JP7139699B2 - Adhesive composition and cured product - Google Patents
Adhesive composition and cured product Download PDFInfo
- Publication number
- JP7139699B2 JP7139699B2 JP2018109563A JP2018109563A JP7139699B2 JP 7139699 B2 JP7139699 B2 JP 7139699B2 JP 2018109563 A JP2018109563 A JP 2018109563A JP 2018109563 A JP2018109563 A JP 2018109563A JP 7139699 B2 JP7139699 B2 JP 7139699B2
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- Prior art keywords
- monomer
- meth
- parts
- mass
- adhesive composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 62
- 239000000853 adhesive Substances 0.000 title claims description 35
- 230000001070 adhesive effect Effects 0.000 title claims description 34
- 239000000178 monomer Substances 0.000 claims description 86
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 43
- 229920000058 polyacrylate Polymers 0.000 claims description 20
- 239000003431 cross linking reagent Substances 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 51
- 239000002313 adhesive film Substances 0.000 description 37
- -1 2-ethylhexyl Chemical group 0.000 description 26
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 239000011521 glass Substances 0.000 description 14
- 239000003963 antioxidant agent Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 9
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002985 plastic film Substances 0.000 description 5
- 229920006255 plastic film Polymers 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 3
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007877 V-601 Substances 0.000 description 3
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- 230000008859 change Effects 0.000 description 3
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- 230000006866 deterioration Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 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
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- MLKIVXXYTZKNMI-UHFFFAOYSA-N 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one Chemical compound CCCCCCCCCCCCC1=CC=C(C(=O)C(C)(C)O)C=C1 MLKIVXXYTZKNMI-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
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- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-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
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
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- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 238000000691 measurement method Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 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 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Description
本発明の実施形態は、粘着剤組成物及び硬化物に関する。 TECHNICAL FIELD Embodiments of the present invention relate to adhesive compositions and cured products.
粘着フィルムは、基材同士を貼り合せる際に、屋内又は屋外の様々な場所で使用されている。粘着フィルムは、基材同士を貼り合せる際、光の透過を損ねないように、透明性が必要となることがある。このような粘着フィルムとしては、例えば、特許文献１に記載の粘着フィルムが挙げられる。 Adhesive films are used in various places indoors or outdoors when bonding substrates together. The pressure-sensitive adhesive film may require transparency so as not to impair the transmission of light when the substrates are laminated together. Such adhesive films include, for example, the adhesive film described in Patent Document 1.
近年、上記のような粘着フィルムは、屋外で使用されることも多く、太陽光等の紫外線が含まれる電磁波に晒されやすい。そのため、粘着フィルムは、紫外線の照射により劣化し、黄変する懸念があり、耐候性に優れた粘着フィルムが必要とされている。 In recent years, the adhesive films as described above are often used outdoors and are likely to be exposed to electromagnetic waves including ultraviolet rays such as sunlight. Therefore, there is a concern that the adhesive film will deteriorate and turn yellow when irradiated with ultraviolet rays, and there is a need for an adhesive film that is excellent in weather resistance.
このような問題を解決する方法として、粘着フィルムを構成する粘着剤組成物に、紫外線吸収剤を添加する方法が考えられる。しかし、紫外線吸収剤を添加した紫外線硬化型の粘着剤組成物に紫外線を照射すると、紫外線は紫外線吸収剤に吸収され、樹脂組成物の硬化反応が阻害され、生産性が低下したり、光学用途として必要な特性が得られなくなったりするという問題がある。 As a method for solving such problems, a method of adding an ultraviolet absorber to the adhesive composition constituting the adhesive film is conceivable. However, when an ultraviolet curable pressure-sensitive adhesive composition containing an ultraviolet absorber is irradiated with ultraviolet light, the ultraviolet light is absorbed by the ultraviolet absorber, inhibiting the curing reaction of the resin composition, resulting in a decrease in productivity and optical applications. As a result, there is a problem that the necessary characteristics cannot be obtained.
そこで、特許文献２は、（メタ）アクリル酸エステル重合体と、熱架橋剤と、紫外線吸収剤とを含有する粘着剤組成物を、熱硬化してなる粘着フィルムについて開示している。しかし、熱硬化する粘着剤組成物では、硬化時間及び養生時間が長く、フィルムの作製に多くの時間を要する。 Therefore, Patent Document 2 discloses an adhesive film obtained by thermally curing an adhesive composition containing a (meth)acrylic acid ester polymer, a thermal cross-linking agent, and an ultraviolet absorber. However, the heat-curable pressure-sensitive adhesive composition requires a long curing time and a long curing time, and takes a long time to produce a film.
本発明の実施形態は、上記を鑑み、十分な粘着力を有し、かつ、紫外線による着色が抑制され、透明性を維持できる硬化物を、生産性を損なうことなく製造できる粘着剤組成物を提供することを目的とする。また、本発明の実施形態は、生産性に優れ、十分な粘着力を有し、かつ、紫外線による着色が抑制され、透明性を維持できる硬化物を提供することを目的とする。 In view of the above, an embodiment of the present invention provides a pressure-sensitive adhesive composition that has sufficient adhesive strength, suppresses coloration due to ultraviolet rays, and can produce a cured product that can maintain transparency without impairing productivity. intended to provide Another object of an embodiment of the present invention is to provide a cured product that is excellent in productivity, has sufficient adhesive strength, is inhibited from being colored by ultraviolet rays, and can maintain transparency.
本発明者らは、検討の結果、粘着剤組成物が特定の構造のモノマを含有する場合、良好な粘着力を維持しつつ、優れた耐候性を有する硬化物が効率よく得られることを見出した。 As a result of investigation, the present inventors have found that when a pressure-sensitive adhesive composition contains a monomer having a specific structure, a cured product having excellent weather resistance while maintaining good adhesive strength can be efficiently obtained. rice field.
本発明は、上記知見に基づくものであり、以下の実施形態を含む。本発明は以下の実施形態に限定されない。
［１］（Ａ）（メタ）アクリル重合体、（Ｂ）モノマ、（Ｃ）架橋剤、及び（Ｄ）光重合開始剤を含有し、
前記（Ｂ）モノマが、下記式（１）で表されるモノマを含む、粘着剤組成物。
[1] (A) a (meth)acrylic polymer, (B) a monomer, (C) a cross-linking agent, and (D) a photopolymerization initiator,
The pressure-sensitive adhesive composition, wherein the monomer (B) contains a monomer represented by the following formula (1).
［２］（Ａ）（メタ）アクリル重合体、（Ｂ）モノマ、（Ｃ）架橋剤、及び（Ｄ）光重合開始剤の合計１００質量部に対して、（Ａ）（メタ）アクリル重合体１５～７０質量部、（Ｂ）モノマ１５～７５質量部、（Ｃ）架橋剤０．０１～２０質量部、及び（Ｄ）光重合開始剤０．００５～５質量部を含有する、前記［１］に記載の粘着剤組成物。 [2] (A) (meth) acrylic polymer, (B) monomer, (C) cross-linking agent, and (D) photopolymerization initiator for a total of 100 parts by mass, (A) (meth) acrylic polymer The above [ 1].
［３］前記［１］又は［２］に記載の粘着剤組成物の硬化物。 [3] A cured product of the pressure-sensitive adhesive composition according to [1] or [2].
本発明の実施形態によれば、十分な粘着力を有し、かつ、紫外線による着色が抑制され、透明性を維持できる硬化物を、生産性を損なうことなく製造できる粘着剤組成物を提供することができる。また、本発明の実施形態によれば、生産性に優れ、十分な粘着力を有し、かつ、紫外線による着色が抑制され、透明性を維持できる硬化物を提供することができる。 ADVANTAGE OF THE INVENTION According to the embodiment of the present invention, there is provided a pressure-sensitive adhesive composition that can produce a cured product that has sufficient adhesive strength, is inhibited from being colored by ultraviolet rays, and can maintain transparency without impairing productivity. be able to. Moreover, according to the embodiment of the present invention, it is possible to provide a cured product that is excellent in productivity, has sufficient adhesive strength, is inhibited from being colored by ultraviolet rays, and can maintain transparency.
＜粘着剤組成物＞
本発明の一実施形態である粘着剤組成物は、（Ａ）（メタ）アクリル重合体、（Ｂ）モノマ、（Ｃ）架橋剤、及び（Ｄ）光重合開始剤を含有する。（Ｂ）モノマは、後述する式（１）で表されるモノマを含有する。（Ａ）～（Ｄ）成分は、それぞれ、１種を単独で用いてもよいし、２種以上を併用してもよい。
<Adhesive composition>
A pressure-sensitive adhesive composition that is one embodiment of the present invention contains (A) a (meth)acrylic polymer, (B) a monomer, (C) a cross-linking agent, and (D) a photopolymerization initiator. (B) Monomer contains a monomer represented by formula (1) described later. The components (A) to (D) may be used singly or in combination of two or more.
［（Ａ）（メタ）アクリル重合体］
（Ａ）（メタ）アクリル重合体は、（メタ）アクリル単量体を含む単量体を重合することにより得られる。
[(A) (meth) acrylic polymer]
(A) The (meth)acrylic polymer is obtained by polymerizing a monomer containing a (meth)acrylic monomer.
単量体としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート等の（メタ）アクリル酸アルキルエステル単量体；（メタ）アクリル酸、マレイン酸、無水マレイン酸、イタコン酸、フマル酸、無水フマル酸等のカルボキシ基含有単量体；２－ヒドロキシエチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート等のヒドロキシル基含有単量体などが挙げられる。単量体は１種を単独で用いてもよいし、２種以上を併用してもよい。後述する（Ｃ）架橋剤と反応し得る基を導入するという観点から、単量体として、少なくとも、カルボキシ基含有単量体及び／又はヒドロキシル基含有単量体を用いることが好ましく、少なくともヒドロキシル基含有単量体を用いることがより好ましい。 Examples of monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) (meth)acrylic acid alkyl ester monomers such as acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; (meth)acrylic acid , maleic acid, maleic anhydride, itaconic acid, fumaric acid, carboxy group-containing monomers such as fumaric anhydride; 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) ) hydroxyl group-containing monomers such as acrylates and polyethylene glycol (meth)acrylates. A monomer may be used individually by 1 type, and may use 2 or more types together. From the viewpoint of introducing a group that can react with the (C) crosslinking agent described later, it is preferable to use at least a carboxy group-containing monomer and/or a hydroxyl group-containing monomer as a monomer, and at least a hydroxyl group It is more preferable to use contained monomers.
なお、「（メタ）アクリル」とは、「アクリル」及び「メタクリル」の総称であり、「（メタ）アクリレート」とは、「アクリレート」及び「メタクリレート」の総称である。 "(Meth)acryl" is a generic term for "acryl" and "methacrylic", and "(meth)acrylate" is a generic term for "acrylate" and "methacrylate".
（メタ）アクリル単量体を含む単量体を重合する際には、例えば、溶液重合法を適用することができる。その際に使用される溶媒としては、酢酸エチル、トルエン、ヘキサン、アセトン、メチルエチルケトン等が挙げられる。また、溶液重合法以外の方法、具体的には、塊状重合法、懸濁重合法、乳化重合法等で重合しても構わない。 When polymerizing a monomer containing a (meth)acrylic monomer, for example, a solution polymerization method can be applied. Solvents used at that time include ethyl acetate, toluene, hexane, acetone, methyl ethyl ketone, and the like. In addition, polymerization may be performed by a method other than the solution polymerization method, specifically, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, or the like.
（Ａ）（メタ）アクリル重合体の含有量は、（Ａ）～（Ｄ）成分の合計１００質量部を基準として、１５～７０質量部が好ましく、２０～６０質量部がより好ましく、３０～５０質量部が更に好ましい。１５質量部以上であると、取扱い性に優れた適度な粘度を持つ粘着剤組成物が得られる傾向がある。一方、７０質量部以下であると、粘着剤組成物が高粘度になり過ぎずに良好な塗工性が得られる傾向がある。 (A) The content of (meth)acrylic polymer is preferably 15 to 70 parts by mass, more preferably 20 to 60 parts by mass, based on 100 parts by mass of components (A) to (D) in total, and 30 to 70 parts by mass. 50 parts by mass is more preferable. When it is 15 parts by mass or more, there is a tendency to obtain a pressure-sensitive adhesive composition that is excellent in handleability and has an appropriate viscosity. On the other hand, when the amount is 70 parts by mass or less, there is a tendency that the pressure-sensitive adhesive composition does not become too viscous and good coatability can be obtained.
［（Ｂ）モノマ］
粘着剤組成物に（Ｂ）モノマを含有させることによって、粘着剤組成物の粘度を低く調整することができ、良好な塗工性を得ることができる。（Ｂ）モノマは１官能のモノマである。（Ｂ）モノマとしては、炭素－炭素不飽和二重結合を有するモノマを使用することが好ましく、（メタ）アクリルモノマと、（メタ）アクリルモノマ以外のビニルモノマとが挙げられ、（メタ）アクリルモノマを使用することが好ましい。また、（Ｂ）モノマとしては、粘着剤組成物に汎用されているアクリロイルモルホリン、ジメチルアクリルアミド等の窒素原子を含むモノマ（「Ｎ含有モノマ」ともいう。）と、窒素原子を含まないモノマ（Ｎ非含有モノマ）とが挙げられ、Ｎ非含有モノマを使用することが好ましい。（Ｂ）モノマは、下記式（１）で表されるモノマを少なくとも含む。
[(B) Monomer]
By including the (B) monomer in the pressure-sensitive adhesive composition, the viscosity of the pressure-sensitive adhesive composition can be adjusted to be low, and good coatability can be obtained. (B) Monomer is a monofunctional monomer. As the monomer (B), it is preferable to use a monomer having a carbon-carbon unsaturated double bond. is preferably used. The (B) monomers include monomers containing nitrogen atoms (also referred to as "N-containing monomers"), such as acryloylmorpholine and dimethylacrylamide, which are commonly used in pressure-sensitive adhesive compositions, and monomers containing no nitrogen atoms (N non-containing monomers), and it is preferable to use N-free monomers. (B) The monomer includes at least a monomer represented by the following formula (1).
式中、Ｘは炭素数１０～２０の２価の炭化水素基を表し、Ｒ１は水素原子又はメチル基を表し、Ｒ２は水素原子又はヒドロキシル基を表す。Ｒ１は水素原子であることが好ましい。Ｒ２は水素原子であることが好ましい。 In the formula, X represents a divalent hydrocarbon group having 10 to 20 carbon atoms, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydrogen atom or a hydroxyl group. R 1 is preferably a hydrogen atom. R2 is preferably a hydrogen atom.
炭化水素基は、飽和又は不飽和の脂肪族炭化水素基、飽和又は不飽和の脂環式炭化水素基、又はこれらを組み合わせた基であることが好ましく、着色の高い抑制効果が得られる傾向があることから、飽和又は不飽和の脂肪族炭化水素基がより好ましい。飽和又は不飽和の脂肪族炭化水素基は、直鎖状又は分岐状の基であってよく、分岐状の基であることが好ましく、分岐状の飽和脂肪族炭化水素基であることがより好ましい。炭化水素基の炭素数は、１０～２０であり、１２～２０が好ましく、１６～２０がより好ましい。 The hydrocarbon group is preferably a saturated or unsaturated aliphatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, or a group combining these, and tends to obtain a high coloration suppressing effect. Therefore, a saturated or unsaturated aliphatic hydrocarbon group is more preferable. The saturated or unsaturated aliphatic hydrocarbon group may be a linear or branched group, preferably a branched group, more preferably a branched saturated aliphatic hydrocarbon group. . The number of carbon atoms in the hydrocarbon group is 10-20, preferably 12-20, more preferably 16-20.
式（１）で表されるモノマとして、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、イソボニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート等が挙げられる。中でも、イソステアリル（メタ）アクリレート、イソボニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、又はジシクロペンテニル（メタ）アクリレートが好ましく、イソステアリル（メタ）アクリレートがより好ましい。 Monomers represented by formula (1) include decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl ( meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate and the like. Among them, isostearyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, or dicyclopentenyl (meth)acrylate is preferable, and isostearyl (meth)acrylate is more preferable.
式（１）で表されるモノマ以外のＮ非含有モノマとして、
メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート等の（メタ）アクリル酸アルキルエステル；
シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、シクロヘプチル（メタ）アクリレート等の（メタ）アクリル酸シクロアルキルエステル：
２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート等の水酸基含有（メタ）アクリル酸エステル；
スチレン、酢酸ビニル等のビニル化合物、などが挙げられる。
As an N-free monomer other than the monomer represented by formula (1),
methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2- (meth)acrylic acid alkyl esters such as ethylhexyl (meth)acrylate and nonyl (meth)acrylate;
Cycloalkyl (meth)acrylates such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, etc.:
hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate;
vinyl compounds such as styrene and vinyl acetate;
（Ｂ）モノマは、（Ａ）（メタ）アクリル重合体との相溶性、又は、凝集性等の所望とする硬化物の物性に応じて適宜選択することが好ましい。 It is preferable that (B) the monomer is appropriately selected according to the desired physical properties of the cured product, such as compatibility with the (A) (meth)acrylic polymer or cohesiveness.
（Ｂ）モノマの含有量は、（Ａ）～（Ｄ）成分の合計１００質量部を基準として、１５～７５質量部が好ましく、３０～７０質量部がより好ましく、４０～６０質量部が更に好ましい。１５質量部以上であると、粘着剤組成物が高粘度となり過ぎずに良好な塗工性が得られる傾向がある。一方、７５質量部以下であると、粘着剤組成物が低粘度になり過ぎることがなく、良好な塗工性が得られる傾向がある。 The content of the monomer (B) is preferably 15 to 75 parts by mass, more preferably 30 to 70 parts by mass, more preferably 40 to 60 parts by mass, based on the total of 100 parts by mass of the components (A) to (D). preferable. When it is 15 parts by mass or more, there is a tendency that the pressure-sensitive adhesive composition does not become too viscous and good coatability can be obtained. On the other hand, when the content is 75 parts by mass or less, the viscosity of the pressure-sensitive adhesive composition does not become too low, and good coatability tends to be obtained.
（Ｂ）モノマ中の式（１）で表されるモノマの含有量は、（Ｂ）成分の合計質量を基準として、５質量％以上が好ましく、２０質量％以上がより好ましく、３０質量％以上が更に好ましい。５質量％以上であると、優れた粘着力及び耐候性が得られやすい傾向がある。一方、上限は１００質量％であってもよく、又は、式（１）で表されるモノマ以外のモノマを含有させる場合は、例えば、８５質量％以下、７０質量％以下、若しくは５０質量％以下にしてもよい。 The content of the monomer represented by formula (1) in the monomer (B) is preferably 5% by mass or more, more preferably 20% by mass or more, and 30% by mass or more, based on the total mass of the component (B). is more preferred. When the amount is 5% by mass or more, excellent adhesive strength and weather resistance tend to be obtained. On the other hand, the upper limit may be 100% by mass, or when a monomer other than the monomer represented by formula (1) is contained, for example, 85% by mass or less, 70% by mass or less, or 50% by mass or less can be
（Ｂ）モノマ中のＮ非含有モノマの含有量は、（Ｂ）モノマの合計質量を基準として、７５質量％以上が好ましく、９０質量％以上がより好ましく、９５質量％以上が更に好ましい。７５質量％以上であると、粘着剤組成物の硬化物の経時による着色を十分に抑制できる傾向がある。詳細な理由は明らかではないが、Ｎ含有モノマを含む粘着剤組成物の硬化物が経時により黄変しやすい傾向がある。その理由は、硬化物が紫外線に晒されることにより、（メタ）アクリル重合体の劣化が促されるためであると推測される。したがって、着色防止の高い効果を得るという観点からは、（Ｂ）モノマはＮ含有モノマを含有しないことが好ましい。すなわち、（Ｂ）モノマ中のＮ非含有モノマの含有量は１００質量％であることが好ましい。 The content of N-free monomers in (B) monomers is preferably 75% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total mass of (B) monomers. When the content is 75% by mass or more, there is a tendency that the cured product of the pressure-sensitive adhesive composition can be sufficiently prevented from being colored over time. Although the detailed reason is not clear, the cured product of the PSA composition containing the N-containing monomer tends to yellow over time. It is presumed that the reason for this is that exposure of the cured product to ultraviolet rays promotes deterioration of the (meth)acrylic polymer. Therefore, from the viewpoint of obtaining a high coloration prevention effect, it is preferable that the (B) monomer does not contain an N-containing monomer. That is, the content of the N-free monomer in the (B) monomer is preferably 100% by mass.
（Ｂ）モノマとして（メタ）アクリル酸アルキルエステルを併用する場合、その含有量は、（Ｂ）モノマの合計質量を基準として、５～５０質量％が好ましく、１５～４５質量％がより好ましく、２０～４０質量％が更に好ましい。（メタ）アクリル酸アルキルエステルの併用により、より高い粘着力が得られる傾向がある。 (B) When a (meth)acrylic acid alkyl ester is used in combination as the monomer (B), the content thereof is preferably 5 to 50% by mass, more preferably 15 to 45% by mass, based on the total mass of the (B) monomer. 20 to 40% by mass is more preferable. A higher adhesive strength tends to be obtained by using a (meth)acrylic acid alkyl ester in combination.
（Ｂ）モノマとして水酸基含有（メタ）アクリル酸エステルを併用する場合、その含有量は、（Ｂ）モノマの合計質量を基準として、１０～８０質量％が好ましく、１５～６０質量％がより好ましく、２０～３０質量％が更に好ましい。１０質量％以上であると、硬化物の粘着力を十分に高めることができる。８０質量％以下であると、良好な耐候性を維持することができる。水酸基含有（メタ）アクリル酸エステルは、好ましくは水酸基含有（メタ）アクリル酸アルキルエステルである。 (B) When a hydroxyl group-containing (meth)acrylic ester is used as the monomer, the content is preferably 10 to 80% by mass, more preferably 15 to 60% by mass, based on the total mass of the (B) monomer. , 20 to 30 mass % is more preferable. When it is 10% by mass or more, the adhesive strength of the cured product can be sufficiently increased. Favorable weather resistance can be maintained as it is 80 mass % or less. The hydroxyl group-containing (meth)acrylic acid ester is preferably a hydroxyl group-containing (meth)acrylic acid alkyl ester.
好ましい一実施形態によれば、（Ｂ）モノマは、式（１）で表されるモノマと水酸基含有（メタ）アクリル酸エステルとを含む。他の好ましい一実施形態によれば、（Ｂ）モノマは、式（１）で表されるモノマと（メタ）アクリル酸アルキルエステルと水酸基含有（メタ）アクリル酸エステルとを含む。 According to a preferred embodiment, the (B) monomer includes a monomer represented by formula (1) and a hydroxyl group-containing (meth)acrylic acid ester. According to another preferred embodiment, the (B) monomer includes a monomer represented by formula (1), a (meth)acrylic acid alkyl ester, and a hydroxyl group-containing (meth)acrylic acid ester.
［（Ｃ）架橋剤］
粘着剤組成物に（Ｃ）架橋剤を含有させることによって、硬化物の凝集力の向上、及び、耐熱性の向上が期待できる。架橋剤は、（メタ）アクリル重合体が有する官能基と反応し得る基を分子内に２つ以上有する化合物であればよい。架橋剤は、例えば、（Ａ）（メタ）アクリル重合体がヒドロキシル基含有単量体を含む単量体を反応させて得られた重合体である場合、ヒドロキシル基と反応し得る基を有することが好ましい。架橋剤としては、例えば、（メタ）アクリレート化合物、イソシアネート化合物、エポキシ化合物、オキサゾリン化合物、アジリジン化合物、金属キレート化合物、メラミン化合物等が挙げられる。これら架橋剤の中でも、（Ａ）（メタ）アクリル重合体がヒドロキシル基を有する場合は、（Ａ）（メタ）アクリル重合体を容易に架橋できることから、（メタ）アクリレート化合物又はイソシアネート化合物が好ましい。
[(C) Crosslinking agent]
By including (C) the cross-linking agent in the pressure-sensitive adhesive composition, improvement in the cohesive strength of the cured product and improvement in heat resistance can be expected. The cross-linking agent may be a compound having two or more groups in the molecule capable of reacting with the functional group of the (meth)acrylic polymer. For example, when the (A) (meth)acrylic polymer is a polymer obtained by reacting a monomer containing a hydroxyl group-containing monomer, the cross-linking agent has a group capable of reacting with a hydroxyl group. is preferred. Examples of cross-linking agents include (meth)acrylate compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, aziridine compounds, metal chelate compounds, and melamine compounds. Among these crosslinking agents, when the (A) (meth)acrylic polymer has a hydroxyl group, the (A) (meth)acrylic polymer can be easily crosslinked, so the (meth)acrylate compound or the isocyanate compound is preferable.
（メタ）アクリレート化合物としては、例えば、ジ（メタ）アクリレート、トリ（メタ）アクリレート、テトラ（メタ）アクリレート等の多官能（メタ）アクリレート化合物が挙げられる。（メタ）アクリレート化合物として、２～４官能の芳香族ウレタンアクリレートを好ましく使用できる。２官能の芳香族ウレタン（メタ）アクリレートが特に好ましい。 (Meth)acrylate compounds include, for example, polyfunctional (meth)acrylate compounds such as di(meth)acrylate, tri(meth)acrylate, and tetra(meth)acrylate. Di- to tetra-functional aromatic urethane acrylates can be preferably used as the (meth)acrylate compound. Bifunctional aromatic urethane (meth)acrylates are particularly preferred.
イソシアネート化合物としては、例えば、トリレンジイソシアネート、キシ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等の多官能イソシアネート化合物が挙げられる。 Examples of isocyanate compounds include polyfunctional isocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
（Ｃ）架橋剤の含有量は、所望とする粘着物性に応じて適宜選択することができる。（Ｃ）架橋剤の含有量は、（Ａ）～（Ｄ）成分の合計１００質量部を基準として、０．０１～２０質量部が好ましく、１～１５質量部がより好ましく、２～１０質量部が更に好ましい。０．０１質量部以上であると凝集力の向上効果が得られやすい傾向がある。一方、２０質量部以下であると粘着力及びタックを維持しやすい傾向がある。 (C) The content of the cross-linking agent can be appropriately selected according to the desired adhesive physical properties. (C) The content of the cross-linking agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 15 parts by mass, and 2 to 10 parts by mass based on the total of 100 parts by mass of components (A) to (D). Part is more preferred. When the amount is 0.01 parts by mass or more, there is a tendency that the effect of improving the cohesive strength is likely to be obtained. On the other hand, when the content is 20 parts by mass or less, there is a tendency to maintain adhesive strength and tack easily.
［（Ｄ）光重合開始剤］
光重合開始剤としては、例えば、４－フェノキシジクロロアセトフェノン、４－ｔ－ブチル－ジクロロアセトフェノン、４－ｔ－ブチル－トリクロロアセトフェノン、ジエトキシアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－（４－イソプロピルフェニル－２－ヒドロキシ－２－メチルプロパン－１－オン、１－（４－ドデシルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、４－（２－ヒドロキシエトキシ）－フェニル－（２－ヒドロキシ－２－プロピル）ケトン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－１－〔４－（メチルチオ）フェニル〕－２－モルホリノプロパン－１等のアセトフェノン系光開始剤；ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタール等のベンゾイン系光開始剤；ベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、ヒドロキシベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルサルファイド、３，３’－ジメチル－４－メトキシベンゾフェノン等のベンゾフェノン系光開始剤；チオキサンソン、２－クロルチオキサンソン、２－メチルチオキサンソン、２，４－ジメチルチオキサンソン、イソプロピルチオキサンソン、２，４－ジクロロチオキサンソン、２，４－ジエチルチオキサンソン、２，４－ジイソプロピルチオキサンソン等のチオキサンソン系光開始剤などが挙げられる。
[(D) Photoinitiator]
Examples of photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1-(4-isopropylphenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-( Acetophenones such as 2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1 -based photoinitiators; benzoin-based photoinitiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, Benzophenone photoinitiators such as hydroxybenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl-4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, Thioxanthone photoinitiators such as 4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone are included.
（Ｄ）光重合開始剤の含有量は、吸光係数等に応じて適宜調整すればよい。（Ｄ）光重合開始剤の含有量は、（Ａ）～（Ｄ）成分の合計１００質量部を基準として、０．００５～５質量部が好ましく、０．０１～４質量部がより好ましく、０．１～３質量部が更に好ましい。０．００５質量部以上であると光重合反応が進行しやすくなる傾向がある。５質量部以下であると粘着剤組成物の硬化物の弾性率が低下しにくくなる傾向がある。 (D) The content of the photopolymerization initiator may be appropriately adjusted according to the absorption coefficient and the like. (D) The content of the photopolymerization initiator is preferably 0.005 to 5 parts by mass, more preferably 0.01 to 4 parts by mass, based on the total of 100 parts by mass of components (A) to (D). 0.1 to 3 parts by mass is more preferable. When the amount is 0.005 parts by mass or more, the photopolymerization reaction tends to proceed easily. When the amount is 5 parts by mass or less, the elastic modulus of the cured product of the pressure-sensitive adhesive composition tends to be less likely to decrease.
［その他の成分］
粘着剤組成物には、必要に応じて上記の（Ａ）～（Ｄ）成分とは別の各種添加剤を含有させてもよい。含有可能な各種添加剤としては、例えば、粘着剤組成物の保存安定性を高める目的で添加するパラメトキシフェノール等の重合禁止剤；硬化物の耐熱性を高める、又は、着色等の劣化現象を抑制する目的で添加するトリフェニルホスファイト等の酸化防止剤；紫外線等の光に対する硬化物の耐性を高める目的で添加するＨＡＬＳ（Ｈｉｎｄｅｒｅｄ Ａｍｉｎｅ Ｌｉｇｈｔ Ｓｔａｂｉｌｉｚｅｒ）等の光安定化剤；ガラス等に対する粘着剤組成物の密着性を高める目的で添加するシランカップリング剤などが挙げられる。
[Other ingredients]
The pressure-sensitive adhesive composition may contain various additives other than the above components (A) to (D), if necessary. Various additives that can be contained include, for example, a polymerization inhibitor such as paramethoxyphenol added for the purpose of improving the storage stability of the adhesive composition; Antioxidants such as triphenyl phosphite added for the purpose of suppression; Light stabilizers such as HALS (Hindered Amine Light Stabilizer) added for the purpose of increasing the resistance of the cured product to light such as ultraviolet rays; Adhesives for glass etc. Examples include a silane coupling agent added for the purpose of enhancing adhesion of the composition.
（酸化防止剤）
酸化防止剤は、特に制限はなく、従来公知の化合物を適宜採用することができる。例を挙げると、ヒンダードフェノール系酸化防止剤、アミン系酸化防止剤等の一次酸化防止剤、及び、リン系酸化防止剤、チオール系酸化防止剤、チオエーテル系酸化防止剤等の二次酸化防止剤がある。酸化防止剤を用いる場合、含有量は、粘着剤組成物１００質量部に対して０．１～１．０質量部が好ましい。
(Antioxidant)
The antioxidant is not particularly limited, and conventionally known compounds can be appropriately employed. Examples include primary antioxidants such as hindered phenol antioxidants and amine antioxidants, and secondary antioxidants such as phosphorus antioxidants, thiol antioxidants, and thioether antioxidants. there is a drug When an antioxidant is used, the content is preferably 0.1 to 1.0 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive composition.
＜粘着剤組成物の硬化物＞
本発明の一実施形態である硬化物は、上記の粘着剤組成物の硬化物である。硬化物は、粘着剤組成物に、紫外線、電子線、α線、β線等の活性エネルギー線を照射して硬化させることにより製造できる。
<Cured Product of Adhesive Composition>
A cured product that is one embodiment of the present invention is a cured product of the pressure-sensitive adhesive composition described above. The cured product can be produced by irradiating the pressure-sensitive adhesive composition with active energy rays such as ultraviolet rays, electron beams, α-rays, and β-rays for curing.
硬化物の用途は特に限定されないが、一実施形態として、フィルムの形状に形成した粘着フィルムは、ガラス、プラスチック、及びこれらの複合材から選ばれる被着体を貼り合わせるために極めて有効である。粘着フィルムは、通常の塗工方式又は印刷方式を適用して粘着剤組成物の塗膜を形成し、塗膜を活性エネルギー線の照射により硬化させることで製造できる。 The use of the cured product is not particularly limited, but as one embodiment, the adhesive film formed in the shape of a film is extremely effective for bonding adherends selected from glass, plastic, and composites thereof. The pressure-sensitive adhesive film can be produced by forming a coating film of the pressure-sensitive adhesive composition by applying a normal coating method or printing method, and curing the coating film by irradiation with active energy rays.
貼り合わせられた被着体を有する部材は、車載用部材、建材、画像表示装置等に用いることができる。例えば、対向する２枚のガラス基材及びそれらの間に粘着フィルムを有する部材において、粘着フィルムは、ガラスが割れたときの飛散防止フィルムとしても機能する。また、対向するガラス基材及びプラスチックフィルムとそれらの間に粘着フィルムを有する部材においても、粘着フィルムは、飛散防止フィルムとしても機能する。 A member having a bonded adherend can be used for a vehicle member, a building material, an image display device, and the like. For example, in a member having two opposing glass substrates and an adhesive film between them, the adhesive film also functions as a scattering prevention film when the glass is broken. In addition, in a member having a glass substrate and a plastic film facing each other and an adhesive film therebetween, the adhesive film also functions as a scattering prevention film.
粘着フィルムを基材同士を貼り合せる用途に使用する場合、基材の種類に制限はない。基材としては、ガラス、プラスチック、木材、皮、金属等が挙げられる。基材の組み合わせにも特に制限はない。例えば、ガラス基材とガラス基材、ガラス基材とプラスチックフィルム、プラスチックフィルムとプラスチックフィルム等の貼り合せなどに使用することができる。プラスチックフィルムとしては、ポリエチレンテレフタレート（ＰＥＴ）、トリアセチルセルロース（ＴＡＣ）、ポリエチレンナフタレート（ＰＥＮ）、ポリメチルメタクリレート（ＰＭＭＡ）、ポリカーボネート（ＰＣ）、ポリイミド（ＰＩ）、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリビニルアルコール（ＰＶＡ）、ポリ塩化ビニル（ＰＶＣ）、シクロオレフィンコポリマー（ＣＯＣ）、シクロオレフィンポリマー（ＣＯＰ）、含ノルボルネン樹脂、ポリエーテルスルホン、セロファン、芳香族ポリアミド又はこれらの組み合わせのフィルムが挙げられる。 When the adhesive film is used for bonding substrates together, the type of substrate is not limited. Substrates include glass, plastic, wood, leather, metal and the like. There is no particular limitation on the combination of base materials. For example, it can be used for bonding a glass substrate to a glass substrate, a glass substrate to a plastic film, or a plastic film to a plastic film. Plastic films include polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP ), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin copolymer (COC), cycloolefin polymer (COP), norbornene-containing resin, polyether sulfone, cellophane, aromatic polyamide or a combination thereof. be done.
粘着剤組成物を用いて形成された硬化物は、優れた粘着力及び耐候性を有するため、紫外線が含まれる電磁波に長時間暴露される環境下でも、着色及び透明性の低下が抑制された粘着フィルムとして使用できる。 The cured product formed using the pressure-sensitive adhesive composition has excellent adhesive strength and weather resistance, so even in an environment where it is exposed to electromagnetic waves including ultraviolet rays for a long time, the deterioration of coloration and transparency is suppressed. Can be used as an adhesive film.
以下に、実施例を挙げて本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。なお、例中の「部」及び「％」は、特に断らない限りそれぞれ「質量部」及び「質量％」を意味する。 EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these. "Parts" and "%" in the examples mean "mass parts" and "mass%", respectively, unless otherwise specified.
＜粘着フィルム（硬化物）の作製＞
（実施例１）
［粘着剤組成物用アクリル重合体の調製］
（重合工程）
撹拌機、温度計、還流冷却機、滴下装置、及び窒素導入管を備えたステンレス製の加圧反応装置に、溶媒であるメチルエチルケトン（ＭＥＫ）を添加し、撹拌した。次に、仕込んだ溶媒に窒素を吹き込みながら溶媒を８２℃まで昇温させた後、アクリル単量体である２－エチルヘキシルアクリレート（２ＥＨＡ）７５部及び２－ヒドロキシエチルアクリレート（２ＨＥＡ）２５部と、光重合開始剤であるジメチル２，２’－アゾビス（２－メチルプロピオネート）（和光純薬工業株式会社製「Ｖ－６０１」）０．１５部との混合液を２時間かけて均等な滴下量で加えた。全ての混合液を滴下し、１時間保温した後、光重合開始剤「Ｖ－６０１」０．２部をＭＥＫに溶解させた溶液を３０分間かけて均等な滴下量で加えた。その後、約１時間保温した後、反応液をＭＥＫで希釈した。次に、光重合開始剤「Ｖ－６０１」の失活工程として、０．３ＭＰａ加圧条件下で反応液を１２５℃まで昇温し、２．５時間保温することで固形分５０％のアクリル重合体溶液を得た。
<Preparation of adhesive film (cured product)>
(Example 1)
[Preparation of acrylic polymer for adhesive composition]
(Polymerization process)
Methyl ethyl ketone (MEK) as a solvent was added to a stainless pressure reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen inlet tube, and stirred. Next, while blowing nitrogen into the charged solvent, the temperature of the solvent is raised to 82° C., and then 75 parts of 2-ethylhexyl acrylate (2EHA) and 25 parts of 2-hydroxyethyl acrylate (2HEA), which are acrylic monomers, Dimethyl 2,2'-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd. "V-601") 0.15 parts of a photopolymerization initiator is mixed with 0.15 parts for 2 hours. Added dropwise. After all the mixed liquids were added dropwise and kept warm for 1 hour, a solution prepared by dissolving 0.2 parts of the photopolymerization initiator "V-601" in MEK was added dropwise in equal amounts over 30 minutes. Then, after keeping the temperature for about 1 hour, the reaction solution was diluted with MEK. Next, as a deactivation step of the photopolymerization initiator "V-601", the reaction solution was heated to 125 ° C. under a pressurized condition of 0.3 MPa and kept at heat for 2.5 hours to obtain an acrylic with a solid content of 50%. A polymer solution was obtained.
（脱溶工程）
撹拌機、温度計及び空気（Ａｉｒ）吹き込み管、並びに真空ポンプを備えたセパラブルフラスコにアクリル重合体溶液（１３０部）とイソステアリルアクリレート（ＩＳＴＡ）（３５部）（固形分：ＩＳＴＡ＝６５：３５）と３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシトルエン（ＢＨＴ）０．０６部とを仕込み、Ａｉｒをバブリングしながら撹拌及び昇温を開始した。５０℃まで昇温したところで、真空ポンプにより減圧を開始した。発泡に注意しながらフラスコ内を減圧し、溶媒を留去しつつ反応液が９０℃となるまで昇温した。９０℃で保温しながら減圧を継続し、２時間後にガスクロマトグラフィーにて反応液内の溶媒残存量が０．０２％以下であること確認し、アクリル重合体を得た。
(Desolution process)
An acrylic polymer solution (130 parts) and isostearyl acrylate (ISTA) (35 parts) (solid content: ISTA = 65: 35) and 0.06 part of 3,5-di-tert-butyl-4-hydroxytoluene (BHT) were charged, and stirring and heating were started while bubbling air. When the temperature was raised to 50° C., pressure reduction was started with a vacuum pump. While paying attention to foaming, the pressure inside the flask was reduced, and the temperature of the reaction solution was raised to 90° C. while distilling off the solvent. The pressure was reduced while maintaining the temperature at 90° C. After 2 hours, it was confirmed by gas chromatography that the amount of solvent remaining in the reaction liquid was 0.02% or less, and an acrylic polymer was obtained.
［粘着剤組成物の調製］
アクリル重合体の固形分４７部に対して、（Ｂ）モノマである４－ヒドロキシブチルアクリレート（４ＨＢＡ）１２部及びＩＳＴＡ３５部と、（Ｂ）架橋剤（ａｌｌｎｅｘ社製「ＥＢＥＣＲＹＬ２３０」、２官能ウレタン（メタ）アクリレート）６部と、（Ｃ）光重合開始剤（ＢＡＳＦ社製「イルガキュア１８４」）０．５部とを混合し、粘着剤組成物を得た。
[Preparation of adhesive composition]
For 47 parts of the solid content of the acrylic polymer, (B) 12 parts of 4-hydroxybutyl acrylate (4HBA) as a monomer and 35 parts of ISTA, and (B) a cross-linking agent (manufactured by allnex "EBECRYL230", bifunctional urethane ( 6 parts of meth)acrylate and 0.5 parts of (C) a photopolymerization initiator (“Irgacure 184” manufactured by BASF) were mixed to obtain an adhesive composition.
［粘着フィルムの作製］
粘着剤組成物を重剥離セパレータ（中本パックス株式会社製「ＨＴＡ－７５」（フィルム厚み；７５μｍ））と軽剥離セパレータ（中本パックス株式会社製「ＢＤ－５０」（フィルム厚み；５０μｍ））の２種の剥離セパレータに挟み、１００μｍのスペーサを用いてローラーで厚さを均一にし、その後、紫外線を照射して硬化させることにより粘着フィルムを作製した。
紫外線照射装置：株式会社ジーエス・ユアサコーポレーション製 コンベヤーＵＶ照射装置「ＵＶ ＳＹＳＴＥＭ ＣＳ６０」
紫外線ランプ：株式会社ジーエス・ユアサコーポレーション製 メタルハライドランプ
露光条件：照度２００ｍＷ／ｃｍ２；積算光量３，０００ｍＪ／ｃｍ２（５００ｍＪ／ｃｍ２×４回）
[Production of adhesive film]
The pressure-sensitive adhesive composition was applied to a heavy release separator (manufactured by Nakamoto Pax Co., Ltd. “HTA-75” (film thickness: 75 μm)) and a light release separator (manufactured by Nakamoto Pax Co., Ltd. “BD-50” (film thickness: 50 μm)). The adhesive film was prepared by sandwiching between two types of release separators of No. 1, making the thickness uniform with a roller using a spacer of 100 μm, and then curing by irradiating with ultraviolet rays.
Ultraviolet irradiation device: Conveyor UV irradiation device “UV SYSTEM CS60” manufactured by GS Yuasa Corporation
Ultraviolet lamp: metal halide lamp manufactured by GS Yuasa Corporation Exposure conditions: illuminance 200 mW/cm 2 ; integrated light intensity 3,000 mJ/cm 2 (500 mJ/cm 2 × 4 times)
（実施例２）
［粘着剤組成物の調製］において、使用する（Ｂ）モノマを２ＥＨＡ１５部、４ＨＢＡ１２部、及びＩＳＴＡ２０部に替えたこと以外は実施例１と同様にして粘着剤組成物を得た。この粘着剤組成物を用い、実施例１と同様にして粘着フィルムを得た。
(Example 2)
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1, except that the (B) monomer used in [Preparation of pressure-sensitive adhesive composition] was changed to 15 parts of 2EHA, 12 parts of 4HBA, and 20 parts of ISTA. An adhesive film was obtained in the same manner as in Example 1 using this adhesive composition.
（実施例３）
［粘着剤組成物の調製］において、使用する（Ｂ）モノマを２ＥＨＡ１５部、４ＨＢＡ１２部、及びイソボルニルアクリレート（ＩＢＸＡ）２０部に替えたこと以外は実施例１と同様にして粘着剤組成物を得た。この粘着剤組成物を用い、実施例１と同様にして粘着フィルムを得た。
(Example 3)
In [Preparation of PSA composition], the PSA composition was prepared in the same manner as in Example 1, except that the (B) monomer used was changed to 15 parts of 2EHA, 12 parts of 4HBA, and 20 parts of isobornyl acrylate (IBXA). got An adhesive film was obtained in the same manner as in Example 1 using this adhesive composition.
（実施例４）
［粘着剤組成物の調製］において、使用する（Ｂ）モノマを２ＥＨＡ２５部、４ＨＢＡ１２部、及びＩＢＸＡ１０部に替えたこと以外は実施例１と同様にして粘着剤組成物を得た。この粘着剤組成物を用い、実施例１と同様にして粘着フィルムを得た。
(Example 4)
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1, except that the (B) monomer used in [Preparation of pressure-sensitive adhesive composition] was changed to 25 parts of 2EHA, 12 parts of 4HBA, and 10 parts of IBXA. An adhesive film was obtained in the same manner as in Example 1 using this adhesive composition.
（実施例５）
［粘着剤組成物の調製］において、使用する（Ｂ）モノマを２ＥＨＡ３０部、４ＨＢＡ１２部、及びジシクロペンテニルアクリレート５部に替えたこと以外は実施例１と同様にして粘着剤組成物を得た。この粘着剤組成物を用い、実施例１と同様にして粘着フィルムを得た。
(Example 5)
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1, except that the monomer (B) used in [Preparation of pressure-sensitive adhesive composition] was changed to 30 parts of 2EHA, 12 parts of 4HBA, and 5 parts of dicyclopentenyl acrylate. . An adhesive film was obtained in the same manner as in Example 1 using this adhesive composition.
（比較例１）
［粘着剤組成物の調製］において、使用する（Ｂ）モノマを２ＥＨＡ２９部、４ＨＢＡ３部、及びアクリロイルモルホリン（ＡＣＭＯ）１５部に替えたこと以外は実施例１と同様にして粘着剤組成物を得た。この粘着剤組成物を用い、実施例１と同様にして粘着フィルムを得た。
(Comparative example 1)
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1, except that the (B) monomer used in [Preparation of pressure-sensitive adhesive composition] was replaced with 29 parts of 2EHA, 3 parts of 4HBA, and 15 parts of acryloylmorpholine (ACMO). rice field. An adhesive film was obtained in the same manner as in Example 1 using this adhesive composition.
（比較例２）
［粘着剤組成物の調製］において、使用する（Ｂ）モノマを２ＥＨＡ２９部、４ＨＢＡ３部、及びジメチルアクリルアミド（ＤＭＡＡ）１５部に替えたこと以外は実施例１と同様にして粘着剤組成物を得た。この粘着剤組成物を用い、実施例１と同様にして粘着フィルムを得た。
(Comparative example 2)
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the (B) monomer used in [Preparation of pressure-sensitive adhesive composition] was changed to 29 parts of 2EHA, 3 parts of 4HBA, and 15 parts of dimethylacrylamide (DMAA). rice field. An adhesive film was obtained in the same manner as in Example 1 using this adhesive composition.
（比較例３）
［粘着剤組成物の調製］において、使用する（Ｂ）モノマを２ＥＨＡ４４部及び４ＨＢＡ３部に替えたこと以外は実施例１と同様にして粘着剤組成物を得た。この粘着剤組成物を用い、実施例１と同様にして粘着フィルムを得た。
(Comparative Example 3)
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1, except that 44 parts of 2EHA and 3 parts of 4HBA were used as the (B) monomers in [Preparation of pressure-sensitive adhesive composition]. An adhesive film was obtained in the same manner as in Example 1 using this adhesive composition.
＜粘着フィルムの評価＞
各実施例及び各比較例の粘着フィルムについて着色性、濁度、及びガラスに対する粘着力を以下の方法により測定した。それらの結果を表１に示す。
<Evaluation of adhesive film>
The colorability, turbidity, and adhesive strength to glass of the adhesive films of each example and each comparative example were measured by the following methods. Those results are shown in Table 1.
［着色性（黄色味）の評価］
作製した粘着フィルムを５０ｍｍ×５０ｍｍサイズに切り出した後、片面の剥離セパレータを剥がしガラス基材に貼り合わせた後に、もう一方の面の剥離セパレータを剥がし、試験片とした。色差計（日本電色工業株式会社製「Ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ ＳＤ６０００」）で試験片の初期ＹＩ値（初期フィルムＹＩ値）を測定した。その後、紫外線照射による試験片の色の変化を促進させるために、試験片に、粘着フィルム側から紫外線を所定の照射量で照射した。次いで、初期ＹＩ値測定と同様の方法で粘着フィルムのＹＩ値を確認した。なお、ＹＩ値が高いほど黄色味又は濁りが強く、変化が大きいほど粘着フィルムの劣化が進んでいることを示す。すなわち、ＹＩ値が低く、変化が小さいほど粘着フィルムの着色及び濁りが抑制されたことを示す。
紫外線照射には下記条件を用いた。
紫外線照射装置：株式会社ジーエス・ユアサコーポレーション製 コンベヤーＵＶ照射装置「ＵＶ ＳＹＳＴＥＭ ＣＳ６０」
紫外線ランプ：株式会社ジーエス・ユアサコーポレーション製 高圧水銀ランプ
露光条件：照度１００ｍＷ／ｃｍ２、露光時間：６０分
[Evaluation of colorability (yellowness)]
After cutting out the produced adhesive film into a size of 50 mm×50 mm, peeling off the release separator on one side and bonding it to a glass base material, peeling off the release separator on the other side to obtain a test piece. The initial YI value (initial film YI value) of the test piece was measured with a color difference meter (“Spectrophotometer SD6000” manufactured by Nippon Denshoku Industries Co., Ltd.). After that, in order to accelerate the color change of the test piece due to the ultraviolet irradiation, the test piece was irradiated with a predetermined amount of ultraviolet rays from the adhesive film side. Then, the YI value of the adhesive film was confirmed by the same method as the initial YI value measurement. Note that the higher the YI value, the stronger the yellowness or turbidity, and the greater the change, the more advanced the deterioration of the adhesive film. That is, the lower the YI value and the smaller the change, the more suppressed the coloration and turbidity of the adhesive film.
The following conditions were used for ultraviolet irradiation.
Ultraviolet irradiation device: Conveyor UV irradiation device “UV SYSTEM CS60” manufactured by GS Yuasa Corporation
Ultraviolet lamp: High-pressure mercury lamp manufactured by GS Yuasa Corporation Exposure conditions: illuminance 100 mW/cm 2 , exposure time: 60 minutes
［濁度の測定方法］
作製した粘着フィルムを５０ｍｍ×５０ｍｍサイズに切り出した後、片面の剥離セパレータを剥がしてガラス基材に貼付し、２ｋｇのローラーを１往復させることにより圧着した。その後、もう一方の面の剥離セパレータを剥がし、試験片とした。ＪＩＳ ７１３６：２０００に従い、ヘイズメーター（スガ試験機株式会社製「ＨＧＭ－２」）を用いて濁度を測定した。
[Measurement method of turbidity]
After cutting out the produced adhesive film into a size of 50 mm×50 mm, the release separator on one side was peeled off, and the adhesive film was adhered to a glass base material and pressed by reciprocating a 2 kg roller once. After that, the release separator on the other side was peeled off to obtain a test piece. Turbidity was measured using a haze meter (“HGM-2” manufactured by Suga Test Instruments Co., Ltd.) according to JIS 7136:2000.
［粘着力（対ガラス１８０°ピール試験）の測定］
作製した粘着フィルムを１００ｍｍ×２５ｍｍサイズに切り出した後、片面の剥離セパレータを剥がしてガラス基材に貼付し、２ｋｇのローラーを１往復させることにより圧着した。その後、もう一方の面の剥離セパレータを剥がして、粘着フィルム面上に１５０ｍｍ×３０ｍｍの易接着ＰＥＴフィルム（東洋紡株式会社製「Ａ４３００」（フィルム厚み：７５μｍ））を貼付し、２ｋｇのローラーを１往復させることにより圧着し、試験片とした。試験片を引っ張り試験機（株式会社島津製作所製「オートグラフ ＡＧ－Ｘ／Ｒ」）に取り付け、剥離速度：３００ｍｍ／ｍｉｎ、測定温度：２５℃で１８０°剥離試験を行い、粘着力を測定した。
[Measurement of adhesive strength (180° peel test against glass)]
After cutting out the produced adhesive film into a size of 100 mm×25 mm, the peelable separator on one side was peeled off, and the adhesive film was adhered to a glass base material and crimped by reciprocating a 2 kg roller once. After that, peel off the release separator on the other side, attach a 150 mm × 30 mm easy-adhesive PET film (manufactured by Toyobo Co., Ltd. "A4300" (film thickness: 75 µm)) on the adhesive film surface, and apply a 2 kg roller 1 It was pressure-bonded by reciprocating to obtain a test piece. The test piece was attached to a tensile tester ("Autograph AG-X/R" manufactured by Shimadzu Corporation), and a 180° peel test was performed at a peel speed of 300 mm/min and a measurement temperature of 25°C to measure the adhesive strength. .
表１からわかるように、式（１）で表されるモノマを含有する粘着剤組成物を用いて作製された粘着フィルムは、粘着力を維持しつつ、着色が抑制され、良好な透明性を有していた。 As can be seen from Table 1, the pressure-sensitive adhesive film produced using the pressure-sensitive adhesive composition containing the monomer represented by formula (1) has good transparency while maintaining adhesive strength and suppressed coloring. had.
Claims (3)
剤を含有し、
前記（Ｂ）モノマが、下記式（１）で表されるモノマと、下記式（１）で表されるモノマ以外の水酸基含有（メタ）アクリル酸エステルとを含み、
前記（Ｂ）モノマ中の下記式（１）で表されるモノマの含有量が、（Ｂ）モノマの合計質量を基準として、３０～８５質量％であり、
前記（Ｂ）モノマ中の前記水酸基含有（メタ）アクリル酸エステルの含有量が、（Ｂ）モノマの合計質量を基準として、１５～６０質量％であり、
前記（Ｂ）モノマ中の窒素原子を含まないモノマの含有量が、（Ｂ）モノマの合計質量を基準として、９５質量％以上である、粘着剤組成物。
The (B) monomer includes a monomer represented by the following formula (1) and a hydroxyl group-containing (meth)acrylic acid ester other than the monomer represented by the following formula (1),
The content of the monomer represented by the following formula (1) in the (B) monomer is 30 to 85% by mass based on the total mass of the (B) monomer,
The content of the hydroxyl group-containing (meth)acrylic acid ester in the (B) monomer is 15 to 60% by mass based on the total mass of the (B) monomer,
The pressure-sensitive adhesive composition , wherein the content of the nitrogen atom-free monomer in the (B) monomer is 95% by mass or more based on the total mass of the (B) monomer .
剤の合計１００質量部に対して、（Ａ）（メタ）アクリル重合体１５～７０質量部、（Ｂ）モノマ１５～７５質量部、（Ｃ）架橋剤０．０１～２０質量部、及び（Ｄ）光重合開始剤０．００５～５質量部を含有する、請求項１に記載の粘着剤組成物。 (A) (meth) acrylic polymer, (B) monomer, (C) cross-linking agent, and (D) photopolymerization initiator for a total of 100 parts by mass, (A) (meth) acrylic polymer 15 to 70 Parts by weight, (B) 15 to 75 parts by weight of a monomer, (C) 0.01 to 20 parts by weight of a cross-linking agent, and (D) 0.005 to 5 parts by weight of a photopolymerization initiator. adhesive composition.
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| JP2014133879A (en) | 2012-12-14 | 2014-07-24 | Nippon Synthetic Chem Ind Co Ltd:The | Acrylic resin composition, acrylic adhesive agent, adhesive sheet, double-sided adhesive sheet, adhesive agent for transparent electrode, touch panel and picture display device, and manufacturing method of adhesive agent layer-containing laminate |
| JP2014181258A (en) | 2013-03-18 | 2014-09-29 | Toray Coatex Co Ltd | Acrylic adhesive composition and method of producing adhesive tape using the same |
| JP2014214198A (en) | 2013-04-24 | 2014-11-17 | 王子ホールディングス株式会社 | Adhesive sheet, application of the same and laminate |
| WO2017022770A1 (en) | 2015-08-03 | 2017-02-09 | 日本合成化学工業株式会社 | Pressure-sensitive adhesive sheet, process for producing laminate including pressure-sensitive adhesive layer, laminate including pressure-sensitive adhesive layer, image display device, and touch panel |
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| JP2012233168A (en) | 2011-04-22 | 2012-11-29 | Nippon Synthetic Chem Ind Co Ltd:The | Acrylic resin composition and application using the same |
| JP2013018937A (en) | 2011-07-14 | 2013-01-31 | Nippon Synthetic Chem Ind Co Ltd:The | Pressure-sensitive adhesive for optical member and optical member with pressure-sensitive adhesive layer, and image display device |
| JP2013209487A (en) | 2012-03-30 | 2013-10-10 | Emulsion Technology Co Ltd | Photo-curable self-adhesive composition and self-adhesive sheet using the same |
| JP2013221065A (en) | 2012-04-16 | 2013-10-28 | Nippon Synthetic Chem Ind Co Ltd:The | Acrylic resin composition, acrylic adhesive, adhesive sheet, double-sided adhesive sheet, adhesive for transparent electrode, touch panel, image display device, and method for manufacturing laminate including adhesive layer |
| JP2013227399A (en) | 2012-04-25 | 2013-11-07 | Nippon Synthetic Chem Ind Co Ltd:The | Acrylic resin composition, acrylic adhesive, adhesive sheet, double-sided adhesive sheet, adhesive for transparent electrode, touch panel and image display device, and manufacturing method of laminate containing adhesive layer |
| JP2013227436A (en) | 2012-04-26 | 2013-11-07 | Nippon Synthetic Chem Ind Co Ltd:The | Acrylic resin composition, acrylic adhesive, adhesive sheet, double-sided adhesive sheet, adhesive for transparent electrode, touch panel and image display device, and manufacturing method of laminate containing adhesive layer |
| WO2014046182A1 (en) | 2012-09-20 | 2014-03-27 | 三菱レイヨン株式会社 | Photo-curable adhesive composition and display panel |
| JP2014133879A (en) | 2012-12-14 | 2014-07-24 | Nippon Synthetic Chem Ind Co Ltd:The | Acrylic resin composition, acrylic adhesive agent, adhesive sheet, double-sided adhesive sheet, adhesive agent for transparent electrode, touch panel and picture display device, and manufacturing method of adhesive agent layer-containing laminate |
| JP2014181258A (en) | 2013-03-18 | 2014-09-29 | Toray Coatex Co Ltd | Acrylic adhesive composition and method of producing adhesive tape using the same |
| JP2014214198A (en) | 2013-04-24 | 2014-11-17 | 王子ホールディングス株式会社 | Adhesive sheet, application of the same and laminate |
| WO2017022770A1 (en) | 2015-08-03 | 2017-02-09 | 日本合成化学工業株式会社 | Pressure-sensitive adhesive sheet, process for producing laminate including pressure-sensitive adhesive layer, laminate including pressure-sensitive adhesive layer, image display device, and touch panel |
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