍ２となるように塗布し、１００℃で２分間加熱乾燥した。次に、塗工面に剥離フィルムとしてＮＳセパレーターＺ（中本パックス社製）を貼付し、粘着シートを作製した。 The obtained adhesive was applied to a 25 μm PET film (Toray Industries, Inc., Lumirer S10) with an applicator so that the dry mass was 25 g / m 2 , and the mixture was heated and dried at 100 ° C. for 2 minutes. Next, NS Separator Z (manufactured by Nakamoto Pax Co., Ltd.) was attached as a release film to the coated surface to prepare an adhesive sheet.
＜皮膚貼付評価＞
得られた粘着シートを直径１０ｍｍの円形状に切り取り、剥離フィルムを除去してパッチとし、このパッチを被験者５名の前腕内側に８時間貼り付けた。８時間後に人差し指でパッチをずらせるかを試験した後、剥離した。この時の接着性と剥離性の評価基準は以下の通りである。なお、いずれの評点も５人の内、最高点および最低点を記録した２人を除外した３人の平均点を評価結果とした。実用可能レベルはいずれも２．５以上である。
<Skin application evaluation>
The obtained adhesive sheet was cut into a circular shape having a diameter of 10 mm, the release film was removed to obtain a patch, and this patch was attached to the inside of the forearms of 5 subjects for 8 hours. After 8 hours, it was tested whether the patch was displaced with the index finger, and then peeled off. The evaluation criteria for adhesiveness and peelability at this time are as follows. In addition, the average score of 3 persons excluding the 2 persons who recorded the highest score and the lowest score among the 5 persons was used as the evaluation result. Practical levels are all 2.5 or higher.
［接着性］
５：８時間の間安定的に接着しており、指でパッチをずらすことは出来ない。
４：８時間の間安定的に接着しているが、強い力を使うと指でパッチが動く。
３：８時間の間安定的に接着しているが、弱い力で指でパッチが動く。
２：４時間以上８時間未満の間で剥離してしまう。
１：貼付直後～４時間未満の間で剥離してしまう。
[Adhesiveness]
It adheres stably for 5: 8 hours, and the patch cannot be shifted with a finger.
It adheres stably for 4: 8 hours, but if you use strong force, the patch will move with your finger.
It adheres stably for 3: 8 hours, but the patch moves with a weak force.
2: It peels off within 4 hours or more and less than 8 hours.
1: It peels off immediately after application to less than 4 hours.
［剥離性］
５：皮膚への糊残りが全く無く、痛みも無い。
４：皮膚への糊残りが全く無いが、軽微な痛みがある。
３：皮膚への糊残りが全く無いが、かなり痛む。
２：皮膚への糊残りがパッチ面積の３０％未満ある。
１：皮膚への糊残りがパッチ面積の３０％以上ある。
[Removability]
5: There is no adhesive residue on the skin and there is no pain.
4: There is no adhesive residue on the skin, but there is slight pain.
3: There is no adhesive residue on the skin, but it hurts considerably.
2: The adhesive residue on the skin is less than 30% of the patch area.
1: The adhesive residue on the skin is 30% or more of the patch area.
表中の略号は以下の通りである。
ＭＭＡ：メチルメタクリレート
ＢＡ：ｎ－ブチルアクリレート
ＢＭＡ：ｎ－ブチルメタクリレート
２ＥＨＡ：２－エチルヘキシルアクリレート
ＯＡ：ｎ－オクチルアクリレート
ＭＡＡ：メタクリル酸
ＡＡ：アクリル酸
ＯＴＧ：チオグリコール酸２－エチルヘキシル
The abbreviations in the table are as follows.
MMA: Methyl methacrylate BA: n-butyl acrylate BMA: n-butyl methacrylate 2EHA: 2-ethylhexyl acrylate OA: n-octyl acrylate MAA: Methacrylic acid AA: Acrylic acid OTG: Thioglycolic acid 2-ethylhexyl
表１、２の結果より、実施例１～１８は、接着力が高く、接着性と剥離性を両立している。
そのため、比較例１～２では得られない優れた皮膚貼付用粘着剤である。
このように、剥離性に関し、皮膚への糊残り性がない、という優れた効果を有していることから、化粧料用としても、好適に用いることができることが確認できた。
From the results of Tables 1 and 2, Examples 1 to 18 have high adhesive strength and have both adhesiveness and peelability.
Therefore, it is an excellent adhesive for skin application that cannot be obtained in Comparative Examples 1 and 2.
As described above, it has been confirmed that it can be suitably used for cosmetics because it has an excellent effect of having no adhesive residue on the skin in terms of peelability.
Claims (7)
A skin-sticking sheet comprising a base material and an adhesive layer formed of the skin-sticking adhesive according to any one of claims 1 to 6.
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| JP2020152303A JP2022046324A (en) | 2020-09-10 | 2020-09-10 | Adhesive for skin application, and sheet for skin application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102022126963A1 (en) | 2021-10-29 | 2023-05-04 | Shimano Inc. | CONTROL DEVICE |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102022126963A1 (en) | 2021-10-29 | 2023-05-04 | Shimano Inc. | CONTROL DEVICE |
| DE102022126962A1 (en) | 2021-10-29 | 2023-05-04 | Shimano Inc. | CONTROL DEVICE |
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