JP6607330B1 - Adhesive and adhesive sheet - Google Patents
Adhesive and adhesive sheet Download PDFInfo
- Publication number
- JP6607330B1 JP6607330B1 JP2019061270A JP2019061270A JP6607330B1 JP 6607330 B1 JP6607330 B1 JP 6607330B1 JP 2019061270 A JP2019061270 A JP 2019061270A JP 2019061270 A JP2019061270 A JP 2019061270A JP 6607330 B1 JP6607330 B1 JP 6607330B1
- Authority
- JP
- Japan
- Prior art keywords
- mass
- monomer
- adhesive
- meth
- antioxidant
- 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.)
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 60
- 239000000853 adhesive Substances 0.000 title claims abstract description 59
- 239000000178 monomer Substances 0.000 claims abstract description 114
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 44
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 32
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 125000000524 functional group Chemical group 0.000 claims abstract description 21
- 229920001577 copolymer Polymers 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 230000009477 glass transition Effects 0.000 claims abstract description 6
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 39
- 229920001519 homopolymer Polymers 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000012790 adhesive layer Substances 0.000 claims description 5
- 230000009257 reactivity Effects 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 28
- 229940048053 acrylate Drugs 0.000 description 28
- -1 2-ethylhexyl Chemical group 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 150000003254 radicals Chemical class 0.000 description 16
- 239000002904 solvent Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 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 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229940114077 acrylic acid Drugs 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- SJPFBRJHYRBAGV-UHFFFAOYSA-N n-[[3-[[bis(oxiran-2-ylmethyl)amino]methyl]phenyl]methyl]-1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC=1C=C(CN(CC2OC2)CC2OC2)C=CC=1)CC1CO1 SJPFBRJHYRBAGV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000008096 xylene Substances 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
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- CDDDRVNOHLVEED-UHFFFAOYSA-N 1-cyclohexyl-3-[1-[[1-(cyclohexylcarbamoylamino)cyclohexyl]diazenyl]cyclohexyl]urea Chemical compound C1CCCCC1(N=NC1(CCCCC1)NC(=O)NC1CCCCC1)NC(=O)NC1CCCCC1 CDDDRVNOHLVEED-UHFFFAOYSA-N 0.000 description 1
- UALKQROXOHJHFG-UHFFFAOYSA-N 1-ethoxy-3-methylbenzene Chemical compound CCOC1=CC=CC(C)=C1 UALKQROXOHJHFG-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- OZDGMOYKSFPLSE-UHFFFAOYSA-N 2-Methylaziridine Chemical compound CC1CN1 OZDGMOYKSFPLSE-UHFFFAOYSA-N 0.000 description 1
- VUDVPVOIALASLB-UHFFFAOYSA-N 2-[(2-cyano-1-hydroxypropan-2-yl)diazenyl]-3-hydroxy-2-methylpropanenitrile Chemical compound OCC(C)(C#N)N=NC(C)(CO)C#N VUDVPVOIALASLB-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
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-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
- VGZZAZYCLRYTNQ-UHFFFAOYSA-N 2-ethoxyethoxycarbonyloxy 2-ethoxyethyl carbonate Chemical compound CCOCCOC(=O)OOC(=O)OCCOCC VGZZAZYCLRYTNQ-UHFFFAOYSA-N 0.000 description 1
- MSXXDBCLAKQJQT-UHFFFAOYSA-N 2-tert-butyl-6-methyl-4-[3-(2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxypropyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCCOP2OC3=C(C=C(C=C3C=3C=C(C=C(C=3O2)C(C)(C)C)C(C)(C)C)C(C)(C)C)C(C)(C)C)=C1 MSXXDBCLAKQJQT-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
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Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
【課題】粘着力が低すぎず適度な粘着力を有しながら剥離時の引っかかり（ジッピング現象）を抑制し、更には高温、高湿熱下に曝された後においても再剥離性に優れる粘着剤を提供すること。【解決手段】ガラス転移温度（Ｔｇ）が−６６〜−５２℃であり、かつアルキル基の炭素数が８である（メタ）アクリル酸アルキルエステルモノマー（ａ１）、および反応性官能基を有するモノマー（ａ２）を含むラジカル重合性モノマー混合物の共重合体であるアクリル系共重合体（Ａ）と、硬化剤（Ｂ）と、リン系酸化防止剤を含む酸化防止剤（Ｃ）とを含み、前記反応性官能基を有するモノマー（ａ２）の含有量は、前記ラジカル重合性モノマー混合物１００質量％中、０を超えて１０質量％以下であり、前記リン系酸化防止剤の含有量は、前記アクリル系共重合体（Ａ）１００質量部に対して、０．１５〜１．５質量部である、粘着剤により解決される。【選択図】 なしThe present invention relates to an adhesive that suppresses catching at the time of peeling (zipping phenomenon) while having an appropriate adhesive strength without being too low, and is excellent in removability even after being exposed to high temperature and high humidity To provide. A (meth) acrylic acid alkyl ester monomer (a1) having a glass transition temperature (Tg) of −66 to −52 ° C. and an alkyl group having 8 carbon atoms, and a monomer having a reactive functional group An acrylic copolymer (A) that is a copolymer of a radical polymerizable monomer mixture containing (a2), a curing agent (B), and an antioxidant (C) containing a phosphorus antioxidant, The content of the monomer (a2) having a reactive functional group is more than 0 and 10% by mass or less in 100% by mass of the radical polymerizable monomer mixture, and the content of the phosphorus antioxidant is It is solved by an adhesive that is 0.15 to 1.5 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A). [Selection figure] None
Description
本発明は、粘着剤および粘着シートに関する。 The present invention relates to an adhesive and an adhesive sheet.
粘着剤として各樹脂系のものがあり、中でもアクリル系が広く用いられている。アクリル系粘着剤は、粘着力やタックといった粘着基本性能の制御がモノマー組成や相溶する添加剤の調整により容易であるメリットがあり、一度貼りつけたら剥がすことの無い強粘着力が必要なものから貼付後一定期間後に剥がす必要がある再剥離用途まで多岐にわたる用途において用いられている。なかでも再剥離用途においては従来から市場ニーズがあったが、近年では適度な粘着力を保持しながらより過酷な環境に曝されても大幅な粘着力の上昇がなく糊残りが発生しないことを要求されることが多くなってきている。
特許文献１では、ガラス転移温度が−４５℃以下のアクリル酸エステル共重合体とシトレート系可塑剤を含有した粘着層を有し、粘着剤層のゲル分率が７０％以上であることを特徴とする粘着シートが開示されている。ここでは室温における再剥離性は有しているが、高温、高湿熱のような過酷な環境に曝された場合に粘着力が上昇する、また、室温時の粘着力が低いため曲面などに貼り合わせした際に剥がれが発生しやすい問題があった。
There are various resin-based pressure-sensitive adhesives, among which acrylic is widely used. Acrylic adhesives have the advantage that control of basic adhesive performance such as adhesive strength and tack is easy by adjusting the monomer composition and compatible additives, and require strong adhesive strength that does not peel off once applied To re-peeling applications that need to be peeled off after a certain period after application. In particular, there has been a market need for re-peeling applications, but in recent years there has been no significant increase in adhesive strength and no adhesive residue even when exposed to harsh environments while maintaining moderate adhesive strength. There is an increasing demand.
Patent Document 1 has a pressure-sensitive adhesive layer containing an acrylic ester copolymer having a glass transition temperature of −45 ° C. or lower and a citrate plasticizer, and the gel fraction of the pressure-sensitive adhesive layer is 70% or more. An adhesive sheet is disclosed. Here, it has removability at room temperature, but the adhesive strength increases when exposed to harsh environments such as high temperature and high humidity, and the adhesive strength at room temperature is low. There was a problem that peeling occurred easily when they were put together.
本発明が解決しようとする課題は、粘着力が低すぎず適度な粘着力を有しながら剥離時の引っかかり（ジッピング現象）を抑制し、更には高温、高湿熱下に曝された後においても再剥離性に優れる粘着剤を提供することである。 The problem to be solved by the present invention is that the adhesive force is not too low and has an appropriate adhesive force to suppress catching at the time of peeling (zipping phenomenon), and even after being exposed to high temperature and high humidity heat. It is to provide an adhesive having excellent removability.
本発明者らは上記課題を解決すべく鋭意検討を重ねた結果、本発明を完成するに至った。
即ち、本発明の実施態様は、アクリル系共重合体（Ａ）と硬化剤（Ｂ）と酸化防止剤（Ｃ）とを含む粘着剤であって、前記アクリル系共重合体（Ａ）は、ガラス転移温度（Ｔｇ）が−６６〜−５２℃であり、かつ前記アクリル系共重合体（Ａ）は、アルキル基の炭素数が８である（メタ）アクリル酸アルキルエステルモノマー（ａ１）、および反応性官能基を有するモノマー（ａ２）を含むラジカル重合性モノマー混合物の共重合体であり、前記反応性官能基を有するモノマー（ａ２）の含有量は、前記ラジカル重合性モノマー混合物１００質量％中、０を超えて１０質量％以下であり、
前記酸化防止剤（Ｃ）はリン系酸化防止剤を含み、前記リン系酸化防止剤の含有量は、前記アクリル系共重合体（Ａ）１００質量部に対して、０．１５〜１．５質量部である、粘着剤である。
As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, an embodiment of the present invention is an adhesive containing an acrylic copolymer (A), a curing agent (B), and an antioxidant (C), wherein the acrylic copolymer (A) (Meth) acrylic acid alkyl ester monomer (a1) having a glass transition temperature (Tg) of −66 to −52 ° C. and the acrylic copolymer (A) having an alkyl group with 8 carbon atoms, and It is a copolymer of a radical polymerizable monomer mixture containing a monomer (a2) having a reactive functional group, and the content of the monomer (a2) having a reactive functional group is 100% by mass in the radical polymerizable monomer mixture. , More than 0 and 10% by mass or less,
The antioxidant (C) contains a phosphorus antioxidant, and the content of the phosphorus antioxidant is 0.15 to 1.5 with respect to 100 parts by mass of the acrylic copolymer (A). It is an adhesive which is a mass part.
また、本発明の実施態様は、さらにホモポリマーのＴｇが−４５℃以上であるラジカル重合性モノマー（ａ３）（ただし、アルキル基の炭素数が８である（メタ）アクリル酸アルキルエステルモノマー（ａ１）、および反応性官能基を有するモノマー（ａ２）である場合を除く）を含む、上記粘着剤である。 In addition, the embodiment of the present invention further includes a radical polymerizable monomer (a3) having a Tg of homopolymer of −45 ° C. or higher (however, a (meth) acrylic acid alkyl ester monomer having an alkyl group having 8 carbon atoms (a1) ), And the monomer (a2) having a reactive functional group)).
また、本発明の実施態様は、前記反応性官能基を有するモノマー（ａ２）が、水酸基を有するモノマーを含む、上記粘着剤である。 Moreover, the embodiment of the present invention is the pressure-sensitive adhesive, wherein the monomer (a2) having a reactive functional group includes a monomer having a hydroxyl group.
また、本発明の実施態様は、前記酸化防止剤（Ｃ）が、２５℃で液状のリン系酸化防止剤を含む、上記粘着剤である。 Moreover, the embodiment of the present invention is the pressure-sensitive adhesive, wherein the antioxidant (C) contains a phosphorus-based antioxidant that is liquid at 25 ° C.
また、本発明の実施態様は、基材および請求項１〜４いずれか１項記載の粘着剤から形成されてなる粘着剤層を備える粘着シートである。 Moreover, the embodiment of this invention is an adhesive sheet provided with the adhesive layer formed from a base material and the adhesive of any one of Claims 1-4.
本発明の粘着剤は、粘着力が低すぎず適度な粘着力を有しながら剥離時の引っかかり（ジッピング現象）を抑制し、更には高温、高湿熱下に曝された後においても再剥離性に優れる。 The pressure-sensitive adhesive of the present invention suppresses catching (zipping phenomenon) at the time of peeling while having an appropriate pressure-sensitive adhesive strength, and further has a removability even after being exposed to high temperature and high humidity heat. Excellent.
以下、本発明の詳細を説明する。なお、本明細書では、「（メタ）アクリル酸」、「（メタ）アクリレート」と表記した場合には、特に説明がない限り、それぞれ、「アクリル酸またはメタクリル酸」、「アクリレートまたはメタクリレート」を表すものとする。「アルキル基の炭素数が８である（メタ）アクリル酸アルキルエステルモノマー（ａ１）、および反応性官能基を有するモノマー（ａ２）を０を超えて１０質量％以下、を含んだラジカル重合性モノマー混合物の共重合体であるアクリル系共重合体（Ａ）」は、「アクリル系共重合体（Ａ）」と略記することがある。また、「部」および「％」は、特に断りのない限り、それぞれ「質量部」および「質量％」を表す。 Details of the present invention will be described below. In the present specification, when expressed as “(meth) acrylic acid” and “(meth) acrylate”, “acrylic acid or methacrylic acid” and “acrylate or methacrylate” are respectively referred to unless otherwise specified. It shall represent. “Radically polymerizable monomer containing (meth) acrylic acid alkyl ester monomer (a1) having 8 carbon atoms in alkyl group and monomer (a2) having a reactive functional group in excess of 0 to 10% by mass or less The “acrylic copolymer (A)” which is a copolymer of the mixture may be abbreviated as “acrylic copolymer (A)”. Further, “parts” and “%” represent “parts by mass” and “% by mass”, respectively, unless otherwise specified.
≪粘着剤≫
本発明の粘着剤は、アクリル系共重合体（Ａ）と硬化剤（Ｂ）と酸化防止剤（Ｃ）とを含む粘着剤であって、前記アクリル系共重合体（Ａ）は、ガラス転移温度（Ｔｇ）が−６６〜−５２℃であり、かつ前記アクリル系共重合体（Ａ）は、アルキル基の炭素数が８である（メタ）アクリル酸アルキルエステルモノマー（ａ１）、および反応性官能基を有するモノマー（ａ２）を含むラジカル重合性モノマー混合物の共重合体であり、前記反応性官能基を有するモノマー（ａ２）の含有量は、前記ラジカル重合性モノマー混合物１００質量％中、０を超えて１０質量％以下であり、
前記酸化防止剤（Ｃ）はリン系酸化防止剤を含み、前記リン系酸化防止剤の含有量は、前記アクリル系共重合体（Ａ）１００質量部に対して、０．１５〜１．５質量部である。
≪Adhesives≫
The pressure-sensitive adhesive of the present invention is a pressure-sensitive adhesive containing an acrylic copolymer (A), a curing agent (B), and an antioxidant (C), and the acrylic copolymer (A) has a glass transition. (Meth) acrylic acid alkyl ester monomer (a1) having a temperature (Tg) of −66 to −52 ° C., and the acrylic copolymer (A) having an alkyl group with 8 carbon atoms, and reactivity It is a copolymer of a radical polymerizable monomer mixture containing a monomer (a2) having a functional group, and the content of the monomer (a2) having a reactive functional group is 0 in 100% by mass of the radical polymerizable monomer mixture. Exceeding 10 mass%,
The antioxidant (C) contains a phosphorus antioxidant, and the content of the phosphorus antioxidant is 0.15 to 1.5 with respect to 100 parts by mass of the acrylic copolymer (A). Part by mass.
＜アクリル系共重合体（Ａ）＞
アクリル系共重合体（Ａ）は、ガラス転移温度（Ｔｇ）が−６６〜−５２℃であり、共重合体を構成するラジカル重合性モノマーとして下記（ａ１）、（ａ２）を含むラジカル重合性モノマー混合物の共重合体である。また、前記反応性官能基を有するモノマー（ａ２）の含有量は、前記ラジカル重合性モノマー混合物１００質量％中、０を超えて１０質量％以下である。共重合体を構成するモノマーとして、さらに下記（ａ３）およびその他モノマーを含んでもよい。
（ａ１）アルキル基の炭素数が８である（メタ）アクリル酸アルキルエステルモノマー
（ａ２）反応性官能基を有するモノマー
（ａ３）ホモポリマーのＴｇが−４５℃以上であるラジカル重合性モノマー
<Acrylic copolymer (A)>
The acrylic copolymer (A) has a glass transition temperature (Tg) of −66 to −52 ° C., and includes the following (a1) and (a2) as radically polymerizable monomers constituting the copolymer. It is a copolymer of a monomer mixture. Moreover, content of the monomer (a2) which has the said reactive functional group is more than 0 and 10 mass% or less in 100 mass% of the said radically polymerizable monomer mixture. As a monomer constituting the copolymer, the following (a3) and other monomers may be further included.
(A1) (meth) acrylic acid alkyl ester monomer having an alkyl group having 8 carbon atoms (a2) monomer having a reactive functional group (a3) radical polymerizable monomer having a homopolymer Tg of −45 ° C. or more
なお、本発明においてアクリル系共重合体（Ａ）のＴｇは、下記式（１）（Ｆｏｘ式）に基づいて計算された値であり、Ｔｇ（単位：℃）＝Ｔｇ（単位：Ｋ）−２７３とする。
１／Ｔｇ＝Ｗ１／Ｔｇ１＋Ｗ２／Ｔｇ２＋・・・＋Ｗｎ／Ｔｇｎ （１）
［式（１）中、Ｔｇは（メタ）アクリル系共重合体（Ａ）のＴｇ（単位：Ｋ）、Ｔｇｉ（ｉ＝１、２、・・・ｎ）はラジカル重合性モノマーｉがホモポリマーを形成した際のＴｇ（単位：Ｋ）、Ｗｉ（ｉ＝１、２、・・・ｎ）はラジカル重合性モノマーｉの全モノマー成分中の質量分率を表す。なお、ホモポリマーのＴｇは文献値やカタログ値などの公表値を使用する。]
上記式（１）は、アクリル系共重合体（Ａ）が、モノマー１、モノマー２、・・・、モノマーｎのｎ種類のモノマー成分から構成される場合の計算式である。
In the present invention, the Tg of the acrylic copolymer (A) is a value calculated based on the following formula (1) (Fox formula), and Tg (unit: ° C.) = Tg (unit: K) − 273.
1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wn / Tgn (1)
[In the formula (1), Tg is Tg (unit: K) of the (meth) acrylic copolymer (A), and Tgi (i = 1, 2,... N) is a homopolymer of the radical polymerizable monomer i. Tg (unit: K) and Wi (i = 1, 2,..., N) at the time of forming the radicals represent mass fractions in all monomer components of the radical polymerizable monomer i. For the Tg of the homopolymer, published values such as literature values and catalog values are used. ]
The above formula (1) is a calculation formula when the acrylic copolymer (A) is composed of n types of monomer components of monomer 1, monomer 2,..., Monomer n.
アクリル系共重合体（Ａ）のＴｇは、−６５℃以上が好ましく、−６３℃以上がより好ましい。また、−５３℃以下が好ましい。上記範囲内であると、粘着力と再剥離性を両立しやすくなる。 The Tg of the acrylic copolymer (A) is preferably −65 ° C. or higher, more preferably −63 ° C. or higher. Moreover, -53 degrees C or less is preferable. Within the above range, it becomes easy to achieve both adhesive strength and removability.
［アルキル基の炭素数が８である（メタ）アクリル酸アルキルエステルモノマー（ａ１）］
ジッピング現象を抑制し、再剥離性の向上をはかるために、本発明では、アクリル系共重合体（Ａ）を構成するモノマーとして、（ａ１）を用いる。ここで、アルキル基の炭素数が８である（メタ）アクリル酸アルキルエステルモノマーとは、（メタ）アクリル酸アルキルエステル中のアルキル基の炭素数が８であるものを意味する。アルキル基の構造としては、直鎖構造および分岐構造のものいずれであっても良い。
[(Meth) acrylic acid alkyl ester monomer (a1) in which alkyl group has 8 carbon atoms]
In order to suppress the zipping phenomenon and improve the removability, in the present invention, (a1) is used as a monomer constituting the acrylic copolymer (A). Here, the (meth) acrylic acid alkyl ester monomer in which the alkyl group has 8 carbon atoms means that the alkyl group in the (meth) acrylic acid alkyl ester has 8 carbon atoms. The structure of the alkyl group may be either a straight chain structure or a branched structure.
（ａ１）としては、例えば、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ノルマルオクチル、（メタ）アクリル酸イソオクチル等が挙げられる。これらの中でも、アクリル酸２−エチルヘキシルが好ましい。
共重合体を構成する全モノマー１００質量％中の（ａ１）の含有量は、４５質量％以上が好ましく、５５質量％以上がより好ましい。また、９５質量％以下が好ましく、９０質量％以下がより好ましい。上記範囲内であると、ジッピング現象が抑制でき、再剥離性を付与しやすくなる。
Examples of (a1) include 2-ethylhexyl (meth) acrylate, normal octyl (meth) acrylate, isooctyl (meth) acrylate, and the like. Among these, 2-ethylhexyl acrylate is preferable.
45 mass% or more is preferable and, as for content of (a1) in 100 mass% of all the monomers which comprise a copolymer, 55 mass% or more is more preferable. Moreover, 95 mass% or less is preferable, and 90 mass% or less is more preferable. When it is within the above range, the zipping phenomenon can be suppressed and re-peelability can be easily imparted.
［反応性官能基を有するモノマー（ａ２）］
凝集力や再剥離性の向上をはかるために、本発明では、アクリル系共重合体（Ａ）を構成するモノマーとして、（ａ２）を用いる。ここで、反応性官能基を有するモノマーとは、硬化剤（Ｂ）と反応しうる官能基を有するラジカル重合性モノマーを意味する。反応性官能基と硬化剤との架橋反応によりポリマーネットワークを形成し、凝集力や再剥離性の向上が期待できる。
[Monomer (a2) having a reactive functional group]
In order to improve the cohesive force and removability, (a2) is used as a monomer constituting the acrylic copolymer (A) in the present invention. Here, the monomer having a reactive functional group means a radical polymerizable monomer having a functional group capable of reacting with the curing agent (B). A polymer network is formed by a cross-linking reaction between a reactive functional group and a curing agent, and an improvement in cohesion and removability can be expected.
（ａ２）としては、カルボキシル基を有するモノマー、水酸基を有するモノマー、およびアミノ基を有するモノマーなどが挙げられ、カルボキシル基を有するモノマーまたは水酸基を有するモノマーが好ましく、水酸基を有するモノマーが剥離感を向上できるためより好ましい。共重合体を構成する全モノマー１００質量％中の（ａ２）の含有量は０を超えて１０質量％以下である必要があり、０．４質量％以上が好ましく、０．６質量％以上がさらに好ましい。また、９質量％以下が好ましい。上記範囲内であると、粘着力と再剥離性を両立しやすくなる。 Examples of (a2) include a monomer having a carboxyl group, a monomer having a hydroxyl group, and a monomer having an amino group, preferably a monomer having a carboxyl group or a monomer having a hydroxyl group, and the monomer having a hydroxyl group improves the feeling of peeling. It is more preferable because it is possible. The content of (a2) in 100% by mass of all monomers constituting the copolymer needs to be more than 0 and 10% by mass or less, preferably 0.4% by mass or more, and more preferably 0.6% by mass or more. Further preferred. Moreover, 9 mass% or less is preferable. Within the above range, it becomes easy to achieve both adhesive strength and removability.
カルボキシル基を有するモノマーの具体例としては、（メタ）アクリル酸、（メタ）アクリル酸β−カルボキシエチル等が挙げられる。これらの中でも、（メタ）アクリル酸が好ましい。
共重合体を構成する全モノマー１００質量％中のカルボキシル基を有するモノマーの含有率は、２質量％以上がより好ましく、５％以上がさらに好ましくい。また、９質量％以下が好ましく、７質量％以下がより好ましい。含有率が上記範囲内であると凝集力と再剥離性を両立しやすくなる。
Specific examples of the monomer having a carboxyl group include (meth) acrylic acid and (meth) acrylic acid β-carboxyethyl. Among these, (meth) acrylic acid is preferable.
The content of the monomer having a carboxyl group in 100% by mass of all monomers constituting the copolymer is more preferably 2% by mass or more, and further preferably 5% or more. Moreover, 9 mass% or less is preferable and 7 mass% or less is more preferable. When the content is within the above range, it becomes easy to achieve both cohesion and removability.
水酸基を有するモノマーの具体例としては、（メタ）アクリル酸ヒドロキシアルキルエステルが好ましい。具体例としては、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸４−ヒドロキシブチル、（メタ）アクリル酸６−ヒドロキシヘキシル等が挙げられる。これらの中でも（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸４−ヒドロキシブチルが、剥離感を向上できるため好ましい。 As a specific example of the monomer having a hydroxyl group, (meth) acrylic acid hydroxyalkyl ester is preferable. Specific examples include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and the like. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable because they can improve the feeling of peeling.
共重合体を構成する全モノマー１００質量％中の水酸基を有するモノマーの含有量は、０．４質量％以上が好ましく、０．６質量％以上がより好ましい。また、９質量％以下が好ましく、７質量％以下がより好ましい。含有率が上記範囲内であると凝集力と再剥離性を両立しやすくなる。 0.4 mass% or more is preferable and, as for content of the monomer which has a hydroxyl group in 100 mass% of all the monomers which comprise a copolymer, 0.6 mass% or more is more preferable. Moreover, 9 mass% or less is preferable and 7 mass% or less is more preferable. When the content is within the above range, it becomes easy to achieve both cohesion and removability.
アミノ基を有するモノマーの具体例としては、無置換のアミノ基を有するモノマーおよび置換されたアミノ基を有するモノマーが挙げられるが、好ましくはアルキル基で置換されたアミノ基を有するモノマーであり、より好ましくは（メタ）アクリル酸Ｎ−アルキルアミノエステルである。ここで、アルキル基としては、炭素数１〜４のアルキル基が好ましい。アミノ基を有するモノマーの具体例としては、（メタ）アクリル酸アミノエチル等が挙げられる。共重合体を構成する全モノマー１００質量％中のアミノ基を有するモノマーの含有量は、０．４質量％以上が好ましく、また、２質量％以下が好ましい。 Specific examples of the monomer having an amino group include a monomer having an unsubstituted amino group and a monomer having a substituted amino group, preferably a monomer having an amino group substituted with an alkyl group, and more (Meth) acrylic acid N-alkylamino ester is preferred. Here, as an alkyl group, a C1-C4 alkyl group is preferable. Specific examples of the monomer having an amino group include aminoethyl (meth) acrylate. The content of the monomer having an amino group in 100% by mass of all monomers constituting the copolymer is preferably 0.4% by mass or more, and more preferably 2% by mass or less.
［ホモポリマーのＴｇが−４５℃以上であるラジカル重合性モノマー（ａ３）］
ラジカル重合性モノマー（ａ３）は、ホモポリマーのＴｇが−４５℃以上であるラジカル重合性モノマーであって、アルキル基の炭素数が８である（メタ）アクリル酸アルキルエステルモノマー（ａ１）、および反応性官能基を有するモノマー（ａ２）以外のラジカル重合性モノマーである。
[Radically polymerizable monomer (a3) having Tg of homopolymer of −45 ° C. or higher]
The radical polymerizable monomer (a3) is a radical polymerizable monomer having a Tg of homopolymer of −45 ° C. or more, and a (meth) acrylic acid alkyl ester monomer (a1) having an alkyl group with 8 carbon atoms, and It is a radical polymerizable monomer other than the monomer (a2) having a reactive functional group.
粘着力や再剥離性の向上をはかるために、本発明では、アクリル系共重合体（Ａ）を構成するモノマーとして、（ａ３）を含有することが好ましい。ここで、ホモポリマーのＴｇが−４５℃以上であるラジカル重合性モノマーとは、ラジカル重合によりホモポリマーを形成したときのＴｇが−４５℃以上であるラジカル重合性モノマーを意味する。なお、ホモポリマーのＴｇは文献値やカタログ値などの公表値を使用する。（ａ３）を含有することで、再剥離性を維持しながらより粘着力が向上する。（ａ３）のＴｇは、−３０℃以上であることで、粘着力が向上しやすくさらに好ましい。 In order to improve the adhesive strength and removability, in the present invention, it is preferable to contain (a3) as a monomer constituting the acrylic copolymer (A). Here, the radical polymerizable monomer having a homopolymer Tg of −45 ° C. or higher means a radical polymerizable monomer having a Tg of −45 ° C. or higher when a homopolymer is formed by radical polymerization. For the Tg of the homopolymer, published values such as literature values and catalog values are used. By containing (a3), the adhesive force is further improved while maintaining removability. The Tg of (a3) is more preferably −30 ° C. or more, and thus the adhesive force is easily improved, which is more preferable.
（ａ３）としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、メタクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ−ブチル、メタクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸フェニル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸イソボルニル等の（メタ）アクリル酸エステルモノマー、スチレン、α−メチルスチレン、酢酸ビニル、アクリロニトリル等のビニルモノマー、（メタ）アクリルアミドなどアミド基を有するビニルモノマーなどが挙げられ、これらの中でも（メタ）アクリル酸エステルモノマーが好ましく、（メタ）アクリル酸メチル、（メタ）アクリル酸エチルが耐熱性を向上できるためさらに好ましい。 Examples of (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl methacrylate, isobutyl (meth) acrylate, (meth) (Meth) acrylate monomers such as t-butyl acrylate, hexyl methacrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, styrene, α -Vinyl monomers such as methylstyrene, vinyl acetate and acrylonitrile, vinyl monomers having an amide group such as (meth) acrylamide, and the like. Among these, (meth) acrylic acid ester monomers are preferred, methyl (meth) acrylate, ( (Meth) ethyl acrylate is heat resistant Further preferred because it can improve.
共重合体を構成する全モノマー１００質量％中の（ａ３）の含有量は、５質量％以上が好ましく、１０質量％以上がより好ましく、１５質量％以上がさらに好ましい。また、４０質量％以下が好ましく、３０質量％以下がより好ましい。上記範囲内であると、粘着力と再剥離性を両立しやすくなる。 The content of (a3) in 100% by mass of all monomers constituting the copolymer is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more. Moreover, 40 mass% or less is preferable, and 30 mass% or less is more preferable. Within the above range, it becomes easy to achieve both adhesive strength and removability.
［その他モノマー］
アクリル系共重合（Ａ）は、共重合体を構成するモノマーとして、上記モノマー（ａ１）〜（ａ３）以外のその他モノマーを含んでも良い。その他モノマーとしては、上記モノマー（ａ１）、（ａ３）以外の（メタ）アクリル酸アルキルエステル、アルコキシ基を有する（メタ）アクリル酸アルキルエステル等が挙げられる。共重合体を構成する全モノマー１００質量％中のその他モノマーの含有量は、５０質量％以下が好ましく、３０質量％以下がより好ましい。
[Other monomers]
The acrylic copolymer (A) may contain other monomers other than the monomers (a1) to (a3) as monomers constituting the copolymer. Examples of the other monomers include (meth) acrylic acid alkyl esters other than the above monomers (a1) and (a3), (meth) acrylic acid alkyl esters having an alkoxy group, and the like. The content of other monomers in 100% by mass of all monomers constituting the copolymer is preferably 50% by mass or less, and more preferably 30% by mass or less.
上記モノマー（ａ１）、（ａ３）以外の（メタ）アクリル酸アルキルエステルとしては、アクリル酸ブチル、アクリル酸ヘキシル、アクリル酸ヘプチル、アクリル酸ノニル、メタクリル酸ドデシル、メタクリル酸テトラデシルなどが挙げられ、その中でもアクリル酸ブチルが好ましい。 Examples of the (meth) acrylic acid alkyl ester other than the monomers (a1) and (a3) include butyl acrylate, hexyl acrylate, heptyl acrylate, nonyl acrylate, dodecyl methacrylate, tetradecyl methacrylate, and the like. Of these, butyl acrylate is preferred.
アルコキシ基を有するモノマーとしては、（メタ）アクリル酸アルコキシアルキルエステルが好ましい。ここで、（メタ）アクリル酸アルコキシアルキルエステル中のアルコキシ基の炭素数は、１〜４であることが好ましく、１または２であることがより好ましい。また、（メタ）アクリル酸アルコキシアルキルエステル中のアルコキシ基に結合したアルキレン基の炭素数は、１〜８であることが好ましく、１〜４であることがより好ましい。
アルコキシ基を有するモノマーの具体例としては、（メタ）アクリル酸２−メトキシメチル、（メタ）アクリル酸２−メトキシエチル、（メタ）アクリル酸２−エトキシメチル、（メタ）アクリル酸２−エトキシエチル、（メタ）アクリル酸３−メトキシプロピル、（メタ）アクリル酸３−エトキシプロピル、（メタ）アクリル酸４−メトキシブチル、（メタ）アクリル酸４−エトキシブチル等が挙げられる。これらの中でも、（メタ）アクリル酸２−メトキシエチル及び（メタ）アクリル酸２−エトキシエチルが好ましい。
As the monomer having an alkoxy group, (meth) acrylic acid alkoxyalkyl ester is preferred. Here, the number of carbon atoms of the alkoxy group in the (meth) acrylic acid alkoxyalkyl ester is preferably 1 to 4, and more preferably 1 or 2. Moreover, it is preferable that it is 1-8, and, as for carbon number of the alkylene group couple | bonded with the alkoxy group in (meth) acrylic-acid alkoxyalkyl ester, it is more preferable that it is 1-4.
Specific examples of the monomer having an alkoxy group include 2-methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxymethyl (meth) acrylate, and 2-ethoxyethyl (meth) acrylate. , (Meth) acrylic acid 3-methoxypropyl, (meth) acrylic acid 3-ethoxypropyl, (meth) acrylic acid 4-methoxybutyl, (meth) acrylic acid 4-ethoxybutyl and the like. Among these, 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate are preferable.
［アクリル系共重合体の製造方法］
アクリル系共重合（Ａ）は、公知の方法により製造することができるが、溶液重合により製造することが好ましい。溶液重合においては、重合する際に使用する溶剤としては、酢酸メチル、酢酸エチル等のエステル系溶剤、アセトン、メチルエチルケトン等のケトン系溶剤、トルエン、キシレン等の等の炭化水素系溶剤を使用することが好ましい。
[Method for producing acrylic copolymer]
The acrylic copolymer (A) can be produced by a known method, but is preferably produced by solution polymerization. In solution polymerization, as solvents used for polymerization, ester solvents such as methyl acetate and ethyl acetate, ketone solvents such as acetone and methyl ethyl ketone, and hydrocarbon solvents such as toluene and xylene should be used. Is preferred.
具体的には、溶剤、モノマー、重合開始剤等を窒素ガスなどの不活性ガス雰囲気下で、反応温度５０〜９０℃程度に加熱し、４〜１２時間で重合反応させるのが一般的である。 Specifically, a solvent, a monomer, a polymerization initiator and the like are generally heated to a reaction temperature of about 50 to 90 ° C. in an inert gas atmosphere such as nitrogen gas, and a polymerization reaction is generally performed in 4 to 12 hours. .
重合開始剤としては、アゾ系開始剤、過酸化物系開始剤を挙げることができる。これらの重合開始剤は、原料モノマー１００質量部に対して、通常は０．０１〜５質量部の範囲内の量で使用される。また、重合反応中に、連鎖移動剤、原料モノマー、溶媒を適宜添加してもよい。 Examples of the polymerization initiator include azo initiators and peroxide initiators. These polymerization initiators are usually used in an amount in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the raw material monomer. Moreover, you may add a chain transfer agent, a raw material monomer, and a solvent suitably during a polymerization reaction.
上記重合開始剤の内、アゾ系化合物としては、例えば、２,２'−アゾビスイソブチロニトリル、２,２'−アゾビス(２−メチルブチロニトリル)、１,１'−アゾビス（シクロヘキサン１−カルボニトリル）、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（２，４−ジメチル−４−メトキシバレロニトリル）、ジメチル２,２'−アゾビス（２−メチルプロピオネート）、４,４'−アゾビス（４−シアノバレリック酸）、２,２'−アゾビス（２−ヒドロキシメチルプロピオニトリル）、２,２'−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］等が挙げられる。 Among the polymerization initiators, examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane). 1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis ( 2-methylpropionate), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2 -Imidazolin-2-yl) propane] and the like.
また、上記重合開始剤の内、有機過酸化物としては、例えば、過酸化ベンゾイル、ｔ-ブチルパーベンゾエイト、クメンヒドロパーオキシド、ジイソプロピルパーオキシジカーボネート、ジ−ｎ−プロピルパーオキシジカーボネート、ジ（２−エトキシエチル）パーオキシジカーボネート、ｔ-ブチルパーオキシネオデカノエート、ｔ-ブチルパーオキシビバレート、（３，５，５−トリメチルヘキサノイル）パーオキシド、ジプロピオニルパーオキシド、ジアセチルパーオキシド等が挙げられる。 Among the polymerization initiators, examples of the organic peroxide include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, Di (2-ethoxyethyl) peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetylperoxide And oxides.
アクリル系共重合体（Ａ）の重量平均分子量は、５０万以上が好ましく、７０万以上がより好ましく、８０万以上がさらに好ましい。また、２００万以下が好ましく、１５０万以下がより好ましい。重量平均分子量が上記範囲内になることで、粘着力と再剥離性を両立しやすくなる。 The weight average molecular weight of the acrylic copolymer (A) is preferably 500,000 or more, more preferably 700,000 or more, and further preferably 800,000 or more. Moreover, 2 million or less is preferable and 1.5 million or less is more preferable. When the weight average molecular weight is within the above range, it becomes easy to achieve both adhesive force and removability.
上記のような条件において、得られる共重合体の重量平均分子量は、使用する溶媒の種類および量、重合開始剤の種類および量、反応時間、反応温度などの反応条件を調整することにより調節することができる。 Under the above conditions, the weight average molecular weight of the copolymer obtained is adjusted by adjusting the reaction conditions such as the type and amount of the solvent used, the type and amount of the polymerization initiator, the reaction time, and the reaction temperature. be able to.
＜硬化剤（Ｂ）＞
本発明の粘着剤は、硬化剤（Ｂ）を含む。
硬化剤（Ｂ）としては、イソシアネート硬化剤、エポキシ硬化剤、金属キレート硬化剤、アジリジン硬化剤などが挙げられ、その中でもイソシアネート硬化剤、エポキシ硬化剤が好ましい。硬化剤（Ｂ）を含むことで、粘着剤の凝集力が高まり再剥離性が向上する。硬化剤（Ｂ）は単独または２種以上を併用できる。
<Curing agent (B)>
The pressure-sensitive adhesive of the present invention contains a curing agent (B).
Examples of the curing agent (B) include an isocyanate curing agent, an epoxy curing agent, a metal chelate curing agent, an aziridine curing agent, and among them, an isocyanate curing agent and an epoxy curing agent are preferable. By including a hardening | curing agent (B), the cohesive force of an adhesive increases and re-peelability improves. A hardening | curing agent (B) can be used individually or in combination of 2 or more types.
イソシアネート硬化剤は、例えば、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添ジフェニルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート、ナフタレンジイソシアネート、トリフェニルメタントリイソシアネート、およびポリメチレンポリフェニルイソシアネート等のジイソシアネートと、トリメチロールプロパン等のポリオール化合物とのアダクト体、ならびにそのビュレット体、ならびにそのイソシアヌレート体、ならびに上記ジイソシアネートと、ポリエーテルポリオール、ポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、およびポリイソプレンポリオール等の内のいずれかのポリオールとのアダクト体などの分子内に３個以上のイソシアネート基を有する化合物；またはこれらのアロファネート体等の分子内に２個のイソシアネート基を有する化合物等が挙げられる。これらの中でも、トリレンジイソシアネートのトリメチロールプロパンアダクト体、キシリレンジイソシアネートのトリメチロールプロパンアダクト体が粘着物性を容易に調整できるため好ましい。なお、イソシアネート基の個数は平均個数である。 Examples of isocyanate curing agents include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate. An adduct of a diisocyanate such as polymethylene polyphenyl isocyanate and a polyol compound such as trimethylolpropane, and a burette thereof, and an isocyanurate thereof, and the diisocyanate, a polyether polyol, a polyester polyol, an acrylic polyol, Polybutadiene polyol, And compounds having three or more isocyanate groups in the molecule such as adducts with any of the polyols such as polyisoprene polyol; or compounds having two isocyanate groups in the molecule such as allophanates Is mentioned. Among these, a trimethylolpropane adduct body of tolylene diisocyanate and a trimethylolpropane adduct body of xylylene diisocyanate are preferable because the adhesive properties can be easily adjusted. In addition, the number of isocyanate groups is an average number.
イソシアネート硬化剤の配合量は、アクリル系共重合体（Ａ）１００質量部に対して、０．３質量部以上であることが好ましく、１質量部以上であることがさらに好ましい。また８質量部以下であることが好ましく、５質量部以下であることがより好ましく、特に好ましくは３質量部以下である。上記範囲内とすることで粘着力と再剥離性を両立しやすくなる。 The compounding amount of the isocyanate curing agent is preferably 0.3 parts by mass or more and more preferably 1 part by mass or more with respect to 100 parts by mass of the acrylic copolymer (A). Further, it is preferably 8 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less. By making it within the above range, it becomes easy to achieve both adhesive force and removability.
エポキシ硬化剤は、例えば、ビスフェノールＡ−エピクロロヒドリン型のエポキシ系樹脂、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、Ｎ，Ｎ，Ｎ'，Ｎ'−テトラグリシジル−ｍ−キシリレンジアミン、１、３−ビス（Ｎ、Ｎ’−ジグリシジルアミノメチル）シクロヘキサン、およびＮ，Ｎ，Ｎ'，Ｎ'−テトラグリシジルアミノフェニルメタン等が挙げられる。 Examples of the epoxy curing agent include bisphenol A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and 1,6-hexanediol diglycidyl. Ether, trimethylolpropane triglycidyl ether, diglycidylaniline, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, And N, N, N ′, N′-tetraglycidylaminophenylmethane and the like.
エポキシ硬化剤は、アクリル系共重合体（Ａ）１００質量部に対して、０．０１質量部以上であることが好ましく、０．５質量部以上であることがさらに好ましい。また３質量部以下であることが好ましく、２質量部以下であるがさらに好ましい。上記範囲内とすることで粘着力と再剥離性を両立しやすくなる。 The epoxy curing agent is preferably 0.01 parts by mass or more, and more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the acrylic copolymer (A). Further, it is preferably 3 parts by mass or less, more preferably 2 parts by mass or less. By making it within the above range, it becomes easy to achieve both adhesive force and removability.
金属キレート硬化剤は、例えば、アルミニウム、鉄、銅、亜鉛、スズ、チタン、ニッケル、アンチモン、マグネシウム、バナジウム、クロムおよびジルコニウムなどの多価金属と、アセチルアセトンまたはアセト酢酸エチルとの配位化合物等が挙げられる。 Examples of the metal chelate curing agent include a coordination compound of a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium, and acetylacetone or ethyl acetoacetate. Can be mentioned.
金属キレート硬化剤は、アクリル系共重合体（Ａ）１００質量部に対して、０．５質量部以上であることが好ましく、１質量部以上であることがさらに好ましい。また３質量部以下であることが好ましく、２質量部以下であるがさらに好ましい。上記範囲内とすることで粘着力と再剥離性を両立しやすくなる。 The metal chelate curing agent is preferably 0.5 parts by mass or more and more preferably 1 part by mass or more with respect to 100 parts by mass of the acrylic copolymer (A). Further, it is preferably 3 parts by mass or less, more preferably 2 parts by mass or less. By making it within the above range, it becomes easy to achieve both adhesive force and removability.
アジリジン硬化剤は、例えばＮ，Ｎ’−ジフェニルメタン−４，４'−ビス（１−アジリジンカルボキサイト）、Ｎ，Ｎ’−トルエン−２，４−ビス（１−アジリジンカルボキサイト）、ビスイソフタロイル−１−（２−メチルアジリジン）、トリ−１−アジリジニルホスフィンオキサイド、Ｎ，Ｎ’−ヘキサメチレン−１，６−ビス（１−アジリジンカルボキサイト）、２，２’−ビスヒドロキシメチルブタノール−トリス［３−（１−アジリジニル）プロピオネート］、トリメチロールプロパントリ−β−アジリジニルプロピオネート、テトラメチロールメタントリ−β−アジリジニルプロピオネート、およびトリス−２，４，６−（１−アジリジニル）−１、３、５−トリアジン等が挙げられる。 Examples of the aziridine curing agent include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxite), bisisophthalo. Yl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite), 2,2′-bishydroxymethyl Butanol-tris [3- (1-aziridinyl) propionate], trimethylolpropane tri-β-aziridinylpropionate, tetramethylolmethane tri-β-aziridinylpropionate, and tris-2,4,6 -(1-aziridinyl) -1,3,5-triazine and the like.
アジリジン硬化剤は、アクリル系共重合体（Ａ）１００質量部に対して、０．１質量部以上であることが好ましく、０．５質量部以上であることがさらに好ましい。また２質量部以下であることが好ましく、１質量部以下であるがさらに好ましい。上記範囲内とすることで粘着力と再剥離性を両立しやすくなる。 The aziridine curing agent is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the acrylic copolymer (A). Further, it is preferably 2 parts by mass or less, more preferably 1 part by mass or less. By making it within the above range, it becomes easy to achieve both adhesive force and removability.
＜酸化防止剤（Ｃ）＞
本発明の粘着剤は、酸化防止剤（Ｃ）として、リン系酸化防止剤を含む。リン系酸化防止剤を含むことで粘着力を確保しながら再剥離性を向上させることが可能である。酸化防止剤（Ｃ）は、例えば、ホスファイト系が挙げられ、具体的にはイルガホス３８、イルガホス１２６、イルガホス１６８（いずれもＢＡＳＦ社製）、スミライザーＧＰ（住友化学社製）、アデカスタブＰＥＰ−８、アデカスタブＰＥＰ−３６、アデカスタブＨＰ−１０、アデカスタブ２１１２、アデカスタブ１１７８、アデカスタブ１５００、アデカスタブ１３５Ａ、アデカスタブ３０１０、アデカスタブＣ、アデカスタブＴＰＰ（いずれもＡＤＥＫＡ社製）等が挙げられる。酸化防止剤（Ｃ）は固体状であっても液状であっても良いが、２５℃において液状であることがより好ましい。液状であることで耐熱性、耐湿熱性がより向上する。
<Antioxidant (C)>
The pressure-sensitive adhesive of the present invention contains a phosphorus-based antioxidant as the antioxidant (C). By including a phosphorus-based antioxidant, it is possible to improve the removability while ensuring adhesive strength. Examples of the antioxidant (C) include a phosphite type, and specifically, Irgafos 38, Irgafos 126, Irgafos 168 (all manufactured by BASF), Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.), Adeka Stab PEP-8 , ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 1178, ADK STAB 1500, ADK STAB 135A, ADK STAB 3010, ADK STAB C, and ADK STAB TPP (all manufactured by ADEKA). The antioxidant (C) may be solid or liquid, but is more preferably liquid at 25 ° C. Heat resistance and moist heat resistance are further improved by being liquid.
酸化防止剤（Ｃ）は、アクリル系共重合体（Ａ）１００質量部に対して、０．１５質量部〜１．５部である必要があり、０．２質量部以上であることが好ましく、０．３質量部以上であることがさらに好ましい。また１質量部以下であることが好ましく、０．８質量部以下であることがさらに好ましい。上記範囲内とすることで粘着力と再剥離性を両立しやすくなる。 The antioxidant (C) needs to be 0.15 parts by mass to 1.5 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A), and preferably 0.2 parts by mass or more. More preferably, it is 0.3 parts by mass or more. Moreover, it is preferable that it is 1 mass part or less, and it is further more preferable that it is 0.8 mass part or less. By making it within the above range, it becomes easy to achieve both adhesive force and removability.
本発明の粘着剤には、本発明の効果を損なわない範囲であれば、所望により各種樹脂や添加剤を添加することができる。例えば、粘着付与剤、酸化防止剤（Ｃ）以外の酸化防止剤、シランカップリング剤、熱または光安定剤、紫外線吸収剤、レベリング剤、消泡剤、抗菌剤、保湿剤、ビタミン類、顔料、染料、香料などを挙げることができる。これらは、必要に応じて有効量を配合する。 If desired, various resins and additives can be added to the pressure-sensitive adhesive of the present invention as long as the effects of the present invention are not impaired. For example, tackifiers, antioxidants other than antioxidants (C), silane coupling agents, heat or light stabilizers, UV absorbers, leveling agents, antifoaming agents, antibacterial agents, moisturizing agents, vitamins, pigments , Dyes and fragrances. These are compounded in effective amounts as necessary.
≪粘着シート≫
本発明の粘着シートは、基材上に本発明の粘着剤の硬化物である粘着剤層を有するものである。粘着シートは、例えば、基材上に粘着剤を塗工、乾燥することにより製造できる。粘着剤層は基材の少なくとも一方の面に設けられていれば良い。
≪Adhesive sheet≫
The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer that is a cured product of the pressure-sensitive adhesive of the present invention on a substrate. The pressure-sensitive adhesive sheet can be produced, for example, by applying a pressure-sensitive adhesive on a substrate and drying it. The adhesive layer should just be provided in the at least one surface of the base material.
粘着剤を塗工するに際し、適当な液状媒体、例えば、トルエン、キシレン、ヘキサン、ヘプタン等の炭化水素系溶剤；酢酸エチル、酢酸ブチル等のエステル系溶剤；アセトン、メチルエチルケトン等のケトン系溶剤；ジクロロメタン、クロロホルム等のハロゲン化炭化水素系溶剤；ジエチルエーテル、メトキシトルエン、ジオキサン等のエーテル系溶剤、その他の炭化水素系溶剤等の有機溶剤を添加して、粘度を調整することもできるし、粘着剤を加熱して粘度を低下させることもできる。 When applying the adhesive, an appropriate liquid medium, for example, a hydrocarbon solvent such as toluene, xylene, hexane, heptane; an ester solvent such as ethyl acetate or butyl acetate; a ketone solvent such as acetone or methyl ethyl ketone; dichloromethane , Halogenated hydrocarbon solvents such as chloroform; ether solvents such as diethyl ether, methoxytoluene, dioxane, and other organic solvents such as hydrocarbon solvents can be added to adjust the viscosity and pressure-sensitive adhesive The viscosity can also be reduced by heating.
基材としては、例えば、セロハン、プラスチックシート、ゴム、発泡体、布帛、ゴム布、樹脂含浸布、ガラス板、木材等が挙げられ、板状であってもフィルム状であっても良い。さらに基材は単独でも用いることもできるし、複数のものを積層してなる多層状態にあるものも用いることができる。更に基材の表面を剥離処理したもの（以下、剥離シートと呼ぶ）を用いることもできる。 Examples of the substrate include cellophane, plastic sheet, rubber, foam, cloth, rubber cloth, resin-impregnated cloth, glass plate, and wood, and may be plate-like or film-like. Furthermore, the base material can be used alone, or a base material in a multilayer state formed by laminating a plurality of base materials can be used. Furthermore, what carried out the peeling process of the surface of a base material (henceforth a peeling sheet) can also be used.
プラスチックシートとしては、プラスチックフィルムともいわれ、ポリビニルアルコールフィルムやトリアセチルセルロースフィルム、ポリプロピレン、ポリエチレン、ポリシクロオレフィン、エチレン−酢酸ビニル共重合体などのポリオレフィン系樹脂のフィルム、ポリエチレンテレフタレート，ポリブチレンテレフタレート，ポリエチレンナフタレートなどのポリエステル系樹脂のフィルム、ポリ塩化ビニルなどのビニル系樹脂のフィルム、ポリカーボネート系樹脂のフィルム、ポリノルボルネン系樹脂のフィルム、ポリアリレート系樹脂のフィルム、アクリル系樹脂のフィルム、ポリフェニレンサルファイド樹脂のフィルム、ポリスチレン樹脂のフィルム、ポリアミド系樹脂のフィルム、ポリイミド系樹脂のフィルム、エポキシ系樹脂のフィルムなどが挙げられる。 The plastic sheet is also called a plastic film. Polyvinyl alcohol film, triacetyl cellulose film, polypropylene, polyethylene, polycycloolefin, polyolefin resin film such as ethylene-vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate, polyethylene Polyester resin film such as naphthalate, vinyl resin film such as polyvinyl chloride, polycarbonate resin film, polynorbornene resin film, polyarylate resin film, acrylic resin film, polyphenylene sulfide resin Film, polystyrene resin film, polyamide resin film, polyimide resin film, epoxy resin Film and the like.
本発明において粘着剤の塗工方法は、特に制限は無く、マイヤーバー、アプリケーター、刷毛、スプレー、ローラー、グラビアコーター、ダイコーター、リップコーター、コンマコーター、ナイフコーター、リバースコ−ター、スピンコーター等が挙げられる。乾燥方法には特に制限はなく、熱風乾燥、赤外線や減圧法を利用したものが挙げられる。乾燥条件としては粘着剤の硬化形態、膜厚や選択した溶剤にもよるが、通常６０〜１３０℃程度の熱風加熱でよい。 In the present invention, the method of applying the adhesive is not particularly limited, and may be a Mayer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, knife coater, reverse coater, spin coater, etc. Can be mentioned. There is no restriction | limiting in particular in a drying method, The thing using hot air drying, infrared rays, and the pressure reduction method is mentioned. As drying conditions, although depending on the cured form of the pressure-sensitive adhesive, the film thickness, and the selected solvent, heating with hot air at about 60 to 130 ° C. is usually sufficient.
本発明の粘着シートは、（ア）剥離処理されたフィルムの剥離処理面に粘着剤を塗工、乾燥し、基材を粘着剤層の表面に積層したり、（イ）基材に粘着剤を直接塗工、乾燥し、粘着剤層の表面に剥離処理されたフィルムの剥離処理面を積層したりすることによって得ることができる。 The pressure-sensitive adhesive sheet of the present invention can be obtained by (a) applying a pressure-sensitive adhesive to the release-treated surface of a film that has been subjected to a release treatment, drying the substrate, and laminating the substrate on the surface of the pressure-sensitive adhesive layer, Can be obtained by directly coating and drying the film, and laminating the peel-treated surface of the peel-treated film on the surface of the pressure-sensitive adhesive layer.
粘着剤層の厚さは、１〜２００μｍであることがより好ましく、３〜１００μｍであることが更に好ましい。 As for the thickness of an adhesive layer, it is more preferable that it is 1-200 micrometers, and it is still more preferable that it is 3-100 micrometers.
以下に実施例及び比較例を挙げて、本発明について具体的に説明する。配合比に関しては、溶剤以外は固形分換算での値を示す。また、以下の例で使用した材料の略号、ラジカル重合性モノマーのＴｇはホモポリマーのＴｇを示す。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Regarding the compounding ratio, values other than the solvent are shown in terms of solid content. Moreover, the abbreviation of the material used in the following examples and Tg of a radical polymerizable monomer indicate Tg of a homopolymer.
［アルキル基の炭素数が８である（メタ）アクリル酸アルキルエステルモノマー（ａ１）］
２ＥＨＡ：アクリル酸２−エチルヘキシル（Ｔｇ：−７０℃）
ＯＡ：アクリル酸ノルマルオクチル（Ｔｇ：−６５℃）
［反応性官能基を有するモノマー（ａ２）］
ＡＡ：アクリル酸（Ｔｇ：１０６℃）
ＨＥＭＡ：メタクリル酸２−ヒドロキシエチル（Ｔｇ：７１℃）
４ＨＢＡ：アクリル酸４−ヒドロキシブチル（Ｔｇ：−３２℃）
［ホモポリマーのＴｇが−４５℃以上であるラジカル重合性モノマー（ａ３）］
ＭＡ：アクリル酸メチル（Ｔｇ：１０℃）
ＥＡ：アクリル酸エチル（Ｔｇ：−２４℃）
ＶＡｃ：酢酸ビニル（Ｔｇ：３２℃）
［その他モノマー］
ＢＡ：アクリル酸ノルマルブチル（Ｔｇ：−５４℃）
[(Meth) acrylic acid alkyl ester monomer (a1) in which alkyl group has 8 carbon atoms]
2EHA: 2-ethylhexyl acrylate (Tg: -70 ° C)
OA: normal octyl acrylate (Tg: -65 ° C)
[Monomer (a2) having a reactive functional group]
AA: Acrylic acid (Tg: 106 ° C)
HEMA: 2-hydroxyethyl methacrylate (Tg: 71 ° C.)
4HBA: 4-hydroxybutyl acrylate (Tg: -32 ° C)
[Radically polymerizable monomer (a3) having Tg of homopolymer of −45 ° C. or higher]
MA: methyl acrylate (Tg: 10 ° C.)
EA: ethyl acrylate (Tg: -24 ° C)
VAc: Vinyl acetate (Tg: 32 ° C.)
[Other monomers]
BA: Normal butyl acrylate (Tg: -54 ° C)
＜硬化剤（Ｂ）＞
ＴＤＩ／ＴＭＰ：トリレンジイソシアネートのトリメチロールプロパンアダクト体
ＸＤＩ／ＴＭＰ：キシリレンジイソシアネートのトリメチロールプロパンアダクト体
ＴＧＸＡ：Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシリレンジアミン
<Curing agent (B)>
TDI / TMP: Trimethylolpropane adduct of tolylene diisocyanate XDI / TMP: Trimethylolpropane adduct of xylylene diisocyanate TGXA: N, N, N ′, N′-tetraglycidyl-m-xylylenediamine
＜酸化防止剤（Ｃ）＞
ＩＲＧ１６８：イルガホス１６８
（リン系酸化防止剤、２５℃性状：白色粉末、ＢＡＳＦ社製）
ＴＰＰ：アデカスタブＴＰＰ
（リン系酸化防止剤、２５℃性状：無色液体、ＡＤＥＫＡ社製）
ＡＯ−６０：アデカスタブＡＯ−６０
（フェノール系酸化防止剤、２５℃性状：白色粉末、ＡＤＥＫＡ社製）
<Antioxidant (C)>
IRG168: Irgafos 168
(Phosphorus antioxidant, 25 ° C. property: white powder, manufactured by BASF)
TPP: ADK STAB TPP
(Phosphorus antioxidant, 25 ° C. property: colorless liquid, manufactured by ADEKA)
AO-60: ADK STAB AO-60
(Phenolic antioxidant, 25 ° C property: white powder, manufactured by ADEKA)
（合成例１）
撹拌機、温度計、還流冷却管、滴下漏斗、窒素導入管を備えた反応容器（以下、単に「反応容器」と称する）に、アクリル酸２−エチルヘキシル４７．５部、アクリル酸２．５部、酢酸エチル６０部、２，２'−アゾビスイソブチロニトリル（ＡＩＢＮ）０．０２部を仕込んだ後、反応容器内の空気を窒素ガスで置換した。更に、滴下漏斗に、アクリル酸２−エチルヘキシル４７．５部、アクリル酸２．５部、酢酸エチル２０部、ＡＩＢＮ０．０２部を仕込んだ。次いで、反応容器内を窒素雰囲気下で撹拌しながら、８０℃まで加熱し、反応を開始した後、滴下漏斗内容物を２時間かけて滴下しながら、窒素雰囲気下にて還流温度で８時間重合反応を行った。反応終了後、冷却し、酢酸エチルを加えて希釈し、不揮発分３０％のアクリル系共重合体（Ａ）溶液を得た（共重合体１）。また、ＧＰＣを用いてアクリル系共重合体（Ａ）の重量平均分子量（Ｍｗ)を測定したところ、重量平均分子量は７０万であった。
(Synthesis Example 1)
In a reaction vessel (hereinafter simply referred to as “reaction vessel”) equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, 47.5 parts of 2-ethylhexyl acrylate, 2.5 parts of acrylic acid Then, 60 parts of ethyl acetate and 0.02 part of 2,2′-azobisisobutyronitrile (AIBN) were charged, and the air in the reaction vessel was replaced with nitrogen gas. Further, 47.5 parts of 2-ethylhexyl acrylate, 2.5 parts of acrylic acid, 20 parts of ethyl acetate and 0.02 part of AIBN were charged into the dropping funnel. Next, the reaction vessel was heated to 80 ° C. with stirring in a nitrogen atmosphere, and the reaction was started. Then, the contents of the dropping funnel were added dropwise over 2 hours, and polymerization was performed at a reflux temperature in a nitrogen atmosphere for 8 hours. Reaction was performed. After completion of the reaction, the reaction mixture was cooled and diluted with ethyl acetate to obtain an acrylic copolymer (A) solution having a nonvolatile content of 30% (copolymer 1). Moreover, when the weight average molecular weight (Mw) of the acrylic copolymer (A) was measured using GPC, the weight average molecular weight was 700,000.
（合成例２〜１７）
表１、２の材料および配合比率に変更した以外は、合成例１と同様の方法でそれぞれアクリル系共重合体を合成した。
上記合成例で得られたアクリル系共重合体の内、合成例１〜１３で得られたアクリル系共重合体はアクリル系共重合体（Ａ）に該当し、合成例１４〜１７で得られたアクリル系共重合体はアクリル系共重合体（Ａ）ではないアクリル系共重合体に該当する。
(Synthesis Examples 2 to 17)
Acrylic copolymers were synthesized in the same manner as in Synthesis Example 1 except that the materials and blending ratios in Tables 1 and 2 were changed.
Among the acrylic copolymers obtained in the above synthesis examples, the acrylic copolymers obtained in synthesis examples 1 to 13 correspond to the acrylic copolymer (A), and are obtained in synthesis examples 14 to 17. The acrylic copolymer corresponds to an acrylic copolymer that is not the acrylic copolymer (A).
＜重量平均分子量（Ｍｗ）＞
Ｍｗは、下記の条件により測定した。Ｍｗの決定は、Ｍｗが既知のポリスチレンを標準物質に用いた検量線法により決定した。
装置名：島津製作所社製、ＬＣ−ＧＰＣシステム「Ｐｒｏｍｉｎｅｎｃｅ」
カラム：東ソー社製ＧＭＨＸＬ ４本、東ソー社製ＨＸＬ-Ｈ １本を直列に連結
移動相溶媒：テトラヒドロフラン（ＴＨＦ）
流量：１．０ｍｌ／分
カラム温度：４０℃
<Weight average molecular weight (Mw)>
Mw was measured under the following conditions. Mw was determined by a calibration curve method using polystyrene having a known Mw as a standard substance.
Device name: LC-GPC system “Prominence” manufactured by Shimadzu Corporation
Column: 4 Tohso GMHXL and 1 Tosoh HXL-H connected in series Mobile phase solvent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min Column temperature: 40 ° C
（実施例１）
＜粘着剤の作成＞
得られたアクリル系共重合体（Ａ）（共重合体１）の不揮発分１００部に対して、硬化剤（Ｂ）としてトリレンジイソシネートのトリメチロールプロパンアダクト体を２部、酸化防止剤（Ｃ）としてイルガホス１６８を０．３部、希釈溶剤として酢酸エチルを添加し、撹拌することで、不揮発分を２５％に調整した粘着剤を得た。
Example 1
<Creation of adhesive>
Antioxidant, 2 parts of trimethylolpropane adduct of tolylene diisocyanate as curing agent (B) with respect to 100 parts of nonvolatile content of the obtained acrylic copolymer (A) (copolymer 1) As (C), 0.3 part of irgafos 168 and ethyl acetate as a diluting solvent were added and stirred to obtain a pressure-sensitive adhesive whose non-volatile content was adjusted to 25%.
＜粘着シートの作成＞
厚さ３８μｍの剥離性シート（ポリエチレンテレフタレート製）上に、乾燥後の厚みが２５μｍとなるように上記で得られた粘着剤を塗工し、熱風オーブンにて１００℃、２分間乾燥して粘着剤層を作製した。乾燥後、厚さ５０μｍの基材（ポリエチレンテレフタレート製）にラミネートし、さらに２３℃５０％ＲＨで７日間養生し、粘着シートを得た。
<Creation of adhesive sheet>
On the 38 μm thick peelable sheet (polyethylene terephthalate), the pressure-sensitive adhesive obtained above was applied so that the thickness after drying was 25 μm, and then dried in a hot air oven at 100 ° C. for 2 minutes for adhesion. An agent layer was prepared. After drying, it was laminated on a 50 μm-thick substrate (made of polyethylene terephthalate), and further cured at 23 ° C. and 50% RH for 7 days to obtain an adhesive sheet.
（実施例２〜１７、比較例１〜７）
表３、４に示す材料、組成、量になるよう変更した以外は、実施例１と同様に、それぞ
れ粘着剤および粘着シートを製造し、測定および評価を行った。尚、表中の数値は、特に
断りがない限り、部を表し、空欄は使用していないことを表す。
ただし、実施例１〜３、５、６、１０、および１２は参考例である。
(Examples 2-17, Comparative Examples 1-7)
A pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were produced in the same manner as in Example 1 except that the materials, compositions, and amounts shown in Tables 3 and 4 were changed, and measurement and evaluation were performed. In addition, unless otherwise indicated, the numerical value in a table | surface represents a part and the blank represents that it is not using.
However, Examples 1-3, 5, 6, 10, and 12 are reference examples.
（１）粘着力
得られた粘着シートを幅２５ｍｍ、長さ１５０ｍｍの大きさに切り出した。次いで２３℃５０％ＲＨの環境下、粘着シートから剥離性シートを剥がして露出した粘着剤層を、ステンレス（ＳＵＳ）板に貼付し、２ｋｇロールにより１往復させて測定試料を作製した。この測定試料を、２３℃５０％ＲＨの環境下で２４時間保存した後、引張試験機（オリエンテック社製「テンシロン」）を用いて、剥離速度３００ｍｍ／分、剥離角度１８０°の条件で、剥離強度を測定した（剥離強度Ａ）。評価は、下記基準に基づいて評価した。
評価基準
◎：剥離強度Ａが４Ｎ／２５ｍｍ以上８Ｎ／２５ｍｍ未満（優良）
○：剥離強度Ａが２Ｎ／２５ｍｍ以上４Ｎ／２５ｍｍ未満または８Ｎ／２５ｍｍ以上１０Ｎ／２５ｍｍ未満（良好）
△：剥離強度Ａが０．５Ｎ／２５ｍｍ以上２Ｎ／２５ｍｍ未満または１０Ｎ／２５ｍｍ以上１２Ｎ／２５ｍｍ未満（使用可）
×：剥離強度Ａが０．５Ｎ／２５ｍｍ未満または１２Ｎ／２５ｍｍ以上（使用不可）
(1) Adhesive strength The obtained adhesive sheet was cut out to have a width of 25 mm and a length of 150 mm. Next, in an environment of 23 ° C. and 50% RH, the adhesive layer exposed by peeling the peelable sheet from the adhesive sheet was attached to a stainless steel (SUS) plate and reciprocated once by a 2 kg roll to prepare a measurement sample. After storing this measurement sample for 24 hours in an environment of 23 ° C. and 50% RH, using a tensile tester (“Tensilon” manufactured by Orientec Co., Ltd.) under the conditions of a peeling speed of 300 mm / min and a peeling angle of 180 °, The peel strength was measured (peel strength A). Evaluation was performed based on the following criteria.
Evaluation criteria A: Peel strength A is 4 N / 25 mm or more and less than 8 N / 25 mm (excellent)
○: Peel strength A is 2N / 25mm or more and less than 4N / 25mm or 8N / 25mm or more and less than 10N / 25mm (good)
Δ: Peel strength A is 0.5 N / 25 mm or more and less than 2 N / 25 mm or 10 N / 25 mm or more and less than 12 N / 25 mm (usable)
X: Peel strength A is less than 0.5 N / 25 mm or 12 N / 25 mm or more (unusable)
（２）保持力
得られた粘着シートを幅２５ｍｍ、長さ１５０ｍｍの大きさに切り出した。切り出した粘着シートから剥離性シートを剥がして露出した粘着剤層を、幅３０ｍｍ、長さ１５０ｍｍのＳＵＳ板の下端部幅２５ｍｍ、長さ２５ｍｍの部分に貼着し、２ｋｇロールで１往復させて圧着後、８０℃雰囲気で粘着シートの下端部に１ｋｇの荷重をかけ、７万秒放置することで保持力を測定した。評価は、粘着シートの貼付面上端部が元の位置から下にずれた長さを測定した。
評価基準
○：ずれた長さが０．５ｍｍ未満（良好）
△：ずれた長さが０．５ｍｍ以上２ｍｍ未満（使用可）
×：ずれた長さが２ｍｍ以上（使用不可）
(2) Holding power The obtained pressure-sensitive adhesive sheet was cut into a size of 25 mm in width and 150 mm in length. The pressure-sensitive adhesive layer exposed by peeling off the peelable sheet from the cut-out pressure-sensitive adhesive sheet is attached to a portion having a width of 25 mm and a length of 25 mm at the lower end of a SUS plate having a width of 30 mm and a length of 150 mm. After crimping, a 1 kg load was applied to the lower end of the pressure-sensitive adhesive sheet in an 80 ° C. atmosphere, and the holding power was measured by leaving it to stand for 70,000 seconds. Evaluation measured the length which the upper end part of the sticking surface of the adhesive sheet shifted | deviated below from the original position.
Evaluation criteria ○: The shifted length is less than 0.5 mm (good)
Δ: The shifted length is 0.5 mm or more and less than 2 mm (usable)
×: The shifted length is 2 mm or more (unusable)
（３）耐熱性および耐湿熱性
得られた粘着シートを幅２５ｍｍ、長さ１５０ｍｍの大きさに切り出した。次いで２３℃５０％ＲＨの環境下、試料から剥離性シートを剥がして露出した粘着剤層を、ＳＵＳ板に貼付し、２ｋｇロールにより１往復させて測定試料を作製した。この測定試料を、８５℃５％ＲＨの環境下で７日間保存した後（耐熱性）、あるいは、６０℃９５％ＲＨの環境下で７日間保存した後（耐湿熱性）、引張試験機（オリエンテック社製「テンシロン」）を用いて、剥離速度３００ｍｍ／分、剥離角度１８０°の条件で測定（剥離強度Ｂ）、および剥離後のＳＵＳ板表面の糊残りを目視で観察し、以下の基準に基づいて評価した。ただし、Ｂ／Ａ＝剥離強度Ｂ／剥離強度Ａとする。
評価基準
◎：Ｂ／Ａが１．５未満かつ糊残りが認められない。（優良）
○：Ｂ／Ａが１．５以上２．０未満かつ糊残りが認められない。（良好）
△：Ｂ／Ａが２．０以上３．０未満かつ糊残りが認められない。（使用可）
×：Ｂ／Ａが３．０以上または糊残りが認められる。（使用不可）
(3) Heat resistance and wet heat resistance The obtained pressure-sensitive adhesive sheet was cut into a size of 25 mm in width and 150 mm in length. Next, in an environment of 23 ° C. and 50% RH, the pressure-sensitive adhesive layer exposed by peeling the peelable sheet from the sample was attached to a SUS plate and reciprocated once by a 2 kg roll to prepare a measurement sample. After storing this measurement sample in an environment of 85 ° C. and 5% RH for 7 days (heat resistance) or after storage in an environment of 60 ° C. and 95% RH for 7 days (moisture heat resistance), a tensile tester (Oriente ("Tensilon" manufactured by Ku-ku) was measured under the conditions of a peeling speed of 300 mm / min and a peeling angle of 180 ° (peeling strength B), and the adhesive residue on the surface of the SUS plate after peeling was visually observed. Based on the evaluation. However, B / A = Peel strength B / Peel strength A.
Evaluation criteria A: B / A is less than 1.5 and no adhesive residue is observed. (Excellent)
A: B / A is 1.5 or more and less than 2.0, and no adhesive residue is observed. (Good)
Δ: B / A is 2.0 or more and less than 3.0 and no adhesive residue is observed. (Available)
X: B / A is 3.0 or more or adhesive residue is recognized. (Usage prohibited)
（４）剥離感
得られた粘着シートを幅２５ｍｍ、長さ１５０ｍｍの大きさに切り出した。次いで２３℃５０％ＲＨの環境下、粘着シートから剥離性シートを剥がして露出した粘着剤層を、ＳＵＳ板に貼付し、２ｋｇロールにより１往復させて測定試料を作製した。この測定試料を、２３℃５０％ＲＨの環境下で７日間保存した後、手による剥離を行い、剥離感および剥離時の引っかかり（ジッピング現象）の有無を確認した。評価は、下記基準に基づいて評価した。
評価基準
◎：剥離は軽く、ジッピング現象が認められない。（優良）
○：剥離は軽いが、わずかにジッピング現象が認められる。（良好）
×：剥離が重い、あるいは、ジッピング現象が認められる。（使用不可）
(4) Peeling feeling The obtained pressure-sensitive adhesive sheet was cut into a size of 25 mm in width and 150 mm in length. Next, in an environment of 23 ° C. and 50% RH, the pressure-sensitive adhesive layer exposed by peeling the peelable sheet from the pressure-sensitive adhesive sheet was attached to a SUS plate and reciprocated once by a 2 kg roll to prepare a measurement sample. This measurement sample was stored for 7 days in an environment of 23 ° C. and 50% RH, and then peeled by hand to confirm the feeling of peeling and the presence or absence of peeling (zipping phenomenon). Evaluation was performed based on the following criteria.
Evaluation criteria A: Peeling is light and no zipping phenomenon is observed. (Excellent)
○: Peeling is light, but a slight zipping phenomenon is observed. (Good)
X: Heavy peeling or zipping phenomenon is observed. (Usage prohibited)
表３、４の結果から、本発明の粘着剤は、粘着力が低すぎず適度な粘着力を有しながら剥離時の引っかかり（ジッピング現象）を抑制し、更には高温、高湿熱下に曝された後においても再剥離性に優れることが確認できた。 From the results shown in Tables 3 and 4, the pressure-sensitive adhesive of the present invention has a moderate pressure-sensitive adhesive strength and suppresses the catching (zipping phenomenon) at the time of peeling, and is further exposed to high temperature and high humidity heat. It was confirmed that the film was excellent in removability even after being applied.
Claims (4)
前記アクリル系共重合体（Ａ）は、ガラス転移温度（Ｔｇ）が−６６〜−５２℃であり、かつ
前記アクリル系共重合体（Ａ）は、アルキル基の炭素数が８である（メタ）アクリル酸アルキルエステルモノマー（ａ１）、反応性官能基を有するモノマー（ａ２）、およびホモポリマーのＴｇが−４５℃以上であるラジカル重合性モノマー（ａ３）(ただし、アルキル基の炭素数が８である（メタ）アクリル酸アルキルエステルモノマー（ａ１）、および反応性官能基を有するモノマー（ａ２）である場合を除く）を含むラジカル重合性モノマー混合物の共重合体であり、
前記反応性官能基を有するモノマー（ａ２）の含有量は、前記ラジカル重合性モノマー混合物１００質量％中、０を超えて１０質量％以下であり、
前記ホモポリマーのＴｇが−４５℃以上であるラジカル重合性モノマー（ａ３）の含有量は、前記ラジカル重合性モノマー混合物１００質量％中、５質量％以上４０質量％以下であり、
前記酸化防止剤（Ｃ）はリン系酸化防止剤を含み、
前記リン系酸化防止剤の含有量は、前記アクリル系共重合体（Ａ）１００質量部に対して、０．１５〜１．５質量部である、粘着剤。 An adhesive comprising an acrylic copolymer (A), a curing agent (B) and an antioxidant (C),
The acrylic copolymer (A) has a glass transition temperature (Tg) of −66 to −52 ° C., and the acrylic copolymer (A) has an alkyl group with 8 carbon atoms (meta ) acrylic acid alkyl ester monomer (a1), a monomer having a reactivity functional group (a2), and a radical polymerizable monomer Tg of -45 ° C. or more homopolymers (a3) (provided that the number of carbon atoms in the alkyl group is 8 (Meth) acrylic acid alkyl ester monomer (a1) and a monomer having a reactive functional group (except for the case where it is a monomer (a2)), a copolymer of a radical polymerizable monomer mixture,
The content of the monomer (a2) having a reactive functional group is more than 0 and 10% by mass or less in 100% by mass of the radical polymerizable monomer mixture,
The content of the radical polymerizable monomer (a3) having a Tg of the homopolymer of −45 ° C. or more is 5% by mass or more and 40% by mass or less in 100% by mass of the radical polymerizable monomer mixture,
The antioxidant (C) includes a phosphorus antioxidant,
Content of the said phosphorus antioxidant is an adhesive which is 0.15-1.5 mass part with respect to 100 mass parts of said acrylic copolymers (A).
An adhesive sheet provided with the adhesive layer formed from a base material and the adhesive of any one of Claims 1-3 .
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004826A (en) * | 2019-12-20 | 2021-06-22 | 3M创新有限公司 | Conductive adhesive tape, laminate and method for producing the same |
| JP2021095483A (en) * | 2019-12-17 | 2021-06-24 | 東洋インキＳｃホールディングス株式会社 | Adhesive agent and adhesive sheet |
| CN114656903A (en) * | 2022-04-28 | 2022-06-24 | 常州都铂高分子有限公司 | Glue with good re-peeling performance |
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| JP5061898B2 (en) * | 2005-06-24 | 2012-10-31 | 東洋インキＳｃホールディングス株式会社 | Antistatic acrylic adhesive |
| WO2008139742A1 (en) * | 2007-05-07 | 2008-11-20 | Lintec Corporation | Pressure-sensitive adhesive sheet |
| JPWO2014092186A1 (en) * | 2012-12-13 | 2017-01-12 | 東亞合成株式会社 | Active energy ray-curable adhesive composition |
| JP6126500B2 (en) * | 2013-08-30 | 2017-05-10 | 日東電工株式会社 | Carrier film and laminate for transparent conductive film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2021095483A (en) * | 2019-12-17 | 2021-06-24 | 東洋インキＳｃホールディングス株式会社 | Adhesive agent and adhesive sheet |
| JP7338444B2 (en) | 2019-12-17 | 2023-09-05 | 東洋インキＳｃホールディングス株式会社 | Adhesives and adhesive sheets |
| CN113004826A (en) * | 2019-12-20 | 2021-06-22 | 3M创新有限公司 | Conductive adhesive tape, laminate and method for producing the same |
| CN114656903A (en) * | 2022-04-28 | 2022-06-24 | 常州都铂高分子有限公司 | Glue with good re-peeling performance |
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