JP5617587B2 - Pressure-sensitive adhesive and laminate using the same - Google Patents
Pressure-sensitive adhesive and laminate using the same Download PDFInfo
- Publication number
- JP5617587B2 JP5617587B2 JP2010276560A JP2010276560A JP5617587B2 JP 5617587 B2 JP5617587 B2 JP 5617587B2 JP 2010276560 A JP2010276560 A JP 2010276560A JP 2010276560 A JP2010276560 A JP 2010276560A JP 5617587 B2 JP5617587 B2 JP 5617587B2
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- acrylic copolymer
- weight
- isocyanate compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims description 97
- 229920006243 acrylic copolymer Polymers 0.000 claims description 82
- -1 isocyanate compound Chemical class 0.000 claims description 74
- 239000012948 isocyanate Substances 0.000 claims description 45
- 239000010410 layer Substances 0.000 claims description 40
- 239000000178 monomer Substances 0.000 claims description 37
- 239000012788 optical film Substances 0.000 claims description 33
- 239000004973 liquid crystal related substance Substances 0.000 claims description 31
- 230000003287 optical effect Effects 0.000 claims description 22
- 210000002858 crystal cell Anatomy 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 5
- DAJFVZRDKCROQC-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propyl-tripropoxysilane Chemical compound CCCO[Si](OCCC)(OCCC)CCCOCC1CO1 DAJFVZRDKCROQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000010408 film Substances 0.000 description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 24
- 238000005187 foaming Methods 0.000 description 23
- 206010040844 Skin exfoliation Diseases 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 6
- 230000001629 suppression Effects 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- 229920002284 Cellulose triacetate Polymers 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000008602 contraction Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003606 tin compounds Chemical class 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- SFFVATKALSIZGN-UHFFFAOYSA-N hexadecan-7-ol Chemical compound CCCCCCCCCC(O)CCCCCC SFFVATKALSIZGN-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- AURYLBASVGNSON-UHFFFAOYSA-N (2,5-dioxopyrrolidin-3-ylidene)methyl prop-2-enoate Chemical compound C=CC(=O)OC=C1CC(=O)NC1=O AURYLBASVGNSON-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- XTKZBPGQKMDFMC-UHFFFAOYSA-N 1-butyl-3-methylidenepyrrolidine-2,5-dione Chemical compound CCCCN1C(=O)CC(=C)C1=O XTKZBPGQKMDFMC-UHFFFAOYSA-N 0.000 description 1
- BGKQCHAKBLWCDU-UHFFFAOYSA-N 1-cyclohexyl-3-methylidenepyrrolidine-2,5-dione Chemical compound O=C1C(=C)CC(=O)N1C1CCCCC1 BGKQCHAKBLWCDU-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- PBDXUGSZYRYWMI-UHFFFAOYSA-N 1-ethyl-3-heptylidenepyrrolidine-2,5-dione Chemical compound CCCCCCC=C1CC(=O)N(CC)C1=O PBDXUGSZYRYWMI-UHFFFAOYSA-N 0.000 description 1
- BMZZOWWYEBTMBX-UHFFFAOYSA-N 1-ethyl-3-methylidenepyrrolidine-2,5-dione Chemical compound CCN1C(=O)CC(=C)C1=O BMZZOWWYEBTMBX-UHFFFAOYSA-N 0.000 description 1
- QSWFISOPXPJUCT-UHFFFAOYSA-N 1-methyl-3-methylidenepyrrolidine-2,5-dione Chemical compound CN1C(=O)CC(=C)C1=O QSWFISOPXPJUCT-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- VUDVPVOIALASLB-UHFFFAOYSA-N 2-[(2-cyano-1-hydroxypropan-2-yl)diazenyl]-3-hydroxy-2-methylpropanenitrile Chemical compound OCC(C)(C#N)N=NC(C)(CO)C#N VUDVPVOIALASLB-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- CAYHVMBQBLYQMT-UHFFFAOYSA-N 2-decyltetradecan-1-ol Chemical compound CCCCCCCCCCCCC(CO)CCCCCCCCCC CAYHVMBQBLYQMT-UHFFFAOYSA-N 0.000 description 1
- VGZZAZYCLRYTNQ-UHFFFAOYSA-N 2-ethoxyethoxycarbonyloxy 2-ethoxyethyl carbonate Chemical compound CCOCCOC(=O)OOC(=O)OCCOCC VGZZAZYCLRYTNQ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- OFWSUXCXADDOFG-UHFFFAOYSA-N 3-[methoxy(methyl)silyl]propan-1-amine Chemical compound CO[SiH](C)CCCN OFWSUXCXADDOFG-UHFFFAOYSA-N 0.000 description 1
- RDRWAAIUFCYJPH-UHFFFAOYSA-N 3-methylidene-1-octylpyrrolidine-2,5-dione Chemical compound CCCCCCCCN1C(=O)CC(=C)C1=O RDRWAAIUFCYJPH-UHFFFAOYSA-N 0.000 description 1
- FKAWETHEYBZGSR-UHFFFAOYSA-N 3-methylidenepyrrolidine-2,5-dione Chemical group C=C1CC(=O)NC1=O FKAWETHEYBZGSR-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-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
- OUYYLJWOLMPEIY-UHFFFAOYSA-N 5-(hydroxymethyl)heptyl prop-2-enoate Chemical compound CCC(CO)CCCCOC(=O)C=C OUYYLJWOLMPEIY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- 239000000654 additive Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
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- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 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
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 150000001925 cycloalkenes Chemical class 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
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 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
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 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
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 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
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- AZQGFVRDZTUHBU-UHFFFAOYSA-N isocyanic acid;triethoxy(propyl)silane Chemical compound N=C=O.CCC[Si](OCC)(OCC)OCC AZQGFVRDZTUHBU-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229960004592 isopropanol Drugs 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 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 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([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
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical compound CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 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 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- UCEOYIRETCABER-UHFFFAOYSA-N tetradecan-5-ol Chemical compound CCCCCCCCCC(O)CCCC UCEOYIRETCABER-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-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
- 239000002023 wood Substances 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
-
- C09J7/02—
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
Landscapes
- Physics & Mathematics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Adhesive Tapes (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
Description
本発明は、液晶表示装置の液晶セル等の光学部品に、偏光板や位相差板等の光学部材を貼付するために好適に用いられる感圧式接着剤、およびそれを用いた積層体に関する。 The present invention relates to a pressure sensitive adhesive suitably used for attaching an optical member such as a polarizing plate or a retardation plate to an optical component such as a liquid crystal cell of a liquid crystal display device, and a laminate using the pressure sensitive adhesive.
液晶表示装置の液晶セル等の光学部品には、偏光板や偏光板と位相差板の積層体が貼付される。偏光板は、一般的にはポリビニルアルコール系偏光子の両面をトリアセチルセルロース系保護フィルムで挟んだ多層構造を有し、この偏光板の片面または両面のトリアセチルセルロース系保護フィルム上に、感圧式接着剤層が形成されている。偏光板は、この感圧式接着剤層を介して液晶セル等の光学部品に貼付され液晶表示装置として使用される。近年、液晶表示装置は、パーソナルコンピューターのディスプレイ、液晶テレビをはじめとする屋内用途から、カーナビゲーション用ディスプレイ等の車両搭載用途等にも広く使用され、その使用環境が非常に苛酷になりつつある。 A polarizing plate or a laminate of a polarizing plate and a retardation plate is attached to an optical component such as a liquid crystal cell of a liquid crystal display device. The polarizing plate generally has a multilayer structure in which both sides of a polyvinyl alcohol-based polarizer are sandwiched between triacetyl cellulose-based protective films, and a pressure-sensitive type is provided on the triacetyl cellulose-based protective film on one or both sides of this polarizing plate. An adhesive layer is formed. The polarizing plate is attached to an optical component such as a liquid crystal cell through this pressure-sensitive adhesive layer and used as a liquid crystal display device. 2. Description of the Related Art In recent years, liquid crystal display devices are widely used in indoor applications such as personal computer displays and liquid crystal televisions, and in vehicle-mounted applications such as car navigation displays, and the usage environment is becoming extremely severe.
液晶表示装置に使用されている偏光板は、その材料特性から寸法安定性が乏しく、熱あるいは湿熱条件下で伸縮して寸法が大きく変化するため、このような条件下では感圧式接着剤層の発泡や偏光板の液晶セルからの浮きハガレなどの問題が生じやすくなる。
これらの問題を解消する感圧式接着剤として、アルキル基の炭素数が１〜１２の（メタ）アクリル酸のアルキルエステルを主成分とするアクリル系ポリマーからなる感圧式接着剤であって、該感圧式接着剤が重量平均分子量１０万以下のポリマー成分を１５重量部以下含有し、かつ重量平均分子量１００万以上のポリマー成分を１０重量部以上含有するアクリル系ポリマーからなる感圧式接着剤が知られている（特許文献１参照）。
A polarizing plate used in a liquid crystal display device has poor dimensional stability due to its material properties, and expands and contracts under heat or wet heat conditions, so that the dimensions change greatly. Under such conditions, the pressure-sensitive adhesive layer Problems such as foaming and floating peeling from the liquid crystal cell of the polarizing plate are likely to occur.
As a pressure-sensitive adhesive that solves these problems, a pressure-sensitive adhesive comprising an acrylic polymer mainly composed of an alkyl ester of (meth) acrylic acid having 1 to 12 carbon atoms in the alkyl group, Pressure-sensitive adhesives comprising an acrylic polymer containing 15 parts by weight or less of a polymer component having a weight average molecular weight of 100,000 or less and 10 parts by weight or more of a polymer component having a weight average molecular weight of 1 million or more are known. (See Patent Document 1).
前記感圧式接着剤を用いることにより、感圧式接着剤層の発泡や偏光板の液晶セルからの浮きハガレは抑制できるが、偏光板の寸法変化による応力を吸収・緩和することができず、偏光板の周縁部に応力が集中するため、液晶表示装置の周縁部と中央部の明るさが異なり、液晶表示装置表面に光漏れが発生する問題があった。
この液晶表示装置表面の光漏れを解消する感圧式接着剤として、重量平均分子量が１００万以上である高分子量（メタ）アクリル系共重合体１００重量部と、重量平均分子量が３万以下の低分子量（メタ）アクリル系共重合体２０〜２００重量部と、多官能性化合物０．００５〜５重量部からなる偏光板用感圧式接着剤が知られている（特許文献２参照）。
By using the pressure-sensitive adhesive, foaming of the pressure-sensitive adhesive layer and floating peeling from the liquid crystal cell of the polarizing plate can be suppressed, but stress due to a dimensional change of the polarizing plate cannot be absorbed / relaxed. Since stress concentrates on the peripheral portion of the plate, the brightness of the peripheral portion and the central portion of the liquid crystal display device are different, and there is a problem that light leakage occurs on the surface of the liquid crystal display device.
As a pressure-sensitive adhesive that eliminates light leakage on the surface of the liquid crystal display device, 100 parts by weight of a high molecular weight (meth) acrylic copolymer having a weight average molecular weight of 1,000,000 or more and a low weight of 30,000 or less are used. A pressure sensitive adhesive for polarizing plates comprising 20 to 200 parts by weight of a molecular weight (meth) acrylic copolymer and 0.005 to 5 parts by weight of a polyfunctional compound is known (see Patent Document 2).
また、特許文献３には、該文献に開示されている偏光フィルム用感圧式接着剤は、光漏れが発生しにくい性能と低分子量アクリル系ポリマーがブリードし難い性能を併せ持つと記載されているが、より過酷な環境下での液晶表示装置の使用において、性能バランスを発揮させることが難しい。
そこで、本発明の目的は、熱あるいは湿熱条件下でも感圧式接着剤層の発泡や偏光板のハガレ等が発生せず、偏光板の伸縮等により生じる応力集中を緩和して液晶表示装置に光漏れ現象を発生させない感圧式接着剤を提供することにある。
Patent Document 3 describes that the pressure-sensitive adhesive for polarizing film disclosed in the document has both the performance of preventing light leakage and the performance of a low molecular weight acrylic polymer difficult to bleed. When using a liquid crystal display device in a harsher environment, it is difficult to achieve a performance balance.
Accordingly, an object of the present invention is to prevent pressure concentration adhesive layer from foaming or polarizing plate peeling even under heat or wet heat conditions, and to relieve stress concentration caused by expansion and contraction of the polarizing plate. An object of the present invention is to provide a pressure-sensitive adhesive that does not cause a leakage phenomenon.
本発明は、加熱あるいは加湿加熱条件下でも感圧式接着剤層の発泡や偏光板からのハガレ等が発生せず、感圧式接着剤層が偏光板の伸縮等により生じる応力集中を緩和して液晶表示装置に光漏れ現象を発生しない光学フィルム用感圧式接着剤の提供を目的とする。 The present invention does not cause foaming of the pressure-sensitive adhesive layer or peeling from the polarizing plate even under heating or humidified heating conditions, and the pressure-sensitive adhesive layer relaxes the stress concentration caused by expansion and contraction of the polarizing plate, etc. An object of the present invention is to provide a pressure-sensitive adhesive for an optical film that does not cause a light leakage phenomenon in a display device.
本発明者らは、上記課題を解決するため鋭意検討した結果、以下に示す感圧式接着剤により上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above object can be achieved by the pressure-sensitive adhesive shown below, and have completed the present invention.
即ち、第１の発明は、アクリル系共重合体（Ａ）と、イソシアネート化合物（Ｂ）とを含む光学フィルム用感圧式接着剤であって、
上記アクリル系共重合体（Ａ）が、水酸基を有する単量体（a−１）０.０１〜０．５重量部と、その他の単量体（ａ−２）を共重合してなり、
上記アクリル系共重合体（Ａ）が有する水酸基１モルに対して、イソシアネート化合物（Ｂ）のイソシアネート基が０．５モル以上３００モル以下である光学フィルム用感圧式接着剤に関する。
That is, the first invention is a pressure sensitive adhesive for an optical film comprising an acrylic copolymer (A) and an isocyanate compound (B),
The acrylic copolymer (A) is obtained by copolymerizing a monomer (a-1) having a hydroxyl group of 0.01 to 0.5 parts by weight and another monomer (a-2),
It is related with the pressure sensitive adhesive for optical films whose isocyanate group (B) is 0.5 mol or more and 300 mol or less with respect to 1 mol of hydroxyl groups which the said acrylic copolymer (A) has.
又、第２の発明は、イソシアネート化合物（Ｂ）が、分子内に２個のイソシアネート基を含有するイソシアネート化合物である第１の発明の光学フィルム用感圧式接着剤に関する。 The second invention relates to the pressure-sensitive adhesive for optical films of the first invention, wherein the isocyanate compound (B) is an isocyanate compound containing two isocyanate groups in the molecule.
又、第３の発明は、イソシアネート化合物（Ｂ）が、３個以上のイソシアネート基を有するイソシアネート化合物に対して、アルコールを反応させてなるものである第２の発明の光学フィルム用感圧式接着剤に関する。 The third invention is the pressure sensitive adhesive for optical films of the second invention, wherein the isocyanate compound (B) is obtained by reacting an alcohol with an isocyanate compound having three or more isocyanate groups. About.
又、第４の発明は、アクリル系共重合体（Ａ）が、重量平均分子量１００万以上２５０万以下のアクリル系共重合体（Ａ−１）と、重量平均分子量１万以上１０万以下のアクリル系共重合体（Ａ−２）を含む第３の発明の光学フィルム用感圧式接着剤に関する。 In addition, the fourth invention is an acrylic copolymer (A) having an acrylic copolymer (A-1) having a weight average molecular weight of 1,000,000 to 2,500,000 and a weight average molecular weight of 10,000 to 100,000. It is related with the pressure sensitive adhesive for optical films of 3rd invention containing an acryl-type copolymer (A-2).
又、第５の発明は、アクリル系共重合体（Ａ−１）とアクリル系共重合体（Ａ−２）の重量比が９０：１０〜７０：３０であることを特徴とする上記いずれかの発明の光学フィルム用感圧式接着剤に関する。 In addition, the fifth invention is any of the above, wherein the weight ratio of the acrylic copolymer (A-1) to the acrylic copolymer (A-2) is 90:10 to 70:30. It relates to the pressure sensitive adhesive for optical films of the invention.
又、第６の発明は、さらに３−グリシドキシプロピルトリエトキシシランまたは３−グリシドキシプロピルトリプロポキシシランを含有する上記いずれかの発明の光学フィルム用感圧式接着剤に関する。 Moreover, 6th invention is related with the pressure sensitive adhesive for optical films of any one of the said invention which further contains 3-glycidoxypropyl triethoxysilane or 3-glycidoxypropyl tripropoxysilane.
又、第７の発明は、基材と、上記いずれかの発明の光学フィルム用感圧式接着剤から形成されてなる感圧式接着剤層とを含む光学フィルムに関する。 Moreover, 7th invention is related with the optical film containing a base material and the pressure sensitive adhesive layer formed from the pressure sensitive adhesive for optical films of one of the said inventions.
又、第８の発明は光学部材と、上記いずれかの発明の光学フィルム用感圧式接着剤から形成されてなる感圧式接着剤層とを含む積層体に関する。 The eighth invention relates to a laminate comprising an optical member and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive for an optical film of any one of the above inventions.
又、第９の発明は光学部材が、偏光板である上記発明の積層体に関する。 The ninth invention relates to the laminate of the invention, wherein the optical member is a polarizing plate.
又、第１０の発明はガラス層と、上記いずれかの発明の光学フィルム用感圧式接着剤から形成されてなる感圧式接着剤層と、光学部材とを順次積層されてなる液晶セル用部材に関する。 The tenth invention relates to a liquid crystal cell member comprising a glass layer, a pressure sensitive adhesive layer formed from the pressure sensitive adhesive for an optical film of any one of the above inventions, and an optical member. .
又、第１１の発明は光学部材が、偏光板である上記発明の液晶セル用部材に関する。 The eleventh invention relates to the liquid crystal cell member according to the invention, wherein the optical member is a polarizing plate.
本発明により、加熱あるいは加湿加熱条件下でも感圧式接着剤層の発泡や偏光板のハガレ等が発生せず、偏光板の伸縮等により生じる応力集中を緩和して液晶表示装置に光漏れ現象を発生させない感圧式接着剤を提供することができた。 The present invention does not cause foaming of the pressure-sensitive adhesive layer or peeling of the polarizing plate even under heating or humidified heating conditions, and relaxes the stress concentration caused by expansion and contraction of the polarizing plate, thereby causing a light leakage phenomenon in the liquid crystal display device. A pressure-sensitive adhesive that does not occur can be provided.
本発明の光学フィルム用感圧式接着剤は、少量の水酸基を有するアクリル系共重合体（Ａ）に対して、当該水酸基のモル数の等モル以上、好ましくは大過剰の、イソシアネート基を用いることが重要である。この光学フィルム用感圧式接着剤から形成した感圧式接着剤層を含む光学フィルムは、例えば、偏光板へ貼り付けた（積層体という）後に高温高湿環境下に置かれた場合でも、感圧式接着剤層に気泡が生じず、さらに偏光板から光学フィルムが剥がれず、さらに当該雰囲気における偏光板の伸縮等により生じる応力集中を感圧式接着剤層が緩和して当該積層体を液晶表示装置に用いたときにも光漏れ現象の発生を抑制する優れた特徴を有する。 The pressure-sensitive adhesive for optical film of the present invention uses an isocyanate group equal to or larger than the number of moles of the hydroxyl group, preferably a large excess, relative to the acrylic copolymer (A) having a small amount of hydroxyl group. is important. An optical film including a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive for optical films is, for example, pressure-sensitive even when placed in a high-temperature and high-humidity environment after being attached to a polarizing plate (referred to as a laminate). Bubbles are not generated in the adhesive layer, the optical film is not peeled off from the polarizing plate, and the pressure sensitive adhesive layer relaxes the stress concentration caused by the expansion and contraction of the polarizing plate in the atmosphere, and the laminate is applied to the liquid crystal display device. Even when used, it has an excellent feature of suppressing the occurrence of light leakage.
本発明においてイソシアネート化合物（Ｂ）は、特に限定はされないがトリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添ジフェニルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート、ナフタレンジイソシアネートなどのジイソシアネート。
トリフェニルメタントリイソシアネート、ポリメチレンポリフェニルイソシアネートなどのポリイソシアネート化合物。
ジイソシネートと、トリメチロールプロパン、ペンタエリスリトールまたはジペンタエリスリトール等のポリオール化合物とのアダクト体、ジイソシネートのビュレット体やイソシアヌレート体等の３官能〜６官能のポリイソシアネート化合物が挙げられる。これらイソシアネート化合物のなかでも、取り扱いの容易さと物性コントロールの観点から３官能のイソシアネート化合物が好ましい。
In the present invention, the isocyanate compound (B) is not particularly limited, but tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, Diisocyanates such as naphthalene diisocyanate.
Polyisocyanate compounds such as triphenylmethane triisocyanate and polymethylene polyphenyl isocyanate.
Examples thereof include adducts of diisocyanate and polyol compounds such as trimethylolpropane, pentaerythritol or dipentaerythritol, and trifunctional to hexafunctional polyisocyanate compounds such as diisocyanate burette and isocyanurate. Among these isocyanate compounds, trifunctional isocyanate compounds are preferable from the viewpoint of easy handling and physical property control.
また、本発明においてイソシアネート化合物（Ｂ）は、一般的な３官能のイソシアネート化合物を用いるよりも、２官能のイソシアネート化合物を用いることが好ましい。２官能のイソシアネート化合物を用いることで感圧式接着剤層の光漏れ防止性能が維持される一方、前記高温高湿環境下における感圧式接着剤の光漏れ現象を防止しつつ、光学フィルムの浮きをさらに抑制できる。具体的には、例えばヘキサメチレンジイソシアネートのアロファネート体（日本ポリウレタン製：コロネート２７７０）などが挙げられる。なお、本発明において２官能のイソシアネート化合物には、例えば３官能であるトリレンジイソシアネートのトリメチロールプロパンのアダクト体の原料として用いる２，４−トリレンジイソシアネートや２，６−トリレンジイソシアネートのようジイソシアネートは含まない。 In the present invention, the isocyanate compound (B) is preferably a bifunctional isocyanate compound rather than a general trifunctional isocyanate compound. While the light leakage prevention performance of the pressure sensitive adhesive layer is maintained by using a bifunctional isocyanate compound, the optical film is lifted while preventing the light leakage phenomenon of the pressure sensitive adhesive in the high temperature and high humidity environment. Further suppression is possible. Specific examples include allophanate of hexamethylene diisocyanate (manufactured by Nippon Polyurethane: Coronate 2770). In the present invention, the difunctional isocyanate compound includes, for example, diisocyanates such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate used as a raw material for adducts of trimethylol propane, which is trifunctional tolylene diisocyanate. Is not included.
また、本発明においてイソシアネート化合物（Ｂ）は、３個以上のイソシアネート基を有するイソシアネート化合物に対して、アルコールを反応させた化合物であることが好ましい。例えば、前記の３官能であるトリレンジイソシアネートのトリメチロールプロパンのアダクト体にエタノールを反応させて、２官能としたイソシアネート化合物等を挙げることができる。この２官能のイソシアネート化合物を用いることで、前記高温高湿環境下における感圧式接着剤層の前記特徴をよりさらに向上させることができる。 In the present invention, the isocyanate compound (B) is preferably a compound obtained by reacting an alcohol with an isocyanate compound having three or more isocyanate groups. For example, the trifunctional diisocyanate trimethylolpropane adduct is reacted with ethanol to give a bifunctional isocyanate compound. By using this bifunctional isocyanate compound, the characteristics of the pressure-sensitive adhesive layer in the high-temperature and high-humidity environment can be further improved.
前記３個以上のイソシアネート基を有するイソシアネート化合物としては上記例示のジイソシアネートの付加体の他、ジイソシアネートのペンタエリスリトール付加体（４官能）、ジペンタエリスリトール付加体などが挙げられる。 Examples of the isocyanate compound having three or more isocyanate groups include diisocyanate pentaerythritol adducts (tetrafunctional) and dipentaerythritol adducts in addition to the diisocyanate adducts exemplified above.
本発明においてアルコールは、炭素数１以上３０以下のアルキル鎖を有する単官能アルコールまたは多官能アルコールを挙げる。またアルコールの構造は、脂肪族・芳香族アルコールの他、ポリエーテル骨格、ポリエステル骨格、ポリカーボネート骨格を有するアルコールが挙げられる。
アルコールとしては、例えばメタノール、エタノール、プロパノール、ブタノール、ヘキサノール、ドデシルアルコール、ミスチルアルコール、セチルアルコール、オレイルアルコール、イソプロピルアルコール、イソオクチルアルコール、イソステアリルアルコール、ブチルデカノール、ヘキシルデカノール、デシルテトラデカノール、オクチルドデシルアルコール、エチレングリコール、プロピレングリコール、ヘキサメチレングリコール、トリメチロールプロパン、ペンタエリスリトールなどが挙げられる。
In the present invention, examples of the alcohol include a monofunctional alcohol or a polyfunctional alcohol having an alkyl chain having 1 to 30 carbon atoms. Examples of the alcohol structure include aliphatic / aromatic alcohols, as well as alcohols having a polyether skeleton, a polyester skeleton, and a polycarbonate skeleton.
Examples of the alcohol include methanol, ethanol, propanol, butanol, hexanol, dodecyl alcohol, misty alcohol, cetyl alcohol, oleyl alcohol, isopropyl alcohol, isooctyl alcohol, isostearyl alcohol, butyl decanol, hexyl decanol, decyl tetradecanol, octyl Examples include dodecyl alcohol, ethylene glycol, propylene glycol, hexamethylene glycol, trimethylolpropane, and pentaerythritol.
また、アクリル系共重合体（Ａ）との相溶性の観点から炭素数が１２以上３０以下の脂肪族アルコールが好ましい。さらにアルコールの脂肪族鎖が分岐構造を有する場合にアクリル系共重合体（Ａ）との相溶性が特に好ましい。その中でもヘキシルデカノール、イソオクチルアルコール、オクチルドデシルアルコールが好適に使用できる。これにより２官能のイソシアネート化合物とアクリル系共重合体（Ａ）の相溶性がより向上することで、高温条件下での感圧式接着剤の発泡をより抑制できる。 In addition, an aliphatic alcohol having 12 to 30 carbon atoms is preferable from the viewpoint of compatibility with the acrylic copolymer (A). Further, when the aliphatic chain of the alcohol has a branched structure, the compatibility with the acrylic copolymer (A) is particularly preferable. Among them, hexyl decanol, isooctyl alcohol, and octyl dodecyl alcohol can be preferably used. Thereby, the compatibility of the bifunctional isocyanate compound and the acrylic copolymer (A) is further improved, whereby foaming of the pressure-sensitive adhesive under high temperature conditions can be further suppressed.
３個以上のイソシアネート基を有するイソシアネート化合物のイソシアネート基とアルコールの水酸基の反応は、窒素雰囲気下４０〜８０℃で２〜１２時間でおこなうことが好ましい。また、サンプリングした反応溶液を滴定することでＮＣＯ価を算出し終点を求めることができる。 The reaction between the isocyanate group of the isocyanate compound having three or more isocyanate groups and the hydroxyl group of the alcohol is preferably performed at 40 to 80 ° C. for 2 to 12 hours in a nitrogen atmosphere. Further, the end point can be determined by calculating the NCO value by titrating the sampled reaction solution.
本発明においてイソシアネート化合物（Ｂ）は、架橋反応の容易さ、光漏れ現象の抑制、さらに高温条件下での感圧式接着剤層に気泡を生じさせない観点からキシリレンジイソシアネートのトリメチロールプロパンアダクト体にオクチルドデシルアルコールを反応させた化合物が最も好ましい。 In the present invention, the isocyanate compound (B) is a trimethylolpropane adduct of xylylene diisocyanate from the viewpoint of ease of crosslinking reaction, suppression of light leakage phenomenon, and generation of bubbles in the pressure-sensitive adhesive layer under high temperature conditions. Most preferred is a compound obtained by reacting octyldodecyl alcohol.
また本発明のイソシアネート化合物（Ｂ）は単独であるいは複数組み合わせて使用することができる。また本発明の目的を逸脱しない範囲であればエポキシ系化合物、アミン系化合物、金属キレート系化合物、アジリジン系化合物などの硬化剤を併用しても良い。 The isocyanate compound (B) of the present invention can be used alone or in combination. Further, a curing agent such as an epoxy compound, an amine compound, a metal chelate compound, or an aziridine compound may be used in combination as long as it does not depart from the object of the present invention.
本発明においてイソシアネート化合物（Ｂ）は、アクリル系共重合体（Ａ）に含まれる単量体（a）の水酸基１モルに対してイソシアネート化合物（Ｂ）のイソシアネート基が０．５モル以上３００モル以下になるように使用するのが好ましい。また０．７モル〜７０モルがより好ましく、０．８モル〜２０モルがさらに好ましい。使用量が０．５モルに満たない場合は感圧式接着剤層の凝集力が不足し高温条件下での発泡の抑制ができなくなる場合がある。一方、３００モル以上添加しても物性が向上しないのみならず、感圧式接着剤層の透明性が低下する。 In the present invention, the isocyanate compound (B) is used in an amount of 0.5 mol or more and 300 mol of the isocyanate group of the isocyanate compound (B) with respect to 1 mol of the hydroxyl group of the monomer (a) contained in the acrylic copolymer (A). It is preferable to use it as follows. Moreover, 0.7 mol-70 mol are more preferable, and 0.8 mol-20 mol are still more preferable. When the amount used is less than 0.5 mol, the cohesive force of the pressure-sensitive adhesive layer may be insufficient, and foaming may not be suppressed under high temperature conditions. On the other hand, adding 300 mol or more does not improve the physical properties, but also lowers the transparency of the pressure-sensitive adhesive layer.
本発明においてアクリル系共重合体（Ａ）は、全単量体１００重量中、少なくとも水酸基を有する単量体（ａ−１）を０．０１〜０．５重量部用いて共重合した共重合体であることが重要である。また０．０５〜０．３重量部用いることがより好ましい。用いる量が０．０１重量部に満たない場合は、高温高湿環境下において耐熱性が不足する。一方、０．５重量部を越えると高温高湿環境下において剥がれの発生や光漏れが発生しやすくなる。 In the present invention, the acrylic copolymer (A) is a copolymer obtained by copolymerizing 0.01 to 0.5 parts by weight of the monomer (a-1) having at least a hydroxyl group in 100 weights of all monomers. It is important that they are coalesced. Moreover, it is more preferable to use 0.05-0.3 weight part. When the amount used is less than 0.01 parts by weight, the heat resistance is insufficient in a high temperature and high humidity environment. On the other hand, if it exceeds 0.5 parts by weight, peeling and light leakage are likely to occur in a high temperature and high humidity environment.
水酸基を有する単量体（ａ−１）は、例えば２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、６−ヒドロキシヘキシル（メタ）アクリレート、８−ヒドロキシオクチル（メタ）アクリレート、１０−ヒドロキシデシル（メタ）アクリレート、１２−ヒドロキシラウリル（メタ）アクリレート、（４−ヒドロキシメチルヘキシル）−メチルアクリレート、クロロ−２−ヒドロキシプロピル（メタ）アクリレート、ジエチレングリコールモノ（メタ）アクリレート、カプロラクトン変性（メタ）アクリレート類、ポリエチレングリコール（メタ）アクリレート類、ポリプロピレングリコール（メタ）アクリレート類等が挙げられる。 Examples of the monomer (a-1) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylhexyl) -methyl acrylate, chloro-2-hydroxypropyl (meth) acrylate, diethylene glycol Examples include mono (meth) acrylate, caprolactone-modified (meth) acrylates, polyethylene glycol (meth) acrylates, and polypropylene glycol (meth) acrylates.
本発明において水酸基を有する単量体（ａ−１）以外の使用できる単量体〔以下単量体（ａ−２）ともいう。〕は、官能基含有単量体、（メタ）アクリル酸エステル系単量体、芳香族ビニルモノマー等を挙げることができる。 In the present invention, usable monomers other than the monomer (a-1) having a hydroxyl group [hereinafter also referred to as a monomer (a-2). ] May include functional group-containing monomers, (meth) acrylic acid ester monomers, aromatic vinyl monomers, and the like.
（メタ）アクリル酸エステル系単量体しては、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、ｎ−ブチル（メタ）アクリレート、ｉｓｏ−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、ｎ−オクチル（メタ）アクリレート、ｉｓｏ−オクチル（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、ｉｓｏ−ノニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等が挙げられる。 (Meth) acrylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, iso-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl ( Examples include meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and phenoxyethyl (meth) acrylate.
前記官能基含有単量体の官能基としては、カルボキシル基、アミノ基、アミド基、ニトリル基、マレイミド基、イタコンイミド基、スクシンイミド基およびエポキシ基等が挙げれられる。 Examples of the functional group of the functional group-containing monomer include a carboxyl group, an amino group, an amide group, a nitrile group, a maleimide group, an itaconimide group, a succinimide group, and an epoxy group.
カルボキシル基を有する単量体の具体例としては、（メタ）アクリル酸、β−カルボキシエチルアクリレート、イタコン酸、クロトン酸、フマル酸、無水フマル酸、マレイン酸、無水マレイン酸、マレイン酸ブチル等があげられる。 Specific examples of the monomer having a carboxyl group include (meth) acrylic acid, β-carboxyethyl acrylate, itaconic acid, crotonic acid, fumaric acid, fumaric anhydride, maleic acid, maleic anhydride, butyl maleate and the like. can give.
アミノ基を有する単量体の具体例としては、アミノメチル（メタ）アクリレート、ジメチルアミノメチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート等が挙げられる。 Specific examples of the monomer having an amino group include aminomethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and the like.
アミド基を有する単量体の具体例としては、（メタ）アクリルアミド、ダイアセトン（メタ）アクリルアミド等が挙げられる。 Specific examples of the monomer having an amide group include (meth) acrylamide, diacetone (meth) acrylamide and the like.
ニトリル基を有する単量体の具体例としては、（メタ）アクリロニトリルが挙げられる。 Specific examples of the monomer having a nitrile group include (meth) acrylonitrile.
マレイミド基を有する単量体の具体例としては、Ｎ−シクロヘキシルマレイミド、Ｎ−イソプロピルマレイミド、Ｎ−ラウリルマレイミド、Ｎ−フェニルマレイミド等が挙げられる。 Specific examples of the monomer having a maleimide group include N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide and the like.
イタコンイミド基を有する単量体の具体例としては、Ｎ−メチルイタコンイミド、Ｎ−エチルイタコンイミド、Ｎ−ブチルイタコンイミド、Ｎ−オクチルイタコンイミド、Ｎ−２−エチルヘキシルイタコンイミド、Ｎ−シクロヘキシルイタコンイミド、Ｎ−ラウリルイタコンイミド等が挙げられる。 Specific examples of the monomer having an itacimide group include N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, and N-cyclohexylitaconimide. N-lauryl itaconimide and the like.
スクシンイミド基を有する単量体の具体例としては、Ｎ−（メタ）アクリロイルオキシメチレンスクシンイミド、Ｎ−（メタ）アクリロイル−６−オキシヘキサメチレンスクシンイミド、Ｎ−（メタ）アクリロイル−８−オキシオクタメチレンスクシンイミド等が挙げられる。 Specific examples of the monomer having a succinimide group include N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide. Etc.
エポキシ基を有する単量体の具体例としては、グリシジル（メタ）アクリレート等が挙げられる。 Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate.
ビニルモノマーの具体例としては酢酸ビニル等が挙げられる。 Specific examples of the vinyl monomer include vinyl acetate.
芳香族ビニルモノマーの具体例としてはスチレン、メチルスチレン、ビニルトルエンなどが挙げられる。これらの単量体は、単独であるいは複数組み合わせて使用することができる。 Specific examples of the aromatic vinyl monomer include styrene, methylstyrene, vinyltoluene and the like. These monomers can be used alone or in combination.
単量体（ａ−２）のうちカルボキシル基を有する単量体は、単量体（ａ−１）の水酸基とイソシアネート化合物（Ｂ）の反応を阻害し、高温条件下での感圧式接着剤層の発泡抑制が困難になる場合があり、最小限の使用に抑えるか使用しないのが好ましい。 Among the monomers (a-2), the monomer having a carboxyl group inhibits the reaction between the hydroxyl group of the monomer (a-1) and the isocyanate compound (B) and is a pressure-sensitive adhesive under high temperature conditions. It may be difficult to suppress foaming of the layer, and it is preferable to minimize or not use the layer.
本発明においてアクリル系共重合体（Ａ）は、重量平均分子量が６０〜２２０万であることが好ましい。また、本発明においてアクリル系共重合体（Ａ）は、重量平均分子量１００万以上のアクリル系共重合体（Ａ−１）と、重量平均分子量１万以上１０万以下のアクリル系共重合体（Ａ−２）を含むことも好ましい。アクリル系共重合体（Ａ）が、２つの共重合体を含むことで加熱加湿環境下での発泡の抑制と光漏れ現象の発生をより抑制することができる。 In the present invention, the acrylic copolymer (A) preferably has a weight average molecular weight of 60 to 2,200,000. In the present invention, the acrylic copolymer (A) includes an acrylic copolymer (A-1) having a weight average molecular weight of 1,000,000 or more and an acrylic copolymer having a weight average molecular weight of 10,000 to 100,000 ( A-2) is also preferably included. When the acrylic copolymer (A) contains two copolymers, it is possible to further suppress the occurrence of foaming and the occurrence of light leakage in a heated and humidified environment.
本発明においてアクリル系共重合体（Ａ−１）は、重量平均分子量が１００万以上２５０万以下であることが好ましく、１２０万以上２００万以下であることが好ましい。重量平均分子量が１００万に満たない場合は、感圧式接着剤層の発泡や光学フィルムの浮きハガレを抑制しにくい場合がある。一方、２５０万を越えると感圧式接着剤の粘度が高く、例えば基材上へ感圧式接着剤を塗工する場合の作業性が低下する恐れがある。 In the present invention, the acrylic copolymer (A-1) preferably has a weight average molecular weight of 1,000,000 to 2,500,000, preferably 1,200,000 to 2,000,000. When the weight average molecular weight is less than 1,000,000, it may be difficult to suppress foaming of the pressure-sensitive adhesive layer and floating peeling of the optical film. On the other hand, when it exceeds 2.5 million, the viscosity of the pressure-sensitive adhesive is high, and for example, workability in the case of applying the pressure-sensitive adhesive onto the substrate may be lowered.
本発明においてアクリル系共重合体（Ａ−１）は、重量平均分子量が１万以上１０万以下であることが好ましく、２万以上５万以下がより好ましい。重量平均分子量が１万に満たない場合は、感圧式接着剤層の発泡や光学フィルムの浮きやハガレを抑制しにくい場合がある。一方、１０万を越えると光漏れ現象の発生をさらに抑制することが難しくなる。なお本発明において重量平均分子量とは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によって算出されたポリスチレン換算による重量平均分子量を指す。 In the present invention, the acrylic copolymer (A-1) preferably has a weight average molecular weight of 10,000 to 100,000, more preferably 20,000 to 50,000. When the weight average molecular weight is less than 10,000, it may be difficult to suppress foaming of the pressure-sensitive adhesive layer, floating of the optical film, and peeling. On the other hand, if it exceeds 100,000, it becomes difficult to further suppress the occurrence of the light leakage phenomenon. In the present invention, the weight average molecular weight refers to a weight average molecular weight in terms of polystyrene calculated by gel permeation chromatography (GPC) measurement.
本発明においてアクリル系共重合体（Ａ−１）の合成に単量体（ａ）を使用し、アクリル系共重合体（Ａ−２）の合成には単量体（ａ）を使用しないことが好ましい。アクリル系共重合体（Ａ−２）の合成に単量体（ａ）を使用すると光漏れ現象の発生の抑制が向上しない恐れがあり、加熱加湿環境下での発泡の抑制をしにくい場合がある。 In the present invention, the monomer (a) is used for the synthesis of the acrylic copolymer (A-1), and the monomer (a) is not used for the synthesis of the acrylic copolymer (A-2). Is preferred. If the monomer (a) is used for the synthesis of the acrylic copolymer (A-2), the suppression of the occurrence of the light leakage phenomenon may not be improved, and it may be difficult to suppress the foaming in a heated and humidified environment. is there.
本発明においてアクリル系共重合体（Ａ−１）とアクリル系共重合体（Ａ−２）は重量比で、（Ａ−１）：（Ａ−２）＝９０：１０〜７０：３０であることが好ましい。前記重量比以外のときは、光漏れ現象の発生の抑制が向上しない恐れがあり、加熱加湿環境下での発泡の抑制をしにくい場合がある。 In the present invention, the acrylic copolymer (A-1) and the acrylic copolymer (A-2) are in a weight ratio of (A-1) :( A-2) = 90: 10 to 70:30. It is preferable. When the weight ratio is other than the above, the suppression of the occurrence of the light leakage phenomenon may not be improved, and it may be difficult to suppress the foaming in a heated and humidified environment.
なお本発明においてアクリル系共重合体（Ａ−１）とアクリル系共重合体（Ａ−２）の重量比は、以下の方法で求められる。すなわち、まず、アクリル系重合体（Ａ−２）の重合を開始する前にサンプリングした溶液の一定量を重量既知の容器に入れて精秤し、この精秤した溶液を加熱乾燥して、不揮発分としてアクリル系共重合体（Ａ−１）のみが残った容器を精秤し、一定量の溶液に含まれるアクリル系共重合体（Ａ−１）の重量を算出する。次にアクリル系共重合体（Ａ−２）の重合完了後に、アクリル系共重合体（Ａ）とアクリル系共重合体（Ａ−２）が含まれる溶液をサンプリングし、アクリル系共重合体（Ａ−１）の重量を算出したときと同様の方法で、一定量の溶液に含まれるアクリル系共重合体（Ａ−１）とアクリル系共重合体（Ａ−２）の重量を算出する。そして一定量の溶液に含まれるアクリル系共重合体（Ａ−１）およびアクリル系共重合体（Ａ−１）とアクリル系共重合体（Ａ−２）の混合物の重量を、同量の溶液に含まれるアクリル系共重合体（Ａ−１）およびアクリル系共重合体（Ａ−２）とアクリル系共重合体（Ａ−２）の混合物の重量に換算し、アクリル系共重合体（Ａ−１）とアクリル系共重合体（Ａ−２）の混合物の重量からアクリル系共重合体（Ａ−１）を差し引くことにより、アクリル系共重合体（Ａ−２）の重量を算出する。 In the present invention, the weight ratio between the acrylic copolymer (A-1) and the acrylic copolymer (A-2) is determined by the following method. That is, first, a predetermined amount of the solution sampled before starting the polymerization of the acrylic polymer (A-2) is put in a container of known weight and weighed precisely. The container in which only the acrylic copolymer (A-1) remains as a minute is precisely weighed, and the weight of the acrylic copolymer (A-1) contained in a certain amount of solution is calculated. Next, after the polymerization of the acrylic copolymer (A-2) is completed, a solution containing the acrylic copolymer (A) and the acrylic copolymer (A-2) is sampled, and the acrylic copolymer ( The weight of the acrylic copolymer (A-1) and acrylic copolymer (A-2) contained in a fixed amount of solution is calculated in the same manner as when the weight of A-1) is calculated. The weight of the acrylic copolymer (A-1) and the mixture of the acrylic copolymer (A-1) and the acrylic copolymer (A-2) contained in a certain amount of solution is equal to the amount of the solution. In terms of the weight of the acrylic copolymer (A-1) and the mixture of the acrylic copolymer (A-2) and the acrylic copolymer (A-2) contained in the acrylic copolymer (A -1) By subtracting the acrylic copolymer (A-1) from the weight of the mixture of the acrylic copolymer (A-2), the weight of the acrylic copolymer (A-2) is calculated.
本発明においてアクリル系共重合体（Ａ）をアクリル系共重合体（Ａ−１）と（Ａ−２）に含むように重合する方法として、例えば、始めにアクリル系共重合体（Ａ−１）の重合を開始し、その重合転化率が９０〜７０％になったところで、アクリル系共重合体（Ａ−２）の重合に用いる単量体を投入し、重合を継続することでアクリル系共重合体（Ａ）得る方法が挙げられる。前記重合法を採ることで、前記（Ａ−１）：（Ａ−２）＝９０：１０〜７０：３０という重量比のアクリル系共重合体（Ａ）を容易に得ることができる。 In the present invention, as a method for polymerizing the acrylic copolymer (A) so as to be included in the acrylic copolymers (A-1) and (A-2), for example, first, the acrylic copolymer (A-1) is used. ) Polymerization was started, and when the polymerization conversion reached 90 to 70%, the monomers used for the polymerization of the acrylic copolymer (A-2) were added, and the polymerization was continued to continue the acrylic polymerization. The method of obtaining a copolymer (A) is mentioned. By adopting the polymerization method, the acrylic copolymer (A) having a weight ratio of (A-1) :( A-2) = 90: 10 to 70:30 can be easily obtained.
また、本発明においてアクリル系共重合体（Ａ）は、重量平均分子量１００万以上のアクリル系共重合体（Ａ−１）と、重量平均分子量１万以上１０万以下のアクリル系共重合体（Ａ−２）を含む場合、下記の工程（１）〜（２）を経ることにより製造することができる。
反応性官能基およびエチレン性不飽和二重結合を有する単量体（ａ−１）および（ａ−２）を転化率７０〜９０％でラジカル共重合してアクリル系共重合体（Ａ−１）を重合する工程（１）。
上記共重合体（Ａ−１）の溶液に、重合開始剤や溶剤等を添加し、共重合体（Ａ−１）の重合時に残留する単量体を重合して共重合体（Ａ−２）を重合する工程（２）。
In the present invention, the acrylic copolymer (A) includes an acrylic copolymer (A-1) having a weight average molecular weight of 1,000,000 or more and an acrylic copolymer having a weight average molecular weight of 10,000 to 100,000 ( When A-2) is included, it can be manufactured through the following steps (1) to (2).
Monomers (a-1) and (a-2) having a reactive functional group and an ethylenically unsaturated double bond are radically copolymerized at a conversion of 70 to 90% to obtain an acrylic copolymer (A-1 Step (1) for polymerizing).
A polymerization initiator, a solvent, or the like is added to the solution of the copolymer (A-1), and a monomer remaining during the polymerization of the copolymer (A-1) is polymerized to copolymer (A-2). Step (2) for polymerizing).
また共重合体（Ａ−１）と共重合体（Ａ−２）を別途合成し、ブレンドすることでも本発明の感圧式接着剤に使用できる共重合体（Ａ）を得ることができる。 The copolymer (A) that can be used in the pressure-sensitive adhesive of the present invention can also be obtained by separately synthesizing and blending the copolymer (A-1) and the copolymer (A-2).
本発明においてアクリル系共重合体（Ａ）は、溶液重合、塊状重合、乳化重合等の公知の重合法により得ることができるが、重量平均分子量の制御や反応制御の観点から溶液重合が好ましい。具体的には、単量体の合計１００重量部に対して、０．００１〜１重量部の重合開始剤を用いて共重合を行うことができる。 In the present invention, the acrylic copolymer (A) can be obtained by a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization or the like, but solution polymerization is preferable from the viewpoint of control of weight average molecular weight and reaction control. Specifically, copolymerization can be performed using 0.001 to 1 part by weight of a polymerization initiator with respect to 100 parts by weight of the total amount of monomers.
重合開始剤は、アゾ系化合物や有機過酸化物を用いることができる。重合開始剤は２種類以上を併用しても良い。また、溶液重合に用いる溶媒としては、例えば酢酸エチル、酢酸ｎ−ブチル、酢酸イソブチル、トルエン、アセトン、ヘキサン、メチルエチルケトン等が用いられる。重合溶媒は２種類以上混合して用いても良い。 As the polymerization initiator, an azo compound or an organic peroxide can be used. Two or more polymerization initiators may be used in combination. Moreover, as a solvent used for solution polymerization, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone, etc. are used, for example. Two or more kinds of polymerization solvents may be mixed and used.
上記重合開始剤のうちアゾ系化合物としては、例えば、２,２'−アゾビスイソブチロニトリル、２,２'−アゾビス(２−メチルブチロニトリル)、１,１'−アゾビス（シクロヘキサン１−カルボニトリル）、２,２'−アゾビス（２，４−ジメチルバレロニトリル）、２,２'−アゾビス（２，４−ジメチル−４−メトキシバレロニトリル）、ジメチル２,２'−アゾビス（２−メチルプロピオネート）、４,４'−アゾビス（４−シアノバレリック酸）、２,２'−アゾビス（２−ヒドロキシメチルプロピオニトリル）、２,２'−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］等が挙げられる。 Among the polymerization initiators, examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1 -Carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2 -Methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis [2- (2- Imidazolin-2-yl) propane] and the like.
また、上記重合開始剤のうち有機過酸化物としては、例えば、過酸化ベンゾイル、ｔ-ブチルパーベンゾエイト、クメンヒドロパーオキシド、ジイソプロピルパーオキシジカーボネート、ジ−ｎ−プロピルパーオキシジカーボネート、ジ（２−エトキシエチル）パーオキシジカーボネート、ｔ-ブチルパーオキシネオデカノエート、ｔ-ブチルパーオキシビバレート、（３，５，５−トリメチルヘキサノイル）パーオキシド、ジプロピオニルパーオキシド、ジアセチルパーオキシド等があげられる。 Examples of the organic peroxide among the polymerization initiators include, for example, benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di- (2-Ethoxyethyl) peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide Etc.
本発明の光学フィルム用感圧式接着剤は、アクリル系共重合体（Ａ）とイソシアネート化合物（Ｂ）との硬化反応を促進するため硬化触媒として錫化合物等を含むこともできる。具体的には、例えば、ジブチル錫ジラウリレート、ジオクチル錫ジラウリレートなどが挙げられる。また、この場合アセチルアセトンなどのキレート化合物を併用することで、ポットライフを延長することができる。 The pressure-sensitive adhesive for optical films of the present invention can also contain a tin compound or the like as a curing catalyst in order to accelerate the curing reaction between the acrylic copolymer (A) and the isocyanate compound (B). Specific examples include dibutyltin dilaurate and dioctyltin dilaurate. In this case, the pot life can be extended by using a chelate compound such as acetylacetone together.
また上記錫化合物を使用する場合、アクリル系共重合体に対し０．００００１〜０．１部添加するのが好ましく、さらに好ましくは０．０００１〜０．０５部添加するのが好ましい。０．００００１部に満たない場合、十分な触媒効果が得られない恐れがある。一方、０．１部を超えると反応が過剰に促進されポットライフが短くなる恐れがある。 Moreover, when using the said tin compound, it is preferable to add 0.00001-0.1 part with respect to an acryl-type copolymer, More preferably, it is preferable to add 0.0001-0.05 part. When it is less than 0.00001 part, there is a possibility that a sufficient catalytic effect cannot be obtained. On the other hand, if it exceeds 0.1 parts, the reaction is excessively promoted and the pot life may be shortened.
本発明の光学フィルム用感圧式接着剤は、耐熱性・耐湿熱性の向上を目的としてシランカップリング剤を配合することが好ましい。シランカップリング剤としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルメチルジメトキシシラン、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トリエトキシシラン、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）エチルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−アミノプロピルメチルメトキシシラン、Ｎ−（２−アミノエチル）３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）３−アミノ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トリエトキシシラン、メルカプトブチルトリメトキシシラン３−メルカプトプロピルメチルジメトキシシラン、イソシアネートプロピルトリエトキシシラン等が挙げられる。 The pressure-sensitive adhesive for optical films of the present invention preferably contains a silane coupling agent for the purpose of improving heat resistance and moist heat resistance. Examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltri Ethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-aminopropylmethylmethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, - mercaptopropyltrimethoxysilane, 3-mercaptopropyl triethoxy silane, mercaptopropyl butyl trimethoxy silane 3-mercaptopropyl methyl dimethoxy silane, and isocyanate propyl triethoxysilane and the like.
上記シランカップリング剤の中でも、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピルトリプロポキシシランを使用した場合、加熱加湿環境下での発泡の抑制や浮きの抑制に特に効果を発揮することができる。 Among the above silane coupling agents, when 3-glycidoxypropyltriethoxysilane or 3-glycidoxypropyltripropoxysilane is used, it is particularly effective for suppressing foaming and floating in a heated and humidified environment. can do.
本発明においてシランカップリング剤は、アクリル系共重合体（Ａ）１００重量部に対して、０．０１〜２重量部用いることが好ましく、０．０１〜２重量部がより好ましい。一方、０．０１重量部に満たない場合は、加熱加湿環境下での発泡の抑制や浮きの抑制に改善効果が乏しく、２重量部を越えてもそれ以上の効果が得られないばかりか、かえって加熱加湿環境下での浮きの原因になる場合がある。 In the present invention, the silane coupling agent is preferably used in an amount of 0.01 to 2 parts by weight, more preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the acrylic copolymer (A). On the other hand, if it is less than 0.01 parts by weight, the improvement effect is poor in the suppression of foaming and the suppression of floating in a heated and humidified environment, and not only the effect exceeding it can be obtained even if it exceeds 2 parts by weight, On the contrary, it may cause floating in a heated and humidified environment.
本発明の光学フィルム用感圧式接着剤は、必要に応じて、他の樹脂、例えばアクリル樹脂、ポリエステル樹脂、アミノ樹脂、エポキシ樹脂、ポリウレタン樹脂を併用することもできる。更に、用途に応じて、有機・無機の顔料、フィラー、着色剤、紫外線吸収剤、酸化防止剤、消泡剤、光安定剤、レベリング剤、帯電防止剤等の添加剤を配合しても良い。 The pressure-sensitive adhesive for optical films of the present invention can be used in combination with other resins such as acrylic resin, polyester resin, amino resin, epoxy resin, and polyurethane resin as necessary. Furthermore, additives such as organic and inorganic pigments, fillers, colorants, ultraviolet absorbers, antioxidants, antifoaming agents, light stabilizers, leveling agents, antistatic agents and the like may be blended depending on the application. .
本発明の感圧式接着剤を使用して、感圧式接着剤層とシート状基材とからなる積層製品（以下、「感圧式接着性シート」という。）を得ることができる。例えば、種々のシート状基材の片面、又は両面に本発明の感圧式接着剤を塗工、乾燥・硬化することによって感圧式接着シートを得ることができる。感圧式接着シートを構成する接着剤層は、「感圧式」であるから室温程度でタックを有する。感圧式接着剤を塗工するに際し、適当な液状媒体、例えば、酢酸エチル、トルエン、メチルエチルケトン、イソプロピルアルコール、その他の炭化水素系溶媒等の有機溶媒や、水を更に添加して、粘度を調整することもできるし、感圧式接着剤を加熱して粘度を低下させることもできる。ただし、水やアルコール等は多量に添加すると共重合体（Ａ）とイソシアネート化合物（Ｂ）との反応阻害を引き起こす可能性があるため注意が必要である。 Using the pressure-sensitive adhesive of the present invention, a laminated product composed of a pressure-sensitive adhesive layer and a sheet-like substrate (hereinafter referred to as “pressure-sensitive adhesive sheet”) can be obtained. For example, a pressure-sensitive adhesive sheet can be obtained by coating, drying and curing the pressure-sensitive adhesive of the present invention on one side or both sides of various sheet-like substrates. Since the adhesive layer constituting the pressure-sensitive adhesive sheet is “pressure-sensitive”, it has tack at about room temperature. When applying a pressure sensitive adhesive, the viscosity is adjusted by further adding an appropriate liquid medium, for example, an organic solvent such as ethyl acetate, toluene, methyl ethyl ketone, isopropyl alcohol, other hydrocarbon solvents, or water. It is also possible to reduce the viscosity by heating the pressure sensitive adhesive. However, care should be taken because addition of a large amount of water, alcohol, or the like may cause reaction inhibition between the copolymer (A) and the isocyanate compound (B).
本発明において感圧式接着剤層を形成する方法としては、特に制限は無く、マイヤーバー、アプリケーター、刷毛、スプレー、ローラー、グラビアコーター、ダイコーター、リップコーター、コンマコーター、ナイフコーター、リバースコ−ター、スピンコーター等種々の塗工方法が挙げられる。乾燥方法には特に制限はなく、熱風乾燥、赤外線や減圧法を利用したものが挙げられる。乾燥条件としては接着剤組成物の硬化形態、膜厚や選択した溶剤にもよるが、通常６０〜１８０℃程度の熱風加熱でよい。 The method for forming the pressure-sensitive adhesive layer in the present invention is not particularly limited, and may be a Mayer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, knife coater, reverse coater, Various coating methods such as a spin coater can be mentioned. There is no restriction | limiting in particular in a drying method, The thing using hot air drying, infrared rays, and the pressure reduction method is mentioned. As drying conditions, although it depends on the cured form of the adhesive composition, the film thickness, and the selected solvent, heating with hot air at about 60 to 180 ° C. is usually sufficient.
常法に従って適当な方法で上記シート状基材に感圧式接着剤を塗工した後、感圧式接着剤が有機溶媒や水等の液状媒体を含有する場合には、液状媒体を除去したり、感圧式接着剤が揮発すべき液状媒体を含有しない場合は、溶融状態にある接着剤層を冷却して固化したりして、シート状基材の上に接着剤層を形成することができる。感圧式接着剤層の厚さは、０．１μｍ〜２００μｍであることが好ましく、５μｍ〜５０μｍであることがより好ましい。０．１μｍ未満では十分な接着力が得られないことがあり、２００μｍを超えても接着力等の特性はそれ以上向上しない場合が多い。 After applying the pressure sensitive adhesive to the sheet-like base material by an appropriate method according to a conventional method, if the pressure sensitive adhesive contains a liquid medium such as an organic solvent or water, the liquid medium is removed, When the pressure-sensitive adhesive does not contain a liquid medium to be volatilized, the adhesive layer can be formed on the sheet-like substrate by cooling and solidifying the adhesive layer in a molten state. The thickness of the pressure sensitive adhesive layer is preferably 0.1 μm to 200 μm, and more preferably 5 μm to 50 μm. If the thickness is less than 0.1 μm, sufficient adhesive strength may not be obtained, and if the thickness exceeds 200 μm, characteristics such as adhesive strength are often not improved further.
本発明において基材は、セロハン、各種プラスチックシート、ゴム、発泡体、布帛、ゴムびき布、樹脂含浸布、ガラス板、金属板、木材、偏光板などの光学フィルム等の平坦な形状のものが挙げられる。又、各種基材は単独でも用いることもできるし、複数のものを積層してなる多層状態にあるものも用いることができる。更に表面を剥離処理したものや帯電防止処理したものを用いることもできる。 In the present invention, the base material has a flat shape such as cellophane, various plastic sheets, rubber, foam, cloth, rubber cloth, resin-impregnated cloth, glass plate, metal plate, wood, polarizing film and other optical films. Can be mentioned. Various base materials can be used alone or in a multi-layered state in which a plurality of base materials are laminated. Furthermore, the surface of which has been subjected to a peeling treatment or an antistatic treatment can also be used.
各種プラスチックシートとしては、各種プラスチックフィルムともいわれ、ポリビニルアルコールフィルムやトリアセチルセルロースフィルム、ポリプロピレン、ポリエチレン、ポリシクロオレフィン、エチレン−酢酸ビニル共重合体等のポリオレフィン系樹脂のフィルム、ポリエチレンテレフタレート，ポリブチレンテレフタレート，ポリエチレンナフタレートなどのポリエステル系樹脂のフィルム、ポリカーボネート系樹脂のフィルム、ポリノルボルネン系樹脂のフィルム、ポリアリレート系樹脂のフィルム、アクリル系樹脂のフィルム、ポリフェニレンサルファイド樹脂のフィルム、ポリスチレン樹脂のフィルム、ビニル系樹脂のフィルム、ポリアミド系樹脂のフィルム、ポリイミド系樹脂のフィルム、エポキシ系樹脂、シクロオレフィン系樹脂のフィルム等が挙げられる。 Various plastic sheets are also called various plastic films, such as polyvinyl alcohol film, triacetyl cellulose film, polypropylene, polyethylene, polycycloolefin, polyolefin resin film such as ethylene-vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate. , Polyester resin film such as polyethylene naphthalate, Polycarbonate resin film, Polynorbornene resin film, Polyarylate resin film, Acrylic resin film, Polyphenylene sulfide resin film, Polystyrene resin film, Vinyl Resin film, polyamide resin film, polyimide resin film, epoxy resin, cycloolefin Films such emissions resins.
本発明において光学部材は、偏光フィルム、位相差フィルム、楕円偏光フィルム、反射防止フィルム、輝度向上フィルム等の種々の光学特性を持ついわゆるシート（前述の通りフィルムともいう）状の光学部材を指す。 In the present invention, the optical member refers to a so-called sheet (also referred to as a film) optical member having various optical properties such as a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film.
本発明の積層体は、前記光学部材に上記本発明の感圧式接着剤から形成される感圧式接着剤層が積層された状態のものである。感圧式接着剤層の他の面には、剥離処理されたシート状基材を積層することができる。 The laminate of the present invention is a state in which a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive of the present invention is laminated on the optical member. On the other surface of the pressure-sensitive adhesive layer, a sheet-like base material subjected to a release treatment can be laminated.
本発明の積層体は、（ア）剥離処理されたシート状基材の剥離処理面に感圧式接着剤を塗工、乾燥し、シート状の光学部材を感圧式接着剤層の表面に積層したり、（イ）シート状の光学部材に感圧式接着剤を塗工、乾燥し、感圧式接着剤層の表面に剥離処理されたシート状基材の剥離処理面を積層したりすることによって得ることができる。 The laminate of the present invention is (a) a pressure-sensitive adhesive is applied to the release-treated surface of the peeled sheet-like substrate and dried, and a sheet-like optical member is laminated on the surface of the pressure-sensitive adhesive layer. Or (b) by applying a pressure-sensitive adhesive to a sheet-like optical member, drying, and laminating the release-treated surface of the release-treated sheet-like substrate on the surface of the pressure-sensitive adhesive layer be able to.
本発明において液晶セル部材は、このようにして得た積層体から感圧式接着剤層の表面を覆っていた剥離処理されたシート状基材を剥がし、例えば、感圧式接着剤層を液晶セル用ガラス部材に貼着することによって、「シート状の光学部材／感圧式接着剤層／液晶セル用ガラス部材」という構成により得るものである。 In the present invention, the liquid crystal cell member peels off the release-treated sheet-like substrate covering the surface of the pressure-sensitive adhesive layer from the thus obtained laminate, for example, the pressure-sensitive adhesive layer is used for a liquid crystal cell. By sticking to a glass member, it is obtained by the configuration of “sheet-like optical member / pressure-sensitive adhesive layer / liquid crystal cell glass member”.
又、本発明の感圧式接着性シートまたは積層体の用途は特に限定されないが、液晶ディスプレイ、プラズマディスプレイ、タッチパネル、電極周辺部材等各種エレクトロニクス関連の部材やプロテクトフィルム用途にも適応できる。 The use of the pressure-sensitive adhesive sheet or laminate of the present invention is not particularly limited, but can be applied to various electronics-related members such as liquid crystal displays, plasma displays, touch panels, electrode peripheral members, and protective film applications.
次に、実施例を示して本発明を更に詳細に説明するが、本発明はこれらによって限定されるものではない。尚、以下の説明において、部および％とあるのは、重量部および重量％をそれぞれ意味するものとする。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the following description, parts and% mean parts by weight and% by weight, respectively.
（合成例１）
攪拌機、温度計、還流冷却器、滴下装置、窒素導入管を備えた反応容器に、ｎ−ブチルアクリレート ９４．８部、メチルアクリレート ５．０部、ヒドロキシエチルアクリレート ０．２部、アセトン１３０部、２，２'−アゾビスイソブチロニトリル ０．０２４部を仕込み、この反応容器内の空気を窒素ガスで置換した後、攪拌しながら窒素雰囲気下中で、この反応溶液を６２℃に昇温させ、４．５時間反応させた。反応終了後、ＭＥＫ １１５部とアセトン５０部を滴下し２５℃に冷却した。続いてアクリルアミド ０．２５部および２，２'−アゾビス（２，４−ジメチルバレロニトリル）０．２５部を添加して、６５℃に昇温し、７．５時間反応させた。反応終了後、ＭＥＫ５５部を添加して冷却し不揮発分１８％のアクリル系共重合体を得た。
(Synthesis Example 1)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, 94.8 parts of n-butyl acrylate, 5.0 parts of methyl acrylate, 0.2 part of hydroxyethyl acrylate, 130 parts of acetone, After charging 0.024 part of 2,2′-azobisisobutyronitrile and replacing the air in the reaction vessel with nitrogen gas, the reaction solution was heated to 62 ° C. in a nitrogen atmosphere with stirring. And allowed to react for 4.5 hours. After completion of the reaction, 115 parts of MEK and 50 parts of acetone were added dropwise and cooled to 25 ° C. Subsequently, 0.25 part of acrylamide and 0.25 part of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, the temperature was raised to 65 ° C., and the reaction was performed for 7.5 hours. After completion of the reaction, 55 parts of MEK was added and cooled to obtain an acrylic copolymer having a nonvolatile content of 18%.
得られた重合体について、アクリル系共重合体（Ａ−１）とアクリル系共重合体（Ａ−２）の重量平均分子量（Ｍｗ）とその重量比を表１に示す。 Table 1 shows the weight average molecular weight (Mw) and the weight ratio of the acrylic copolymer (A-1) and the acrylic copolymer (A-2) for the obtained polymer.
（合成例２〜１４）
原料を表１に記載した組成へ変更した以外は、合成例１と同様に重合を行いアクリル系共重合体を得た。得られた重合体について、アクリル系共重合体（Ａ−１）とアクリル系共重合体（Ａ−２）の重量平均分子量（Ｍｗ）とその重量比を表１に示す。
(Synthesis Examples 2-14)
Except having changed the raw material into the composition described in Table 1, polymerization was performed in the same manner as in Synthesis Example 1 to obtain an acrylic copolymer. Table 1 shows the weight average molecular weight (Mw) and the weight ratio of the acrylic copolymer (A-1) and the acrylic copolymer (A-2) for the obtained polymer.
（合成例１５）
攪拌機、温度計、還流冷却器、滴下装置、窒素導入管を備えた反応容器に、ｎ−ブチルアクリレート ８２．４部、メチルアクリレート １４．５部、メチルメタクリレート３．０部、ヒドロキシエチルアクリレート ０．１部、酢酸エチル １００部、２，２'−アゾビスイソブチロニトリル ０．０２部を仕込み、この反応容器内の空気を窒素ガスで置換した後、攪拌しながら窒素雰囲気下中で、この反応溶液を８０℃に昇温させ、７時間反応させた。反応終了後、酢酸エチル１１０部を添加して冷却し不揮発分３０％のアクリル系共重合体を得た。得られたアクリル系共重合体について、重量平均分子量（Ｍｗ）を表２に示す。
(Synthesis Example 15)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube, 82.4 parts of n-butyl acrylate, 14.5 parts of methyl acrylate, 3.0 parts of methyl methacrylate, hydroxyethyl acrylate 0. 1 part, 100 parts of ethyl acetate, 0.02 part of 2,2′-azobisisobutyronitrile were charged, and the air in the reaction vessel was replaced with nitrogen gas. The reaction solution was heated to 80 ° C. and reacted for 7 hours. After completion of the reaction, 110 parts of ethyl acetate was added and cooled to obtain an acrylic copolymer having a nonvolatile content of 30%. Table 2 shows the weight average molecular weight (Mw) of the obtained acrylic copolymer.
（合成例１６〜１９）
原料を表２に記載した組成へ変更した以外は、合成例１５と同様に重合を行いアクリル系共重合体を得た。得られた重合体について、アクリル系共重合体（Ａ−１）とアクリル系共重合体（Ａ−２）の重量平均分子量（Ｍｗ）とその重量比を表２に示す。
(Synthesis Examples 16 to 19)
Polymerization was performed in the same manner as in Synthesis Example 15 except that the raw material was changed to the composition described in Table 2, to obtain an acrylic copolymer. Table 2 shows the weight average molecular weight (Mw) and the weight ratio of the acrylic copolymer (A-1) and the acrylic copolymer (A-2) for the obtained polymer.
ＢＡ：ブチルアクリレート
ＥＨＡ：エチルヘキシルアクリレート
ＭＡ：メチルアクリレート
ＭＭＡ：メチルメタクリレート
ＭＴＡ：メトキシエチルアクリレート
ＡＡｍ：アクリルアミド
ＨＥＡ：ヒドロキシエチルアクリレート
ＨＢＡ：ヒドロキシブチルアクリレート
ＡＡ：アクリル酸
BA: butyl acrylate EHA: ethyl hexyl acrylate MA: methyl acrylate MMA: methyl methacrylate MTA: methoxyethyl acrylate AAm: acrylamide HEA: hydroxyethyl acrylate HBA: hydroxybutyl acrylate AA: acrylic acid
《重量平均分子量（Ｍｗ）の測定》
Ｍｗの測定は島津製作所製ＧＰＣ（ゲルパーミエーションクロマトグラフィー）「ＬＣ−ＧＰＣシステム」を用いた。ＧＰＣは溶媒（ＴＨＦ；テトラヒドロフラン）に溶解した物質をその分子サイズの差によって分離定量する液体クロマトグラフィーであり、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）の決定はポリスチレン換算で行った。
装置名：島津製作所製、ＬＣ−ＧＰＣシステム「Ｐｒｏｍｉｎｅｎｃｅ」
カラム：東ソー（株）製、ＧＭＨＸＬ ４本
：東ソー（株）製、ＨＸＬ-Ｈ １本
移動相溶媒：テトラヒドロフラン
流量：１．０ｍｌ／ｍｉｎ
カラム温度：４０℃
<< Measurement of weight average molecular weight (Mw) >>
Mw was measured using Shimadzu GPC (gel permeation chromatography) “LC-GPC system”. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size, and the weight average molecular weight (Mw) and number average molecular weight (Mn) are determined in terms of polystyrene.
Device name: LC-GPC system “Prominence” manufactured by Shimadzu Corporation
Column: Tosoh Co., Ltd., 4 GMHXL
: Tosoh Co., Ltd., one HXL-H Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 ml / min
Column temperature: 40 ° C
（イソシアネート化合物（Ｂ−２）の合成）
攪拌機、温度計、還流冷却器、滴下装置、窒素導入管を備えた反応容器の反応容器内の空気を窒素ガスで置換した後、キシリレンジイソシアネートのトリメチロールアダクト体（３官能のイソシアネート）の酢酸エチル溶液４０部（不揮発分５０％）を仕込んだ。次いでカルコール２００ＧＤ（花王株式会社製：オクチルドデシルアルコール）７．３部を仕込み、攪拌しながら窒素雰囲気下中で、この溶液を６０℃へ昇温し、４．５時間反応することで２官能のイソシアネート化合物（Ｂ−２）溶液を得た（不揮発分５７．７％ ＮＣＯ％＝４．３％）。
(Synthesis of Isocyanate Compound (B-2))
After replacing the air in the reaction vessel of the reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping device and nitrogen introduction tube with nitrogen gas, acetic acid of trimethylol adduct (trifunctional isocyanate) of xylylene diisocyanate 40 parts of an ethyl solution (non-volatile content: 50%) was charged. Next, 7.3 parts of Calcoal 200GD (manufactured by Kao Corporation: octyldodecyl alcohol) was charged, and this solution was heated to 60 ° C. in a nitrogen atmosphere with stirring, and reacted for 4.5 hours to react with bifunctionality. An isocyanate compound (B-2) solution was obtained (non-volatile content: 57.7% NCO% = 4.3%).
（イソシアネート化合物（Ｂ−３）の合成）
攪拌機、温度計、還流冷却器、滴下装置、窒素導入管を備えた反応容器の反応容器内の空気を窒素ガスで置換した後、キシリレンジイソシアネートのトリメチロールアダクト体（３官能のイソシアネート）の酢酸エチル溶液３０部（不揮発分５０％）を仕込んだ。さらにカルコール２０９８（花王株式会社製：ラウリルアルコール）３．４部を仕込み、攪拌しながら窒素雰囲気下中で、この溶液を５０℃へ昇温し、４．５時間反応することで２官能のイソシアネート化合物（Ｂ−３）溶液を得た（不揮発分５５．１％ ＮＣＯ％＝４．６％）。
(Synthesis of Isocyanate Compound (B-3))
After replacing the air in the reaction vessel of the reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping device and nitrogen introduction tube with nitrogen gas, acetic acid of trimethylol adduct (trifunctional isocyanate) of xylylene diisocyanate 30 parts of an ethyl solution (non-volatile content: 50%) was charged. Furthermore, 3.4 parts of Calcoal 2098 (Kao Co., Ltd .: Lauryl alcohol) was added, and this solution was heated to 50 ° C. in a nitrogen atmosphere with stirring, and reacted for 4.5 hours to react for 4.5 hours. A compound (B-3) solution was obtained (nonvolatile content: 55.1% NCO% = 4.6%).
（実施例１〜２５）
合成例１〜１２、１５〜１７で得られたアクリル系共重合体１００重量部に対し、イソシアネート化合物（Ｂ）、シランカップリング剤、錫化合物、アセチルアセトンをそれぞれ表３、４に従って配合して感圧式接着剤を得た。なお、表３及び４の「イソシアネート基のモル数」はアクリル系共重合体（Ａ）の水酸基１モルに対するイソシアネート化合物（Ｂ）のイソシアネート基のモル数を意味するものである。
(Examples 1 to 25)
An isocyanate compound (B), a silane coupling agent, a tin compound, and acetylacetone are blended according to Tables 3 and 4 with respect to 100 parts by weight of the acrylic copolymers obtained in Synthesis Examples 1 to 12 and 15 to 17, respectively. A pressure adhesive was obtained. “Mole number of isocyanate group” in Tables 3 and 4 means the number of moles of isocyanate group of the isocyanate compound (B) with respect to 1 mole of hydroxyl group of the acrylic copolymer (A).
（比較例１〜７）
合成例１、１３、１４、１８、１９で得られたアクリル系共重合体１００重量部に対し、イソシアネート化合物（Ｂ）、シランカップリング剤、錫化合物、アセチルアセトン、エポキシ硬化剤をそれぞれ表５に従って配合して感圧式接着剤を得た。なお、表５の「イソシアネート基のモル数」はアクリル系共重合体（Ａ）の水酸基１モルに対するイソシアネート化合物（Ｂ）のイソシアネート基のモル数を意味するものである。
(Comparative Examples 1-7)
The isocyanate compound (B), the silane coupling agent, the tin compound, acetylacetone, and the epoxy curing agent were each in accordance with Table 5 with respect to 100 parts by weight of the acrylic copolymer obtained in Synthesis Examples 1, 13, 14, 18, and 19. A pressure sensitive adhesive was obtained by blending. “Mole number of isocyanate group” in Table 5 means the number of moles of isocyanate group of the isocyanate compound (B) relative to 1 mole of hydroxyl group of the acrylic copolymer (A).
イソシアネート化合物（Ｂ−１）：キシリレンジイソシアネートのトリメチロールアダクト付加物（３官能のイソシアネート）の酢酸エチル溶液 不揮発分５０％ ＮＣＯ％＝７．７％
イソシアネート化合物（Ｂ−４）：ヘキサメチレンジイソシアネートのアロファネート体（２官能のイソシアネート）日本ポリウレタン製 コロネート２７７０
不揮発分１００％ ＮＣＯ％＝１９．４
シランカップリング剤（Ｓ−１）：３−グリシドキシプロピルトリメトキシシラン（ＫＢＭ−４０３ 信越化学製）
シランカップリング剤（Ｓ−２）：３−グリシドキシプロピルトリエトキシシラン（ＫＢＥ−４０３ 信越化学製）
シランカップリング剤（Ｓ−３）：３−グリシドキシプロピルトリプロポキシシラン
錫化合物：ジオクチル錫ジラウレート
エポキシ硬化剤（Ｅ−１）：三菱ガス化学製 ＴＥＴＲＡＤ−Ｘ
Isocyanate compound (B-1): Ethyl acetate solution of trimethylol adduct adduct of xylylene diisocyanate (trifunctional isocyanate) Non-volatile content: 50% NCO% = 7.7%
Isocyanate compound (B-4): hexamethylene diisocyanate allophanate (bifunctional isocyanate) Coronate 2770 made by Nippon Polyurethane
Nonvolatile content 100% NCO% = 19.4
Silane coupling agent (S-1): 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical)
Silane coupling agent (S-2): 3-glycidoxypropyltriethoxysilane (KBE-403 manufactured by Shin-Etsu Chemical)
Silane coupling agent (S-3): 3-glycidoxypropyl tripropoxysilane tin compound: Dioctyltin dilaurate epoxy curing agent (E-1): TETRAD-X manufactured by Mitsubishi Gas Chemical
（液晶セル用部材の作成）
得られた感圧式接着剤を剥離フィルム上に乾燥膜厚が２５μｍになるように塗工し、１００℃で２分間乾燥させ、感圧式接着剤層を形成した。次いで、感圧式接着剤層に、ポリビニルアルコール（ＰＶＡ）系偏光子の両面をトリアセチルセルロース系保護フィルム（以下、「ＴＡＣフィルム」という）で挟んだ多層構造の偏光板の片面を貼り合せ、さらに温度３５℃相対湿度５５％の条件で１週間熟成し「剥離フィルム／感圧式接着剤層／ＴＡＣフィルム／ＰＶＡ／ＴＡＣフィルム」の構成の積層体を得た。得られた積層体を３５０ｍｍ×２５０ｍｍの大きさに２枚切り取り、剥離フィルムを剥がし、厚さ１．１ｍｍのフロートガラス板の両面に、偏光板の吸収軸が直交するようにラミネーターを用いて貼り付けた。続いて、この偏光板が貼り付けられたガラス板を５０℃−５気圧の条件のオートクレーブ内に２０分保持させて、偏光板をガラス板に強固に密着させ、液晶セル用部材を得た。
(Creation of liquid crystal cell materials)
The obtained pressure-sensitive adhesive was coated on a release film so that the dry film thickness was 25 μm, and dried at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. Next, one side of a polarizing plate having a multilayer structure in which both sides of a polyvinyl alcohol (PVA) polarizer are sandwiched between triacetyl cellulose-based protective films (hereinafter referred to as “TAC film”) is bonded to the pressure-sensitive adhesive layer. The laminate was aged for one week under conditions of a temperature of 35 ° C. and a relative humidity of 55% to obtain a laminate having a configuration of “peel film / pressure-sensitive adhesive layer / TAC film / PVA / TAC film”. Cut out the obtained laminate to a size of 350 mm x 250 mm, peel off the release film, and paste it on both sides of a 1.1 mm thick float glass plate using a laminator so that the absorption axes of the polarizing plates are orthogonal to each other I attached. Subsequently, the glass plate on which the polarizing plate was attached was held in an autoclave at 50 ° C.-5 atm for 20 minutes, and the polarizing plate was firmly adhered to the glass plate to obtain a liquid crystal cell member.
得られた液晶セル部材について、耐熱性、耐湿熱性、光学特性を以下の方法で評価した。 About the obtained liquid crystal cell member, the heat resistance, heat-and-moisture resistance, and optical characteristics were evaluated by the following methods.
＜耐熱性の評価方法＞
耐湿熱性の評価として、上記液晶セル用部材を９０℃、相対湿度０％で１０００時間放置した後の偏光板の浮きやハガレ、感圧式接着剤層の発泡を目視で観察した。耐熱性について、下記の３段階の評価基準に基づいて評価をおこなった。
◎：「浮きハガレ・発泡が全く認められず、実用上全く問題なし。」
○：「わずかに浮きハガレ・発泡が認められるが、実用上問題なし。」
△：「浮きハガレ・発泡が認められるが、実用上問題がない。」
×：「全面的に浮きハガレ・発泡があり、実用不可である。」
<Method for evaluating heat resistance>
As evaluation of the heat and moisture resistance, the liquid crystal cell member was visually observed for floating and peeling of the polarizing plate and foaming of the pressure-sensitive adhesive layer after being left for 1000 hours at 90 ° C. and 0% relative humidity. The heat resistance was evaluated based on the following three-stage evaluation criteria.
A: “No floating peeling or foaming is observed, and there is no problem in practical use.”
○: “Slightly floating peeling or foaming is recognized, but there is no practical problem.”
Δ: “Floating peeling / foaming is recognized, but there is no practical problem”
×: “There is floating peeling and foaming on the whole surface, which is impractical.”
＜耐湿熱性の評価方法＞
耐湿熱性の評価として、上記液晶セル用部材を８０℃、相対湿度９０％で１０００時間放置した後の偏光板の浮きやハガレ、感圧式接着剤層の発泡を目視で観察した。耐湿熱性について、下記の３段階の評価基準に基づいて評価をおこなった。
○：「浮きハガレ・発泡が全く認められず、実用上全く問題なし。」
△：「若干浮きハガレ・発泡が認められるが、実用上問題がない。」
×：「全面的に浮きハガレ・発泡があり、実用不可である。」
<Method for evaluating wet heat resistance>
As an evaluation of the heat and humidity resistance, the liquid crystal cell member was left at 80 ° C. and a relative humidity of 90% for 1000 hours for 1000 hours, and then the polarization plate was lifted and peeled off, and the pressure-sensitive adhesive layer was foamed. The wet heat resistance was evaluated based on the following three evaluation criteria.
○: “No floating peeling or foaming is observed, and there is no problem in practical use.”
Δ: “Slightly floating peeling / foaming is observed, but there is no practical problem”
×: “There is floating peeling and foaming on the whole surface, which is impractical.”
＜光学特性の評価方法＞
光学特性の評価として、９０℃で１０００時間放置した後の上記液晶セル用部材を暗室内で光源上に設置し、光を透過させたときに観測される光漏れを目視で観察した。光漏れの程度について、下記の３段階の評価基準に基づいて評価をおこなった。
◎：「光漏れが全く認められず、実用上全く問題なし。」
○：「わずかに端部からの光漏れが認められるが、実用上問題なし。
△：「光漏れが認められるが、実用上問題がない。」
×：「全面的に光漏れがあり、実用不可である。」
<Evaluation method of optical characteristics>
As an evaluation of optical characteristics, the liquid crystal cell member after being left at 90 ° C. for 1000 hours was placed on a light source in a dark room, and light leakage observed when light was transmitted was visually observed. The degree of light leakage was evaluated based on the following three evaluation criteria.
A: “No light leakage was observed and there was no problem in practical use.”
○: “Slight leakage from the edge is recognized, but there is no practical problem.
Δ: “Light leakage is observed, but there is no practical problem”
X: “There is light leakage over the entire surface and it is not practical.”
以上、評価結果を表３〜表５に示す。 The evaluation results are shown in Tables 3 to 5.
表３および表４の実施例１〜２５に示すように本発明の光学フィルム用感圧式接着剤は耐熱性・耐湿熱性・光漏れ防止性を満足するものであった。一方、表５に示すように、比較例１〜７の感圧式接着剤は、耐熱性・耐湿熱性・光漏れ防止性のいずれかが不良であり、すべての特性を満足できなかった。 As shown in Examples 1 to 25 in Table 3 and Table 4, the pressure-sensitive adhesive for optical films of the present invention satisfied heat resistance, moist heat resistance and light leakage prevention properties. On the other hand, as shown in Table 5, the pressure-sensitive adhesives of Comparative Examples 1 to 7 had poor heat resistance, moist heat resistance, and light leakage prevention properties, and could not satisfy all the characteristics.
Claims (9)
前記アクリル系共重合体（Ａ）が、水酸基を有する単量体（a−１）０.０１〜０．５重量部と、その他の単量体（ａ−２）を共重合してなり、
前記アクリル系共重合体（Ａ）が有する水酸基１モルに対して、イソシアネート化合物（Ｂ）のイソシアネート基が０．５モル以上３００モル以下であり、
前記イソシアネート化合物（Ｂ）が、３個以上のイソシアネート基を有するイソシアネート化合物に対して、アルコールを反応させてなる分子内に２個のイソシアネート基を含有するイソシアネート化合物であることを特徴とする光学フィルム用感圧式接着剤。 A pressure-sensitive adhesive for an optical film comprising an acrylic copolymer (A) and an isocyanate compound (B),
The acrylic copolymer (A) is obtained by copolymerizing a monomer (a-1) having a hydroxyl group of 0.01 to 0.5 parts by weight and another monomer (a-2),
Relative to 1 mole of the hydroxyl groups of the acrylic copolymer (A) has, Ri 300 mol der isocyanate groups of 0.5 mol or more of the isocyanate compound (B),
An optical film characterized in that the isocyanate compound (B) is an isocyanate compound containing two isocyanate groups in a molecule obtained by reacting an alcohol with an isocyanate compound having three or more isocyanate groups. Pressure sensitive adhesive.
The liquid crystal cell member according to claim 8 , wherein the optical member is a polarizing plate.
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| JP6347945B2 (en) * | 2012-12-27 | 2018-06-27 | 日本合成化学工業株式会社 | Method for producing acrylic resin for heat-resistant adhesive film |
| JP6279316B2 (en) * | 2012-12-27 | 2018-02-14 | 日本合成化学工業株式会社 | Method for producing acrylic resin for heat-resistant adhesive film |
| US9758705B2 (en) | 2013-06-19 | 2017-09-12 | Lg Chem, Ltd. | Pressure sensitive adhesive composition |
| JP6325328B2 (en) * | 2014-04-24 | 2018-05-16 | 綜研化学株式会社 | Adhesive composition, adhesive layer, adhesive sheet and laminate for touch panel |
| JP6484484B2 (en) * | 2015-03-30 | 2019-03-13 | 日本カーバイド工業株式会社 | Adhesive composition and adhesive sheet |
| JP6536389B2 (en) * | 2015-12-10 | 2019-07-03 | 東洋インキＳｃホールディングス株式会社 | Adhesive for fixing polishing member, and adhesive sheet for fixing polishing member |
| JP2017200975A (en) * | 2016-05-06 | 2017-11-09 | 王子ホールディングス株式会社 | Adhesive sheet and laminate |
| JP7139698B2 (en) * | 2018-06-07 | 2022-09-21 | 昭和電工マテリアルズ株式会社 | PSA COMPOSITION FOR IMAGE DISPLAY DEVICE AND ADHESIVE SHEET FOR IMAGE DISPLAY DEVICE |
| JP2019206726A (en) * | 2019-09-12 | 2019-12-05 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| WO2023136052A1 (en) * | 2022-01-12 | 2023-07-20 | 綜研化学株式会社 | Pressure-sensitive adhesive composition for polarizing plate, and polarizing plate with pressure-sensitive adhesive layer |
| WO2024150782A1 (en) * | 2023-01-13 | 2024-07-18 | 住友化学株式会社 | Adhesive composition, adhesive layer, optical film with adhesive layer, and display device |
| JP2024100727A (en) * | 2023-01-13 | 2024-07-26 | 住友化学株式会社 | Adhesive composition, adhesive layer, optical film with adhesive layer, and display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH08120236A (en) * | 1994-10-26 | 1996-05-14 | Nippon Synthetic Chem Ind Co Ltd:The | Pressure-sensitive adhesive composition |
| JP4673952B2 (en) * | 2000-03-14 | 2011-04-20 | リンテック株式会社 | Adhesive composition, adhesive sheet using the same, and adhesive optical member |
| JP4072309B2 (en) * | 2000-10-13 | 2008-04-09 | 日本カーバイド工業株式会社 | Adhesive composition for polarizing film and polarizing film |
| JP4534431B2 (en) * | 2003-04-30 | 2010-09-01 | 東洋インキ製造株式会社 | Adhesive and optical member using the same |
| JP4481020B2 (en) * | 2004-01-22 | 2010-06-16 | 日東電工株式会社 | Optical member adhesive composition, optical member adhesive layer, optical member adhesive sheet, and optical member |
| JP4992337B2 (en) * | 2006-08-11 | 2012-08-08 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition and adhesive film using the adhesive composition |
| JP5696994B2 (en) * | 2008-07-16 | 2015-04-08 | エルジー・ケム・リミテッド | Adhesive composition, polarizing plate and liquid crystal display device |
| KR101718558B1 (en) * | 2009-03-24 | 2017-03-21 | 닛뽕 카바이도 고교 가부시키가이샤 | Adhesive composition |
| JP5364491B2 (en) * | 2009-07-24 | 2013-12-11 | リンテック株式会社 | Adhesive sheet |
| JP5825619B2 (en) * | 2009-09-18 | 2015-12-02 | 綜研化学株式会社 | Adhesive composition for optical film and optical film using the same |
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