JP7310135B2 - Adhesive sheet for vinyl chloride film containing plasticizer and acrylic adhesive - Google Patents
Adhesive sheet for vinyl chloride film containing plasticizer and acrylic adhesive Download PDFInfo
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- JP7310135B2 JP7310135B2 JP2018244973A JP2018244973A JP7310135B2 JP 7310135 B2 JP7310135 B2 JP 7310135B2 JP 2018244973 A JP2018244973 A JP 2018244973A JP 2018244973 A JP2018244973 A JP 2018244973A JP 7310135 B2 JP7310135 B2 JP 7310135B2
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- sensitive adhesive
- meth
- plasticizer
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- 239000004014 plasticizer Substances 0.000 title claims description 90
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 81
- 239000000853 adhesive Substances 0.000 title claims description 57
- 230000001070 adhesive effect Effects 0.000 title claims description 57
- 239000003522 acrylic cement Substances 0.000 title description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 105
- 239000000178 monomer Substances 0.000 claims description 80
- 239000012790 adhesive layer Substances 0.000 claims description 50
- 239000010410 layer Substances 0.000 claims description 47
- 239000003795 chemical substances by application Substances 0.000 claims description 44
- 239000004925 Acrylic resin Substances 0.000 claims description 42
- 229920000178 Acrylic resin Polymers 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 238000003860 storage Methods 0.000 claims description 18
- 230000009477 glass transition Effects 0.000 claims description 14
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 12
- 150000002513 isocyanates Chemical class 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 229920001567 vinyl ester resin Polymers 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920006243 acrylic copolymer Polymers 0.000 claims description 2
- 239000010408 film Substances 0.000 description 89
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 54
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 40
- -1 (meth)acrylic acid acrylic ester Chemical class 0.000 description 39
- 238000001723 curing Methods 0.000 description 34
- 239000004342 Benzoyl peroxide Substances 0.000 description 29
- 235000019400 benzoyl peroxide Nutrition 0.000 description 29
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 230000005012 migration Effects 0.000 description 11
- 238000013508 migration Methods 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 230000000977 initiatory effect Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000013522 chelant Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 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 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 2
- 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 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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 2
- 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 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000002928 artificial marble Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- 229920003067 (meth)acrylic acid ester copolymer Polymers 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
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-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
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 1
- RESLDRQKMNCSIC-UHFFFAOYSA-N 2-(2-hydroxyethoxycarbonyl)benzoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOC(=O)C1=CC=CC=C1C(O)=O RESLDRQKMNCSIC-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
- 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
- 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
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Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、可塑剤を含有する塩化ビニルフィルムに用いられる粘着剤層を形成するための粘着シート、およびアクリル系粘着剤に関する。 TECHNICAL FIELD The present invention relates to a pressure-sensitive adhesive sheet for forming a pressure-sensitive adhesive layer used in a vinyl chloride film containing a plasticizer, and an acrylic pressure-sensitive adhesive.
シールやラベルといった粘着剤層を含む粘着シートは、対象物（被着体）に対し容易に貼り合せが可能であることから幅広い分野で使用されており、耐久性、透明性等に優れていることから、アクリル系粘着剤が一般的に用いられている。
しかしこのようなアクリル系粘着剤を用いて形成されてなるアクリル系粘着シートを被着体として塩化ビニルフィルム（以下、ＰＶＣフィルムということもある）にラベルとして使用する場合、ポリ塩化ビニル中に含まれる可塑剤が、粘着シートの粘着剤層表面へ移行することで粘着力が低下し、加熱時の塩ビフィルムの収縮に追従できず剥がれ易いという問題があった。
Adhesive sheets including an adhesive layer such as stickers and labels are used in a wide range of fields because they can be easily attached to an object (adherend), and are excellent in durability, transparency, etc. Therefore, acrylic adhesives are generally used.
However, when an acrylic pressure-sensitive adhesive sheet formed using such an acrylic pressure-sensitive adhesive is used as a label on a vinyl chloride film (hereinafter sometimes referred to as a PVC film) as an adherend, There is a problem that the plasticizer in the adhesive sheet migrates to the surface of the adhesive layer of the adhesive sheet, resulting in a decrease in adhesive strength, and the adhesive sheet cannot follow the shrinkage of the PVC film during heating and is easily peeled off.
このような問題を解決するための方法として、例えば特許文献１には、ポリ塩化ビニル基材フィルム上に、メチル（メタ）アクリレート単位を３５～８５質量％、２－エチルへキシルアクリレート単位を１０～６０質量％、カルボキシル基を有する単量体単位を０．５～１０質量％、ヒドロキシル基を有する単量体単位を０．０１～５質量％を含む（メタ）アクリル酸エステル共重合体１００質量部と、イソシアネート系硬化剤０．１～７質量部と、エポキシ系硬化剤０～０．２５質量部を含む粘着シートが開示されている。 As a method for solving such problems, for example, in Patent Document 1, 35 to 85% by mass of methyl (meth)acrylate units and 10 of 2-ethylhexyl acrylate units are added to a polyvinyl chloride base film. ~60% by mass, 0.5 to 10% by mass of monomer units having a carboxyl group, and 0.01 to 5% by mass of monomer units having a hydroxyl group (meth)acrylic acid ester copolymer 100 A pressure-sensitive adhesive sheet containing parts by weight, 0.1 to 7 parts by weight of an isocyanate curing agent, and 0 to 0.25 parts by weight of an epoxy curing agent is disclosed.
また、特許文献２には、アルキル基の炭素数４である（メタ）アクリル酸アルキルエステルモノマー、アルキル基の炭素数１～２である（メタ）アクリル酸アルキルエステルモノマーおよびカルボキシル基含有モノマーを含むモノマー混合物の共重合物であるアクリル系樹脂、ならびにイソシアネート硬化剤、エポキシ化合物および金属キレートから選ばれる少なくとも１種の硬化剤を含んでなる粘着剤から形成された粘着剤層の周波数１Ｈｚ、７０℃での貯蔵弾性率が、０．０５～１ＭＰａであるポリ塩化ビニル用粘着剤が開示されている。 Further, Patent Document 2 includes a (meth)acrylic acid alkyl ester monomer having an alkyl group having 4 carbon atoms, a (meth)acrylic acid alkyl ester monomer having an alkyl group having 1 to 2 carbon atoms, and a carboxyl group-containing monomer. Frequency 1 Hz, 70° C. of the pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive comprising an acrylic resin that is a copolymer of a monomer mixture and at least one curing agent selected from an isocyanate curing agent, an epoxy compound and a metal chelate. A pressure-sensitive adhesive for polyvinyl chloride having a storage modulus of 0.05 to 1 MPa is disclosed.
これらのように、可塑剤が移行することを想定してあらかじめ硬い粘着剤層とすることで当該問題を解決しようとする試みは見られるものの、そうした粘着シートでは、塩化ビニルフィルムの収縮に粘着剤層が追従できない、という問題があった。 Although there are attempts to solve this problem by presuming that the plasticizer will migrate, the pressure-sensitive adhesive layer is made hard in advance. There was a problem that the layer could not follow.
本発明が解決しようとする課題は、良好な耐可塑剤性と、ＰＶＣフィルム変形追従性と、加工性とを有する粘着シート、および該粘着シートを形成するアクリル系粘着剤を提供することである。 The problem to be solved by the present invention is to provide a pressure-sensitive adhesive sheet having good plasticizer resistance, PVC film deformation followability, and workability, and an acrylic pressure-sensitive adhesive forming the pressure-sensitive adhesive sheet. .
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、以下に示す可塑剤含有塩化ビニルフィルム用粘着シートにより、上記課題を解決できることを見出し、本発明を完成するに至った。 The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by the plasticizer-containing pressure-sensitive adhesive sheet for vinyl chloride film shown below, and have completed the present invention.
即ち、アクリル系樹脂（Ａ）および硬化剤（Ｂ）を含む粘着剤層（Ｘ）を有する可塑剤含有塩化ビニルフィルム用粘着シートであって、前記粘着剤層（Ｘ）の周波数１Ｈｚ、７０℃でのせん断貯蔵弾性率は０．０５ＭＰａ未満であり、かつ可塑剤を３６質量％含有する、厚み４００μｍの塩化ビニルフィルムに、前記粘着剤層（Ｘ）を貼付し、７０℃５日間加熱後、さらに２５℃―５０％ＲＨ環境下５日経時後の前記塩化ビニルフィルムから粘着剤層（Ｘ）への可塑剤移行量が、粘着剤層（Ｘ）１００質量部に対して２０質量部以上である、可塑剤含有塩化ビニルフィルム用粘着シートに関する。 That is, a pressure-sensitive adhesive sheet for a plasticizer-containing vinyl chloride film having a pressure-sensitive adhesive layer (X) containing an acrylic resin (A) and a curing agent (B), wherein the frequency of the pressure-sensitive adhesive layer (X) is 1 Hz, 70 ° C. The pressure-sensitive adhesive layer (X) is attached to a vinyl chloride film having a thickness of 400 μm, which has a shear storage elastic modulus of less than 0.05 MPa and contains 36% by mass of a plasticizer, and after heating at 70° C. for 5 days, Furthermore, the plasticizer migration amount from the vinyl chloride film to the adhesive layer (X) after 5 days in a 25 ° C.-50% RH environment is 20 parts by mass or more with respect to 100 parts by mass of the adhesive layer (X). The present invention relates to a pressure-sensitive adhesive sheet for a plasticizer-containing vinyl chloride film.
また、本発明は、前記アクリル系樹脂（Ａ）は、モノマー混合物を共重合してなるアクリル系共重合体であって、前記モノマー混合物１００質量％中、水酸基を有するモノマー（ａ２）を０．０１～１質量％含む、前記可塑剤含有塩化ビニルフィルム用粘着シートに関する。 Further, according to the present invention, the acrylic resin (A) is an acrylic copolymer obtained by copolymerizing a monomer mixture, wherein 0.0% of the monomer (a2) having a hydroxyl group is contained in 100% by mass of the monomer mixture. It relates to the plasticizer-containing pressure-sensitive adhesive sheet for vinyl chloride film containing 01 to 1% by mass.
また、本発明は、前記硬化剤（Ｂ）は、イソシアネート硬化剤を含み、かつ前記硬化剤（Ｂ）の含有量は、アクリル系樹脂（Ａ）１００質量部に対して、０．０１～０．６質量部である、前記可塑剤含有塩化ビニルフィルム用粘着シートに関する。 Further, in the present invention, the curing agent (B) contains an isocyanate curing agent, and the content of the curing agent (B) is 0.01 to 0 with respect to 100 parts by mass of the acrylic resin (A). .6 parts by mass of the pressure-sensitive adhesive sheet for a plasticizer-containing vinyl chloride film.
また、本発明は、前記アクリル系樹脂（Ａ）の重量平均分子量は、６０万～１５０万である、前記可塑剤含有塩化ビニルフィルム用粘着シートに関する。 The present invention also relates to the plasticizer-containing pressure-sensitive adhesive sheet for a vinyl chloride film, wherein the acrylic resin (A) has a weight average molecular weight of 600,000 to 1,500,000.
また、本発明は、前記モノマー混合物は、アルキル基の炭素数８～１２の（メタ）アクリル酸アルキルエステルを含む、前記可塑剤含有塩化ビニルフィルム用粘着シートに関する。 The present invention also relates to the plasticizer-containing pressure-sensitive adhesive sheet for a vinyl chloride film, wherein the monomer mixture contains a (meth)acrylic acid alkyl ester having an alkyl group of 8 to 12 carbon atoms.
また、本発明は、前記モノマー混合物１００質量％中、アルキル基の炭素数８～１２の（メタ）アクリル酸アルキルエステルの含有量が６０～８４質量％である、前記可塑剤含有塩化ビニルフィルム用粘着シートに関する。 Further, the present invention provides the plasticizer-containing vinyl chloride film, wherein the content of (meth)acrylic acid alkyl ester having an alkyl group with 8 to 12 carbon atoms in 100% by mass of the monomer mixture is 60 to 84% by mass. Regarding the adhesive sheet.
また、本発明は、前記モノマー混合物は、ガラス転移温度Ｔｇが０℃以上の、（メタ）アクリル酸アクリルエステルまたはビニルエステル類を含む、前記可塑剤含有塩化ビニルフィルム用粘着シートに関する。 The present invention also relates to the plasticizer-containing pressure-sensitive adhesive sheet for a vinyl chloride film, wherein the monomer mixture contains a (meth)acrylic acid acrylic ester or vinyl ester having a glass transition temperature Tg of 0° C. or higher.
また、本発明は、前記モノマー混合物１００質量％中、ガラス転移温度Ｔｇが０℃以上の、（メタ）アクリル酸アクリルエステルまたはビニルモノマーを１５～３５質量％含む、前記可塑剤含有塩化ビニルフィルム用粘着シートに関する。 Further, the present invention provides the plasticizer-containing vinyl chloride film containing 15 to 35% by mass of a (meth)acrylic acid acrylic ester or a vinyl monomer having a glass transition temperature Tg of 0 ° C. or higher in 100% by mass of the monomer mixture. Regarding the adhesive sheet.
また、本発明は、請求項１～８いずれか１項記載の可塑剤含有塩化ビニルフィルム用粘着シートの粘着剤層（Ｘ）を形成するためのアクリル系粘着剤に関する。 The present invention also relates to an acrylic pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer (X) of the plasticizer-containing pressure-sensitive adhesive sheet for vinyl chloride film according to any one of claims 1 to 8.
本発明により、良好な耐可塑剤性、塩化ビニルフィルム変形追従性、加工性を有する粘着シート、および該粘着シートを形成するためのアクリル系粘着剤を提供できるようになった。 ADVANTAGE OF THE INVENTION By this invention, the acrylic pressure sensitive adhesive for forming the adhesive sheet which has favorable plasticizer resistance, vinyl chloride film deformation|transformation followability, and processability, and this adhesive sheet can now be provided.
本発明について詳細に説明する前に用語を定義する。まず、シート、フィルムおよびテープは、同義である。（メタ）アクリル酸とは、アクリル酸およびメタクリル酸を意味する。モノマーとは、エチレン性不飽和二重結合含有単量体を意味する。被着体とは、粘着シートを貼り付ける相手方を指す。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。 Terms are defined before describing the present invention in detail. First, sheet, film and tape are synonymous. (Meth)acrylic acid means acrylic acid and methacrylic acid. By monomer is meant an ethylenically unsaturated double bond-containing monomer. The adherend refers to the other party to which the pressure-sensitive adhesive sheet is attached. In addition, "parts" and "%" represent "mass parts" and "mass%", respectively, unless otherwise specified.
《可塑剤含有塩化ビニルフィルム用粘着シート》
本発明の粘着シートは、可塑剤含有塩化ビニルフィルムと、粘着剤層（Ｘ）とを貼付するために用いられるが、粘着シートが有する基材が可塑剤含有塩化ビニルフィルムであってもよく、または被着体が可塑剤含有塩化ビニルフィルムである場合であってもよい。
なお、基材が可塑剤含有塩化ビニルフィルムである場合には、粘着剤層（Ｘ）のせん断貯蔵弾性率および可塑剤移行量は、可塑剤含有塩化ビニルフィルムではない基材を用いて同条件（粘着剤層の組成、膜厚等）にて粘着剤層を作製した粘着シートを用いて求めることができる。
本発明の可塑剤含有塩化ビニルフィルム用粘着シートの粘着剤層（Ｘ）は、アクリル系樹脂（Ａ）および硬化剤（Ｂ）を含み、前記粘着剤層（Ｘ）の周波数１Ｈｚ、７０℃でのせん断貯蔵弾性率は０．０５ＭＰａ未満であり、かつ可塑剤を３６質量％含有する、厚み４００μｍの塩化ビニルフィルムに、前記粘着剤層（Ｘ）を貼付し、７０℃５日間加熱後、さらに２５℃―５０％ＲＨ環境下５日経時後の前記塩化ビニルフィルムから粘着剤層（Ｘ）への可塑剤移行量が、粘着剤層（Ｘ）１００質量部に対して２０質量部以上である。
《Adhesive sheet for vinyl chloride film containing plasticizer》
The pressure-sensitive adhesive sheet of the present invention is used for attaching the plasticizer-containing vinyl chloride film and the pressure-sensitive adhesive layer (X). Alternatively, the adherend may be a vinyl chloride film containing a plasticizer.
When the substrate is a plasticizer-containing vinyl chloride film, the shear storage modulus and the amount of plasticizer migration of the pressure-sensitive adhesive layer (X) are measured under the same conditions using a substrate that is not a plasticizer-containing vinyl chloride film. (Composition of adhesive layer, film thickness, etc.) can be determined using an adhesive sheet having an adhesive layer formed thereon.
The pressure-sensitive adhesive layer (X) of the pressure-sensitive adhesive sheet for a plasticizer-containing vinyl chloride film of the present invention contains an acrylic resin (A) and a curing agent (B), and the frequency of the pressure-sensitive adhesive layer (X) is 1 Hz at 70°C. The adhesive layer (X) is attached to a vinyl chloride film having a thickness of 400 μm, which has a shear storage modulus of less than 0.05 MPa and contains 36% by mass of a plasticizer, and after heating at 70 ° C. for 5 days, further The amount of plasticizer transferred from the vinyl chloride film to the adhesive layer (X) after 5 days in a 25° C.-50% RH environment is 20 parts by mass or more with respect to 100 parts by mass of the adhesive layer (X). .
本発明の粘着シートは、本発明の粘着シートを用いて形成した粘着剤層に加え、基材を備えていることが好ましい。また別の態様として、芯材の両面に粘着剤層を有する両面粘着シート、または基材および芯材を有さず粘着剤層のみで構成されたキャスト粘着シートも好ましい。前記粘着剤層は、粘着剤を基材上に塗工し、乾燥することで形成できる。または、粘着剤を剥離性シート上に塗工し、乾燥して粘着剤層を形成した後、基材を貼り合わせることで形成できる。 The pressure-sensitive adhesive sheet of the present invention preferably has a substrate in addition to the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive sheet of the present invention. As another aspect, a double-sided pressure-sensitive adhesive sheet having pressure-sensitive adhesive layers on both sides of a core material, or a cast pressure-sensitive adhesive sheet having only a pressure-sensitive adhesive layer without a base material and a core material is also preferable. The pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive onto a substrate and drying it. Alternatively, it can be formed by coating a release sheet with an adhesive, drying it to form an adhesive layer, and then laminating a substrate.
前記粘着剤を塗工する際に、溶液重合で説明した溶剤を添加して粘度を調整することができる。 When applying the pressure-sensitive adhesive, the viscosity can be adjusted by adding the solvent described in the solution polymerization.
被着体が可塑剤含有塩化ビニルフィルムである場合、粘着シートの基材は、塩化ビニルフィルム以外にも、例えばセロハン、その他プラスチック、ゴム、発泡体、布帛、ゴムびき布、樹脂含浸布、ガラス、および木材等を用いることができる。基材の形状は、板状およびフィルム状を選択できるが、取り扱いが容易であるフィルム状が好ましい。基材は、単独または２種以上の積層体を使用できる。 When the adherend is a vinyl chloride film containing a plasticizer, the base material of the pressure-sensitive adhesive sheet may be, in addition to the vinyl chloride film, for example, cellophane, other plastics, rubber, foam, fabric, rubberized cloth, resin-impregnated cloth, glass. , and wood etc. can be used. The shape of the base material can be selected from a plate shape and a film shape, but the film shape is preferable because it is easy to handle. A single substrate or a laminate of two or more substrates can be used.
＜塩化ビニルフィルム＞
被着体として用いられる塩化ビニルフィルムは、塩化ビニルモノマーを重合させた後、可塑剤等の添加剤にて軟質化・安定化させた樹脂をフィルム状に成形したものである。重合条件や添加剤の調整により優れた耐久性、耐候性、耐薬品性、透明性、加工性を発現する。非常に低価格で製造可能なことから、工業材、建築材、自動車部材は勿論、消費者が使用する一般消費財としても広く用いられている。
塩化ビニルフィルムが含有する好ましい可塑剤量としては、塩化ビニルフィルム中に５質量％～５５質量％である。
また、塩化ビニルフィルムの厚さは、用途により適宜選択することができ、特に制限されないが、好ましくは２５μｍ～２０００ｍｍ程度である。
<Vinyl chloride film>
A vinyl chloride film used as an adherend is formed by polymerizing a vinyl chloride monomer and then softening and stabilizing the resin with an additive such as a plasticizer to form a film. Excellent durability, weather resistance, chemical resistance, transparency and workability can be achieved by adjusting the polymerization conditions and additives. Since it can be manufactured at a very low cost, it is widely used not only for industrial materials, construction materials, and automobile materials, but also for general consumer goods used by consumers.
A preferred amount of the plasticizer contained in the vinyl chloride film is 5% by mass to 55% by mass in the vinyl chloride film.
The thickness of the vinyl chloride film can be appropriately selected depending on the application and is not particularly limited, but is preferably about 25 μm to 2000 mm.
［可塑剤］
塩化ビニルフィルムが含有する可塑剤には、塩化ビニル樹脂との相溶性に優れ、少ない添加量で必要な柔軟性を発現し、また揮発性の低いものが用いられる。これら基本性能に加え、用途別に求められる性質に合致した可塑剤が選定されており、例えば食品ラップフィルムではアジピン酸エステル、医療用途ではフタル酸エステル、乳児用玩具ではクエン酸エステル等が代表的に用いられる。
本発明の塩化ビニルフィルム用粘着シートは、上記塩化ビニルフィルムが含有する可塑剤の、粘着層への移行量を制御することで、種々の用途に展開される塩化ビニルフィルム全般に好適に使用可能である。
[Plasticizer]
As the plasticizer contained in the vinyl chloride film, one having excellent compatibility with the vinyl chloride resin, exhibiting the necessary flexibility with a small addition amount, and having low volatility is used. In addition to these basic functions, plasticizers are selected according to the properties required for each application. For example, adipate esters for food wrap films, phthalate esters for medical applications, and citrate esters for baby toys are typical. Used.
The pressure-sensitive adhesive sheet for vinyl chloride films of the present invention can be suitably used for general vinyl chloride films that are developed for various purposes by controlling the amount of migration of the plasticizer contained in the vinyl chloride film to the adhesive layer. is.
前記その他プラスチックは、例えばポリビニルアルコール、トリアセチルセルロース、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等のポリオレフィン；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、およびポリエチレンナフタレート等のポリエステル；ポリカーボネート、ポリノルボルネン、ポリアリレート、ポリアクリル、ポリフェニレンサルファイドム、ポリスチレン、ポリアミド、およびポリイミド等が挙げられる。 The other plastics include, for example, polyolefins such as polyvinyl alcohol, triacetyl cellulose, polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymer; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; norbornene, polyarylate, polyacryl, polyphenylene sulfide, polystyrene, polyamide, polyimide, and the like.
＜粘着剤層＞
粘着剤層は、アクリル系樹脂（Ａ）および硬化剤（Ｂ）を含み、アクリル系樹脂（Ａ）および硬化剤（Ｂ）を含有するアクリル系粘着剤を用いて形成することができる。
本発明は、粘着剤層の周波数１Ｈｚ、７０℃でのせん断貯蔵弾性率が０．０５ＭＰａ未満である。さらに、可塑剤を３６％含有する、厚み４００μｍの塩化ビニルフィルムに、粘着剤層を貼付し、７０℃５日間加熱後、さらに２５℃―５０％ＲＨ環境下５日経時後の塩化ビニルフィルムから粘着剤層への可塑剤移行量が、粘着剤層１００質量部に対して２０質量部以上である。
このような粘着剤層を有することにより、良好な耐可塑剤性、塩化ビニルフィルム変形追従性、加工性を有することができる。
<Adhesive layer>
The adhesive layer contains an acrylic resin (A) and a curing agent (B), and can be formed using an acrylic adhesive containing the acrylic resin (A) and the curing agent (B).
In the present invention, the pressure-sensitive adhesive layer has a shear storage modulus of less than 0.05 MPa at a frequency of 1 Hz and 70°C. Furthermore, a 400 μm thick vinyl chloride film containing 36% of a plasticizer is attached with an adhesive layer, heated at 70 ° C. for 5 days, and further from the vinyl chloride film after 5 days in a 25 ° C.-50% RH environment. The amount of plasticizer migrated to the adhesive layer is 20 parts by mass or more with respect to 100 parts by mass of the adhesive layer.
By having such an adhesive layer, it is possible to have good plasticizer resistance, vinyl chloride film deformation followability, and workability.
粘着剤の塗工方法は、特に制限は無く、例えばマイヤーバー、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、およびスピンコーター等が挙げられる。塗工に際して乾燥工程を行うことが好ましい。乾燥装置は、特に制限は無く、例えば熱風乾燥機、赤外線ヒーターおよび減圧法等が挙げられる。乾燥温度は、通常６０～１４０℃程度である。 The method of applying the adhesive is not particularly limited, and examples thereof include Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, knife coater, reverse coater, and spin coater. be done. It is preferable to carry out a drying process during coating. The drying apparatus is not particularly limited, and examples thereof include hot air dryers, infrared heaters, decompression methods, and the like. The drying temperature is usually about 60 to 140°C.
粘着剤層の厚さは、１～３００μｍが好ましく、５～１００μｍがより好ましい。１～３００μｍの範囲にあることで粘着物性を適切な範囲に調整できる。 The thickness of the adhesive layer is preferably 1-300 μm, more preferably 5-100 μm. When the thickness is in the range of 1 to 300 μm, the adhesive physical properties can be adjusted to an appropriate range.
［可塑剤移行量］
本発明の粘着シートは、塩化ビニルフィルム（１００質量％）中に可塑剤を３６質量％含有する、厚み４００μｍの塩化ビニルフィルムに、粘着シートの粘着剤層（Ｘ）を貼付し、７０℃５日間加熱後、さらに２５℃―５０％ＲＨ環境下５日経時後の前記塩化ビニルフィルムから粘着剤層（Ｘ）への可塑剤移行量が、粘着剤層（Ｘ）１００質量部に対して２０質量部以上である。
[Amount of plasticizer migration]
The pressure-sensitive adhesive sheet of the present invention is obtained by attaching the pressure-sensitive adhesive layer (X) of the pressure-sensitive adhesive sheet to a vinyl chloride film (100% by weight) containing 36% by weight of a plasticizer and having a thickness of 400 μm. After heating for 5 days, the amount of plasticizer transferred from the vinyl chloride film to the adhesive layer (X) after 5 days in a 25 ° C.-50% RH environment was 20 parts per 100 parts by mass of the adhesive layer (X). Part by mass or more.
可塑剤移行量は、粘着剤層（Ｘ）に対し、あらかじめ塩化ビニルフィルムが含有する可塑剤と、同じ可塑剤を加えて作成した検量線を用い、粘着剤層中の可塑剤量を測定することで求めることができる。すなわち、粘着シートの粘着剤層（Ｘ）を塩化ビニルフィルム（１００質量％）中に可塑剤を３６質量％含有する、厚み４００μｍの塩化ビニルフィルムに貼付、７０℃５日間加熱後、さらに２５℃―５０％ＲＨ環境下５日経時後の粘着層（Ｘ’）について、粘着剤層（Ｘ’）中の可塑剤量を測定して求めることができる。 The plasticizer migration amount is measured by using a calibration curve prepared by adding the same plasticizer as the plasticizer contained in the vinyl chloride film to the adhesive layer (X), and measuring the amount of plasticizer in the adhesive layer. can be obtained by That is, the pressure-sensitive adhesive layer (X) of the pressure-sensitive adhesive sheet was attached to a 400 μm thick vinyl chloride film containing 36% by mass of a plasticizer in a vinyl chloride film (100% by mass), heated at 70°C for 5 days, and then further heated at 25°C. It can be determined by measuring the amount of plasticizer in the adhesive layer (X') of the adhesive layer (X') after 5 days in an environment of -50% RH.
可塑剤移行量は、塩化ビニルフィルムが含有するアジピン酸エステル、フタル酸エステル、またはクエン酸エステル等の可塑剤と同じ可塑剤を用いて求めた値であり、上記特定の移行量となるように制御することで、良好な耐可塑剤性、塩化ビニルフィルム変形追従性を発現できる。 The plasticizer migration amount is a value obtained using the same plasticizer as the plasticizer such as adipate, phthalate, or citric acid ester contained in the vinyl chloride film. By controlling, good plasticizer resistance and vinyl chloride film deformation followability can be expressed.
可塑剤移行量は、２０質量部以上であるが、好ましい範囲は２５質量部以上、さらに好ましくは３０質量部以上である。また上限は５０質量部以下、より好ましくは４５質量部以下、さらに好ましくは４０質量部以下である。この範囲であることで、耐可塑剤性、塩化ビニルフィルム変形追従性により優れたものとすることができる。 The plasticizer migration amount is 20 parts by mass or more, preferably 25 parts by mass or more, more preferably 30 parts by mass or more. The upper limit is 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less. Within this range, the plasticizer resistance and the vinyl chloride film deformation followability can be improved.
従来の粘着シートでは、塩化ビニルフィルムから排出されたものの移行されなかった可塑剤が粘着剤層と被着体との界面に溜り、粘着剤層の実質的な被着体への接触面積が減少してしまうことで粘着力が減少し、塩化ビニルフィルムの収縮に粘着剤層が追従できなくなってしまっていた。これに対し本発明の粘着シートは、可塑剤が塩化ビニルフィルムと粘着剤層の界面、および粘着剤層内部に侵入することによる性能劣化を抑制した設計とすることで、良好な耐可塑剤性、塩化ビニルフィルム変形追従性、加工性を有する粘着シートとすることが可能となったものである。
すなわち、従来検討されてきたように、塩化ビニルフィルム由来の可塑剤を吸収せず、完全にはじく設計とすると、塩化ビニルフィルムと粘着剤層の界面に可塑剤が溜り、塩化ビニルフィルムと粘着剤層の間の相互作用が失われ、粘着力が大幅に劣化してしまう。反対に、可塑剤をすべて吸収してしまうと、粘着剤層自体の凝集力がなくなり、弾性を失ったことによる粘着力の劣化が発生する。よって、貯蔵弾性率や架橋密度、重量平均分子量を制御することで可塑剤の吸収量を適度に保ち、加熱試験前後の粘着力のバランスを取ることができる。
With conventional PSA sheets, the plasticizer that is discharged from the vinyl chloride film but not migrated accumulates at the interface between the PSA layer and the adherend, reducing the actual contact area of the PSA layer with the adherend. As a result, the adhesive strength is reduced, and the adhesive layer cannot follow the shrinkage of the vinyl chloride film. In contrast, the pressure-sensitive adhesive sheet of the present invention is designed to suppress performance deterioration due to the plasticizer entering the interface between the vinyl chloride film and the pressure-sensitive adhesive layer, and the inside of the pressure-sensitive adhesive layer. It has become possible to produce a pressure-sensitive adhesive sheet having a vinyl chloride film deformation followability and workability.
That is, as has been studied in the past, if the plasticizer derived from the vinyl chloride film is not absorbed and is completely repelled, the plasticizer will accumulate at the interface between the vinyl chloride film and the adhesive layer, The interaction between the layers is lost and the adhesion is greatly degraded. Conversely, when all the plasticizer is absorbed, the cohesive strength of the adhesive layer itself is lost, and the adhesive strength deteriorates due to the loss of elasticity. Therefore, by controlling the storage modulus, cross-linking density, and weight average molecular weight, it is possible to maintain an appropriate absorption amount of the plasticizer and balance the adhesive force before and after the heating test.
［せん断貯蔵弾性率］
粘着剤層（Ｘ）の周波数１Ｈｚ 、７０℃におけるせん断貯蔵弾性率は、０．０５ＭＰａ未満である。粘着剤層（Ｘ）のせん断貯蔵弾性率がこの範囲にあることで、基材または被着体に塩化ビニルフィルムを用いて、耐熱性に優れるものとすることができるため、熱をかけることで塩化ビニルフィルムが収縮するような状況下（例えば電子レンジ加熱等）において、塩化ビニルフィルムの変形に対し粘着剤層がはがれることなく当該変形に追従することが可能となる。また、せん断貯蔵弾性率が０．０５ＭＰａ以上であると粘着剤層が固すぎてしまい基材または被着体の変形に対応できなくなる。
[Shear storage modulus]
The pressure-sensitive adhesive layer (X) has a shear storage modulus of less than 0.05 MPa at a frequency of 1 Hz and 70°C. When the shear storage modulus of the pressure-sensitive adhesive layer (X) is within this range, a vinyl chloride film can be used as the base material or the adherend, and excellent heat resistance can be obtained. Under conditions where the vinyl chloride film shrinks (for example, heating in a microwave oven), it is possible to follow the deformation of the vinyl chloride film without peeling off the adhesive layer. On the other hand, when the shear storage modulus is 0.05 MPa or more, the pressure-sensitive adhesive layer becomes too hard and cannot cope with the deformation of the substrate or the adherend.
周波数１Ｈｚ、７０℃におけるせん断貯蔵弾性率の好ましい範囲としては、下限が０．００５ＭＰａ以上であり、より好ましくは０．００８ＭＰａ以上、さらに好ましくは０．０１５ＭＰａ以上である。また上限は０．０４５ＭＰａ未満、さらに好ましくは０．０４０ＭＰａ未満である。せん断貯蔵弾性率を上記範囲とすることで、加工性および塩化ビニルフィルム変形追従性を両立できる。 The preferred range of shear storage modulus at a frequency of 1 Hz and 70° C. has a lower limit of 0.005 MPa or higher, more preferably 0.008 MPa or higher, and still more preferably 0.015 MPa or higher. Also, the upper limit is less than 0.045 MPa, more preferably less than 0.040 MPa. By setting the shear storage elastic modulus within the above range, both workability and vinyl chloride film deformation followability can be achieved.
粘着剤層（Ｘ）のせん断貯蔵弾性率は、例えば粘着剤層を重ねあわせ、厚みが１ｍｍの粘着剤層を形成し、ティー・エイ・インスツルメント・ジャパン社製動的粘弾性測定装置『ＤＹＮＡＭＩＣ ＡＮＡＬＹＺＥＲ ＲＤＡ ＩＩＩ』を用いて測定することができる。 The shear storage modulus of the adhesive layer (X) is measured, for example, by stacking the adhesive layers to form an adhesive layer with a thickness of 1 mm, and using a dynamic viscoelasticity measuring device manufactured by TA Instruments Japan. DYNAMIC ANALYZER RDA III".
《アクリル系粘着剤》
本発明のアクリル系粘着剤は、アクリル系樹脂（Ａ）および硬化剤（Ｂ）を含む。
《Acrylic adhesive》
The acrylic pressure-sensitive adhesive of the present invention contains an acrylic resin (A) and a curing agent (B).
＜アクリル系樹脂（Ａ）＞
アクリル系樹脂（Ａ）は、（メタ）アクリル酸エステル等の共重合体であって、その他ビニルエステル類等を併用して用いることもできる。
用いることのできるモノマーとしては、（メタ）アクリル酸アルキルエステル（ａ１）、水酸基を有するモノマー（ａ２）、カルボキシル基を有するモノマー（ａ３）、アミド結合を有するモノマー、エポキシ基を有するモノマー、アミノ基を有するモノマー、スチレン類、ビニルエーテル類、ビニルエステル類のその他モノマー等を含むモノマー混合物を共重合してなる共重合体である。
<Acrylic resin (A)>
The acrylic resin (A) is a copolymer such as (meth)acrylic acid ester, and can also be used in combination with other vinyl esters or the like.
Monomers that can be used include (meth)acrylic acid alkyl esters (a1), hydroxyl group-containing monomers (a2), carboxyl group-containing monomers (a3), amide bond-containing monomers, epoxy group-containing monomers, and amino group-containing monomers. is a copolymer obtained by copolymerizing a monomer mixture containing a monomer having
水酸基を有するモノマー（ａ２）を用いることで、凝集力に優れた粘着剤層とすることができるために好ましい。
また、アルキル基の炭素数８～１２の（メタ）アクリル酸アクリルエステルは、粘着力、タック、塩化ビニルフィルム変形追従性により優れるものとすることができるために好ましい。
モノマー混合物１００質量％中、アルキル基の炭素数８～１２のモノマーの含有量は、５０～８９質量％であることが好ましく、５５～８４質量％がより好ましく、６０～８４質量％が更に好ましい。５０～８９質量％であることで粘着力とＰＶＣフィルム変形追従性の付与が良好である。
It is preferable to use the monomer (a2) having a hydroxyl group, because the pressure-sensitive adhesive layer can have excellent cohesion.
In addition, (meth)acrylic acid acrylic esters having an alkyl group of 8 to 12 carbon atoms are preferable because they can be made more excellent in adhesive strength, tackiness, and vinyl chloride film deformation followability.
In 100% by mass of the monomer mixture, the content of the monomer having an alkyl group with 8 to 12 carbon atoms is preferably 50 to 89% by mass, more preferably 55 to 84% by mass, and even more preferably 60 to 84% by mass. . When the content is 50 to 89% by mass, the adhesive strength and the PVC film deformation followability are excellently imparted.
また、ガラス転移温度Ｔｇが０℃以上の（メタ）アクリル酸アルキルエステル、またはガラス転移温度Ｔｇが０℃以上のビニルエステル類を用いることで、アクリル系樹脂（Ａ）に凝集力を付与し、塩化ビニルフィルム由来の可塑剤を吸収した粘着剤層でも凝集力を保持することができる。一方で、加工性により塩化ビニルフィルムからの可塑剤流出量を抑制する機能も備える。
なお、ガラス転移温度Ｔｇが０℃以上の（メタ）アクリル酸アルキルエステルとして、アルキル基の炭素数８～１２の（メタ）アクリル酸アクリルエステルは除く。
In addition, by using a (meth)acrylic acid alkyl ester having a glass transition temperature Tg of 0° C. or higher or a vinyl ester having a glass transition temperature Tg of 0° C. or higher, cohesive force is imparted to the acrylic resin (A), Even the pressure-sensitive adhesive layer that has absorbed the plasticizer derived from the vinyl chloride film can retain its cohesive force. On the other hand, it also has the function of suppressing the outflow of the plasticizer from the vinyl chloride film due to its workability.
Incidentally, (meth)acrylic acid alkyl esters having a glass transition temperature Tg of 0° C. or higher exclude (meth)acrylic acid acrylic esters having alkyl groups of 8 to 12 carbon atoms.
ガラス転移温度Ｔｇが０℃以上の（メタ）アクリル酸アルキルエステル、またはガラス転移温度Ｔｇが０℃以上のビニルエステル類の含有量としては、モノマー混合物１００質量部中に１０～４０質量部を使用することが好ましく、１５～４０質量部がより好ましく、１５～３５質量部が更に好ましい。１０～４０質量部を使用することで塩化ビニルフィルム変形追従性、並びに加工性の発現が容易になる。なお、これらを併用する場合、好ましい含有量は合計量を指す。 The content of the (meth)acrylic acid alkyl ester having a glass transition temperature Tg of 0°C or higher or the vinyl ester having a glass transition temperature Tg of 0°C or higher is 10 to 40 parts by weight in 100 parts by weight of the monomer mixture. preferably 15 to 40 parts by mass, and even more preferably 15 to 35 parts by mass. Use of 10 to 40 parts by mass facilitates the development of vinyl chloride film deformation followability and workability. In addition, when using these together, preferable content points out a total amount.
ガラス転移温度Ｔｇ０℃以上の（メタ）アクリル酸アクリルエステルとしては、例えば、アクリル酸メチル（Ｔｇ：１０℃）、メタクリル酸メチル（１０５℃）、メタクリル酸エチル（Ｔｇ：１０℃）、メタクリル酸プロピル（Ｔｇ：３５℃）、およびメタクリル酸ブチル（Ｔｇ：２０℃）等が挙げられる。ガラス転移温度Ｔｇが０℃以上のビニルエステル類としては、酢酸ビニル（Ｔｇ：３２℃）等が挙げられる。これらの中でも、アクリル酸メチルが好ましい。これらは併用することも可能である。 (Meth)acrylic acid acrylic esters having a glass transition temperature Tg of 0° C. or higher include, for example, methyl acrylate (Tg: 10° C.), methyl methacrylate (105° C.), ethyl methacrylate (Tg: 10° C.), and propyl methacrylate. (Tg: 35°C), and butyl methacrylate (Tg: 20°C). Examples of vinyl esters having a glass transition temperature Tg of 0° C. or higher include vinyl acetate (Tg: 32° C.). Among these, methyl acrylate is preferred. These can also be used in combination.
なかでも、アルキル基の炭素数８～１２の（メタ）アクリル酸アクリルエステルと、ガラス転移温度Ｔｇが０℃以上の（メタ）アクリル酸アクリルエステル、またはガラス転移温度Ｔｇが０℃以上のビニルモノマーとを含むことで、良好な耐可塑剤性や加工性を発現できるために好ましい。
尚、ここでいうガラス転移温度Ｔｇは、「ポリマーハンドブック 第４版（Ｐｏｌｙｍｅｒ Ｈａｎｄｂｏｏｋ，Ｆｏｕｒｔｈ Ｅｄｉｔｉｏｎ）」、Ｊ．Ｂｒａｎｄｒｕｐ，Ｅ．Ｈ．Ｉｍｍｅｒｇｕｔ，ａｎｄ Ｅ．Ａ．Ｇｒｕｌｋｅ著（１９９９）に記載のホモポリマーのＴｇを指す。
Among them, a (meth)acrylic acid ester having an alkyl group with 8 to 12 carbon atoms, a (meth)acrylic acid acrylic ester having a glass transition temperature Tg of 0°C or higher, or a vinyl monomer having a glass transition temperature Tg of 0°C or higher It is preferable because it can express good plasticizer resistance and workability by including.
Incidentally, the glass transition temperature Tg referred to here is determined according to "Polymer Handbook, Fourth Edition", J. Am. Brandrup, E. H. Immergut, andE. A. It refers to the Tg of the homopolymer as described by Grulke (1999).
・（メタ）アクリル酸アルキルエステル（ａ１）
（メタ）アクリル酸アルキルエステルは、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）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸オレイル、および（メタ）アクリル酸ステアリル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸テトラデシル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸オクタデシル、または（メタ）アクリル酸ラウリル等が挙げられる。
- (meth)acrylic acid alkyl ester (a1)
(Meth)acrylic acid alkyl esters, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, (meth)acryl isobutyl (meth)acrylate, hexyl (meth)acrylate, oleyl (meth)acrylate, and stearyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, (meth)acrylic isooctyl acid, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylate Examples include tetradecyl acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, lauryl (meth)acrylate, and the like.
これらの中でも、アルキル基の炭素数８～１２の（メタ）アクリル酸アルキルエステルは、アクリル系樹脂（Ａ）に粘着力およびタックなど粘着剤としての基本性能に加え、塩化ビニルフィルム変形追従性を付与することができるために好ましい。
アルキル基の炭素数８～１２の（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ）アクリル酸オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、および（メタ）アクリル酸ラウリル等が挙げられる。これらの中でも、アクリル酸２－エチルヘキシル、アクリル酸イソノニルが好ましい。
これらのモノマーは、単独または２種類以上を併用できる。
Among these, (meth)acrylic acid alkyl esters with an alkyl group of 8 to 12 carbon atoms provide the acrylic resin (A) with basic performance as an adhesive such as adhesion and tackiness, as well as vinyl chloride film deformation followability. It is preferable because it can be given.
Examples of (meth)acrylic acid alkyl esters having an alkyl group of 8 to 12 carbon atoms include octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and nonyl (meth)acrylate. , isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, and lauryl (meth)acrylate. Among these, 2-ethylhexyl acrylate and isononyl acrylate are preferred.
These monomers can be used alone or in combination of two or more.
（メタ）アクリル酸アルキルエステルの含有量は、粘着力および塩化ビニルフィルム変形追従性の付与の点で、モノマー混合物１００質量％中、５０～８９質量％であることが好ましく、５５～８４質量％がより好ましく、６０～８４質量％が更に好ましい。 The content of the (meth)acrylic acid alkyl ester is preferably 50 to 89% by mass, more preferably 55 to 84% by mass, based on 100% by mass of the monomer mixture in terms of imparting adhesive strength and deformation followability to vinyl chloride film. is more preferred, and 60 to 84% by mass is even more preferred.
・水酸基を有するモノマー（ａ２）
水酸基を有するモノマーは、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、（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、（メタ）アクリル酸８－ヒドロキシオクチル等の（メタ）アクリル酸ヒドロキシアルキルエステルや、ポリエチレングリコールモノ（メタ）アクリル酸エステル、ポリプロピレングリコールモノ（メタ）アクリル酸エステル、１，４－シクロヘキサンジメタノールモノ（メタ）アクリル酸エステルなどのグリコールモノ（メタ）アクリル酸エステル、カプロラクトン変性（メタ）アクリル酸エステル、Ｎ－ヒドロキシメチル（メタ）アクリルアミド、Ｎ－ヒドロキシエチル（メタ）アクリルアミドなどのＮ－ヒドロキシアルキル（メタ）アクリルアミド等が挙げられる。 これらの中でも、（メタ）アクリル酸２－ヒドロキシエチルが好ましい。
- A monomer having a hydroxyl group (a2)
Monomers having a hydroxyl group include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth) ) hydroxyalkyl (meth)acrylates such as 3-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, and polyethylene Glycol mono(meth)acrylates, polypropylene glycol mono(meth)acrylates, 1,4-cyclohexanedimethanol mono(meth)acrylates and other glycol mono(meth)acrylates, caprolactone-modified (meth)acrylics Acid esters, N-hydroxyalkyl(meth)acrylamides such as N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, and the like. Among these, 2-hydroxyethyl (meth)acrylate is preferred.
水酸基を有するモノマーは、粘着剤層に凝集力を付与するためアクリル系樹脂（Ａ）同士を、硬化剤（Ｂ）を介して架橋させる目的で用いることができる。含有量としては、モノマー混合物１００質量％中に０．０１～５質量％を含むことが好ましく、０．０３～２質量％がより好ましく、０．０５～１質量％が更に好ましい。水酸基を有するモノマーをこの含有量とすることで、粘着力と凝集力をより高度に両立できる。 A monomer having a hydroxyl group can be used for the purpose of cross-linking the acrylic resins (A) via the curing agent (B) in order to impart cohesive force to the pressure-sensitive adhesive layer. The content is preferably 0.01 to 5% by mass, more preferably 0.03 to 2% by mass, still more preferably 0.05 to 1% by mass, based on 100% by mass of the monomer mixture. By setting the content of the hydroxyl group-containing monomer to this level, both adhesive strength and cohesive strength can be achieved at a higher level.
・カルボキシル基を有するモノマー（ａ３）
カルボキシル基を有するモノマーは、例えば（メタ）アクリル酸、フタル酸モノヒドロキシエチルアクリル酸エステル、ｐ－カルボキシベンジルアクリル酸エステル、エチレンオキサイド変性（エチレンオキサイド付加モル数：（２～１８）フタル酸アクリル酸エステル、コハク酸モノヒドロキシエチルアクリル酸エステル、アクリル酸β－カルボキシエチル、イタコン酸等が挙げられる。これらの中でも、（メタ）アクリル酸が好ましい。
- A monomer having a carboxyl group (a3)
Monomers having a carboxyl group include, for example, (meth)acrylic acid, monohydroxyethyl phthalate acrylate, p-carboxybenzyl acrylate, ethylene oxide-modified (moles of ethylene oxide added: (2 to 18)) phthalate acrylic acid ester, monohydroxyethyl succinate acrylate, β-carboxyethyl acrylate, itaconic acid, etc. Among these, (meth)acrylic acid is preferred.
カルボキシル基を有するモノマーは、粘着剤層に凝集力を付与するための架橋点としてのみならず、塩化ビニルフィルム由来の可塑剤吸収後の粘着力保持という役割を担う。含有量としては、モノマー混合物１００質量％中、０．５～１０質量％であることが好ましく、１～８質量％がより好ましく、１～５質量％が更に好ましい。０．５～１０質量％であることで、塩化ビニルフィルムに対する密着性がより向上する。
カルボキシル基を有するモノマーは、塩化ビニルフィルムに対する密着性がより優れたものとすることができるために好ましい。
A monomer having a carboxyl group plays a role not only as a cross-linking point for imparting cohesive strength to the adhesive layer, but also as maintaining adhesive strength after absorption of a plasticizer derived from a vinyl chloride film. The content is preferably 0.5 to 10% by mass, more preferably 1 to 8% by mass, even more preferably 1 to 5% by mass, based on 100% by mass of the monomer mixture. When it is 0.5 to 10% by mass, the adhesion to the vinyl chloride film is further improved.
A monomer having a carboxyl group is preferable because it can provide better adhesion to a vinyl chloride film.
・アミド結合を有するモノマー
アミド結合を有するモノマーは、例えば（メタ）アクリルアミド、Ｎ－メチル（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，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ、Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、ジアセトン（メタ）アクリルアミド、Ｎ－（ブトキシメチル）アクリルアミド等の（メタ）アクリルアミド系化合物；Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、およびアクリロイルモルホリン等の複素環を有する化合物等が挙げられる。
- Monomers having an amide bond Monomers having an amide bond are, for example, (meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl (Meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, diacetone (meth)acrylamide, N-(butoxymethyl)acrylamide and other (meth)acrylamide compounds; N-vinylpyrrolidone, N-vinylcaprolactam, and compounds having a heterocyclic ring such as acryloylmorpholine;
・エポキシ基を有するモノマー
エポキシ基を有するモノマーは、例えば（メタ）アクリル酸グリシジル、（メタ）アクリル酸メチルグリシジル、および（メタ）アクリル酸３，４－エポキシシクロヘキシルメチル等が挙げられる。
Epoxy Group-Containing Monomer Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate.
・アミノ基を有するモノマー
アミノ基を有するモノマーは、例えば（メタ）アクリル酸モノメチルアミノエチル、（メタ）アクリル酸モノエチルアミノエチル、（メタ）アクリル酸モノメチルアミノプロピル、および（メタ）アクリル酸モノエチルアミノプロピル等の（メタ）アクリル酸モノアルキルアミノエステル等が挙げられる。
Monomers having an amino group Examples of monomers having an amino group are monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, monomethylaminopropyl (meth)acrylate, and monoethyl (meth)acrylate. (Meth)acrylic acid monoalkylaminoesters such as aminopropyl and the like.
アミド結合を有するモノマー、エポキシ基を有するモノマーおよびアミノ基を有するモノマーは、モノマー混合物１００質量部中、それぞれ０．１～１質量部を含むことが好ましい。 The monomer having an amide bond, the monomer having an epoxy group, and the monomer having an amino group are preferably included in 0.1 to 1 part by mass each in 100 parts by mass of the monomer mixture.
・芳香環を有するモノマー
芳香環を有するモノマーは、例えばアクリル酸フェノキシエチル、アクリル酸ベンジル、（メタ）アクリル酸フェノキシジエチレングリコール、および（メタ）アクリル酸エチレンオキサイド変性ノニルフェノール等が挙げられる。
Aromatic Ring-Containing Monomer Examples of aromatic ring-containing monomers include phenoxyethyl acrylate, benzyl acrylate, phenoxydiethylene glycol (meth)acrylate, and ethylene oxide-modified nonylphenol (meth)acrylate.
芳香環を有するモノマーは、モノマー混合物１００質量部中、０．１～１０質量部を含むことが好ましい。 The aromatic ring-containing monomer is preferably contained in 0.1 to 10 parts by mass in 100 parts by mass of the monomer mixture.
・アルコキシ（ポリ）アルキレンオキサイドを有するモノマー
アルコキシ（ポリ）アルキレンオキサイドを有するモノマーは、例えばアクリル酸２－メトキシエチル、アクリル酸２－エトキシエチル、アクリル酸２－フェノキシエチル、メトキシポリエチレングリコール（メタ）アクリル酸エステル、エトキシポリエチレングリコール（メタ）アクリル酸エステル、メトキシポリプロピレングリコール（メタ）アクリル酸エステル、エトキシポリプロピレングリコール（メタ）アクリル酸エステル、フェノキシポリエチレングリコール（メタ）アクリル酸エステル、およびフェノキシポリプロピレングリコール（メタ）アクリル酸エステル等が挙げられる。
Alkoxy(poly)alkylene oxide-containing monomer Monomers containing alkoxy(poly)alkylene oxide are, for example, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-phenoxyethyl acrylate, methoxypolyethylene glycol (meth)acryl acid esters, ethoxypolyethylene glycol (meth)acrylates, methoxypolypropyleneglycol (meth)acrylates, ethoxypolypropyleneglycol (meth)acrylates, phenoxypolyethyleneglycol (meth)acrylates, and phenoxypolypropyleneglycol (meth)acrylates Examples include acrylic acid esters.
アルコキシ（ポリ）アルキレンオキサイドを有するモノマーは、モノマー混合物１００質量部中、０．１～１０質量部を含むことが好ましい。 The monomer having alkoxy(poly)alkylene oxide is preferably contained in 0.1 to 10 parts by mass in 100 parts by mass of the monomer mixture.
・その他モノマー
用いることのできるその他モノマーとしては、スチレン、α－メチルスチレン等のスチレン類、エチルビニルエーテル、ｎ－プロピルビニルエーテル、イソプロピルビニルエーテル、ｎ－ブチルビニルエーテル、イソブチルビニルエーテル等のビニルエーテル類、酢酸ビニル、プロピオン酸ビニル等のビニルエステル類、またはアクリロニトリル等のシアン化ビニル類等が挙げられる。
・Other monomers Other monomers that can be used include styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether, vinyl acetate, and propion. Examples thereof include vinyl esters such as vinyl acid and vinyl cyanides such as acrylonitrile.
その他モノマーは、モノマー混合物１００質量部中、０．１～１０質量部を含むことが好ましい。 Other monomers are preferably contained in an amount of 0.1 to 10 parts by mass in 100 parts by mass of the monomer mixture.
アクリル系樹脂（Ａ）は、モノマー混合物に重合開始剤を加え、溶液重合、塊状重合、乳化重合、各種ラジカル重合などの公知の製造方法を適宜選択して行うことができる。これらの中でも、溶液重合が、アクリル系樹脂の重量平均分子量の調整が容易である点から好ましい。 The acrylic resin (A) can be produced by adding a polymerization initiator to the monomer mixture and appropriately selecting known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations. Among these, solution polymerization is preferred because it facilitates adjustment of the weight-average molecular weight of the acrylic resin.
前記溶液重合に使用する溶剤は、例えば、酢酸メチル、酢酸エチル、酢酸ｎ－ブチル、酢酸イソブチル、トルエン、キシレン、ヘキサン、アセトン、メチルエチルケトン、メチルイソブチルケトン、メタノール、エタノール、ｎ－プロパノール、およびイソプロパノール等が好ましく、酢酸エチルがより好ましい。 溶剤は単独また２種類以上を併用できる。 Solvents used in the solution polymerization include, for example, methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, hexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, and isopropanol. is preferred, and ethyl acetate is more preferred. Solvents can be used alone or in combination of two or more.
前記溶液重合は、モノマー混合物１００質量部に対して重合開始剤を０．００１～１質量部程度加えて重合を行うことが好ましい。通常、重合は、窒素気流下で、５０℃～９０℃程度の温度で４時間～１２時間行うことができる。また、重合の際、連鎖移動剤を使用してアクリル系樹脂の重量平均分子量を適宜調整することができる。 The solution polymerization is preferably carried out by adding about 0.001 to 1 part by mass of a polymerization initiator to 100 parts by mass of the monomer mixture. Generally, the polymerization can be carried out at a temperature of about 50° C. to 90° C. for 4 to 12 hours under nitrogen stream. Moreover, the weight average molecular weight of the acrylic resin can be appropriately adjusted by using a chain transfer agent during the polymerization.
本発明においてアクリル系樹脂（Ａ）の重量平均分子量（以下、Ｍｗともいう）は、４０万～２００万が好ましく、６０万～１５０万がより好ましく、８０万～１３０万が更に好ましい。Ｍｗを４０万～２００万の範囲にすることで、加熱後粘着力の保持や後述する硬化剤量を少なくできるため塩化ビニルフィルム変形追従性の効果を得られやすい。 In the present invention, the acrylic resin (A) preferably has a weight average molecular weight (hereinafter also referred to as Mw) of 400,000 to 2,000,000, more preferably 600,000 to 1,500,000, and even more preferably 800,000 to 1,300,000. By setting the Mw in the range of 400,000 to 2,000,000, the adhesive strength after heating can be maintained and the amount of the curing agent described later can be reduced, so that the effect of vinyl chloride film deformation followability can be easily obtained.
重合開始剤としては、アゾ系化合物および有機過酸化物等を使用することができる。 As the polymerization initiator, azo compounds, organic peroxides, and the like can be used.
アゾ系化合物は、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）、および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。 Azo compounds include, for example, 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), and 2,2′-azobis(2-(2-imidazolin-2-yl)propane ) and the like.
有機過酸化物は、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。
重合開始剤は単独または２種以上を併用できる。
Organic peroxides are, for example, benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate , t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.
A polymerization initiator can be used alone or in combination of two or more.
連鎖移動剤は、例えばｎ－ドデシルメルカプタン、メルカプトイソブチルアルコール、メルカプト酢酸、２－メルカプトエタノール、チオグリコール酸、チオグルコール酸２－エチルヘキシル、２，３－ジメルカプト－１－プロパノール、グリシジルメルカプタン、α－メチルスチレンダイマー、四塩化炭素、クロロホルム、およびハイドロキノン等が挙げられる。
連鎖移動剤は、モノマー混合物１００質量部に対して０．０１～１質量部程度を使用できる。
Chain transfer agents are, for example, n-dodecylmercaptan, mercaptoisobutyl alcohol, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2,3-dimercapto-1-propanol, glycidylmercaptan, α-methylstyrene. Dimer, carbon tetrachloride, chloroform, hydroquinone, and the like.
About 0.01 to 1 part by mass of the chain transfer agent can be used with respect to 100 parts by mass of the monomer mixture.
＜硬化剤（Ｂ）＞
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、または金属キレート硬化剤等の既知の硬化剤を使用することができる。これらの中でも耐可塑剤性の観点で、イソシアネート硬化剤が好ましい。
<Curing agent (B)>
As the curing agent (B), known curing agents such as isocyanate curing agents, epoxy curing agents, or metal chelate curing agents can be used. Among these, isocyanate curing agents are preferred from the viewpoint of plasticizer resistance.
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、ならびに前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うち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； 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、ならびにヘキサメチレンジイソシアネート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が可塑剤吸収による性能劣化を抑えるため好ましい。なお、イソシアネート基の個数は平均個数である。 Isocyanate curing agents include, for example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate. , and an adduct of a diisocyanate such as polymethylene polyphenyl isocyanate and a polyol compound such as trimethylolpropane, a burette thereof, an isocyanurate thereof, and the diisocyanate, polyether polyol, polyester polyol, acrylic polyol, polybutadiene Compounds having 3 or more isocyanate groups in the molecule, such as polyols and adducts with polyols such as polyisoprene polyol; Diisocyanates such as xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and polymethylene polyphenyl isocyanate, and allophanate forms of hexamethylene diisocyanate, etc. a compound having one isocyanate group; and the like. Among these, the trimethylolpropane adduct of tolylene diisocyanate is preferable because it suppresses performance deterioration due to plasticizer absorption. In addition, the number of isocyanate groups is the average number.
イソシアネート硬化剤は、アクリル系樹脂（Ａ）１００質量部に対して、０．０１～１質量部を含むことが好ましく、０．０１～０．６質量部を含むことがより好ましく、０．０５～０．６質量部がさらに好ましく、０．１～０．６質量部がとくに好ましい。０．０１～１質量部含むことでＰＶＣフィルム変形追従性および加工性により優れたものとすることができる。イソシアネート硬化剤は単独または２種以上を併用できる。 The isocyanate curing agent preferably contains 0.01 to 1 part by mass, more preferably 0.01 to 0.6 parts by mass, with respect to 100 parts by mass of the acrylic resin (A), and 0.05 0.6 parts by weight is more preferred, and 0.1 to 0.6 parts by weight is particularly preferred. By including 0.01 to 1 part by mass, it is possible to make the PVC film more excellent in deformation followability and workability. An isocyanate curing agent can be used alone or in combination of two or more.
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。 Epoxy curing agents include, for example, bisphenol A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 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、アクリル系樹脂（Ａ）１００質量部に対して、０．０１～１質量部を含むことが好ましい。０．０１～１質量部を含むと粘着剤層の凝集力と粘着力のバランスを取ることが容易になる。エポキシ化合物は単独または２種以上を併用できる。 The epoxy curing agent preferably contains 0.01 to 1 part by mass with respect to 100 parts by mass of the acrylic resin (A). When 0.01 to 1 part by mass is included, it becomes easy to balance the cohesive strength and adhesive strength of the pressure-sensitive adhesive layer. Epoxy compounds can be used alone or in combination of two or more.
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。 Metal chelate curing agents include, for example, coordination compounds of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium and acetylacetone or ethyl acetoacetate. mentioned.
金属キレート硬化剤は、アクリル系樹脂（Ａ）１００質量部に対して、０．１～５質量部を含むことが好ましい。０．１～５質量部を含むと粘着剤層の凝集力と粘着力のバランスを取ることが容易になる。金属キレートは単独または２種以上を併用できる。 The metal chelate curing agent preferably contains 0.1 to 5 parts by mass with respect to 100 parts by mass of the acrylic resin (A). When 0.1 to 5 parts by mass is contained, it becomes easy to balance the cohesive strength and adhesive strength of the pressure-sensitive adhesive layer. A metal chelate can be used alone or in combination of two or more.
硬化剤（Ｂ）は単独または２種以上を併用できる。 Curing agents (B) can be used alone or in combination of two or more.
なお、本発明の課題解決ができる範囲で粘着付与樹脂を含んでもよい。例えば、ロジン樹脂、テルペン樹脂、脂環族炭化水素樹脂、脂肪族石油樹脂、芳香族石油樹脂、アルキルフェノールホルムアルデヒド樹脂（油性フェノール樹脂）等が好ましい。粘着付与樹脂は、単独または２種以上を併用できる。粘着剤が粘着付与樹脂を含むことで、ポリ塩化ビニルに対する粘着力がより向上させやすい。 In addition, a tackifying resin may be included within the range in which the problems of the present invention can be solved. For example, rosin resins, terpene resins, alicyclic hydrocarbon resins, aliphatic petroleum resins, aromatic petroleum resins, alkylphenol formaldehyde resins (oily phenolic resins) and the like are preferred. The tackifying resin can be used alone or in combination of two or more. By including a tackifying resin in the adhesive, the adhesive strength to polyvinyl chloride can be more easily improved.
粘着付与樹脂は、アクリル系樹脂（Ａ）１００質量部に対して、１０～３０質量部配合することが好ましい。 The tackifying resin is preferably blended in an amount of 10 to 30 parts by mass with respect to 100 parts by mass of the acrylic resin (A).
粘着付与樹脂の軟化点は、８０～１４０℃が好ましい。軟化点を８０～１４０℃にすると粘着力および凝集力を両立することが容易となる。 The softening point of the tackifier resin is preferably 80 to 140°C. A softening point of 80 to 140° C. makes it easy to achieve both adhesive strength and cohesive strength.
本発明の粘着剤は、本発明の課題解決ができる範囲で、任意成分として各種樹脂、硬化触媒、シランカップリング剤、オイル、軟化剤、染料、顔料、酸化防止剤、紫外線吸収剤、耐候安定剤、充填剤、老化防止剤および帯電防止剤等を配合しても良い。 The pressure-sensitive adhesive of the present invention has various resins, curing catalysts, silane coupling agents, oils, softeners, dyes, pigments, antioxidants, ultraviolet absorbers, and weather-resistant components as optional components within the range where the problems of the present invention can be solved. Agents, fillers, anti-aging agents, anti-static agents, etc. may be added.
本発明の粘着剤は、塩化ビニルフィルムの貼り合わせ用粘着剤として好適であるほか、一般ラベル・シール、粘着性光学フィルム、塗料、弾性壁材、塗膜防水材、床材、粘着性付与剤、粘着剤、積層構造体用粘着剤、シーリング剤、成形材料、表面改質用コーティング剤、バインダー（磁気記録媒体、インキバインダー、鋳物バインダー、焼成レンガバインダー、グラフト材、マイクロカプセル、グラスファイバーサイジング等）、ウレタンフォーム（硬質、半硬質、軟質）、ウレタンＲＩＭ、ＵＶ・ＥＢ硬化樹脂、ハイソリッド塗料、熱硬化型エラストマー、マイクロセルラー、繊維加工剤、可塑剤、吸音材料、制振材料、界面活性剤、ゲルコート剤、人工大理石用樹脂、人工大理石用耐衝撃性付与剤、インキ用樹脂、フィルム（ラミネート粘着剤、保護フィルム等）、合わせガラス用樹脂、反応性希釈剤、各種成形材料、弾性繊維、人工皮革、合成皮革等の原料として、又、各種樹脂添加剤およびその原料等としても有用に使用できる。 The pressure-sensitive adhesive of the present invention is suitable as a pressure-sensitive adhesive for bonding vinyl chloride films, as well as general labels and stickers, adhesive optical films, paints, elastic wall materials, waterproof coating materials, flooring materials, and tackifiers. , adhesives, adhesives for laminated structures, sealing agents, molding materials, coating agents for surface modification, binders (magnetic recording media, ink binders, casting binders, baked brick binders, graft materials, microcapsules, glass fiber sizing, etc.) ), urethane foam (hard, semi-hard, soft), urethane RIM, UV/EB curing resin, high solid paint, thermosetting elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, damping material, surfactant agent, gel coat agent, resin for artificial marble, impact resistance agent for artificial marble, resin for ink, film (laminating adhesive, protective film, etc.), resin for laminated glass, reactive diluent, various molding materials, elastic fiber , as a raw material for artificial leather, synthetic leather, etc., and also as various resin additives and their raw materials.
次に本発明の実施例を示して更に詳細を説明するが、本発明はこれらによって限定されるものではない。例中、「部」とは「質量部」、「％」とは「質量部」をそれぞれ意味するものとする。尚、溶剤以外は不揮発分を記載したものとする。 EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these. In the examples, "part" means "mass part" and "%" means "mass part". In addition, non-volatile matter shall be described except the solvent.
なお、アクリル系樹脂の重量平均分子量（Ｍｗ）および分散度（Ｍｗ／Ｍｎ）の測定方法を下記に示す。 Methods for measuring the weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the acrylic resin are shown below.
［重量平均分子量（Ｍｗ）および分散度（Ｍｗ／Ｍｎ）の測定］
Ｍｗ、Ｍｗ／Ｍｎの測定はＧＰＣを用いた。ＧＰＣは溶媒（ＴＨＦ；テトラヒドロフラン）に溶解した物質をその分子サイズの差によって分離定量する液体クロマトグラフィーであり、Ｍｗ、Ｍｗ／Ｍｎの決定はポリスチレン換算で行った。
装置名 ： 島津製作所製、
ＬＣ－ＧＰＣシステム「Ｐｒｏｍｉｎｅｎｃｅ」
カラム ： 東ソー社製ＧＭＨＸＬ ４本、東ソー（株）製ＨＸＬ-Ｈ １本を直列連結
移動相溶媒 ： テトラヒドロフラン
流量 ： １．０ｍｌ／分
カラム温度 ： ４０℃
[Measurement of Weight Average Molecular Weight (Mw) and Dispersity (Mw/Mn)]
GPC was used to measure Mw and Mw/Mn. GPC is liquid chromatography for separating and quantifying a substance dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size, and Mw and Mw/Mn were determined in terms of polystyrene.
Device name: Shimadzu Corporation,
LC-GPC system "Prominence"
Column: 4 GMHXL manufactured by Tosoh Corporation and 1 HXL-H manufactured by Tosoh Corporation connected in series Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 ml/min Column temperature: 40°C
続いて、実施例および比較例で用いた材料の略語を下記に記載する。
＜（メタ）アクリル酸アルキルエステル（ａ１）＞
２ＥＨＡ：アクリル酸２－エチルヘキシル（アルキル基の炭素数；８、Ｔｇ：―７０℃）
ＮＡ：アクリル酸ノニル（アルキル基の炭素数；９、Ｔｇ：－５８℃）
ＭＡ：アクリル酸メチル（アルキル基の炭素数；１、Ｔｇ：１０℃）
ＭＭＡ：メタクリル酸メチル（アルキル基の炭素数；１、Ｔｇ：１０５℃）
ＥＡ：アクリル酸エチル（アルキル基の炭素数；２、Ｔｇ：―２４℃）
ＢＡ：アクリル酸ブチル（アルキル基の炭素数；４、Ｔｇ：―５４℃）
＜水酸基を有するモノマー（ａ２）＞
ＨＥＡ：アクリル酸２－ヒドロキシエチル
＜カルボキシル基を有するモノマー（ａ３）＞
ＡＡ：アクリル酸
ＭＡＡ：メタクリル酸
＜その他＞
ＶＡｃ：酢酸ビニル（Ｔｇ：３２℃）
＜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
ＴＥＴＲＡＤ Ｘ：Ｎ，Ｎ，Ｎ‘，Ｎ’，－テトラグリシジルーｍ－キシリレンジアミン（三菱ガス化学社製）
Subsequently, abbreviations of materials used in Examples and Comparative Examples are described below.
<(Meth)acrylic acid alkyl ester (a1)>
2EHA: 2-ethylhexyl acrylate (number of carbon atoms in alkyl group; 8, Tg: -70°C)
NA: nonyl acrylate (carbon number of alkyl group; 9, Tg: -58 ° C.)
MA: methyl acrylate (number of carbon atoms in alkyl group; 1, Tg: 10°C)
MMA: methyl methacrylate (number of carbon atoms in alkyl group; 1, Tg: 105°C)
EA: ethyl acrylate (number of carbon atoms in alkyl group; 2, Tg: -24°C)
BA: butyl acrylate (number of carbon atoms in alkyl group; 4, Tg: -54°C)
<Monomer (a2) having a hydroxyl group>
HEA: 2-hydroxyethyl acrylate <monomer (a3) having a carboxyl group>
AA: acrylic acid MAA: methacrylic acid <others>
VAc: vinyl acetate (Tg: 32°C)
<Curing agent (B)>
TDI/TMP: trimethylolpropane adduct of tolylene diisocyanate TETRAD X: N,N,N',N',-tetraglycidyl-m-xylylenediamine (manufactured by Mitsubishi Gas Chemical Company)
［アクリル系樹脂（Ａ）の合成］
（合成例１）
撹拌機、温度計、還流冷却管、滴下装置、窒素導入管を備えた反応容器（以下、単に「反応容器」と記述する。）に窒素雰囲気下、アクリル酸２－エチルヘキシル９０．８部、アクリル酸メチル８．５部、アクリル酸ヒドロキシエチル０．２部、アクリル酸０．５部、酢酸エチル７５部、アセトン２０．０部、ベンゾイルパーオキシド（以下、ＢＰＯ）０．２部を仕込んだ。撹拌しながら加熱を行い重合反応の開始を確認して還流温度で２時間反応した。次いで、ＢＰＯ ０．０４部を反応溶液に添加し２時間反応し、さらにＢＰＯ ０．０４部を反応溶液に添加し４時間反応を継続した。その後、反応容器を冷却し酢酸エチル７７部を加え、重量平均分子量１１６万のアクリル系樹脂（Ａ－１）溶液を得た。
[Synthesis of acrylic resin (A)]
(Synthesis example 1)
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping device, and nitrogen inlet tube (hereinafter simply referred to as the "reaction vessel"), under a nitrogen atmosphere, 90.8 parts of 2-ethylhexyl acrylate, acrylic 8.5 parts of methyl acid, 0.2 parts of hydroxyethyl acrylate, 0.5 parts of acrylic acid, 75 parts of ethyl acetate, 20.0 parts of acetone, and 0.2 parts of benzoyl peroxide (hereinafter referred to as BPO) were charged. The mixture was heated while stirring, and after confirming the initiation of the polymerization reaction, the reaction was carried out at the reflux temperature for 2 hours. Next, 0.04 part of BPO was added to the reaction solution and reacted for 2 hours, and further 0.04 part of BPO was added to the reaction solution and the reaction was continued for 4 hours. After that, the reactor was cooled and 77 parts of ethyl acetate was added to obtain an acrylic resin (A-1) solution having a weight average molecular weight of 1,160,000.
（合成例２～１２、１８～２２、２４、２６～２８、３０）
モノマーの種類及び配合量を表１の記載に従った他は、合成例１と同様に行うことで合成例２～１２、１８～３２のアクリル系樹脂（Ａ－２～１２、１８～２２、２４、２６～２８、３０）溶液を得た。
(Synthesis Examples 2-12, 18-22, 24, 26-28, 30)
The acrylic resins of Synthesis Examples 2 to 12, 18 to 32 (A-2 to 12, 18 to 22, 24,26-28,30) solutions were obtained.
（合成例１３）
反応容器に窒素雰囲気下、アクリル酸２－エチルヘキシル７３．３部、アクリル酸メチル２３．５部、アクリル酸ヒドロキシエチル０．２部、アクリル酸３．０部、酢酸エチル１１２．０部、ベンゾイルパーオキシド（以下、ＢＰＯ）０．２部を仕込んだ。撹拌しながら加熱を行い重合反応の開始を確認して還流温度で２時間反応した。次いで、ＢＰＯ ０．０４部を反応溶液に添加し２時間反応し、さらにＢＰＯ ０．０４部を反応溶液に添加し４時間反応を継続した。その後、反応容器を冷却し酢酸エチル３５部を加え、重量平均分子量４５万のアクリル系樹脂（Ａ－１３）溶液を得た。
(Synthesis Example 13)
In a reaction vessel under a nitrogen atmosphere, 73.3 parts of 2-ethylhexyl acrylate, 23.5 parts of methyl acrylate, 0.2 parts of hydroxyethyl acrylate, 3.0 parts of acrylic acid, 112.0 parts of ethyl acetate, and benzoyl peroxide were added. 0.2 part of oxide (hereinafter referred to as BPO) was charged. The mixture was heated while stirring, and after confirming the initiation of the polymerization reaction, the reaction was carried out at the reflux temperature for 2 hours. Next, 0.04 part of BPO was added to the reaction solution and reacted for 2 hours, and further 0.04 part of BPO was added to the reaction solution and the reaction was continued for 4 hours. After that, the reaction vessel was cooled and 35 parts of ethyl acetate was added to obtain an acrylic resin (A-13) solution having a weight average molecular weight of 450,000.
（合成例１４）
反応容器に窒素雰囲気下、アクリル酸２－エチルヘキシル７３．３部、アクリル酸メチル２３．５部、アクリル酸ヒドロキシエチル０．２部、アクリル酸３．０部、酢酸エチル８０．０部、ベンゾイルパーオキシド（以下、ＢＰＯ）０．２部を仕込んだ。撹拌しながら加熱を行い重合反応の開始を確認して還流温度で２時間反応した。次いで、 ＢＰＯ０．０４部を反応溶液に添加し２時間反応し、さらにＢＰＯ ０．０４部を反応溶液に添加し４時間反応を継続した。その後、反応容器を冷却し酢酸エチル６６部を加え、重量平均分子量６１万のアクリル系樹脂（Ａ－１４）溶液を得た。
(Synthesis Example 14)
In a reaction vessel under a nitrogen atmosphere, 73.3 parts of 2-ethylhexyl acrylate, 23.5 parts of methyl acrylate, 0.2 parts of hydroxyethyl acrylate, 3.0 parts of acrylic acid, 80.0 parts of ethyl acetate, and benzoyl peroxide were added. 0.2 part of oxide (hereinafter referred to as BPO) was charged. The mixture was heated while stirring, and after confirming the initiation of the polymerization reaction, the reaction was carried out at the reflux temperature for 2 hours. Next, 0.04 part of BPO was added to the reaction solution and reacted for 2 hours, and further 0.04 part of BPO was added to the reaction solution and the reaction was continued for 4 hours. After that, the reaction vessel was cooled and 66 parts of ethyl acetate was added to obtain an acrylic resin (A-14) solution having a weight average molecular weight of 610,000.
（合成例１５）
反応容器に窒素雰囲気下、アクリル酸２－エチルヘキシル７３．３部、アクリル酸メチル２３．５部、アクリル酸ヒドロキシエチル０．２部、アクリル酸３．０部、酢酸エチル７０．０部、アセトン１０．０部、ベンゾイルパーオキシド（以下、ＢＰＯ）０．２部を仕込んだ。撹拌しながら加熱を行い重合反応の開始を確認して還流温度で２時間反応した。次いで、 ＢＰＯ０．０４部を反応溶液に添加し２時間反応し、さらにＢＰＯ ０．０４部を反応溶液に添加し４時間反応を継続した。その後、反応容器を冷却し酢酸エチル６６部を加え、重量平均分子量９０万のアクリル系樹脂（Ａ－１５）溶液を得た。
(Synthesis Example 15)
73.3 parts of 2-ethylhexyl acrylate, 23.5 parts of methyl acrylate, 0.2 parts of hydroxyethyl acrylate, 3.0 parts of acrylic acid, 70.0 parts of ethyl acetate, and 10 parts of acetone were placed in a reaction vessel under a nitrogen atmosphere. 0.0 part and 0.2 part of benzoyl peroxide (hereinafter referred to as BPO) were charged. The mixture was heated while stirring, and after confirming the initiation of the polymerization reaction, the reaction was carried out at the reflux temperature for 2 hours. Next, 0.04 part of BPO was added to the reaction solution and reacted for 2 hours, and further 0.04 part of BPO was added to the reaction solution and the reaction was continued for 4 hours. After that, the reaction vessel was cooled and 66 parts of ethyl acetate was added to obtain an acrylic resin (A-15) solution having a weight average molecular weight of 900,000.
（合成例１６）
反応容器に窒素雰囲気下、アクリル酸２－エチルヘキシル７３．３部、アクリル酸メチル２３．５部、アクリル酸ヒドロキシエチル０．２部、アクリル酸３．０部、酢酸エチル４０．０部、アセトン４０．０部、ベンゾイルパーオキシド（以下、ＢＰＯ）０．２部を仕込んだ。撹拌しながら加熱を行い重合反応の開始を確認して還流温度で２時間反応した。次いで、ＢＰＯ ０．０４部を反応溶液に添加し２時間反応し、さらにＢＰＯ ０．０４部を反応溶液に添加し４時間反応を継続した。その後、反応容器を冷却し酢酸エチル６６部を加え、重量平均分子量１４７万のアクリル系樹脂（Ａ－１６）溶液を得た。
(Synthesis Example 16)
73.3 parts of 2-ethylhexyl acrylate, 23.5 parts of methyl acrylate, 0.2 parts of hydroxyethyl acrylate, 3.0 parts of acrylic acid, 40.0 parts of ethyl acetate, and 40 parts of acetone were placed in a reaction vessel under a nitrogen atmosphere. 0.0 part and 0.2 part of benzoyl peroxide (hereinafter referred to as BPO) were charged. The mixture was heated while stirring, and after confirming the initiation of the polymerization reaction, the reaction was carried out at the reflux temperature for 2 hours. Next, 0.04 part of BPO was added to the reaction solution and reacted for 2 hours, and further 0.04 part of BPO was added to the reaction solution and the reaction was continued for 4 hours. After that, the reactor was cooled and 66 parts of ethyl acetate was added to obtain an acrylic resin (A-16) solution having a weight average molecular weight of 1,470,000.
（合成例１７）
反応容器に窒素雰囲気下、アクリル酸２－エチルヘキシル７３．３部、アクリル酸メチル２３．５部、アクリル酸ヒドロキシエチル０．２部、アクリル酸３．０部、酢酸エチル２５．０部、アセトン５５．０部、ベンゾイルパーオキシド（以下、ＢＰＯ）０．２部を仕込んだ。撹拌しながら加熱を行い重合反応の開始を確認して還流温度で２時間反応した。次いで、ＢＰＯ ０．０４部を反応溶液に添加し２時間反応し、さらにＢＰＯ ０．０４部を反応溶液に添加し４時間反応を継続した。その後、反応容器を冷却し酢酸エチル６６部を加え、重量平均分子量１８０万のアクリル系樹脂（Ａ－１７）溶液を得た。
(Synthesis Example 17)
73.3 parts of 2-ethylhexyl acrylate, 23.5 parts of methyl acrylate, 0.2 parts of hydroxyethyl acrylate, 3.0 parts of acrylic acid, 25.0 parts of ethyl acetate, and 55 parts of acetone were placed in a reaction vessel under a nitrogen atmosphere. 0.0 part and 0.2 part of benzoyl peroxide (hereinafter referred to as BPO) were charged. The mixture was heated while stirring, and after confirming the initiation of the polymerization reaction, the reaction was carried out at the reflux temperature for 2 hours. Next, 0.04 part of BPO was added to the reaction solution and reacted for 2 hours, and further 0.04 part of BPO was added to the reaction solution and the reaction was continued for 4 hours. After that, the reactor was cooled and 66 parts of ethyl acetate was added to obtain an acrylic resin (A-17) solution having a weight average molecular weight of 1,800,000.
（合成例２３）
モノマーの種類及び配合量を表１の記載に従った他は、合成例１７と同様に行うことで合成例２３のアクリル系樹脂（Ａ－２３）溶液を得た。
(Synthesis Example 23)
A solution of acrylic resin (A-23) of Synthesis Example 23 was obtained in the same manner as in Synthesis Example 17 except that the types and blending amounts of the monomers were as described in Table 1.
（合成例２５、２９）
モノマーの種類及び配合量を表１の記載に従った他は、合成例１６と同様に行うことで合成例２５、２９のアクリル系樹脂（Ａ－２５、２９）溶液を得た。
(Synthesis Examples 25 and 29)
Acrylic resin (A-25, 29) solutions of Synthesis Examples 25 and 29 were obtained in the same manner as in Synthesis Example 16, except that the types and blending amounts of the monomers were as described in Table 1.
（合成例３１）
モノマーの種類及び配合量を表１の記載に従った他は、合成例１５と同様に行うことで合成例３１のアクリル系樹脂（Ａ－３１）溶液を得た。
(Synthesis Example 31)
A solution of acrylic resin (A-31) of Synthesis Example 31 was obtained in the same manner as in Synthesis Example 15 except that the types and blending amounts of the monomers were as described in Table 1.
（合成例３２）
反応容器に窒素雰囲気下、アクリル酸２－エチルヘキシル４０．０部、アクリル酸メチル５４．５部、アクリル酸ヒドロキシエチル０．５部、アクリル酸５．０部、酢酸エチル３０．０部、メチルエチルケトン７０．０部、ベンゾイルパーオキシド（以下、ＢＰＯ）０．２部を仕込んだ。撹拌しながら加熱を行い重合反応の開始を確認して還流温度で２時間反応した。次いで、ＢＰＯ ０．０４部を反応溶液に添加し２時間反応し、さらにＢＰＯ ０．０４部を反応溶液に添加し４時間反応を継続した。その後、反応容器を冷却し酢酸エチル６６部を加え、重量平均分子量２０万のアクリル系樹脂（Ａ－３２）溶液を得た。
(Synthesis Example 32)
40.0 parts of 2-ethylhexyl acrylate, 54.5 parts of methyl acrylate, 0.5 parts of hydroxyethyl acrylate, 5.0 parts of acrylic acid, 30.0 parts of ethyl acetate, and 70 parts of methyl ethyl ketone were placed in a reaction vessel under a nitrogen atmosphere. 0.0 part and 0.2 part of benzoyl peroxide (hereinafter referred to as BPO) were charged. The mixture was heated while stirring, and after confirming the initiation of the polymerization reaction, the reaction was carried out at the reflux temperature for 2 hours. Next, 0.04 part of BPO was added to the reaction solution and reacted for 2 hours, and further 0.04 part of BPO was added to the reaction solution and the reaction was continued for 4 hours. After that, the reaction vessel was cooled and 66 parts of ethyl acetate was added to obtain an acrylic resin (A-32) solution having a weight average molecular weight of 200,000.
（実施例１）
合成例１で得られたアクリル系樹脂溶液中のアクリル系樹脂（Ａ－１）１００部（不揮発分）に対して、イソシアネート硬化剤として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０．３部（不揮発分換算）配合し、更に溶剤として酢酸エチルを加えて不揮発分を３０％に調整してアクリル系粘着剤を得た。
前記アクリル系粘着剤を、厚さ３８μｍの市販剥離性シート（ポリエチレンテレフタレート製）上に、乾燥後の厚さが２５μｍになるようにコンマコーターで塗工を行い、１００℃で２分間乾燥することで粘着剤層を形成した。次いで、この粘着剤層に、厚さ５０μｍの基材（ポリエチレンテレフタレート製基材（「ルミラーＴ－６０」、東レ社製）以下、ＰＥＴシートという）を貼り合せ、温度２５℃―５０％ＲＨ条件で１週間熟成することで「剥離性シート／粘着剤層／ＰＥＴシート」という構成の、粘着層（Ｘ）を有する粘着シートを得た。ただし、実施例１は参考例である。
(Example 1)
Per 100 parts of the acrylic resin (A-1) (non-volatile) in the acrylic resin solution obtained in Synthesis Example 1, 0.3 parts of trimethylolpropane adduct of tolylene diisocyanate as an isocyanate curing agent (non-volatile (in terms of minutes), and ethyl acetate was added as a solvent to adjust the non-volatile content to 30% to obtain an acrylic pressure-sensitive adhesive.
The acrylic pressure-sensitive adhesive is coated on a commercially available release sheet (made of polyethylene terephthalate) having a thickness of 38 μm with a comma coater so that the thickness after drying becomes 25 μm, and dried at 100° C. for 2 minutes. to form an adhesive layer. Next, a substrate with a thickness of 50 μm (polyethylene terephthalate substrate (“Lumirror T-60”, manufactured by Toray Industries, Inc.), hereinafter referred to as a PET sheet) is attached to this adhesive layer, and the temperature is 25° C.-50% RH. A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer (X) having a structure of "releasable sheet/pressure-sensitive adhesive layer/PET sheet" was obtained by aging for 1 week. However, Example 1 is a reference example.
（実施例２～３５、比較例１～２）
材料を表２、３の配合に従って変更した以外は、実施例１と同様に行うことで、実施例２～３５および比較例１～２のアクリル系粘着剤、および粘着シートをそれぞれ得た。
ただし、実施２、１０、１１、１６、２１、２３、２５、２８、２９、３０、３４、３５は参考例である。
(Examples 2-35, Comparative Examples 1-2)
Acrylic pressure-sensitive adhesives and pressure-sensitive adhesive sheets of Examples 2-35 and Comparative Examples 1-2 were obtained in the same manner as in Example 1 except that the materials were changed according to the formulations in Tables 2 and 3.
However, Examples 2, 10, 11, 16, 21, 23, 25, 28, 29, 30, 34, and 35 are reference examples.
＜粘着剤層の物性測定および粘着シートの評価＞
粘着剤層の貯蔵弾性率および可塑剤移行量の測定と、耐可塑剤性、塩化ビニル（ＰＶＣ）フィルム追従性、加工性の評価を以下の方法で行った。結果を表１に示す。
<Measurement of physical properties of pressure-sensitive adhesive layer and evaluation of pressure-sensitive adhesive sheet>
The storage elastic modulus and the amount of plasticizer migration of the pressure-sensitive adhesive layer were measured, and the evaluation of plasticizer resistance, vinyl chloride (PVC) film followability, and workability were performed by the following methods. Table 1 shows the results.
［せん断貯蔵弾性率］
得られた粘着剤を用い、厚さ７５μｍの市販剥離性シート上に、乾燥後の厚さが５０μｍになるようにコンマコーター（登録商標）で塗工を行い、１００℃で２分間乾燥することで粘着剤層を形成した。次いで、基材の代わりに厚さ３８μｍの別の市販剥離性シート（ポリエチレンテレフタレート製）を貼り合わせ、温度２５℃―５０％ＲＨ条件で１週間熟成し、「７５μｍ剥離性シート／粘着剤層／３８μｍ剥離性シート」という構成の２枚の剥離性シートで挟まれた粘着剤層を作成した。次いで、片方の剥離性シートを剥がし、粘着剤層が重なるように積層を繰り返し、厚みが１ｍｍの粘着剤層を得た。オートクレーブで気泡を除去した後、直径８ｍｍの円柱形に型抜きして貯蔵弾性率測定用の試料を作成した。両側の剥離性シートを剥がし、この試料のねじり剪断法により、下記の条件で測定した。
[Shear storage modulus]
Using the obtained pressure-sensitive adhesive, coat a commercially available release sheet having a thickness of 75 μm with a comma coater (registered trademark) so that the thickness after drying becomes 50 μm, and dry at 100° C. for 2 minutes. to form an adhesive layer. Next, another commercially available release sheet (made of polyethylene terephthalate) with a thickness of 38 μm was laminated instead of the base material, and aged at a temperature of 25 ° C.-50% RH for 1 week, and "75 μm release sheet/adhesive layer/ A pressure-sensitive adhesive layer sandwiched between two release sheets having a structure of "38 μm release sheet" was prepared. Then, one of the release sheets was peeled off, and lamination was repeated so that the adhesive layers overlapped to obtain an adhesive layer with a thickness of 1 mm. After removing air bubbles with an autoclave, a cylinder with a diameter of 8 mm was die-cut to prepare a sample for storage modulus measurement. The peelable sheets on both sides were peeled off, and the sample was measured by the torsional shear method under the following conditions.
測定装置：ティー・エイ・インスツルメント・ジャパン社製動的粘弾性測定装置「ＤＹＮＡＭＩＣ ＡＮＡＬＹＺＥＲ ＲＤＡ ＩＩＩ」
周波数：１Ｈｚ
測定温度： －５０℃から２００℃まで測定し、７０℃での貯蔵弾性率を読み取った。
昇温速度： １０℃／分
Measuring device: Dynamic viscoelasticity measuring device “DYNAMIC ANALYZER RDA III” manufactured by TA Instruments Japan
Frequency: 1Hz
Measurement temperature: Measurement was carried out from -50°C to 200°C, and the storage modulus at 70°C was read.
Heating rate: 10°C/min
［可塑剤移行量］
アクリル系樹脂（アクリル酸ブチル５３部、アクリル酸２－エチルヘキシル４１部、アクリル酸６部）１００部（不揮発分）に対して、イソシアネート硬化剤として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０．４部（不揮発分換算）、可塑剤（フタル酸ジオクチル）をそれぞれ所定量（０、５、１０、２０、５０部）配合し、更に溶剤として酢酸エチルを加えて不揮発分を３０％に調整して、検量線作成のためのポリ塩化ビニル用粘着剤を得た。前記粘着剤を、厚さ３８μｍの市販剥離性シート上に、乾燥後の厚さが２５μｍになるようにコンマコーターで塗工を行い、１００℃で２分間乾燥することで粘着剤層を形成した。次いで、この粘着剤層に、厚さ５０μｍの基材を貼り合せ、温度２５℃―５０％ＲＨ条件で１週間熟成することで「剥離性シート／粘着剤層／ＰＥＴシート」という構成の粘着シートを得た。
可塑剤含有量の異なる可塑剤含有粘着シートを幅２５ｍｍ、長さ１００ｍｍの大きさに切り出し、剥離性シートを剥離した後、テトラヒドロフラン（ＴＨＦ）に溶解（１枚/２０ｇＴＨＦ）し、ＧＰＣ測定を行い、得られた低分子（可塑剤）由来のピーク強度から検量線を作成した。
尚、可塑剤は、前記アクリル系樹脂や硬化剤と反応せず、また溶出分のＧＰＣ測定により得られるピークは他の成分と被らないため、上記方法にて検量線として用いることが可能であることを確認した。
[Amount of plasticizer migration]
Acrylic resin (53 parts of butyl acrylate, 41 parts of 2-ethylhexyl acrylate, 6 parts of acrylic acid) per 100 parts (non-volatile), 0.4 parts of trimethylolpropane adduct of tolylene diisocyanate as an isocyanate curing agent (in terms of non-volatile content) and a plasticizer (dioctyl phthalate) in predetermined amounts (0, 5, 10, 20, 50 parts) respectively, and ethyl acetate is added as a solvent to adjust the non-volatile content to 30%, An adhesive for polyvinyl chloride was obtained for preparing a calibration curve. The pressure-sensitive adhesive was coated on a commercially available release sheet having a thickness of 38 μm with a comma coater so that the thickness after drying was 25 μm, and dried at 100° C. for 2 minutes to form a pressure-sensitive adhesive layer. . Next, a base material having a thickness of 50 μm is attached to this pressure-sensitive adhesive layer, and the pressure-sensitive adhesive sheet having a configuration of “releasable sheet/adhesive layer/PET sheet” is aged for one week at a temperature of 25° C.-50% RH. got
A plasticizer-containing pressure-sensitive adhesive sheet with a different plasticizer content was cut into a size of 25 mm in width and 100 mm in length. , a calibration curve was created from the obtained low-molecular-weight (plasticizer)-derived peak intensities.
In addition, since the plasticizer does not react with the acrylic resin or curing agent, and the peak obtained by GPC measurement of the eluted portion does not overlap with other components, it can be used as a calibration curve in the above method. Confirmed that there is.
まず、実施例および比較例により得られた粘着シートを幅２５ｍｍ、長さ１００ｍｍの大きさに切り出した。続いて２５℃―５０％ＲＨ雰囲気下、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（Ｘ）を、可塑剤（フタル酸ジオクチル）を３６質量％含有する厚み４００μｍの塩化ビニルフィルム（以下、ＰＶＣフィルム）に貼り付け、２ｋｇロールにより１往復させて圧着後２４時間放置した試料を作製した。作製した試料を７０℃５日間加熱後、さらに２５℃―５０％ＲＨ環境下５日経時させ、粘着シート（粘着剤層／ＰＥＴシート）をＰＶＣフィルムから剥離し、可塑剤を移行させた粘着剤層（Ｘ’）を有する粘着シートを得た。可塑剤を移行させた粘着シートをＴＨＦに溶解（１枚/２０ｇＴＨＦ）し、ＧＰＣ測定を行うことで粘着剤層（Ｘ’）のフタル酸ジオクチル由来のピーク強度を得て、上記の検量線から７０℃５日間加熱後、さらに２５℃―５０％ＲＨ環境下５日経時後の粘着剤層（Ｘ’）が含有する可塑剤量を求め、粘着剤層（Ｘ）に対する可塑剤量を算出し、可塑剤移行量とした。 First, the adhesive sheets obtained in Examples and Comparative Examples were cut into pieces having a width of 25 mm and a length of 100 mm. Subsequently, under an atmosphere of 25° C.-50% RH, the adhesive layer (X) exposed by peeling off the release sheet from the cut adhesive sheet was coated with a 400 μm-thick vinyl chloride containing 36% by mass of a plasticizer (dioctyl phthalate). A sample was prepared by attaching it to a film (hereinafter referred to as a PVC film), reciprocating it once with a 2 kg roll, and leaving it for 24 hours after pressure bonding. After heating the prepared sample at 70° C. for 5 days, it is further aged for 5 days in a 25° C.-50% RH environment, and the adhesive sheet (adhesive layer/PET sheet) is peeled off from the PVC film to transfer the plasticizer. A pressure-sensitive adhesive sheet having a layer (X') was obtained. The pressure-sensitive adhesive sheet to which the plasticizer has been migrated is dissolved in THF (1 sheet/20 g THF), and the peak intensity derived from dioctyl phthalate in the pressure-sensitive adhesive layer (X') is obtained by GPC measurement. After heating at 70° C. for 5 days, the amount of plasticizer contained in the adhesive layer (X′) after 5 days in a 25° C.-50% RH environment was determined, and the amount of plasticizer for the adhesive layer (X) was calculated. , the amount of plasticizer migration.
＜耐可塑剤性＞
得られた粘着シートを幅２５ｍｍ、長さ１００ｍｍの大きさに切り出した。２５℃―５０％ＲＨ雰囲気下、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可塑剤（フタル酸ジオクチル）３６％含有する塩化ビニルシート（以下、ＰＶＣシート）に貼り付け、２ｋｇロールにより１往復させて圧着後２４時間放置した試料を作製した。上記＜可塑剤移行量＞の条件に従いＰＶＣシートに貼りつけ後、この試料を引張試験機を用いて１８０度方向に３００ｍｍ／分の速度で引き剥がす１８０°ピール試験によって粘着力を測定した（熱経時前粘着力）。
別途、得られた粘着シートを上記粘着力の条件に従いＰＶＣシートに貼りつけ後、７０℃ＤＲＹ５日間放置した後、上記、熱経時前粘着力と同様に粘着力測定を行い（熱経時後粘着力）、下記の評価基準に基づいて評価を行った。
保持率＝（熱経時後粘着力／熱経時前粘着力）×１００
◎：保持率９０以上であり、優良。
○：保持率７５以上９０未満であり、良好。
△：保持率５０以上７５未満であり、実用可能。
×：保持率５０未満または凝集破壊のため保持率が算出できず、実用不可。
<Plasticizer resistance>
The obtained adhesive sheet was cut into a size of 25 mm in width and 100 mm in length. In an atmosphere of 25° C.-50% RH, the peelable adhesive layer was peeled off from the cut adhesive sheet, and the exposed adhesive layer was attached to a vinyl chloride sheet (hereinafter referred to as a PVC sheet) containing 36% plasticizer (dioctyl phthalate), A sample was prepared by reciprocating once with a 2 kg roll and leaving it for 24 hours after pressure bonding. After affixing to the PVC sheet according to the conditions of <Plasticizer Migration Amount>, the adhesive strength was measured by a 180° peel test in which the sample was peeled off at a rate of 300 mm/min in a 180° direction using a tensile tester (thermal Adhesive strength before aging).
Separately, after attaching the obtained adhesive sheet to the PVC sheet according to the above adhesive strength conditions, leaving it for 5 days at 70 ° C. DRY, the adhesive strength was measured in the same manner as the adhesive strength before heat aging (adhesive strength after heat aging ), and was evaluated based on the following evaluation criteria.
Retention rate = (adhesive strength after heat aging/adhesive strength before heat aging) x 100
A: The retention rate is 90 or more, which is excellent.
◯: The retention rate is 75 or more and less than 90, which is good.
Δ: The retention rate is 50 or more and less than 75, and is practical.
x: The retention rate is less than 50, or the retention rate cannot be calculated due to cohesive failure, and is not practical.
＜ＰＶＣフィルム変形追従性＞
得られた粘着シートを幅１００ｍｍ、縦１００ｍｍの大きさに準備した。次いで水１００ｍＬを注いだ容器に塩化ビニル製ラップフィルム（日立ラップ、日立化成社製）を張り、前記粘着シートを前記ラップフィルムの中心平面部に貼り合せた後、５００Ｗ１分間の条件で電子レンジ加熱した。電子レンジから容器ごと取り出した後、加熱により収縮変形した粘着シートのラップフィルムからの粘着シートの浮き・ハガレ具合を目視にて評価した。評価基準は以下の通りである。
◎：粘着シートの浮き・ハガレが認められない、優良。
○：粘着シートの端部に０．５ｍｍ未満の粘着シートの浮き・ハガレが認められる、良好。
△：粘着シートの端部に０．５ｍｍ以上２ｍｍ未満の粘着シートの浮き・ハガレが認められる、実用可能。
×：２ｍｍ以上の粘着シートの浮き・ハガレが認められる、実用不可。
<PVC film deformation followability>
The obtained pressure-sensitive adhesive sheet was prepared in a size of 100 mm in width and 100 mm in length. Next, a vinyl chloride wrap film (Hitachi Wrap, manufactured by Hitachi Chemical Co., Ltd.) is attached to the container in which 100 mL of water is poured, and the adhesive sheet is attached to the center plane of the wrap film, and then heated in a microwave oven at 500 W for 1 minute. bottom. After the container was taken out from the microwave oven, the pressure-sensitive adhesive sheet that had shrunk and deformed due to heating was visually evaluated for floating or peeling from the wrap film. Evaluation criteria are as follows.
⊚: Excellent, no floating or peeling of the adhesive sheet.
Good: Lifting or peeling of the adhesive sheet of less than 0.5 mm is observed at the edge of the adhesive sheet.
Δ: Lifting and peeling of the adhesive sheet of 0.5 mm or more and less than 2 mm are observed at the edge of the adhesive sheet, practically usable.
x: Lifting and peeling of the adhesive sheet of 2 mm or more are observed, not practical.
＜加工性＞
得られた粘着シートを幅１００ｍｍ、縦１００ｍｍの大きさに準備した。次いで前記粘着シートを５ｋｇ／ｃｍ２の条件で４０℃―５０％ＲＨ２４時間圧着を行い粘着シートの側面から粘着剤層がはみ出した状態を評価した。評価基準は以下の通りである。
◎：粘着剤層のはみ出しが無い、優良。
○：０．２ｍｍ未満の粘着剤層のはみ出しがあったが実用上問題ない、良好。
△：０．２ｍｍ以上０．５ｍｍ未満の粘着剤層のはみ出しがあったが実用上問題ない、実用可能。
×：０．５ｍｍ以上の粘着剤層のはみ出しがあり使用できない、実用不可。
<Workability>
The obtained pressure-sensitive adhesive sheet was prepared in a size of 100 mm in width and 100 mm in length. Next, the pressure-sensitive adhesive sheet was pressed under conditions of 40° C.-50% RH for 24 hours under conditions of 5 kg/cm 2 , and the state in which the pressure-sensitive adhesive layer protruded from the side surface of the pressure-sensitive adhesive sheet was evaluated. Evaluation criteria are as follows.
⊚: Excellent with no protrusion of the adhesive layer.
◯: Protrusion of less than 0.2 mm of the adhesive layer was observed, but there was no problem in practical use.
Δ: Protrusion of the pressure-sensitive adhesive layer of 0.2 mm or more and less than 0.5 mm was observed, but there was no problem in practical use, and it was practicable.
x: Unusable due to protrusion of the adhesive layer of 0.5 mm or more, impractical.
Claims (4)
前記アクリル系樹脂（Ａ）は、アルキル基の炭素数８～１２の（メタ）アクリル酸アルキルエステル、水酸基を有するモノマー（ａ２）およびカルボキシル基を有するモノマー（ａ３）を含むモノマー混合物を共重合してなる重量平均分子量６０万～１５０万のアクリル系共重合体であり、
前記アルキル基の炭素数８～１２の（メタ）アクリル酸アルキルエステルは、アクリル酸２－エチルへキシルまたはアクリル酸イソノニルを含み、
モノマー混合物１００質量％中、アルキル基の炭素数８～１２の（メタ）アクリル酸アルキルエステルの含有量が６０～８４質量％、水酸基を有するモノマー（ａ２）の含有量が０．０５～１質量％であり、
前記硬化剤（Ｂ）は、イソシアネート硬化剤を含み、かつイソシアネート硬化剤の含有量は、アクリル系樹脂（Ａ）１００質量部に対して、０．０１～０．６質量部であり、
前記粘着剤層（Ｘ）の周波数１Ｈｚ、７０℃でのせん断貯蔵弾性率は０．０５ＭＰａ未満であり、かつ
可塑剤を３６質量％含有する厚み４００μｍの塩化ビニルフィルムに、前記粘着剤層（Ｘ）を貼付した試料の、７０℃５日間加熱後、さらに２５℃－環境下５日経時後における前記塩化ビニルフィルムから粘着剤層への可塑剤移行量が、粘着剤層（Ｘ）１００質量部に対して２０質量部以上である、可塑剤含有塩化ビニルフィルム用粘着シート。 A pressure-sensitive adhesive sheet for a plasticizer-containing vinyl chloride film having a pressure-sensitive adhesive layer (X) containing an acrylic resin (A) and a curing agent (B),
The acrylic resin (A) is obtained by copolymerizing a monomer mixture containing a (meth)acrylic acid alkyl ester having an alkyl group with 8 to 12 carbon atoms, a monomer (a2) having a hydroxyl group, and a monomer (a3) having a carboxyl group. An acrylic copolymer having a weight average molecular weight of 600,000 to 1,500,000 ,
The (meth)acrylic acid alkyl ester having 8 to 12 carbon atoms in the alkyl group includes 2-ethylhexyl acrylate or isononyl acrylate,
In 100% by mass of the monomer mixture, the content of (meth)acrylic acid alkyl ester having an alkyl group of 8 to 12 carbon atoms is 60 to 84% by mass, and the content of the monomer (a2) having a hydroxyl group is 0.05 to 1 mass%. % and
The curing agent (B) contains an isocyanate curing agent, and the content of the isocyanate curing agent is 0.01 to 0.6 parts by mass with respect to 100 parts by mass of the acrylic resin (A),
The pressure-sensitive adhesive layer (X) has a shear storage modulus of less than 0.05 MPa at a frequency of 1 Hz and 70 ° C., and a vinyl chloride film having a thickness of 400 μm containing 36% by mass of a plasticizer is coated with the pressure-sensitive adhesive layer (X ), after heating at 70 ° C. for 5 days, and after 5 days in a 25 ° C.-environment, the amount of plasticizer transferred from the vinyl chloride film to the adhesive layer was 100 parts by mass of the adhesive layer (X). 20 parts by mass or more of the plasticizer-containing pressure-sensitive adhesive sheet for a vinyl chloride film.
An acrylic pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer (X) of the plasticizer-containing pressure-sensitive adhesive sheet for vinyl chloride film according to any one of claims 1 to 3 .
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| JP2006199843A (en) | 2005-01-21 | 2006-08-03 | Toyo Ink Mfg Co Ltd | Adhesive composition and adhesive sheet using the same |
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