JP7429752B2 - Adhesive compositions, adhesive films, optical films with adhesive layers, liquid crystal panels - Google Patents
Adhesive compositions, adhesive films, optical films with adhesive layers, liquid crystal panels Download PDFInfo
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- JP7429752B2 JP7429752B2 JP2022168423A JP2022168423A JP7429752B2 JP 7429752 B2 JP7429752 B2 JP 7429752B2 JP 2022168423 A JP2022168423 A JP 2022168423A JP 2022168423 A JP2022168423 A JP 2022168423A JP 7429752 B2 JP7429752 B2 JP 7429752B2
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- Prior art keywords
- meth
- group
- adhesive
- acrylate
- film
- Prior art date
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- 239000012790 adhesive layer Substances 0.000 title claims description 76
- 239000000853 adhesive Substances 0.000 title claims description 70
- 230000001070 adhesive effect Effects 0.000 title claims description 70
- 239000000203 mixture Substances 0.000 title claims description 64
- 239000002313 adhesive film Substances 0.000 title claims description 42
- 239000012788 optical film Substances 0.000 title claims description 27
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 64
- 239000010408 film Substances 0.000 claims description 57
- -1 isocyanate compounds Chemical class 0.000 claims description 54
- 239000000178 monomer Substances 0.000 claims description 53
- 229920000058 polyacrylate Polymers 0.000 claims description 38
- 239000002216 antistatic agent Substances 0.000 claims description 23
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 150000008040 ionic compounds Chemical group 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- 239000010410 layer Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004018 acid anhydride group Chemical group 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 5
- 230000001588 bifunctional effect Effects 0.000 claims description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-O Pyrazolium Chemical compound C1=CN[NH+]=C1 WTKZEGDFNFYCGP-UHFFFAOYSA-O 0.000 claims description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 claims description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical compound [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 claims description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-O morpholinium Chemical compound [H+].C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-O 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 2
- DVPHDWQFZRBFND-DMHDVGBCSA-N 1-o-[2-[(3ar,5r,6s,6ar)-2,2-dimethyl-6-prop-2-enoyloxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-2-[4-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chlorophenyl)-4-oxoazetidin-3-yl]oxy-4-oxobutanoyl]oxyethyl] 4-o-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chloropheny Chemical group C1([C@H]2[C@H](C(N2SC(C)CC)=O)OC(=O)CCC(=O)OC(COC(=O)CCC(=O)O[C@@H]2[C@@H](N(C2=O)SC(C)CC)C=2C(=CC=CC=2)Cl)[C@@H]2[C@@H]([C@H]3OC(C)(C)O[C@H]3O2)OC(=O)C=C)=CC=CC=C1Cl DVPHDWQFZRBFND-DMHDVGBCSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 9
- 229920001296 polysiloxane Polymers 0.000 description 8
- 238000005187 foaming Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- JGTNAGYHADQMCM-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000002542 deteriorative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-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
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 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 2
- UVDJCNHULJXIIU-UHFFFAOYSA-M 1,1,2,2,3,3,3-heptafluoropropane-1-sulfonate 1-methyl-3-octylpyridin-1-ium Chemical compound FC(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F.C[N+]1=CC(=CC=C1)CCCCCCCC UVDJCNHULJXIIU-UHFFFAOYSA-M 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- ROUAVLUBIONILF-UHFFFAOYSA-N 1-[dimethoxy(methyl)silyl]propane-2-thiol Chemical compound CO[Si](C)(OC)CC(C)S ROUAVLUBIONILF-UHFFFAOYSA-N 0.000 description 1
- UOYPBMPPFOQUMO-UHFFFAOYSA-M 1-methyl-3-octylimidazol-1-ium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound CCCCCCCC[N+]=1C=CN(C)C=1.[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UOYPBMPPFOQUMO-UHFFFAOYSA-M 0.000 description 1
- ZQRPAZRYFLPSFD-UHFFFAOYSA-M 1-methyl-3-octylpyridin-1-ium 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F.C[N+]1=CC(=CC=C1)CCCCCCCC ZQRPAZRYFLPSFD-UHFFFAOYSA-M 0.000 description 1
- LXSIQGDUUMRNOG-UHFFFAOYSA-M 1-methyl-3-octylpyridin-1-ium trifluoromethanesulfonate Chemical compound FC(S(=O)(=O)[O-])(F)F.C[N+]1=CC(=CC=C1)CCCCCCCC LXSIQGDUUMRNOG-UHFFFAOYSA-M 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DVNPFNZTPMWRAX-UHFFFAOYSA-N 2-triethoxysilylethanethiol Chemical compound CCO[Si](CCS)(OCC)OCC DVNPFNZTPMWRAX-UHFFFAOYSA-N 0.000 description 1
- LOSLJXKHQKRRFN-UHFFFAOYSA-N 2-trimethoxysilylethanethiol Chemical compound CO[Si](OC)(OC)CCS LOSLJXKHQKRRFN-UHFFFAOYSA-N 0.000 description 1
- GXDMUOPCQNLBCZ-UHFFFAOYSA-N 3-(3-triethoxysilylpropyl)oxolane-2,5-dione Chemical compound CCO[Si](OCC)(OCC)CCCC1CC(=O)OC1=O GXDMUOPCQNLBCZ-UHFFFAOYSA-N 0.000 description 1
- ZADOWCXTUZWAKL-UHFFFAOYSA-N 3-(3-trimethoxysilylpropyl)oxolane-2,5-dione Chemical compound CO[Si](OC)(OC)CCCC1CC(=O)OC1=O ZADOWCXTUZWAKL-UHFFFAOYSA-N 0.000 description 1
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- AVFZRVATGMEQNJ-UHFFFAOYSA-N 3-methyl-1-octylpyridin-1-ium Chemical compound CCCCCCCC[N+]1=CC=CC(C)=C1 AVFZRVATGMEQNJ-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- RKMYIMHYKDNAES-UHFFFAOYSA-N 4-(3-trimethoxysilylpropyl)-2-benzofuran-1,3-dione Chemical compound CO[Si](OC)(OC)CCCC1=CC=CC2=C1C(=O)OC2=O RKMYIMHYKDNAES-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- PKNKATCTSXBIRP-UHFFFAOYSA-M 4-methyl-1-octylpyridin-1-ium 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F.CC1=CC=[N+](C=C1)CCCCCCCC PKNKATCTSXBIRP-UHFFFAOYSA-M 0.000 description 1
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- MITQBRGOZCVGIJ-UHFFFAOYSA-N CCO[Si](CCCc1cccc2C(=O)OC(=O)c12)(OCC)OCC Chemical compound CCO[Si](CCCc1cccc2C(=O)OC(=O)c12)(OCC)OCC MITQBRGOZCVGIJ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KVKJXFFWHIXZHQ-UHFFFAOYSA-M FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F.C[N+]1=CC=C(C=C1)CCCCCCCC Chemical compound FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F.C[N+]1=CC=C(C=C1)CCCCCCCC KVKJXFFWHIXZHQ-UHFFFAOYSA-M 0.000 description 1
- GSEFKIAEVFYITJ-UHFFFAOYSA-M FC(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F.CC=1C=[N+](C=CC1)CCCCCCCC Chemical compound FC(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F.CC=1C=[N+](C=CC1)CCCCCCCC GSEFKIAEVFYITJ-UHFFFAOYSA-M 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical class CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 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 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- ASGKDLGXPOIMTM-UHFFFAOYSA-N diethoxy-methyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](C)(OCC)OCC)CCC2OC21 ASGKDLGXPOIMTM-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- SLQTWNAJXFHMHM-UHFFFAOYSA-N dimethoxy-methyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](C)(OC)OC)CCC2OC21 SLQTWNAJXFHMHM-UHFFFAOYSA-N 0.000 description 1
- UJAQYWOJKDVLSV-UHFFFAOYSA-M dimethyl(dioctyl)azanium 1,1,2,2,2-pentafluoroethanesulfonate Chemical compound FC(C(S(=O)(=O)[O-])(F)F)(F)F.C[N+](CCCCCCCC)(CCCCCCCC)C UJAQYWOJKDVLSV-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 238000001035 drying Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- FEDFHMISXKDOJI-UHFFFAOYSA-M lithium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F FEDFHMISXKDOJI-UHFFFAOYSA-M 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 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 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 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
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- LTOKKZDSYQQAHL-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCC1CO1 LTOKKZDSYQQAHL-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
Description
本発明は、帯電防止剤を含有する粘着剤組成物、及び粘着フィルムに関する。さらに詳細には、帯電防止剤として、ノナフルオロブタンスルホナート等の、特定のスルホナートアニオンを有するイオン性化合物を含有する粘着剤組成物であり、それにより優れた粘着性能を含めた耐久性、及び帯電防止性能を有する粘着剤組成物、及びそれを用いた粘着フィルムに関するものである。 The present invention relates to an adhesive composition containing an antistatic agent and an adhesive film. More specifically, it is an adhesive composition containing an ionic compound having a specific sulfonate anion, such as nonafluorobutane sulfonate, as an antistatic agent. The present invention also relates to a pressure-sensitive adhesive composition having antistatic properties, and a pressure-sensitive adhesive film using the same.
偏光板、位相差板などの光学部材を、粘着剤層を介して、液晶セルなどの被着体に貼合するための、種々の粘着フィルムが提案されている（例えば特許文献１～２参照）。
特許文献１には、ブチルアクリレートなどを主成分のモノマーとし、アクリルアミド化合物などを共重合させたアクリル系ポリマーを含有する光学用粘着剤組成物が記載されている。
特許文献２には、炭素数４～８のアルキル基を有する（メタ）アクリレートを主成分のモノマーとし、カルボキシル基含有モノマー、及び窒素含有ビニルモノマーを共重合させたアクリル系ポリマーを含有する光学用粘着剤組成物が記載されている。
Various adhesive films have been proposed for bonding optical members such as polarizing plates and retardation plates to adherends such as liquid crystal cells via adhesive layers (see, for example, Patent Documents 1 and 2). ).
Patent Document 1 describes an optical pressure-sensitive adhesive composition containing an acrylic polymer made by copolymerizing an acrylamide compound or the like with butyl acrylate as a main monomer.
Patent Document 2 describes an optical product containing an acrylic polymer in which the main component is a (meth)acrylate having an alkyl group having 4 to 8 carbon atoms, and a carboxyl group-containing monomer and a nitrogen-containing vinyl monomer are copolymerized. Adhesive compositions are described.
ところで、光学フィルムの表面が、シリコーン化合物などを含有する組成物で防汚処理や低反射表面処理が施されている場合には、このような光学フィルムに使用された粘着フィルムを、被着体から剥離する時の剥離帯電圧が高くなる。 By the way, if the surface of the optical film has been subjected to antifouling treatment or low-reflection surface treatment with a composition containing a silicone compound, etc., the adhesive film used for such optical film may be used as an adherend. The peeling voltage increases when peeling from the surface.
また、帯電防止性能を備えた粘着剤組成物、及びそれを用いた粘着フィルムの、帯電防止性能と、被着体への粘着性能を含めた耐久性との関係はトレードオフの関係であり、帯電防止性能を維持したまま、粘着性能を含めた耐久性を改善することは困難であった。
このため、光学フィルムの表面がシリコーン化合物などを含有する組成物で表面処理が施されている場合でも、粘着フィルムを前記光学フィルムから剥離する時の、剥離帯電圧を低く抑え、且つ、粘着性能を含めた耐久性を有する粘着剤組成物が求められている。
Furthermore, the relationship between antistatic performance and durability, including adhesive performance to adherends, of adhesive compositions with antistatic performance and adhesive films using the same is a trade-off relationship, It has been difficult to improve durability, including adhesive performance, while maintaining antistatic performance.
Therefore, even if the surface of the optical film is surface-treated with a composition containing a silicone compound, etc., when the adhesive film is peeled off from the optical film, the peeling voltage can be kept low and the adhesive performance can be maintained. There is a need for adhesive compositions that have durability including:
本発明は、上記事情に鑑みてなされたものであり、優れた帯電防止性能と、粘着性能を含めた耐久性とを両立することが可能な粘着剤組成物、及びそれを用いた粘着フィルムを提供するという新規な課題を解決するものである。 The present invention has been made in view of the above circumstances, and provides an adhesive composition capable of achieving both excellent antistatic performance and durability including adhesive performance, and an adhesive film using the same. It solves the new problem of providing
本発明者らは、粘着剤組成物のアクリル系ポリマーを構成するアルキル（メタ）アクリレートのアルキル基の炭素数を特定の範囲に限定し、特定の組み合わせの２種以上のアルキル（メタ）アクリレートを共重合させた共重合体と、ノナフルオロブタンスルホナート等の、特定のスルホナートアニオンを有する融点２５℃以上のイオン性化合物からなる帯電防止剤とを含有した新たな粘着剤組成物を作成した。このことにより、従来の粘着フィルム用粘着剤組成物と比べて、優れた粘着性能を含めた耐久性を有し、且つ、経時劣化しないで優れた剥離帯電防止性能を有する粘着剤組成物が得られることを見つけ出し、本発明を完成した。
特に、本発明に係わる粘着フィルムは、従来技術に比べて、優れた粘着性能を含めた耐久性を有し、且つ、経時劣化しないで優れた剥離帯電防止性能を有することから、帯電防止性能と、粘着性能を含めた耐久性との両立に効果があることが判明した。
The present inventors limited the number of carbon atoms in the alkyl group of the alkyl (meth)acrylate constituting the acrylic polymer of the adhesive composition to a specific range, and created a specific combination of two or more alkyl (meth)acrylates. A new adhesive composition containing a copolymerized copolymer and an antistatic agent made of an ionic compound having a specific sulfonate anion and a melting point of 25°C or higher, such as nonafluorobutane sulfonate, was created. . As a result, compared to conventional adhesive compositions for adhesive films, it is possible to obtain an adhesive composition that has durability including excellent adhesive performance, and has excellent peeling and antistatic performance without deteriorating over time. The present invention has been completed.
In particular, the adhesive film according to the present invention has excellent durability including adhesive performance compared to conventional technology, and has excellent antistatic peeling performance without deteriorating over time. It has been found that this method is effective in achieving both durability and adhesive performance.
前記課題を解決するため、本発明は、アクリル系ポリマーと、帯電防止剤と、架橋剤とを含有する粘着剤組成物であって、
前記アクリル系ポリマーが、０℃以下のガラス転移温度を有してなり、
前記（Ｄ）架橋剤が、３官能以上のイソシアネート化合物、及び２官能以上のエポキシ化合物からなる群から選ばれた１種以上の架橋剤であり、
前記粘着剤組成物が、さらに、（Ｈ）エポキシ基、メルカプト基、酸無水物基からなる群から選ばれた少なくとも１種以上の官能基を含有するモノマータイプ、もしくはオリゴマータイプのシランカップリング剤を含有してなり、
前記帯電防止剤が、カチオンとアニオンとからなる融点２５℃以上のイオン性化合物であり、前記アニオンが、トリフルオロメタンスルホナートアニオン、ペンタフルオロエタンスルホナートアニオン、ヘプタフルオロプロパンスルホナートアニオン、ノナフルオロブタンスルホナートアニオン、からなる群から選択された１種であり、
前記アクリル系ポリマーの１００重量部に対して、前記帯電防止剤を０．０１～１０重量部の割合で必須成分として含有してなることを特徴とする粘着剤組成物を提供する。
In order to solve the above problems, the present invention provides an adhesive composition containing an acrylic polymer, an antistatic agent, and a crosslinking agent,
The acrylic polymer has a glass transition temperature of 0° C. or lower,
The crosslinking agent (D) is one or more crosslinking agents selected from the group consisting of trifunctional or higher functional isocyanate compounds and bifunctional or higher functional epoxy compounds,
The adhesive composition further includes (H) a monomer type or oligomer type silane coupling agent containing at least one functional group selected from the group consisting of an epoxy group, a mercapto group, and an acid anhydride group. Contains
The antistatic agent is an ionic compound consisting of a cation and an anion and having a melting point of 25° C. or higher, and the anion is a trifluoromethanesulfonate anion, a pentafluoroethanesulfonate anion, a heptafluoropropanesulfonate anion, or nonafluorobutane. Sulfonate anion, one selected from the group consisting of,
A pressure-sensitive adhesive composition is provided, characterized in that the antistatic agent is contained as an essential component in a proportion of 0.01 to 10 parts by weight based on 100 parts by weight of the acrylic polymer.
前記アクリル系ポリマーが、
（Ａ）アルキル基の炭素数Ｃ１～Ｃ１４のアルキル（メタ）アクリレートモノマーの少なくとも１種と、
（Ｂ）水酸基及び／又はカルボキシル基を含有する共重合性ビニルモノマーの少なくとも１種と、
（Ｃ）芳香族基を含有する共重合性ビニルモノマーの少なくとも１種と、を共重合させた共重合体のアクリル系ポリマーであり、
前記アクリル系ポリマーのうち、前記（Ａ）と前記（Ｃ）との合計１００重量部に対して、前記（Ｂ）水酸基及び／又はカルボキシル基を含有する共重合性ビニルモノマーの少なくとも１種の合計を０．１～５重量部の割合で含有してなり、
前記粘着剤組成物を架橋させた厚みが２０μｍの粘着剤層を、総厚みが８０μｍの偏光板に貼り合せた試験片において、厚みが２０μｍの前記粘着剤層の無アルカリガラスに対する粘着力が６Ｎ／２５ｍｍ以下であり、かつ、１０５℃×５００ｈｒの耐久性試験後にも発泡、及びハガレのないことが好ましい。
The acrylic polymer is
(A) at least one alkyl (meth)acrylate monomer whose alkyl group has a carbon number of C1 to C14;
(B) at least one copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group;
(C) an acrylic polymer copolymerized with at least one copolymerizable vinyl monomer containing an aromatic group;
Of the acrylic polymer, the total of at least one copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group (B) based on a total of 100 parts by weight of the above (A) and the above (C). containing 0.1 to 5 parts by weight,
In a test piece in which a 20 μm thick adhesive layer made by crosslinking the adhesive composition was laminated to a polarizing plate with a total thickness of 80 μm, the adhesive force of the 20 μm thick adhesive layer to alkali-free glass was 6N. /25 mm or less, and it is preferable that there is no foaming or peeling even after a durability test of 105° C. x 500 hr.
前記カチオンが、ピリジニウム、イミダゾリウム、ホスホニウム、スルホニウム、ピロリジニウム、グアニジニウム、アンモニウム、イソウロニウム、チオウロニウム、ピペリジニウム、ピラゾリウム、メチリウム、リチウム、モルホリニウムからなる群から選択された１種であることが好ましい。 The cation is preferably one selected from the group consisting of pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidinium, ammonium, isouronium, thiouronium, piperidinium, pyrazolium, methylium, lithium, and morpholinium.
前記粘着剤組成物を架橋させた粘着剤層の、表面抵抗率が１．０×１０＋１２Ω／□以下であることが好ましい。 It is preferable that the surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition is 1.0×10+ 12 Ω/□ or less.
前記（Ｂ）水酸基及び／又はカルボキシル基を含有する共重合性ビニルモノマーが、水酸基を含有する共重合可能なモノマー、及びカルボキシル基を含有する共重合可能なモノマーからなる群から選択された少なくとも１種以上であり、
前記水酸基を含有する共重合可能なモノマーが、８－ヒドロキシオクチル（メタ）アクリレート、６－ヒドロキシヘキシル（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－ヒドロキシエチル（メタ）アクリレート、Ｎ－ヒドロキシ（メタ）アクリルアミド、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）アクリルアミドからなる化合物群の中から選択された少なくとも１種以上であり、
前記カルボキシル基を含有する共重合可能なモノマーが、（メタ）アクリル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシプロピルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチルフタル酸、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルマレイン酸、カルボキシポリカプロラクトンモノ（メタ）アクリレート、２－（メタ）アクリロイロキシエチルテトラヒドロフタル酸からなる化合物群の中から選択された少なくとも１種以上であることが好ましい。
The copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group (B) is at least one selected from the group consisting of a copolymerizable monomer containing a hydroxyl group and a copolymerizable monomer containing a carboxyl group. More than a species,
The copolymerizable monomer containing a hydroxyl group is 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N- At least one or more selected from the group of compounds consisting of hydroxy (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, and N-hydroxyethyl (meth)acrylamide,
The copolymerizable monomer containing a carboxyl group is (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-( meth)acryloyloxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylmaleic acid, carboxypolycaprolactone Preferably, it is at least one selected from the group of compounds consisting of mono(meth)acrylate and 2-(meth)acryloyloxyethyltetrahydrophthalic acid.
また、本発明は、樹脂フィルムの片面に、上記の粘着剤組成物を架橋させた粘着剤層が積層されていることを特徴とする粘着フィルムを提供する。 Further, the present invention provides an adhesive film characterized in that an adhesive layer formed by crosslinking the above-mentioned adhesive composition is laminated on one side of the resin film.
また、本発明は、光学フィルムの少なくとも一方の面に、上記の粘着剤組成物を架橋させた粘着剤層が積層されている粘着剤層付き光学フィルムを提供する。 The present invention also provides an optical film with an adhesive layer, in which an adhesive layer made of the above-mentioned adhesive composition is laminated on at least one surface of the optical film.
また、本発明は、前記樹脂フィルムの片面の、前記粘着剤層が積層された側とは反対面に、帯電防止処理および防汚処理が施されている粘着フィルムを提供する。 Further, the present invention provides an adhesive film in which one side of the resin film, which is opposite to the side on which the adhesive layer is laminated, is subjected to antistatic treatment and antifouling treatment.
また、本発明は、上記の粘着フィルムが用いられた、偏光板用粘着フィルムを提供する。 The present invention also provides an adhesive film for a polarizing plate, using the above-mentioned adhesive film.
また、本発明は、離形フィルムの片面に、上記の粘着剤組成物を架橋させてなる粘着剤層が、厚みが１μｍ～２５μｍで積層されてなり、離形フィルム／粘着剤層／離形フィルムの構成であることを特徴とする粘着フィルムを提供する。 Further, the present invention provides a release film in which a pressure-sensitive adhesive layer formed by crosslinking the above-mentioned pressure-sensitive adhesive composition is laminated on one side of the release film to a thickness of 1 μm to 25 μm. To provide an adhesive film characterized by having a film structure.
また、本発明は、上記の粘着剤層付き光学フィルムが用いられていることを特徴とする液晶パネルを提供する。 Further, the present invention provides a liquid crystal panel characterized in that the optical film with an adhesive layer described above is used.
本発明によれば、優れた帯電防止性能と、粘着性能を含めた耐久性とを両立することが可能な粘着剤組成物、及び粘着フィルムを提供することができる。
本発明に係わる粘着剤組成物、及びそれを用いた粘着フィルムは、被着体である光学フィルムの表面が、シリコーン化合物などを含有する組成物で表面処理が施されている場合であっても、従来技術に比べて、優れた粘着性能を含めた耐久性を有し、且つ、経時劣化しないで優れた剥離帯電防止性能を有する。
すなわち、本発明に係わる粘着剤組成物、及びそれを用いた粘着フィルムは、優れた帯電防止性能と、優れた粘着性能を含めた耐久性とを備えているため、産業上の利用価値が極めて大である。
According to the present invention, it is possible to provide a pressure-sensitive adhesive composition and a pressure-sensitive adhesive film that are capable of achieving both excellent antistatic performance and durability including adhesive performance.
The adhesive composition according to the present invention and the adhesive film using the same can be used even when the surface of an optical film as an adherend is surface-treated with a composition containing a silicone compound or the like. Compared to the conventional technology, it has durability including excellent adhesive performance, and has excellent peeling and antistatic performance without deteriorating over time.
In other words, the adhesive composition according to the present invention and the adhesive film using the same have excellent antistatic performance and durability including excellent adhesive performance, and therefore have extremely high industrial utility value. It's large.
以下、好適な実施形態に基づいて、本発明を説明する。
本実施形態の粘着剤組成物は、アクリル系ポリマーと、帯電防止剤と、架橋剤とを含有する粘着剤組成物であって、前記アクリル系ポリマーが、０℃以下のガラス転移温度を有してなり、前記（Ｄ）架橋剤が、３官能以上のイソシアネート化合物、及び２官能以上のエポキシ化合物からなる群から選ばれた１種以上の架橋剤であり、前記粘着剤組成物が、さらに、（Ｈ）エポキシ基、メルカプト基、酸無水物基からなる群から選ばれた少なくとも１種以上の官能基を含有するモノマータイプ、もしくはオリゴマータイプのシランカップリング剤を含有してなり、前記帯電防止剤が、カチオンとアニオンとからなる融点２５℃以上のイオン性化合物であり、前記アニオンが、トリフルオロメタンスルホナートアニオン、ペンタフルオロエタンスルホナートアニオン、ヘプタフルオロプロパンスルホナートアニオン、ノナフルオロブタンスルホナートアニオン、からなる群から選択された１種であり、前記アクリル系ポリマーの１００重量部に対して、前記帯電防止剤を０．０１～１０重量部の割合で必須成分として含有してなることを特徴とする。
また、前記帯電防止剤は、温度２５℃において固体の融点２５℃以上のイオン性化合物であることが好ましく、さらに、前記帯電防止剤の融点が４５０℃以下であることが好ましい。
The present invention will be described below based on preferred embodiments.
The adhesive composition of the present embodiment is an adhesive composition containing an acrylic polymer, an antistatic agent, and a crosslinking agent, wherein the acrylic polymer has a glass transition temperature of 0°C or lower. The crosslinking agent (D) is one or more crosslinking agents selected from the group consisting of trifunctional or higher functional isocyanate compounds and difunctional or higher functional epoxy compounds, and the adhesive composition further comprises: (H) Contains a monomer-type or oligomer-type silane coupling agent containing at least one functional group selected from the group consisting of an epoxy group, a mercapto group, and an acid anhydride group, and the antistatic agent The agent is an ionic compound consisting of a cation and an anion and having a melting point of 25°C or higher, and the anion is a trifluoromethanesulfonate anion, a pentafluoroethanesulfonate anion, a heptafluoropropanesulfonate anion, or a nonafluorobutanesulfonate anion. , and is characterized by containing the antistatic agent as an essential component in a ratio of 0.01 to 10 parts by weight per 100 parts by weight of the acrylic polymer. shall be.
Further, the antistatic agent is preferably an ionic compound having a solid melting point of 25°C or higher at a temperature of 25°C, and further preferably has a melting point of 450°C or lower.
本実施形態の粘着剤組成物に用いられるアクリル系ポリマーは、０℃以下のガラス転移温度を有する。また、アクリル系ポリマーは、（Ａ）アルキル基の炭素数Ｃ１～Ｃ１４のアルキル（メタ）アクリレートモノマーの少なくとも１種を主成分とする共重合体が好ましい。 The acrylic polymer used in the adhesive composition of this embodiment has a glass transition temperature of 0° C. or lower. The acrylic polymer is preferably a copolymer containing at least one alkyl (meth)acrylate monomer having an alkyl group of C1 to C14 as a main component.
また、（Ａ）アルキル基の炭素数Ｃ１～Ｃ１４のアルキル（メタ）アクリレートモノマーとしては、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、ヘプチル（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、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、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレートなどが挙げられる。アルキル（メタ）アクリレートモノマーのアルキル基は、直鎖、分枝状、環状のいずれでもよい。 In addition, (A) alkyl (meth)acrylate monomers in which the alkyl group has carbon atoms of C1 to C14 include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate. ) acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate ) acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like. The alkyl group of the alkyl (meth)acrylate monomer may be linear, branched, or cyclic.
本実施形態の粘着剤組成物に用いられるアクリル系ポリマーは、（Ｂ）水酸基及び／又はカルボキシル基を含有する共重合性ビニルモノマーの少なくとも１種を、任意成分として共重合させることができる。（Ｂ）水酸基及び／又はカルボキシル基を含有する共重合性ビニルモノマーとしては、水酸基を含有する共重合可能なモノマー（ヒドロキシル基含有モノマー）、及びカルボキシル基を含有する共重合可能なモノマー（カルボキシル基含有モノマー）からなる群から選択された少なくとも１種以上が挙げられる。すなわち、ヒドロキシル基含有モノマー、又はカルボキシル基含有モノマーのいずれか一方のみを選択して共重合させてもよく、ヒドロキシル基含有モノマー、及びカルボキシル基含有モノマーの両方を共重合させてもよい。
アクリル系ポリマーのうち、前記（Ａ）と前記（Ｃ）との合計１００重量部に対して、（Ｂ）水酸基及び／又はカルボキシル基を含有する共重合性ビニルモノマーの少なくとも１種の合計を０．１～５重量部の割合で含有してなることが好ましく、０．１～４．２重量部の割合で含有してなることがより好ましく、０．１～２．８重量部の割合で含有してなることが特に好ましい。
The acrylic polymer used in the adhesive composition of this embodiment can be copolymerized with at least one copolymerizable vinyl monomer containing (B) a hydroxyl group and/or a carboxyl group as an optional component. (B) The copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group includes a copolymerizable monomer containing a hydroxyl group (hydroxyl group-containing monomer), and a copolymerizable monomer containing a carboxyl group (a carboxyl group-containing monomer). At least one kind selected from the group consisting of monomers (containing monomers). That is, either the hydroxyl group-containing monomer or the carboxyl group-containing monomer may be selected and copolymerized, or both the hydroxyl group-containing monomer and the carboxyl group-containing monomer may be copolymerized.
Of the acrylic polymer, the total of at least one copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group (B) is 0 with respect to a total of 100 parts by weight of the above (A) and the above (C). .1 to 5 parts by weight, more preferably 0.1 to 4.2 parts by weight, and 0.1 to 2.8 parts by weight. It is particularly preferable that the compound be contained.
また、ヒドロキシル基含有モノマーとしては、８－ヒドロキシオクチル（メタ）アクリレート、６－ヒドロキシヘキシル（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－ヒドロキシエチル（メタ）アクリレート、Ｎ－ヒドロキシ（メタ）アクリルアミド、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からなる化合物群の中から選択された少なくとも１種以上が挙げられる。本実施形態の粘着剤組成物に含有させるヒドロキシル基含有モノマーの割合は、アクリル系ポリマーのうち、前記（Ａ）と前記（Ｃ）との合計１００重量部に対して、０．１～５重量部の割合であることが好ましく、０．１～４．２重量部の割合であることがより好ましく、０．１～２．８重量部の割合で含有してなることが特に好ましい。 Furthermore, examples of hydroxyl group-containing monomers include 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and N-hydroxy (meth)acrylate. ) acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, and the like. The proportion of the hydroxyl group-containing monomer contained in the adhesive composition of the present embodiment is 0.1 to 5 parts by weight per 100 parts by weight of the total of (A) and (C) in the acrylic polymer. The content is preferably 0.1 to 4.2 parts by weight, more preferably 0.1 to 4.2 parts by weight, and particularly preferably 0.1 to 2.8 parts by weight.
また、カルボキシル基含有モノマーとしては、（メタ）アクリル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシプロピルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチルフタル酸、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルマレイン酸、カルボキシポリカプロラクトンモノ（メタ）アクリレート、２－（メタ）アクリロイロキシエチルテトラヒドロフタル酸などからなる化合物群の中から選択された少なくとも１種以上が挙げられる。本実施形態に係わる粘着剤組成物におけるカルボキシル基含有モノマーの割合は、アクリル系ポリマーのうち、前記（Ａ）と前記（Ｃ）との合計１００重量部に対して、０～５．０重量部である（カルボキシル基含有モノマーを共重合させない場合も許容される）ことが好ましく、カルボキシル基含有モノマーを共重合させる場合には、０．１～５重量部の割合であることがより好ましく、０．１～２．４重量部の割合であることが特に好ましく、０．１～１．２重量部の割合であることが最も好ましい。 In addition, examples of carboxyl group-containing monomers include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyl Roxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylmaleic acid, carboxypolycaprolactone mono(meth) At least one kind selected from the group of compounds consisting of acrylate, 2-(meth)acryloyloxyethyltetrahydrophthalic acid, etc. can be mentioned. The proportion of the carboxyl group-containing monomer in the adhesive composition according to the present embodiment is 0 to 5.0 parts by weight based on the total of 100 parts by weight of the above (A) and the above (C) in the acrylic polymer. It is preferable that the proportion is (even if the carboxyl group-containing monomer is not copolymerized), and when the carboxyl group-containing monomer is copolymerized, the proportion is more preferably 0.1 to 5 parts by weight, and 0. A proportion of 0.1 to 2.4 parts by weight is particularly preferred, and a proportion of 0.1 to 1.2 parts by weight is most preferred.
本実施形態の粘着剤組成物に用いられるアクリル系ポリマーは、（Ｃ）芳香族基を含有する共重合性ビニルモノマーを、任意成分として共重合させてもよい。（Ｃ）芳香族基を含有する共重合性ビニルモノマーとしては、例えば、ベンジル（メタ）アクリレート、ナフチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシブチル（メタ）アクリレート、２－（１－ナフチルオキシ）エチル（メタ）アクリレート、２－（２－ナフチルオキシ）エチル（メタ）アクリレート、６－（１－ナフチルオキシ）ヘキシル（メタ）アクリレート、６－（２－ナフチルオキシ）ヘキシル（メタ）アクリレート、８－（１－ナフチルオキシ）オクチル（メタ）アクリレート、８－（２－ナフチルオキシ）オクチル（メタ）アクリレートなどの少なくとも１種以上が挙げられる。芳香族基を含有する共重合性ビニルモノマーとして、芳香族基を含有する（メタ）アクリレートモノマーを含有する場合には、アルキル（メタ）アクリレートモノマーとの共重合性に優れるので、好ましい。 The acrylic polymer used in the adhesive composition of this embodiment may be copolymerized with (C) a copolymerizable vinyl monomer containing an aromatic group as an optional component. (C) Examples of the copolymerizable vinyl monomer containing an aromatic group include benzyl (meth)acrylate, naphthyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxybutyl (meth)acrylate, 2-(1- naphthyloxy)ethyl (meth)acrylate, 2-(2-naphthyloxy)ethyl (meth)acrylate, 6-(1-naphthyloxy)hexyl (meth)acrylate, 6-(2-naphthyloxy)hexyl (meth)acrylate , 8-(1-naphthyloxy)octyl (meth)acrylate, and 8-(2-naphthyloxy)octyl (meth)acrylate. As the copolymerizable vinyl monomer containing an aromatic group, it is preferable to use a (meth)acrylate monomer containing an aromatic group because it exhibits excellent copolymerizability with an alkyl (meth)acrylate monomer.
本実施形態に係わる粘着剤組成物に含有させるアクリル系ポリマーの製造方法は、特に限定されるものではなく、溶液重合法、乳化重合法等、適宜、公知の重合方法が使用可能である。本実施形態に係わる粘着剤組成物は、用いられるアクリル系ポリマーの共重合体の重量平均分子量が、１００～３００万であることが好ましい。 The method for producing the acrylic polymer contained in the adhesive composition according to the present embodiment is not particularly limited, and any known polymerization method such as a solution polymerization method or an emulsion polymerization method can be used as appropriate. In the pressure-sensitive adhesive composition according to the present embodiment, the weight average molecular weight of the acrylic polymer copolymer used is preferably 1 million to 3 million.
本実施形態に係わる粘着剤組成物は、帯電防止性能を得るために、（Ｇ）帯電防止剤を含有する。（Ｇ）帯電防止剤は、カチオンとアニオンとからなる融点２５℃以上のイオン性化合物であって、そのアニオンが、トリフルオロメタンスルホナートアニオン（ＣＦ３ＳＯ３ －）、ペンタフルオロエタンスルホナートアニオン（ＣＦ３ＣＦ２ＳＯ３ －）、ヘプタフルオロプロパンスルホナートアニオン（ＣＦ３ＣＦ２ＣＦ２ＳＯ３ －）、ノナフルオロブタンスルホナートアニオン（ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＳＯ３ －）、からなる群から選択された１種である。本実施形態に係わる粘着剤組成物は、アクリル系ポリマーの１００重量部に対して、（Ｇ）帯電防止剤を０．０１～１０重量部の割合で必須成分として含有してなるのが好ましく、さらに粘着剤層の帯電防止性能を高めて表面抵抗率の下限値を１．０×１０＋１０Ω／□以下にまで低減させることが必要な場合には、（Ｇ）帯電防止剤を０．０１～１５重量部の割合で含有するのがより好ましい。 The adhesive composition according to this embodiment contains (G) an antistatic agent in order to obtain antistatic performance. (G) The antistatic agent is an ionic compound consisting of a cation and an anion and having a melting point of 25°C or higher, and the anion is trifluoromethanesulfonate anion (CF 3 SO 3 - ), pentafluoroethanesulfonate anion ( CF 3 CF 2 SO 3 − ), heptafluoropropanesulfonate anion (CF 3 CF 2 CF 2 SO 3 − ), nonafluorobutanesulfonate anion (CF 3 CF 2 CF 2 CF 2 SO 3 − ), This is one type selected from. The adhesive composition according to the present embodiment preferably contains (G) an antistatic agent as an essential component in a ratio of 0.01 to 10 parts by weight based on 100 parts by weight of the acrylic polymer. If it is necessary to further improve the antistatic performance of the adhesive layer and reduce the lower limit of the surface resistivity to 1.0 × 10 +10 Ω/□, add (G) the antistatic agent to 0.01 More preferably, it is contained in a proportion of 15 parts by weight.
また、イオン性化合物に含有されるカチオンとしては、ピリジニウム、イミダゾリウム、ホスホニウム、スルホニウム、ピロリジニウム、グアニジニウム、アンモニウム、イソウロニウム、チオウロニウム、ピペリジニウム、ピラゾリウム、メチリウム、リチウム、モルホリニウムからなる群から選択された１種が挙げられる。
また、（Ｇ）帯電防止剤の具体例としては、トリフルオロメタンスルホン酸リチウム、ノナフルオロブタンスルホン酸リチウム、１－メチル－３－オクチルピリジニウム トリフルオロメタンスルホナート塩、３－メチル－１－オクチルピリジニウム トリフルオロメタンスルホナート塩、１－メチル－４－オクチルピリジニウム ノナフルオロブタンスルホナート塩、４－メチル－１－オクチルピリジニウム ノナフルオロブタンスルホナート塩、ジメチルジオクチルアンモニウム ペンタフルオロエタンスルホナート塩、１－メチル－３－オクチルピリジニウム ヘプタフルオロプロパンスルホナート塩、３－メチル－１－オクチルピリジニウム ヘプタフルオロプロパンスルホナート塩、１－メチル－３－オクチルピリジニウム ノナフルオロブタンスルホナート塩、３－メチル－１－オクチルピリジニウム ノナフルオロブタンスルホナート塩、１－オクチル－３－メチルイミダゾリウム ノナフルオロブタンスルホナート塩などが挙げられる。
The cation contained in the ionic compound is one selected from the group consisting of pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidinium, ammonium, isouronium, thiouronium, piperidinium, pyrazolium, methylium, lithium, and morpholinium. can be mentioned.
Specific examples of the antistatic agent (G) include lithium trifluoromethanesulfonate, lithium nonafluorobutanesulfonate, 1-methyl-3-octylpyridinium trifluoromethanesulfonate salt, and 3-methyl-1-octylpyridinium trifluoride. lomethanesulfonate salt, 1-methyl-4-octylpyridinium nonafluorobutanesulfonate salt, 4-methyl-1-octylpyridinium nonafluorobutanesulfonate salt, dimethyldioctyl ammonium pentafluoroethanesulfonate salt, 1-methyl-3 -Octylpyridinium heptafluoropropanesulfonate salt, 3-methyl-1-octylpyridinium heptafluoropropanesulfonate salt, 1-methyl-3-octylpyridinium nonafluorobutanesulfonate salt, 3-methyl-1-octylpyridinium nonafluoro Examples include butanesulfonate salt, 1-octyl-3-methylimidazolium nonafluorobutanesulfonate salt, and the like.
本実施形態に係わる粘着剤組成物は、さらに、（Ｄ）架橋剤として、３官能以上のイソシアネート化合物、及び２官能以上のエポキシ化合物からなる群から選択された少なくとも１種以上の架橋剤を含有する。（Ｄ）架橋剤として、３官能以上のイソシアネート化合物と、２官能以上のエポキシ化合物とが併用されてもよい。（Ｄ）架橋剤の少なくとも１種以上の合計の含有割合としては、例えば、アクリル系ポリマーの１００重量部に対して０．０１～５重量部が好ましく、０．０１～２重量部がより好ましく、０．０３～０．８重量部が特に好ましい。 The adhesive composition according to the present embodiment further contains (D) as a crosslinking agent, at least one crosslinking agent selected from the group consisting of trifunctional or higher functional isocyanate compounds and bifunctional or higher functional epoxy compounds. do. (D) As a crosslinking agent, a trifunctional or higher functional isocyanate compound and a bifunctional or higher functional epoxy compound may be used together. (D) The total content of at least one crosslinking agent is preferably 0.01 to 5 parts by weight, more preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the acrylic polymer. , 0.03 to 0.8 parts by weight are particularly preferred.
また、３官能以上のイソシアネート化合物としては、例えば、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、ジフェニルメタンジイソシアネート、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等のジイソシアネート類のビュレット変性体やイソシアヌレート変性体、トリメチロールプロパンや、グリセリン等の３価以上のポリオールとのアダクト体などが挙げられる。
また、２官能以上のエポキシ化合物としては、グリコール類のジグリシジルエーテル、ビスフェノール類のジグリシジルエーテル、トリオール類のトリグリシジルエーテル、ジカルボン酸のジグリシジルエステル、ジグリシジル置換のアミン類、テトラグリシジル置換のジアミン類などが挙げられる。
Examples of trifunctional or more functional isocyanate compounds include biuret-modified and isocyanurate-modified diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, and xylylene diisocyanate, trimethylolpropane, and glycerin. Examples include adducts with polyols having a valence of 3 or higher.
In addition, examples of di- or higher-functional epoxy compounds include diglycidyl ethers of glycols, diglycidyl ethers of bisphenols, triglycidyl ethers of triols, diglycidyl esters of dicarboxylic acids, diglycidyl-substituted amines, and tetraglycidyl-substituted diamines. Examples include the following.
本実施形態に係わる粘着剤組成物は、さらに、（Ｈ）シランカップリング剤を含有する。（Ｈ）シランカップリング剤としては、１分子中に、少なくとも１つの有機官能基と、少なくとも１つの加水分解性基を有し、前記加水分解性基が、ケイ素原子に結合したアルコキシ基等である化合物が挙げられる。（Ｈ）シランカップリング剤は、エポキシ基、メルカプト基、酸無水物基からなる群から選択された少なくとも１種以上の官能基を含有する。（Ｈ）シランカップリング剤は、モノマータイプ又はオリゴマータイプの一方又は両方を、少なくとも１種以上用いることができる。シランカップリング剤の含有割合は、例えば、アクリル系ポリマーの１００重量部に対して、０．０１～２．０重量部が好ましく、０．０１～１．０重量部がより好ましく、０．０１～０．５重量部が特に好ましい。 The adhesive composition according to this embodiment further contains (H) a silane coupling agent. (H) The silane coupling agent has at least one organic functional group and at least one hydrolyzable group in one molecule, and the hydrolyzable group is an alkoxy group bonded to a silicon atom, etc. One example is a compound. (H) The silane coupling agent contains at least one functional group selected from the group consisting of an epoxy group, a mercapto group, and an acid anhydride group. (H) As the silane coupling agent, at least one type of monomer type or oligomer type or both can be used. For example, the content ratio of the silane coupling agent is preferably 0.01 to 2.0 parts by weight, more preferably 0.01 to 1.0 parts by weight, and 0.01 to 1.0 parts by weight, based on 100 parts by weight of the acrylic polymer. Particularly preferred is 0.5 part by weight.
また、エポキシ基を有するシランカップリング剤としては、例えば、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルメチルジメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルメチルジエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリエトキシシラン、５，６－エポキシヘキシルトリメトキシシラン、５，６－エポキシヘキシルメチルジメトキシシラン、５，６－エポキシヘキシルメチルジエトキシシラン、５，６－エポキシヘキシルトリエトキシシランなどが挙げられる。
また、メルカプト基を有するシランカップリング剤としては、例えば、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルメチルジエトキシシラン、３－メルカプトプロピルトリエトキシシラン、２－メルカプトプロピルトリエトキシシラン、２－メルカプトエチルトリメトキシシラン、２－メルカプトエチルトリエトキシシランなどが挙げられる。
また、酸無水物基を有するシランカップリング剤としては、例えば、３－トリメトキシシリルプロピルコハク酸無水物、３－トリエトキシシリルプロピルコハク酸無水物、３－ジメチルメトキシシリルプロピルコハク酸無水物、３－ジメチルエトキシシリルプロピルコハク酸無水物、３－トリメトキシシリルプロピルシクロヘキシルジカルボン酸無水物、３－トリエトキシシリルプロピルシクロヘキシルジカルボン酸無水物、３－ジメチルメトキシシリルプロピルシクロヘキシルジカルボン酸無水物、３－ジメチルエトキシシリルプロピルシクロヘキシルジカルボン酸無水物、３－トリメトキシシリルプロピルフタル酸無水物、３－トリエトキシシリルプロピルフタル酸無水物などが挙げられる。
また、オリゴマー化したアルコキシオリゴマー（アルコキシル基を含有するシリコーンアルコキシオリゴマー）なども、シランカップリング剤として用いることができる。
また、シリコーンアルコキシオリゴマーは、例えぱ、分子末端がＳｉ－ＯＲで表されるアルコキシシリル基で封鎖された、テトラアルコキシシロキサン、トリアルコキシシロキサン、ジアルコキシシロキサンなどの、分子量が６００以上３０００未満の比較的に分子量の小さいシリコーンアルコキシオリゴマーを用いるのが好ましい。
Further, examples of the silane coupling agent having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. Xypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxy Silane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 5,6-epoxyhexylmethyldimethoxysilane, 5,6-epoxyhexylmethyldiethoxysilane, 5, Examples include 6-epoxyhexyltriethoxysilane.
Further, examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptopropylmethyldimethoxysilane, Examples include mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyltriethoxysilane.
Further, examples of the silane coupling agent having an acid anhydride group include 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-dimethylmethoxysilylpropylsuccinic anhydride, 3-dimethylethoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-triethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-dimethylmethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-dimethyl Examples thereof include ethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride, and 3-triethoxysilylpropylphthalic anhydride.
Furthermore, oligomerized alkoxy oligomers (silicone alkoxy oligomers containing alkoxyl groups) can also be used as the silane coupling agent.
In addition, silicone alkoxy oligomers include, for example, tetraalkoxysiloxanes, trialkoxysiloxanes, dialkoxysiloxanes whose molecular terminals are blocked with alkoxysilyl groups represented by Si-OR, and which have a molecular weight of 600 or more and less than 3,000. It is preferable to use a silicone alkoxy oligomer having a relatively small molecular weight.
本実施形態の粘着剤組成物は、上述の添加剤に限らず、酸化防止剤、界面活性剤、硬化促進剤、可塑剤、充填剤、硬化遅延剤、加工助剤、老化防止剤などの公知の添加剤が適宜に配合されてもよい。これらは、単独で、もしくは２種以上を併せて用いることができる。 The adhesive composition of this embodiment is not limited to the above-mentioned additives, but also contains known additives such as antioxidants, surfactants, hardening accelerators, plasticizers, fillers, hardening retarders, processing aids, and anti-aging agents. Additives may be appropriately blended. These can be used alone or in combination of two or more.
本実施形態の粘着剤組成物を架橋させた粘着剤層は、粘着剤層の表面抵抗率が１．０×１０＋１２Ω／□以下であることが好ましく、表面抵抗率が５．０×１０＋１１Ω／□以下であることがより好ましく、表面抵抗率が２．０×１０＋１１Ω／□以下であることが特に好ましい。表面抵抗率が大きいと、粘着剤層を被着体から剥離する時に帯電で発生した静電気を逃がす性能に劣る。このため、粘着剤層の表面抵抗率を十分に小さくすることにより、粘着剤層を被着体から剥がす時に発生する静電気に伴って生じる剥離帯電圧が低減され、被着体に影響することを抑制できる。 The adhesive layer crosslinked with the adhesive composition of this embodiment preferably has a surface resistivity of 1.0×10 +12 Ω/□ or less, and has a surface resistivity of 5.0×10 Ω/□ or less. The surface resistivity is more preferably +11 Ω/□ or less, and particularly preferably the surface resistivity is 2.0×10 +11 Ω/□ or less. If the surface resistivity is high, the performance of dissipating static electricity generated by charging when the adhesive layer is peeled off from the adherend is poor. Therefore, by making the surface resistivity of the adhesive layer sufficiently small, the peeling voltage generated due to static electricity generated when the adhesive layer is peeled off from the adherend can be reduced, thereby preventing it from affecting the adherend. It can be suppressed.
本実施形態の粘着剤組成物は、粘着剤組成物を架橋させた厚みが２０μｍの粘着剤層を、総厚みが８０μｍの偏光板に貼り合せた試験片において、厚みが２０μｍの粘着剤層の無アルカリガラスに対する粘着力が６Ｎ／２５ｍｍ以下であり、かつ、１０５℃×５００ｈｒの耐久性試験後にも発泡、及びハガレのないものとなる。前記厚みが２０μｍの粘着剤層の無アルカリガラスに対する粘着力は、１Ｎ／２５ｍｍ以上６Ｎ／２５ｍｍ以下であることが好ましく、１．５Ｎ／２５ｍｍ以上６Ｎ／２５ｍｍ以下であることがより好ましい。 The adhesive composition of the present embodiment was obtained by bonding a 20 μm thick adhesive layer made by crosslinking the adhesive composition to a polarizing plate with a total thickness of 80 μm. The adhesive strength to alkali-free glass is 6 N/25 mm or less, and there is no foaming or peeling even after a durability test at 105° C. for 500 hours. The adhesive force of the adhesive layer having a thickness of 20 μm to alkali-free glass is preferably 1 N/25 mm or more and 6 N/25 mm or less, and more preferably 1.5 N/25 mm or more and 6 N/25 mm or less.
本実施形態に係わる粘着剤層は、本実施形態の粘着剤組成物を樹脂フィルムや離形フィルム等の基材に塗布した後、粘着剤組成物を架橋することで得ることができる。 The adhesive layer according to this embodiment can be obtained by applying the adhesive composition of this embodiment to a base material such as a resin film or a release film, and then crosslinking the adhesive composition.
本実施形態に係わる粘着剤層を、光学部材の貼合に用いる場合、粘着剤層と光学部材との界面での光線の反射を低減させる必要がある。つまり、光学部材と粘着剤層との屈折率の差がなるべく小さいことが望ましい。このため、粘着剤層の屈折率が１．４７～１．５０であることが好ましい。 When the adhesive layer according to this embodiment is used to bond an optical member, it is necessary to reduce the reflection of light rays at the interface between the adhesive layer and the optical member. In other words, it is desirable that the difference in refractive index between the optical member and the adhesive layer be as small as possible. For this reason, it is preferable that the refractive index of the adhesive layer is 1.47 to 1.50.
本実施形態に係わる粘着フィルムは、本実施形態に係わる粘着剤層を、樹脂フィルムや離形フィルム等の基材の片面上に形成することで製造することができる。樹脂フィルムや離形フィルム（セパレーター）の基材としては、ポリエステルフィルムなどを用いることができる。離形フィルムには、粘着剤層の粘着面と合わされる側の面に、シリコーン系、フッ素系の離形剤などにより離形処理が施されてもよい。本実施形態に係わる粘着フィルムの基材となる樹脂フィルムには、樹脂フィルムの粘着剤層が形成された側とは反対面に、シリコーン系、フッ素系の離形剤やコート剤、シリカ微粒子等による防汚処理、帯電防止剤の塗布や練り込み等による帯電防止処理を施すことができる。また、本実施形態に係わる粘着フィルムの粘着剤層の厚みとしては、例えば、１μｍ～２５μｍの厚みが好ましく、３μｍ～２０μｍの厚みがより好ましく、５μｍ～２０μｍの厚みが特に好ましい。 The adhesive film according to this embodiment can be manufactured by forming the adhesive layer according to this embodiment on one side of a base material such as a resin film or a release film. A polyester film or the like can be used as a base material for the resin film or release film (separator). The release film may be subjected to a release treatment using a silicone-based, fluorine-based release agent, or the like on the side that is to be combined with the adhesive surface of the adhesive layer. The resin film, which is the base material of the adhesive film according to this embodiment, has silicone-based or fluorine-based release agents, coating agents, silica fine particles, etc. on the opposite side of the resin film from the side on which the adhesive layer is formed. It is possible to perform antifouling treatment by applying an antistatic agent, and antistatic treatment by applying or kneading an antistatic agent. Further, the thickness of the adhesive layer of the adhesive film according to the present embodiment is preferably, for example, 1 μm to 25 μm, more preferably 3 μm to 20 μm, and particularly preferably 5 μm to 20 μm.
本実施形態に係わる粘着フィルムは、１つの粘着剤層の両面に、それぞれ離形フィルムの離形処理が施された面を合わせることで、「離形フィルム／粘着剤層／離形フィルム」の構成とすることもできる。この場合、両側の離形フィルムを、順次、あるいは同時に剥離して粘着面を表出することにより、光学フィルム等の光学部材と貼合可能になる。光学フィルムとしては、偏光フィルム、位相差フィルム、反射防止フィルム、防眩（アンチグレア）フィルム、紫外線吸収フィルム、赤外線吸収フィルム、光学補償フィルム、輝度向上フィルム等が挙げられる。光学部材が適用される機器としては、液晶パネル、有機ＥＬパネル、タッチパネル等が挙げられる。 The pressure-sensitive adhesive film according to the present embodiment has a structure of "release film/adhesive layer/release film" by aligning the release-treated surfaces of the release film with both sides of one pressure-sensitive adhesive layer. It can also be configured. In this case, by peeling off the release films on both sides one after another or simultaneously to expose the adhesive surface, it becomes possible to bond it to an optical member such as an optical film. Examples of optical films include polarizing films, retardation films, antireflection films, antiglare films, ultraviolet absorbing films, infrared absorbing films, optical compensation films, brightness enhancement films, and the like. Examples of devices to which the optical member is applied include liquid crystal panels, organic EL panels, touch panels, and the like.
本実施形態に係わる粘着フィルムは、偏光板用粘着フィルムとして好適である。上記の光学フィルムの少なくとも一方の面に、前記粘着剤層が積層されてなる粘着剤層付き光学フィルムとすることができる。また、偏光板の片面に、上記の粘着フィルムを用いることにより、粘着剤層付き偏光板を提供することができる。上記の粘着剤層付き光学フィルムを用いて、液晶パネルを提供することができる。
このような、粘着剤層付き光学フィルムの積層構成の具体例としては、「離形フィルム／粘着剤層／光学フィルム」、「離形フィルム／粘着剤層／光学フィルム／粘着剤層／離形フィルム」、「光学フィルム／粘着剤層／光学フィルム」、「光学フィルム／粘着剤層」、「粘着剤層／光学フィルム／粘着剤層」等が挙げられる。粘着剤層付き偏光板の積層構成の具体例として、「離形フィルム／粘着剤層／偏光板」、「離形フィルム／粘着剤層／偏光板／粘着剤層／離形フィルム」、「偏光板／粘着剤層」、「粘着剤層／偏光板／粘着剤層」等が挙げられる。液晶パネル等の部分構造として、これらの粘着剤層付き光学フィルム、又は粘着剤層付き偏光板が組み込まれてもよい。
なお、「離形フィルム／粘着剤層／光学フィルム」、「離形フィルム／粘着剤層／偏光板」などのように、離形フィルムを積層構成に含まれる場合には、離形フィルムを剥がした後、粘着剤層を介して、光学フィルム又は偏光板が被着体に貼合される。
The adhesive film according to this embodiment is suitable as an adhesive film for a polarizing plate. An optical film with an adhesive layer may be obtained by laminating the adhesive layer on at least one surface of the optical film. Moreover, by using the above-mentioned adhesive film on one side of the polarizing plate, a polarizing plate with an adhesive layer can be provided. A liquid crystal panel can be provided using the above optical film with an adhesive layer.
Specific examples of such laminated structures of optical films with adhesive layers include "release film/adhesive layer/optical film" and "release film/adhesive layer/optical film/adhesive layer/release film". Examples include "film", "optical film/adhesive layer/optical film", "optical film/adhesive layer", "adhesive layer/optical film/adhesive layer", and the like. Specific examples of the laminated structure of polarizing plates with adhesive layers include "release film/adhesive layer/polarizing plate", "release film/adhesive layer/polarizing plate/adhesive layer/release film", and "polarizing film/adhesive layer/polarizing plate". Examples include "plate/adhesive layer" and "adhesive layer/polarizing plate/adhesive layer." An optical film with an adhesive layer or a polarizing plate with an adhesive layer may be incorporated as a partial structure of a liquid crystal panel or the like.
In addition, if a release film is included in the laminated structure, such as "release film/adhesive layer/optical film" or "release film/adhesive layer/polarizing plate", remove the release film. After that, an optical film or a polarizing plate is bonded to the adherend via an adhesive layer.
以下、実施例をもって本発明を具体的に説明する。 The present invention will be specifically explained below with reference to Examples.
＜アクリル系ポリマーの製造＞
［実施例１］
撹拌機、温度計、還流冷却器及び窒素導入管を備えた反応装置に、窒素ガスを導入して、反応装置内の空気を窒素ガスで置換した。その後、反応装置にブチルアクリレート５０重量部、メチルアクリレート１０重量部、２－エチルヘキシルアクリレート２０重量部、６－ヒドロキシヘキシルアクリレート１．０重量部、４－ヒドロキシブチルアクリレート０．５重量部、ベンジルアクリレート２０重量部とともに、溶剤（酢酸エチル）を１００部加えた。その後、重合開始剤としてアゾビスイソブチロニトリル０．１重量部を２時間かけて滴下させ、６５℃で８時間反応させ、実施例１のアクリル系ポリマー溶液を得た。
［実施例２～６及び比較例１～３］
モノマーの組成を各々、表１の記載のようにする以外は、上記の実施例１に用いるアクリル系ポリマー溶液と同様にして、実施例２～６及び比較例１～３に用いるアクリル系ポリマー溶液を得た。
<Manufacture of acrylic polymer>
[Example 1]
Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, and the air in the reaction apparatus was replaced with nitrogen gas. Thereafter, 50 parts by weight of butyl acrylate, 10 parts by weight of methyl acrylate, 20 parts by weight of 2-ethylhexyl acrylate, 1.0 parts by weight of 6-hydroxyhexyl acrylate, 0.5 parts by weight of 4-hydroxybutyl acrylate, and 20 parts by weight of benzyl acrylate were added to the reactor. Along with parts by weight, 100 parts of a solvent (ethyl acetate) were added. Thereafter, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and the mixture was reacted at 65° C. for 8 hours to obtain the acrylic polymer solution of Example 1.
[Examples 2 to 6 and Comparative Examples 1 to 3]
The acrylic polymer solutions used in Examples 2 to 6 and Comparative Examples 1 to 3 were prepared in the same manner as the acrylic polymer solutions used in Example 1 above, except that the compositions of the monomers were changed as shown in Table 1. I got it.
＜粘着剤組成物及び粘着フィルムの製造＞
［実施例１］
上記のとおり製造した実施例１のアクリル系ポリマー溶液に対して、架橋剤としてＤ－１１０Ｎを０．１重量部及びＴ－Ｘを０．０１重量部、帯電防止剤として１－メチル－３－オクチルピリジニウム ノナフルオロブタンスルホナート塩を１．５重量部、シランカップリング剤としてＫＢＭ－４０３を０．１重量部及びＸ－４１－１８０５を０．１重量部の割合で加えて撹拌混合して実施例１の粘着剤組成物を得た。この粘着剤組成物を、シリコーン樹脂コートされたポリエチレンテレフタレート（ＰＥＴ）フィルムからなる離形フィルムの上に塗布後、９０℃で乾燥することによって溶剤を除去し、厚みが２０μｍの粘着剤層を得た。その後、２３℃、５０％ＲＨの雰囲気下で７日間エージングすることにより、粘着剤組成物を架橋させた粘着剤層を、離形フィルムの片面上に有し、離形フィルム／粘着剤層／離形フィルムの構成である、実施例１の粘着フィルムを得た。
［実施例２～６及び比較例１～３］
添加剤の組成を各々、表１の記載のようにした以外は、上記の実施例１の粘着フィルムと同様にして、実施例２～６及び比較例１～３の粘着フィルムを得た。
<Production of adhesive composition and adhesive film>
[Example 1]
To the acrylic polymer solution of Example 1 produced as described above, 0.1 part by weight of D-110N and 0.01 part by weight of TX were added as a crosslinking agent, and 1-methyl-3- as an antistatic agent. 1.5 parts by weight of octylpyridinium nonafluorobutanesulfonate salt, 0.1 parts by weight of KBM-403 as a silane coupling agent, and 0.1 parts by weight of X-41-1805 were added and mixed with stirring. The adhesive composition of Example 1 was obtained. This adhesive composition was applied onto a release film made of polyethylene terephthalate (PET) film coated with a silicone resin, and the solvent was removed by drying at 90°C to obtain an adhesive layer with a thickness of 20 μm. Ta. Thereafter, by aging in an atmosphere of 23° C. and 50% RH for 7 days, a pressure-sensitive adhesive layer obtained by crosslinking the pressure-sensitive adhesive composition is formed on one side of the release film, and a release film/adhesive layer/ The adhesive film of Example 1, which has the structure of a release film, was obtained.
[Examples 2 to 6 and Comparative Examples 1 to 3]
Adhesive films of Examples 2 to 6 and Comparative Examples 1 to 3 were obtained in the same manner as the adhesive film of Example 1, except that the compositions of the additives were changed as shown in Table 1.
表１において、各成分の重量部は、（Ａ）アルキル基の炭素数Ｃ１～Ｃ１４のアルキル（メタ）アクリレートモノマーの少なくとも１種と、（Ｃ）芳香族基を含有する共重合性ビニルモノマーの少なくとも１種との合計を１００重量部として求めた。
なお、表１において、（Ｄ）、（Ｈ）、（Ｇ）の各欄では、アクリル系ポリマーを１００重量部として、各成分の含有割合（重量部）を括弧（ ）内の数値として示した。
また、表１に用いた各成分の略記号の化合物名を、表２に示す。Ｇ－１～Ｇ－７はすべて融点が２５℃以上で、２５℃において固体のイオン性化合物である。
In Table 1, the parts by weight of each component are: (A) at least one alkyl (meth)acrylate monomer having an alkyl group having a carbon number of C1 to C14; and (C) a copolymerizable vinyl monomer containing an aromatic group. The total amount including at least one type was determined as 100 parts by weight.
In addition, in Table 1, in each column (D), (H), and (G), the content ratio (parts by weight) of each component is shown as a value in parentheses ( ), assuming that the acrylic polymer is 100 parts by weight. .
Further, the compound names of the abbreviations of each component used in Table 1 are shown in Table 2. G-1 to G-7 all have melting points of 25°C or higher and are solid ionic compounds at 25°C.
なお、コロネート（登録商標）ＨＸ、同ＨＬ及び同Ｌは東ソー株式会社の商品名であり、Ｄ－１１０Ｎ、Ｄ－１２７Ｎ、タケネート（登録商標）Ｄ－１４０Ｎは三井化学株式会社の商品名であり、ＴＥＴＲＡＤ（登録商標）－Ｘは三菱ガス化学株式会社の商品名である。また、ＨＤＩはヘキサメチレンジイソシアネートを意味し、ＩＰＤＩはイソホロンジイソシアネートを意味し、ＸＤＩはキシリレンジイソシアネートを意味し、ＴＤＩはトリレンジイソシアネートを意味し、ＴＭＰはトリメチロールプロパンを意味する。また、ＫＢＭ－４０３、Ｘ－１２－９６７Ｃ、Ｘ－４１－１８０５は、いずれも、信越化学工業株式会社の商品名である。 Furthermore, Coronate (registered trademark) HX, Coronate HL, and Coronate L are product names of Tosoh Corporation, and D-110N, D-127N, and Takenate (registered trademark) D-140N are product names of Mitsui Chemicals Co., Ltd. , TETRAD (registered trademark)-X is a trade name of Mitsubishi Gas Chemical Co., Ltd. Further, HDI means hexamethylene diisocyanate, IPDI means isophorone diisocyanate, XDI means xylylene diisocyanate, TDI means tolylene diisocyanate, and TMP means trimethylolpropane. Furthermore, KBM-403, X-12-967C, and X-41-1805 are all trade names of Shin-Etsu Chemical Co., Ltd.
＜試験方法及び評価＞
実施例１～６及び比較例１～３における粘着フィルムを、それぞれ２３℃、５０％ＲＨの雰囲気下で７日間エージングしてから、以下の試験方法により評価した。
<Test method and evaluation>
The adhesive films in Examples 1 to 6 and Comparative Examples 1 to 3 were aged for 7 days in an atmosphere of 23° C. and 50% RH, and then evaluated by the following test method.
＜粘着力の試験方法＞
実施例１～６及び比較例１～３における粘着フィルムから、片方の離形フィルムを剥がして、前記粘着フィルムの粘着剤層の片面を表出させた。その後、厚みが８０μｍの偏光板（樹脂フィルム；偏光子の保護層がＴＡＣである偏光板を使用）の片面に、前記粘着剤層を介して、前記粘着フィルムを貼合して、離形フィルム／粘着剤層／偏光板の構成である、粘着剤層付き偏光板を得た。さらに、粘着剤層付き偏光板の離形フィルムを剥がして、無アルカリガラス（コーニング社製 イーグルＸＧ）のアセトンで洗浄した面に、前記粘着剤層を介して、粘着剤層付き偏光板を圧着ロールで貼合して、試験片を作成した。その後、当該試験片を、５０℃、０．５ＭＰａ×２０分間の条件で、オートクレーブ処理した。その後、２３℃×５０％ＲＨの雰囲気下に戻し、１時間経過後の粘着剤層付き偏光板の剥離強度を引張試験機によって、ＪＩＳ Ｚ０２３７「粘着テープ・粘着シート試験方法」に準拠して測定し、１８０°方向に０．３ｍ／ｍｉｎの速度で剥離した時の剥離強度を、無アルカリガラスに対する粘着剤層の粘着力とした。
<Adhesive strength test method>
One side of the release film was peeled off from the adhesive films of Examples 1 to 6 and Comparative Examples 1 to 3 to expose one side of the adhesive layer of the adhesive film. Thereafter, the adhesive film is laminated on one side of a polarizing plate (resin film; the protective layer of the polarizer is TAC) with a thickness of 80 μm via the adhesive layer, and a release film is formed. A polarizing plate with an adhesive layer having the configuration of /adhesive layer/polarizing plate was obtained. Furthermore, the release film of the polarizing plate with the adhesive layer was peeled off, and the polarizing plate with the adhesive layer was pressed onto the acetone-cleaned surface of non-alkali glass (Eagle XG manufactured by Corning) through the adhesive layer. A test piece was created by laminating with a roll. Thereafter, the test piece was autoclaved at 50° C. and 0.5 MPa for 20 minutes. After that, it was returned to the atmosphere of 23°C x 50% RH, and after 1 hour, the peel strength of the polarizing plate with the adhesive layer was measured using a tensile tester in accordance with JIS Z0237 "Adhesive tape/adhesive sheet testing method". The peel strength when peeled in a 180° direction at a speed of 0.3 m/min was defined as the adhesive strength of the pressure-sensitive adhesive layer to alkali-free glass.
＜表面抵抗率の試験方法＞
粘着フィルムをエージングした後、被着体に貼り合わせる前に、離形フィルムを剥がして粘着剤層を表出し、抵抗率計ハイレスタＵＰ－ＨＴ４５０（三菱化学アナリテック製）を用いて粘着剤層の表面抵抗率を測定した。
<Surface resistivity test method>
After aging the adhesive film and before bonding it to the adherend, peel off the release film to expose the adhesive layer, and measure the adhesive layer using a resistivity meter Hiresta UP-HT450 (manufactured by Mitsubishi Chemical Analytech). Surface resistivity was measured.
＜耐久性の試験方法＞
粘着力の測定と同様の方法で、１０ｃｍ角の粘着剤層付き偏光板の離形フィルムを剥がして、無アルカリガラスのアセトンで洗浄した面に貼合して、試験片を作成した。その後、該試験片について、１０５℃×５００ｈｒの試験環境下における耐久性試験をした後、２３℃×５０％ＲＨ雰囲気下に取り出し、１時間後に粘着剤層の状態を目視で観察して、粘着剤層の耐久性を判断した。耐久性の判断基準は、粘着剤層の発泡及びハガレが全く無い場合を「○」、粘着剤層の一部に発泡、ハガレが発生している場合を「△」、粘着剤層の全体に発泡、ハガレが発生している場合を「×」と評価した。
<Durability test method>
In the same manner as in the measurement of adhesive strength, the release film of a 10 cm square polarizing plate with an adhesive layer was peeled off and bonded to the acetone-cleaned surface of non-alkali glass to prepare a test piece. After that, the test piece was subjected to a durability test under a test environment of 105°C x 500 hr, and then taken out in an atmosphere of 23°C x 50% RH, and after 1 hour, the state of the adhesive layer was visually observed. The durability of the agent layer was judged. The criteria for judging durability is "○" if there is no foaming or peeling of the adhesive layer, "△" if foaming or peeling occurs in a part of the adhesive layer, and "△" if there is no foaming or peeling of the adhesive layer at all. A case where foaming or peeling occurred was evaluated as "x".
表３に、実施例１～６及び比較例１～３における、粘着フィルムについての評価結果を示す。「表面抵抗率」は、「ｍ×１０＋ｎ」を「ｍＥ＋ｎ」とする方式（ただし、ｍは任意の実数値、ｎは正の整数）により表記した。 Table 3 shows the evaluation results for the adhesive films in Examples 1 to 6 and Comparative Examples 1 to 3. "Surface resistivity" was expressed by a method in which "m×10 +n " is expressed as "mE+n" (where m is any real value and n is a positive integer).
実施例１～６の粘着フィルムは、粘着剤層の表面抵抗率が１．０×１０＋１２Ω／□以下であり、２０μｍの粘着剤層の無アルカリガラスに対する粘着力が６Ｎ／２５ｍｍ以下であり、かつ、１０５℃×５００ｈｒの耐久性試験後にも発泡、及びハガレがなく、粘着性能及び帯電防止性能が優れているのに加えて、耐久性に優れていた。
すなわち、実施例１～６の粘着フィルムについての、表３に示された評価結果では、本発明の課題を解決できたことが実証されている。
In the adhesive films of Examples 1 to 6, the surface resistivity of the adhesive layer is 1.0 × 10 +12 Ω/□ or less, and the adhesive strength of the 20 μm adhesive layer to alkali-free glass is 6 N/25 mm or less. Moreover, there was no foaming or peeling even after a durability test at 105° C. for 500 hours, and in addition to excellent adhesive performance and antistatic performance, it was also excellent in durability.
That is, the evaluation results shown in Table 3 for the adhesive films of Examples 1 to 6 demonstrate that the problems of the present invention were solved.
比較例１の粘着フィルムは、粘着剤組成物に含有されている（Ｇ）帯電防止剤として、ＰＦ６
－アニオンを有するイオン性化合物が用いられているため、粘着剤層の表面抵抗率が高く、耐久性が悪かった。
比較例２の粘着フィルムは、粘着剤組成物に含有されているアクリル系ポリマーのガラス転移温度が０℃超過（計算値では、＋４．８℃）となった。このため、粘着性能が悪く、粘着力が過大となり、粘着剤層の表面抵抗率が高く、耐久性が悪かった。なお、比較例２に用いたアクリル系ポリマーでは、ホモポリマーのガラス転移温度が高い値（０℃超過）であるメチルアクリレート及びアクリル酸の割合が多くされている。
比較例３の粘着フィルムは、粘着剤組成物に（Ｈ）シランカップリング剤も、（Ｇ）（Ｇ）帯電防止剤も配合されていないため、粘着力が過大となり、粘着剤層の表面抵抗率が高く、耐久性が悪かった。
このように、比較例１～３の粘着フィルムでは、本発明の課題を解決することができなかった。
In the adhesive film of Comparative Example 1, since an ionic compound having a PF 6 -anion is used as the antistatic agent (G) contained in the adhesive composition, the surface resistivity of the adhesive layer is high. , durability was poor.
In the adhesive film of Comparative Example 2, the glass transition temperature of the acrylic polymer contained in the adhesive composition exceeded 0°C (calculated value: +4.8°C). Therefore, the adhesive performance was poor, the adhesive force was excessive, the surface resistivity of the adhesive layer was high, and the durability was poor. In addition, in the acrylic polymer used in Comparative Example 2, the ratio of methyl acrylate and acrylic acid whose homopolymer glass transition temperature is a high value (over 0° C.) is increased.
In the adhesive film of Comparative Example 3, neither (H) silane coupling agent nor (G) (G) antistatic agent was blended in the adhesive composition, so the adhesive strength was excessive and the surface resistance of the adhesive layer was The rate was high and the durability was poor.
As described above, the adhesive films of Comparative Examples 1 to 3 were unable to solve the problems of the present invention.
Claims (7)
前記アクリル系ポリマーが、
（Ａ）アルキル基の炭素数Ｃ１～Ｃ１４のアルキル（メタ）アクリレートモノマーの少なくとも１種と、
（Ｂ）水酸基及び／又はカルボキシル基を含有する共重合性ビニルモノマーの少なくとも１種と、
（Ｃ）芳香族基を含有する共重合性ビニルモノマーの少なくとも１種と、
を共重合させた共重合体のアクリル系ポリマー（Ｎ－ビニル基含有ラクタム系モノマーを含有する（メタ）アクリル系ポリマーを除く。）であり、
前記アクリル系ポリマーが、０℃以下のガラス転移温度を有してなり、
前記（Ｄ）架橋剤が、３官能以上のイソシアネート化合物、及び２官能以上のエポキシ化合物からなる群から選ばれた１種以上の架橋剤であり、
前記粘着剤組成物が、可塑剤を含有せず、かつ、（Ｈ）エポキシ基、メルカプト基、酸無水物基からなる群から選ばれた少なくとも１種以上の官能基を含有するモノマータイプ、もしくはオリゴマータイプのシランカップリング剤を含有してなり、
前記帯電防止剤が、カチオンとアニオンとからなる融点２５℃以上のイオン性化合物であり、前記アニオンが、トリフルオロメタンスルホナートアニオン、ペンタフルオロエタンスルホナートアニオン、ヘプタフルオロプロパンスルホナートアニオン、ノナフルオロブタンスルホナートアニオン、からなる群から選択された１種であり、
前記カチオンが、ピリジニウム、イミダゾリウム、ホスホニウム、スルホニウム、ピロリジニウム、グアニジニウム、アンモニウム、イソウロニウム、チオウロニウム、ピペリジニウム、ピラゾリウム、メチリウム、リチウム、モルホリニウムからなる群から選択された１種であり、
前記アクリル系ポリマーの１００重量部に対して、前記帯電防止剤を０．０１～１０重量部の割合で必須成分として含有してなることを特徴とする粘着剤組成物。 An adhesive composition containing an acrylic polymer, an antistatic agent, and a crosslinking agent,
The acrylic polymer is
(A) at least one alkyl (meth)acrylate monomer whose alkyl group has a carbon number of C1 to C14;
(B) at least one copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group;
(C) at least one copolymerizable vinyl monomer containing an aromatic group;
An acrylic polymer (excluding (meth)acrylic polymer containing an N-vinyl group-containing lactam monomer), which is a copolymer of
The acrylic polymer has a glass transition temperature of 0° C. or lower,
The crosslinking agent (D) is one or more crosslinking agents selected from the group consisting of trifunctional or higher functional isocyanate compounds and bifunctional or higher functional epoxy compounds,
A monomer type in which the adhesive composition does not contain a plasticizer and (H) contains at least one functional group selected from the group consisting of an epoxy group, a mercapto group, and an acid anhydride group, or Contains an oligomer type silane coupling agent,
The antistatic agent is an ionic compound consisting of a cation and an anion and having a melting point of 25° C. or higher, and the anion is a trifluoromethanesulfonate anion, a pentafluoroethanesulfonate anion, a heptafluoropropanesulfonate anion, or nonafluorobutane. Sulfonate anion, one selected from the group consisting of,
The cation is one selected from the group consisting of pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidinium, ammonium, isouronium, thiouronium, piperidinium, pyrazolium, methylium, lithium, and morpholinium,
An adhesive composition comprising the antistatic agent as an essential component in a proportion of 0.01 to 10 parts by weight based on 100 parts by weight of the acrylic polymer.
前記水酸基を含有する共重合可能なモノマーが、８－ヒドロキシオクチル（メタ）アクリレート、６－ヒドロキシヘキシル（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－ヒドロキシエチル（メタ）アクリレート、Ｎ－ヒドロキシ（メタ）アクリルアミド、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）アクリルアミドからなる化合物群の中から選択された少なくとも１種以上であり、
前記カルボキシル基を含有する共重合可能なモノマーが、（メタ）アクリル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシプロピルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチルフタル酸、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルマレイン酸、カルボキシポリカプロラクトンモノ（メタ）アクリレート、２－（メタ）アクリロイロキシエチルテトラヒドロフタル酸からなる化合物群の中から選択された少なくとも１種以上であることを特徴とする請求項１に記載の粘着剤組成物。 The copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group (B) is at least one selected from the group consisting of a copolymerizable monomer containing a hydroxyl group and a copolymerizable monomer containing a carboxyl group. More than a species,
The copolymerizable monomer containing a hydroxyl group is 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N- At least one or more selected from the group of compounds consisting of hydroxy (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, and N-hydroxyethyl (meth)acrylamide,
The copolymerizable monomer containing a carboxyl group is (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-( meth)acryloyloxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylmaleic acid, carboxypolycaprolactone The pressure-sensitive adhesive composition according to claim 1, characterized in that it is at least one selected from the group of compounds consisting of mono(meth)acrylate and 2-(meth)acryloyloxyethyltetrahydrophthalic acid.
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