JP5639448B2 - Acrylic adhesive composition, acrylic adhesive and optical member with adhesive layer - Google Patents
Acrylic adhesive composition, acrylic adhesive and optical member with adhesive layer Download PDFInfo
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- JP5639448B2 JP5639448B2 JP2010253565A JP2010253565A JP5639448B2 JP 5639448 B2 JP5639448 B2 JP 5639448B2 JP 2010253565 A JP2010253565 A JP 2010253565A JP 2010253565 A JP2010253565 A JP 2010253565A JP 5639448 B2 JP5639448 B2 JP 5639448B2
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- meth
- sensitive adhesive
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- adhesive composition
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- 239000000203 mixture Substances 0.000 title claims description 68
- 239000012790 adhesive layer Substances 0.000 title claims description 24
- 230000003287 optical effect Effects 0.000 title claims description 22
- 239000003522 acrylic cement Substances 0.000 title claims description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 108
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 86
- 239000000178 monomer Substances 0.000 claims description 62
- 229920000642 polymer Polymers 0.000 claims description 60
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 45
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 44
- 229920000428 triblock copolymer Polymers 0.000 claims description 44
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 32
- 238000004132 cross linking Methods 0.000 claims description 30
- 239000000853 adhesive Substances 0.000 claims description 26
- 230000001070 adhesive effect Effects 0.000 claims description 26
- 125000000524 functional group Chemical group 0.000 claims description 26
- 239000003431 cross linking reagent Substances 0.000 claims description 22
- 238000010526 radical polymerization reaction Methods 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 16
- 150000002513 isocyanates Chemical class 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 162
- -1 isocyanate compound Chemical class 0.000 description 26
- 239000010410 layer Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 24
- 239000010408 film Substances 0.000 description 19
- 239000004973 liquid crystal related substance Substances 0.000 description 18
- 125000000217 alkyl group Chemical group 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 13
- 150000003498 tellurium compounds Chemical class 0.000 description 13
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 241000519995 Stachys sylvatica Species 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 230000008602 contraction Effects 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 239000005056 polyisocyanate Substances 0.000 description 7
- 229920001228 polyisocyanate Polymers 0.000 description 7
- 230000002265 prevention Effects 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 125000003107 substituted aryl group Chemical group 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- 229920006243 acrylic copolymer Polymers 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 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 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 4
- 239000007869 azo polymerization initiator Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 2
- 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 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
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 229920006222 acrylic ester polymer Polymers 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- SFLRURCEBYIKSS-UHFFFAOYSA-N n-butyl-2-[[1-(butylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound CCCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCCC SFLRURCEBYIKSS-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VBZBISQOWJYWCC-UHFFFAOYSA-N 2-(2-carboxypropan-2-yldiazenyl)-2-methylpropanoic acid Chemical compound OC(=O)C(C)(C)N=NC(C)(C)C(O)=O VBZBISQOWJYWCC-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
- VUKYWZYFZZJLRZ-UHFFFAOYSA-N 2-[(1-amino-2-methyl-1-methyliminopropan-2-yl)diazenyl]-n',2-dimethylpropanimidamide;dihydrochloride Chemical compound Cl.Cl.CNC(=N)C(C)(C)N=NC(C)(C)C(=N)NC VUKYWZYFZZJLRZ-UHFFFAOYSA-N 0.000 description 1
- KWZULKIVMJKFKM-UHFFFAOYSA-N 2-[(1-amino-2-methyl-1-oxobutan-2-yl)diazenyl]-2-methylbutanamide Chemical compound CCC(C)(C(N)=O)N=NC(C)(CC)C(N)=O KWZULKIVMJKFKM-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
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- RXXCIBALSKQCAE-UHFFFAOYSA-N 3-methylbutoxymethylbenzene Chemical compound CC(C)CCOCC1=CC=CC=C1 RXXCIBALSKQCAE-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
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Landscapes
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- Optics & Photonics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Liquid Crystal (AREA)
Description
本発明は、アクリル系粘着剤組成物、それを熱架橋してなるアクリル系粘着剤、及び粘着剤層付き光学部材に関する。さらに詳しくは、本発明は、液晶表示装置を構成する偏光板などに好適に用いられ、該偏光板の伸縮に起因する白抜け現象の発生を防止し得る粘着剤層を形成するためのアクリル系粘着剤組成物、それから得られたアクリル系粘着剤及びこの粘着剤層付き光学部材に関するものである。 The present invention relates to an acrylic pressure-sensitive adhesive composition, an acrylic pressure-sensitive adhesive obtained by thermally crosslinking it, and an optical member with a pressure-sensitive adhesive layer. More specifically, the present invention is preferably used for a polarizing plate constituting a liquid crystal display device, and is an acrylic type for forming an adhesive layer that can prevent the occurrence of white spots due to expansion and contraction of the polarizing plate. The present invention relates to a pressure-sensitive adhesive composition, an acrylic pressure-sensitive adhesive obtained therefrom, and an optical member with this pressure-sensitive adhesive layer.
偏光板の伸縮により生じる内部応力を、粘着剤層が吸収・緩和することができないと、偏光板に作用する残留応力の分布が不均一となり、特にその周縁部に応力が集中する。その結果、液晶表示装置の周縁部が中央より明るくなり、液晶表示装置に白抜け現象が発生する原因になる。液晶表示装置に白抜け現象が発生する他の要因として、応力によって光学機能性フィルムや粘着剤層に発生する光学的な歪（複屈折の発生など）が考えられる。 If the pressure-sensitive adhesive layer cannot absorb or relieve internal stress caused by expansion and contraction of the polarizing plate, the distribution of residual stress acting on the polarizing plate becomes non-uniform, and stress is concentrated particularly on the peripheral portion. As a result, the peripheral edge of the liquid crystal display device becomes brighter than the center, causing a white spot phenomenon in the liquid crystal display device. Another factor that causes white spots in the liquid crystal display device is optical distortion (such as the occurrence of birefringence) that occurs in the optical functional film or the pressure-sensitive adhesive layer due to stress.
特許文献１には、高分子量アクリル系共重合体と、重量平均分子量が３万以下の低分子量アクリル系共重合体と、多官能性化合物からなる偏光板用粘着剤組成物が開示されており、該粘着剤組成物は偏光板の寸法変化に追随し白ヌケが発生しにくいと記載されている。しかしながら、特許文献１に記載の粘着剤組成物では重量平均分子量が３万以下の低分子量アクリル系共重合体の含有量が多いため、高温高湿下での発泡や剥がれを防ぐのは難しい。［比較例２］ Patent Document 1 discloses a pressure-sensitive adhesive composition for a polarizing plate comprising a high molecular weight acrylic copolymer, a low molecular weight acrylic copolymer having a weight average molecular weight of 30,000 or less, and a polyfunctional compound. It is described that the pressure-sensitive adhesive composition follows the change in dimensions of the polarizing plate and hardly causes white spots. However, since the pressure-sensitive adhesive composition described in Patent Document 1 has a high content of a low molecular weight acrylic copolymer having a weight average molecular weight of 30,000 or less, it is difficult to prevent foaming and peeling at high temperature and high humidity. [Comparative Example 2]
特許文献２には、官能基含有単量体が０.５重量％以下である低ガラス転移温度（Ｔｇ）アクリル系共重合体と官能基含有単量体が６重量％以上である高Ｔｇアクリル系共重合体の混合物と、官能基と反応可能な架橋剤のイソシアネート化合物とからなるゲル分率３０重量％未満の粘着剤組成物が開示されている。この粘着剤組成物は高Ｔｇアクリル系共重合体の分子内に架橋構造を形成し、低Ｔｇアクリル系共重合体の分子間をイソシアネート化合物の多量体で拘束することにより凝集力を発現している。しかしながら、この粘着剤組成物は分子間に架橋構造がほとんど形成されていないため白ヌケが生じにくいが、高温下での凝集力が低く、耐久性評価において発泡や剥がれの発生を抑制するのは難しい。 Patent Document 2 discloses a low glass transition temperature (Tg) acrylic copolymer having a functional group-containing monomer of 0.5% by weight or less and a high Tg acrylic having a functional group-containing monomer of 6% by weight or more. A pressure-sensitive adhesive composition having a gel fraction of less than 30% by weight comprising a mixture of a copolymer and an isocyanate compound as a crosslinking agent capable of reacting with a functional group is disclosed. This pressure-sensitive adhesive composition exhibits a cohesive force by forming a cross-linked structure in the molecule of a high Tg acrylic copolymer and constraining the molecules of the low Tg acrylic copolymer with a multimer of isocyanate compounds. Yes. However, this pressure-sensitive adhesive composition has little cross-linking structure between molecules, so white spots are hardly generated. However, the cohesive force at low temperatures is low, and it is difficult to suppress the occurrence of foaming and peeling in durability evaluation. difficult.
特許文献３には、アクリル系ポリマーを主成分とする粘着性ポリマー１００重量部と、それ単独でのガラス転移温度が−５℃以下となる重合体ブロックを含むブロック共重合体からなる上記アクリル系オリゴマー１〜１００重量部からなることを特徴とする粘着剤組成物が開示されている。このアクリル系オリゴマーは、それ単独でのガラス転移温度が−５℃以下となる重合体ブロックを含むことにより、被着体への固定時には被着体から剥離しない程度の接着力を有し、しかも経日により接着力の上昇がほとんど生じず、被着体からの剥離時には被着体を汚染することなく極めて容易に剥離することができる。また、これとは単量体組成の異なる重合体ブロックとの共重合体とすることで、少ないアクリル系オリゴマーの使用であっても前記効果を発揮することができる。このような優れた効果が発揮される理由について詳細は不明だが、各ブロックの相乗効果によってアクリル系ポリマーとの相溶性が向上するなどの作用で、接着力と剥離力などの上記特性を発揮できるものと考えられると記載されている。しかし、オリゴマー成分がフリーな状態で存在するために、湿熱条件化での耐久性に劣っていた。［比較例３］ Patent Document 3 discloses the above acrylic system comprising a block copolymer containing 100 parts by weight of an adhesive polymer having an acrylic polymer as a main component and a polymer block having a glass transition temperature of -5 ° C. or less alone. A pressure-sensitive adhesive composition comprising 1 to 100 parts by weight of an oligomer is disclosed. This acrylic oligomer contains a polymer block having a glass transition temperature of -5 ° C. or less by itself, so that it has an adhesive force that does not peel from the adherend when fixed to the adherend. The adhesive force hardly increases with the passage of time, and when peeling from the adherend, it can be peeled off very easily without contaminating the adherend. Moreover, the said effect can be exhibited even if it is the use of few acrylic oligomers by making it a copolymer with the polymer block from which a monomer composition differs from this. The details of why such an excellent effect is exhibited are unknown, but the above characteristics such as adhesive strength and peel strength can be exhibited by actions such as improved compatibility with acrylic polymers due to the synergistic effect of each block It is described that it is considered to be. However, since the oligomer component exists in a free state, the durability under wet heat conditions was inferior. [Comparative Example 3]
本発明は、このような状況下になされたもので、液晶表示装置を構成する偏光板などに好適に用いられ、該偏光板の伸縮に起因する白抜け現象の発生を防止し得る粘着剤からなる層を形成するためのアクリル系粘着剤組成物、及びそれから得られた上記性状を有するアクリル系粘着剤を提供することを目的とするものである。 The present invention has been made under such circumstances, and is suitably used for a polarizing plate constituting a liquid crystal display device, and from an adhesive that can prevent the occurrence of white spots due to expansion and contraction of the polarizing plate. It is an object to provide an acrylic pressure-sensitive adhesive composition for forming a layer and an acrylic pressure-sensitive adhesive having the above properties obtained therefrom.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、下記の知見を得た。
重量平均分子量が特定の範囲にある高分子量の第１の(メタ)アクリル酸エステル重合体と、重量平均分子量が特定の範囲にある低分子量の第２の(メタ)アクリル酸エステル重合体と、イソシアネート系架橋剤を含む粘着剤組成物において、前記第２の(メタ)アクリル酸エステル重合体を、水酸基含有(メタ)アクリレート系モノマー単位を有するトリブロック共重合体とし、かつそれを特定の割合で含有させたものを熱架橋することにより、前記低分子量のトリブロック共重合体における水酸基が架橋点となって架橋が生じる。
その結果、低分子量トリブロック共重合体の架橋により形成された三次元網目構造の中に、高分子量である第１の(メタ)アクリル酸エステル重合体が貫入することにより、偏光板などの光学部材の伸縮により生じる内部応力を、効果的に吸収・緩和することができるものと推定される。
また、前記粘着剤組成物により形成される粘着剤のゲル分率を４０％以上とすることにより、前記の内部応力の吸収・緩和を維持しながら、光学用途に必要な凝集力を粘着剤に与えることができることを見出した。
本発明は、かかる知見に基づいて完成したものである。
As a result of intensive studies to achieve the above object, the present inventors have obtained the following knowledge.
A high molecular weight first (meth) acrylate polymer having a weight average molecular weight in a specific range; a low molecular weight second (meth) acrylate polymer having a weight average molecular weight in a specific range; In the pressure-sensitive adhesive composition containing an isocyanate-based crosslinking agent, the second (meth) acrylic acid ester polymer is a triblock copolymer having a hydroxyl group-containing (meth) acrylate-based monomer unit, and a specific ratio thereof. By thermally cross-linking what is contained in the above, the hydroxyl group in the low molecular weight triblock copolymer becomes a cross-linking point to cause cross-linking.
As a result, the first (meth) acrylic acid ester polymer having a high molecular weight penetrates into the three-dimensional network structure formed by crosslinking of the low molecular weight triblock copolymer. It is presumed that the internal stress generated by the expansion and contraction of the member can be effectively absorbed and relaxed.
In addition, by setting the gel fraction of the pressure-sensitive adhesive formed by the pressure-sensitive adhesive composition to 40% or more, the cohesive force necessary for optical applications is maintained in the pressure-sensitive adhesive while maintaining absorption and relaxation of the internal stress. Found that can be given.
The present invention has been completed based on such findings.
すなわち、本発明は、
［１］重量平均分子量が１００万〜２５０万の第１の(メタ)アクリル酸エステル重合体（Ａ）と、重量平均分子量が２万〜１５万の第２の(メタ)アクリル酸エステル重合体（Ｂ）と、イソシアネート系架橋剤（Ｃ）とを含有する粘着剤組成物であって、
（１）前記第２の(メタ)アクリル酸エステル重合体（Ｂ）が、水酸基含有(メタ)アクリレート系モノマー単位を１．５質量％以上有するトリブロック共重合体であること、
（２）前記第２の(メタ)アクリル酸エステル重合体（Ｂ）の含有量が、前記第１の(メタ)アクリル酸エステル重合体（Ａ）１００質量部に対して、４０質量部未満であること、及び
（３）粘着剤組成物から形成される粘着剤のゲル分率が４０％以上であること、
を特徴とするアクリル系粘着剤組成物、
［２］前記第１の(メタ)アクリル酸エステル重合体（Ａ）が、反応性官能基を有しない（メタ）アクリレート系モノマーのみから構成されるか、もしくは、反応性官能基を有しない（メタ）アクリレート系モノマーとカルボキシル基含有（メタ）アクリレート系モノマーのみから構成されることを特徴とする上記[１]に記載のアクリル系粘着剤組成物、
［３］トリブロック共重合体の形態が、ｂ２−ｂ１−ｂ２型又はｂ１−ｂ２−ｂ１型（ただし、ｂ１は架橋点となる官能基を有しない(メタ)アクリレート系モノマー単位からなるブロックを示し、ｂ２は水酸基含有(メタ)アクリレート系モノマー単位からなるブロックを示す。）である、上記[１]又は［２］項に記載のアクリル系粘着剤組成物、
［４］トリブロック共重合体の重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が、１.０〜１.８である、上記[１]〜[３]項のいずれかに記載のアクリル系粘着剤組成物、
［５］トリブロック共重合体における水酸基含有(メタ)アクリレート系モノマー単位の含有量が１.５〜２０質量％であり、かつトリブロック共重合体の含有量が、第１の(メタ)アクリル酸エステル重合体（Ａ）１００質量部に対して、１０〜３０質量部である、上記[１]〜[４]項のいずれかに記載のアクリル系粘着剤組成物、
［６］トリブロック共重合体を、リビングラジカル重合によって形成する、上記[１]〜[５]項のいずれかに記載のアクリル系粘着剤組成物、
［７］イソシアネート系架橋剤（Ｃ）の含有量が、第２の(メタ)アクリル酸エステル重合体（Ｂ）１００質量部に対して、５〜２０質量部である、上記[１]〜[６]項のいずれかに記載のアクリル系粘着剤組成物、
［８］上記[１]〜[７]項のいずれかに記載のアクリル系粘着剤組成物を、熱架橋してなることを特徴とするアクリル系粘着剤、及び
［９］光学部材上に、上記[８]項に記載のアクリル系粘着剤を層状に積層してなることを特徴とする粘着剤層付き光学部材、
を提供するものである。
That is, the present invention
[1] A first (meth) acrylic acid ester polymer (A) having a weight average molecular weight of 1,000,000 to 2.5 million and a second (meth) acrylic acid ester polymer having a weight average molecular weight of 20,000 to 150,000. A pressure-sensitive adhesive composition containing (B) and an isocyanate-based crosslinking agent (C),
(1) The second (meth) acrylic acid ester polymer (B) is a triblock copolymer having a hydroxyl group-containing (meth) acrylate monomer unit of 1.5% by mass or more ,
(2) The content of the second (meth) acrylic acid ester polymer (B) is less than 40 parts by mass with respect to 100 parts by mass of the first (meth) acrylic acid ester polymer (A). And (3) the gel fraction of the pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition is 40% or more,
An acrylic pressure-sensitive adhesive composition,
[2] The first (meth) acrylic acid ester polymer (A) is composed only of a (meth) acrylate monomer having no reactive functional group, or has no reactive functional group ( The acrylic pressure-sensitive adhesive composition according to the above [1], comprising only a (meth) acrylate monomer and a carboxyl group-containing (meth) acrylate monomer,
[ 3 ] The form of the triblock copolymer is b2-b1-b2 type or b1-b2-b1 type (where b1 is a block composed of a (meth) acrylate monomer unit having no functional group that serves as a crosslinking point. An acrylic pressure-sensitive adhesive composition according to the above [1] or [2] , wherein b2 is a block comprising a hydroxyl group-containing (meth) acrylate monomer unit),
[ 4 ] The above [1] to [ 3 ], wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the triblock copolymer is 1.0 to 1.8. The acrylic pressure-sensitive adhesive composition according to any one of the items,
[ 5 ] The content of the hydroxyl group-containing (meth) acrylate monomer unit in the triblock copolymer is 1.5 to 20% by mass, and the content of the triblock copolymer is the first (meth) acrylic. The acrylic pressure-sensitive adhesive composition according to any one of [1] to [ 4 ], which is 10 to 30 parts by mass with respect to 100 parts by mass of the acid ester polymer (A),
[ 6 ] The acrylic pressure-sensitive adhesive composition according to any one of [1] to [ 5 ] above, wherein the triblock copolymer is formed by living radical polymerization.
[ 7 ] The content of the isocyanate-based crosslinking agent (C) is 5 to 20 parts by mass with respect to 100 parts by mass of the second (meth) acrylic acid ester polymer (B). 6 ] The acrylic pressure-sensitive adhesive composition according to any one of items
[ 8 ] An acrylic pressure-sensitive adhesive obtained by thermally crosslinking the acrylic pressure-sensitive adhesive composition according to any one of [1] to [ 7 ] above, and [ 9 ] an optical member, An optical member with a pressure-sensitive adhesive layer, wherein the acrylic pressure-sensitive adhesive according to item [ 8 ] is laminated in layers;
Is to provide.
本発明によれば、液晶表示装置を構成する偏光板などに好適に用いられ、偏光板の伸縮に起因する白抜け現象の発生を防止し得る粘着剤層を形成するためのアクリル系粘着剤組成物、それから得られたアクリル系粘着剤及びこの粘着剤層付き光学部材を提供することができる。 According to the present invention, an acrylic pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer that can be suitably used for a polarizing plate constituting a liquid crystal display device and can prevent occurrence of white spots due to expansion and contraction of the polarizing plate. An acrylic pressure-sensitive adhesive obtained therefrom and an optical member with this pressure-sensitive adhesive layer can be provided.
まず、本発明のアクリル系粘着剤組成物について説明する。
［アクリル系粘着剤組成物］
本発明のアクリル系粘着剤組成物（以下、単に粘着剤組成物と称することがある。）は、重量平均分子量が１００万〜２５０万の第１の(メタ)アクリル酸エステル重合体（Ａ）と、重量平均分子量が２万〜１５万の第２の(メタ)アクリル酸エステル重合体（Ｂ）と、イソシアネート系架橋剤（Ｃ）とを含有する粘着剤組成物であって、
（１）前記第２の(メタ)アクリル酸エステル重合体（Ｂ）が、水酸基含有(メタ)アクリレート系モノマー単位を有するトリブロック共重合体であること、
（２）前記第２の(メタ)アクリル酸エステル重合体（Ｂ）の含有量が、前記第１の(メタ)アクリル酸エステル重合体（Ａ）１００質量部に対して、４０質量部未満であること、及び
（３）粘着剤組成物から形成される粘着剤のゲル分率が４０％以上であること、
を特徴とする。
該粘着剤組成物により得られる粘着剤は、重合体（Ｂ）と架橋剤（Ｃ）により三次元網目構造を形成し、該三次元網目構造中に２つ以上の重合体（Ａ）が挿入されることにより重合体（Ａ）間に擬似的な架橋構造が形成されているものと推定される。すなわち、各重合体（Ａ）間は、その大部分が化学的な架橋構造でなく、前記三次元網目構造を介した擬似的な架橋構造により繋がれているため、架橋部分の可動性が化学的な架橋による場合よりも大きいものと推定される。そのため、形成される粘着剤は応力緩和性に富んだものになっている。
さらに、本発明においては、重合体（Ｂ）中の架橋点がブロック的に配置されることにより、形成される粘着剤の前記三次元網目構造の網目の大きさを最適となるように調節することができ、これにより、高い次元での応力緩和性の向上と凝集力の向上の両立を実現しているものと推定される。
First, the acrylic pressure-sensitive adhesive composition of the present invention will be described.
[Acrylic adhesive composition]
The acrylic pressure-sensitive adhesive composition of the present invention (hereinafter sometimes simply referred to as a pressure-sensitive adhesive composition) is a first (meth) acrylic acid ester polymer (A) having a weight average molecular weight of 1,000,000 to 2,500,000. A pressure-sensitive adhesive composition containing a second (meth) acrylic acid ester polymer (B) having a weight average molecular weight of 20,000 to 150,000, and an isocyanate-based crosslinking agent (C),
(1) The second (meth) acrylic acid ester polymer (B) is a triblock copolymer having a hydroxyl group-containing (meth) acrylate monomer unit,
(2) The content of the second (meth) acrylic acid ester polymer (B) is less than 40 parts by mass with respect to 100 parts by mass of the first (meth) acrylic acid ester polymer (A). And (3) the gel fraction of the pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition is 40% or more,
It is characterized by.
The pressure-sensitive adhesive obtained from the pressure-sensitive adhesive composition forms a three-dimensional network structure with the polymer (B) and the crosslinking agent (C), and two or more polymers (A) are inserted into the three-dimensional network structure. As a result, it is presumed that a pseudo cross-linked structure is formed between the polymers (A). That is, most of the polymers (A) are connected not by a chemical cross-linked structure but by a pseudo cross-linked structure via the three-dimensional network structure. It is presumed to be larger than in the case of general crosslinking. For this reason, the pressure-sensitive adhesive formed is rich in stress relaxation properties.
Furthermore, in the present invention, the cross-linking points in the polymer (B) are arranged in a block manner so that the size of the three-dimensional network structure of the pressure-sensitive adhesive to be formed is adjusted to be optimal. Thus, it is presumed that the improvement of the stress relaxation property and the improvement of the cohesive force are realized at a high level.
（第１の(メタ)アクリル酸エステル重合体（Ａ））
本発明のアクリル系粘着剤組成物において、成分（Ａ）として用いられる第１の(メタ)アクリル酸エステル重合体としては、反応性官能基を有しない(メタ)アクリレート系モノマーを主要な構成成分とすることが好ましい。第１の該重合体は、反応性官能基を有しない(メタ)アクリレート系モノマーのみから構成されてもよいが、液晶ガラスセル等のガラス表面への接着性等を考慮して、カルボキシル基を有する(メタ)アクリレート系モノマーを少量共重合させることがより好ましい。
(First (meth) acrylic acid ester polymer (A))
In the acrylic pressure-sensitive adhesive composition of the present invention, the first (meth) acrylic acid ester polymer used as the component (A) is a (meth) acrylate monomer having no reactive functional group as a main component. It is preferable that The first polymer may be composed of only a (meth) acrylate-based monomer having no reactive functional group. However, in consideration of adhesion to a glass surface such as a liquid crystal glass cell, a carboxyl group is included. It is more preferable to copolymerize a small amount of the (meth) acrylate monomer.
反応性官能基を有しない(メタ)アクリレート系モノマーとしては特に制限はなく、例えば、エステル部分のアルキル基の炭素数が１〜２０の(メタ)アクリル酸エステルを好ましく挙げることができる。ここで、エステル部分のアルキル基の炭素数が１〜２０の(メタ)アクリル酸エステルの例としては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸２−エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸デシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸ミリスチル、(メタ)アクリル酸パルミチル、(メタ)アクリル酸ステアリルなどが挙げられる。これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
これらの化合物のうち、特に、アクリル酸ブチルが、適度な粘着性能を得ることができ、かつ、重量平均分子量１００万以上の(メタ)アクリル酸エステル共重合体を容易に製造できる点で好ましい。
There is no restriction | limiting in particular as a (meth) acrylate type monomer which does not have a reactive functional group, For example, the C1-C20 (meth) acrylic acid ester whose carbon number of the ester part can be mentioned preferably is mentioned. Here, examples of the (meth) acrylic acid ester having 1 to 20 carbon atoms of the alkyl group in the ester portion include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth ) Butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, Examples include dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.
Among these compounds, butyl acrylate is particularly preferable in that it can obtain an appropriate pressure-sensitive adhesive performance and can easily produce a (meth) acrylic acid ester copolymer having a weight average molecular weight of 1,000,000 or more.
一方、所望により配合されるカルボキシル基含有(メタ)アクリレート系モノマーの具体例としては、(メタ)アクリル酸、クロトン酸、マレイン酸、イタコン酸、シトラコン酸などが挙げられる。これらは１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよいが、これらの中で重量平均分子量１００万以上の(メタ)アクリル酸エステル共重合体を容易に製造できる点から、アクリル酸が好ましい。
また、水酸基含有(メタ)アクリレート系モノマー、アミノ基含有(メタ)アクリレート系モノマー、及びチオール基含有(メタ)アクリレート系モノマー等のカルボキシル基含有(メタ)アクリレート系モノマー以外の反応性官能基含有(メタ)アクリレート系モノマーは、第１の(メタ)アクリル酸エステル重合体（Ａ）の構成単位として含まれないことが好ましい。第２の(メタ)アクリル酸エステル重合体（Ｂ）とイソシアネート系架橋剤（Ｃ）による三次元網目構造の形成を阻害するおそれがあるからである。
その他の官能基含有モノマーとして、(メタ)アクリル酸フェニル等の芳香族環を有する(メタ)アクリル酸エステル、アクリルアミド、メタクリルアミド等の非架橋性のアクリルアミド、(メタ)アクリル酸Ｎ,Ｎ−ジメチルアミノエチル、(メタ)アクリル酸Ｎ,Ｎ−ジメチルアミノプロピル等の非架橋性の３級アミノ基を有する(メタ)アクリル酸エステル、酢酸ビニル、スチレンなどが挙げられ、これらは本発明の効果を損なわない範囲で適宜用いることができる。
On the other hand, specific examples of the carboxyl group-containing (meth) acrylate monomer blended as desired include (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid and the like. These may be used singly or in combination of two or more, among which a (meth) acrylic acid ester copolymer having a weight average molecular weight of 1 million or more can be easily produced. From the viewpoint, acrylic acid is preferable.
In addition, reactive functional groups other than carboxyl group-containing (meth) acrylate monomers such as hydroxyl group-containing (meth) acrylate monomers, amino group-containing (meth) acrylate monomers, and thiol group-containing (meth) acrylate monomers ( It is preferable that the (meth) acrylate monomer is not included as a constituent unit of the first (meth) acrylic acid ester polymer (A). This is because the formation of a three-dimensional network structure by the second (meth) acrylic acid ester polymer (B) and the isocyanate-based crosslinking agent (C) may be hindered.
Other functional group-containing monomers include (meth) acrylic acid esters having aromatic rings such as phenyl (meth) acrylate, non-crosslinkable acrylamides such as acrylamide and methacrylamide, N, N-dimethyl (meth) acrylate Examples include aminoethyl, (meth) acrylic acid ester having a non-crosslinkable tertiary amino group such as N, N-dimethylaminopropyl (meth) acrylate, vinyl acetate, styrene, and the like. It can be used as appropriate within the range not damaged.
当該第１の(メタ)アクリル酸エステル重合体において、反応性官能基を有しない(メタ)アクリレート系モノマー単位と、カルボキシル基含有(メタ)アクリレート系モノマー単位との含有割合は、リワーク性の観点から、質量比で１００：０〜８０：２０の範囲にあることが好ましく、上記観点に加え、耐久性の観点から９８：２〜９０：１０の範囲にあることがより好ましい。
また、当該第１の(メタ)アクリル酸エステル重合体（Ａ）は、後述の（Ｂ）成分のようにリビングラジカル重合により得る必要はなく、通常のラジカル重合法により得られるものでよい。ここで、該重合体（Ａ）の重量平均分子量（Ｍｗ）は、１００万〜２５０万であることを要する。該重量平均分子量が１００万未満であると耐久性を低下させる場合があり、該重量平均分子量が２５０万を超えると応力緩和性が阻害され、光漏れ防止性を低下させる場合があるからである。同様の観点から該重量平均分子量は、好ましくは１２０万〜２００万の範囲であり、より好ましくは１４０万〜１８０万の範囲である。
なお、上記重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定したポリスチレン換算の値である。
本発明の粘着剤組成物においては、成分（Ａ）として、第１の(メタ)アクリル酸エステル重合体は１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
In the first (meth) acrylic acid ester polymer, the content ratio of the (meth) acrylate monomer unit having no reactive functional group and the carboxyl group-containing (meth) acrylate monomer unit is determined from the viewpoint of reworkability. Therefore, the mass ratio is preferably in the range of 100: 0 to 80:20, and more preferably in the range of 98: 2 to 90:10 from the viewpoint of durability in addition to the above viewpoint.
Further, the first (meth) acrylic acid ester polymer (A) does not need to be obtained by living radical polymerization as in the later-described component (B), and may be obtained by a normal radical polymerization method. Here, the weight average molecular weight (Mw) of the polymer (A) is required to be 1 million to 2.5 million. If the weight average molecular weight is less than 1,000,000, the durability may be lowered, and if the weight average molecular weight exceeds 2.5 million, the stress relaxation property may be inhibited and the light leakage prevention property may be lowered. . From the same viewpoint, the weight average molecular weight is preferably in the range of 1,200,000 to 2,000,000, more preferably in the range of 1,400,000 to 1,800,000.
In addition, the said weight average molecular weight is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
In the pressure-sensitive adhesive composition of the present invention, as the component (A), the first (meth) acrylic acid ester polymer may be used alone or in combination of two or more.
（第２の(メタ)アクリル酸エステル重合体（Ｂ））
本発明のアクリル系粘着剤組成物において、成分（Ｂ）として用いられる第２の(メタ)アクリル酸エステル重合体は、水酸基含有(メタ)アクリレート系モノマー単位を有するトリブロック共重合体であることを要する。
このトリブロック共重合体の形態は、ｂ２−ｂ１−ｂ２型又はｂ１−ｂ２−ｂ１型（ただし、ｂ１は反応性官能基を有しない(メタ)アクリレート系モノマー単位からなるブロックを示し、ｂ２は水酸基含有(メタ)アクリレート系モノマー単位からなるブロックを示す。）であることが好ましい。
当該成分（Ｂ）のトリブロック共重合体は、原料成分として反応性官能基を有しない(メタ)アクリレート系モノマーと、反応性官能基である水酸基を有する水酸基含有(メタ)アクリレート系モノマーが用いられる。
なお、本発明において、ブロック共重合体とは、反応性官能基を有しない(メタ)アクリレート系モノマーからなるブロック部分と水酸基含有(メタ)アクリレート系モノマーからなるブロック部分を有する共重合体であることを意味し、それぞれのブロック部分内は複数種類のモノマーから構成されていても良いし、そのブロック部分内では複数種類のモノマーがブロック的に配置されていてもランダム的に配置されていてもよい。しかし、三次元網目構造の制御の観点から、反応性官能基を有しない(メタ)アクリレート系モノマーからなるブロック部分も水酸基含有(メタ)アクリレート系モノマーからなるブロック部分のいずれについても、それぞれ１種類のモノマーのみから構成されていることが好ましい。
(Second (meth) acrylic ester polymer (B))
In the acrylic pressure-sensitive adhesive composition of the present invention, the second (meth) acrylic acid ester polymer used as the component (B) is a triblock copolymer having a hydroxyl group-containing (meth) acrylate monomer unit. Cost.
The form of this triblock copolymer is b2-b1-b2 type or b1-b2-b1 type (where b1 is a block composed of a (meth) acrylate monomer unit having no reactive functional group, and b2 is It is preferably a hydroxyl group-containing (meth) acrylate monomer block.
The triblock copolymer of the component (B) uses a (meth) acrylate monomer having no reactive functional group and a hydroxyl group-containing (meth) acrylate monomer having a reactive functional group as a raw material component. It is done.
In the present invention, the block copolymer is a copolymer having a block portion composed of a (meth) acrylate monomer having no reactive functional group and a block portion composed of a hydroxyl group-containing (meth) acrylate monomer. This means that each block portion may be composed of a plurality of types of monomers, and within that block portion, a plurality of types of monomers may be arranged in blocks or randomly. Good. However, from the viewpoint of controlling the three-dimensional network structure, each of the block portion made of a (meth) acrylate monomer having no reactive functional group and the block portion made of a hydroxyl group-containing (meth) acrylate monomer is used. It is preferable that it is comprised only from the monomer of.
反応性官能基を有しない(メタ)アクリレート系モノマーとしては特に制限はなく、例えば、エステル部分のアルキル基の炭素数が１〜２０の(メタ)アクリル酸エステルを好ましく挙げることができる。ここで、エステル部分のアルキル基の炭素数が１〜２０の(メタ)アクリル酸エステルの例としては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸２−エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸デシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸ミリスチル、(メタ)アクリル酸パルミチル、(メタ)アクリル酸ステアリルなどが挙げられる。これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
これらの化合物のうち、特に、アクリル酸ブチルが、重合性がよく、かつ適度な粘着性能を得ることができる点から好ましい。
There is no restriction | limiting in particular as a (meth) acrylate type monomer which does not have a reactive functional group, For example, the C1-C20 (meth) acrylic acid ester whose carbon number of the ester part can be mentioned preferably is mentioned. Here, examples of the (meth) acrylic acid ester having 1 to 20 carbon atoms of the alkyl group in the ester portion include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth ) Butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, Examples include dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.
Among these compounds, butyl acrylate is particularly preferable from the viewpoint of good polymerizability and appropriate adhesive performance.
一方、水酸基含有(メタ)アクリレート系モノマーの具体例としては、(メタ)アクリル酸２−ヒドロキシエチル、(メタ)アクリル酸２−ヒドロキシプロピル、(メタ)アクリル酸３−ヒドロキシプロピル、(メタ)アクリル酸２−ヒドロキシブチル、(メタ)アクリル酸３−ヒドロキシブチル、(メタ)アクリル酸４−ヒドロキシブチルなどの(メタ)アクリル酸ヒドロキシアルキルエステルなどが挙げられる。これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。これらのうち特にアクリル酸２−ヒドロキシエチル、アクリル酸３−ヒドロキシプロピル、アクリル酸４−ヒドロキシブチルがより好ましい。重合体（Ｂ）中に組み込まれた際に架橋点となる水酸基が隣接の炭素原子や側鎖部分により架橋剤（Ｃ）との接触が制限される恐れが少ないからである。 On the other hand, specific examples of the hydroxyl group-containing (meth) acrylate monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic. Examples include (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxybutyl acid, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. These may be used alone or in combination of two or more. Of these, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate are more preferable. This is because the hydroxyl group that becomes a crosslinking point when incorporated into the polymer (B) is less likely to be limited in contact with the crosslinking agent (C) by the adjacent carbon atom or side chain portion.
当該成分（Ｂ）のトリブロック共重合体は、重量平均分子量が２万〜１５万の範囲にあることを要する。
このような低分子量の熱架橋性トリブロック共重合体を含む粘着剤組成物を熱架橋することにより、当該低分子量のトリブロック共重合体における水酸基が架橋点となってトリブロック共重合体間に架橋が生じる。
その結果、低分子量のトリブロック共重合体の架橋により形成された三次元網目構造の中に、前述した高分子量である第１の(メタ)アクリル酸エステル重合体が貫入することにより、偏光板などの光学部材の伸縮により生じる内部応力を、効果的に吸収・緩和することができるものと考えられる。
当該トリブロック共重合体の重量平均分子量は、好ましくは２.５万〜１２万であり、より好ましくは３万〜１０万である。また、得られる三次元網目構造の均一化を図る観点から、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）、すなわち分子量分布（ＰＤＩ）が、１.０〜１.８であることが好ましい。
なお、当該トリブロック共重合体の重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、ゲルパーミエーションクロマトグラフィー法（ＧＰＣ法）により測定された標準ポリスチレン換算の値である。
The triblock copolymer of the said component (B) requires that a weight average molecular weight exists in the range of 20,000-150,000.
By thermally cross-linking the pressure-sensitive adhesive composition containing such a low molecular weight heat-crosslinkable triblock copolymer, the hydroxyl group in the low molecular weight triblock copolymer becomes a crosslinking point between the triblock copolymers. Cross-linking occurs.
As a result, the first (meth) acrylate polymer having a high molecular weight penetrates into the three-dimensional network structure formed by crosslinking of the low molecular weight triblock copolymer, whereby the polarizing plate It is considered that the internal stress generated by the expansion and contraction of the optical member such as can be effectively absorbed and relaxed.
The weight average molecular weight of the triblock copolymer is preferably 25,000 to 120,000, and more preferably 30,000 to 100,000. Further, from the viewpoint of making the obtained three-dimensional network structure uniform, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), that is, the molecular weight distribution (PDI) is 1.0 to 1.0. It is preferably 1.8.
In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the said triblock copolymer are the values of standard polystyrene conversion measured by the gel permeation chromatography method (GPC method).
＜トリブロック共重合体の製造＞
当該トリブロック共重合体は、リビングラジカル重合により、効果的に製造することができる。
これにより、重合体（Ｂ）及び架橋剤（Ｃ）により形成される三次元網目構造の網目の大きさを、重合体（Ａ）がある程度の自由度を持って拘束される好適な範囲に調節することができると推定される。そのため、応力緩和性に富みながら優れた凝集力を有する粘着剤を得ることが可能となる。
さらに、リビングラジカル重合を利用することにより、重合体（Ｂ）の分子鎖の長さが揃い、架橋部位の配置も一定とできるため、得られる粘着剤中に均一な三次元網目構造体を配置させることができると推定される。これにより、粘着剤全体で均一な応力緩和性の実現が期待される。
リビングラジカル重合法としては、従来公知の方法、例えば重合制御剤として、原子移動ラジカル重合剤を用いる原子移動ラジカル重合法（ＡＴＲＰ重合法）、可逆付加−開裂連鎖移動剤を用いる可逆付加−開裂連鎖移動による重合法（ＲＡＦＴ重合法）、重合開始剤として有機テルル化合物を用いる重合法などを採用することができる。これらのリビングラジカル重合法の中で、有機テルル化合物を重合開始剤として用いる方法が、分子量の制御性及び水系においても重合が可能であることなどから好ましい。以下に、有機テルル化合物を重合開始剤として用いる方法を示す。
<Manufacture of triblock copolymer>
The triblock copolymer can be effectively produced by living radical polymerization.
As a result, the size of the three-dimensional network formed by the polymer (B) and the crosslinking agent (C) is adjusted to a suitable range in which the polymer (A) is constrained with a certain degree of freedom. It is estimated that you can. Therefore, it is possible to obtain a pressure-sensitive adhesive having excellent cohesive strength while being rich in stress relaxation.
Furthermore, by using living radical polymerization, the molecular chain length of the polymer (B) is uniform, and the arrangement of the cross-linking sites can be made constant, so a uniform three-dimensional network structure is arranged in the resulting adhesive. It is estimated that Thereby, the realization of uniform stress relaxation property is expected in the entire pressure-sensitive adhesive.
As the living radical polymerization method, a conventionally known method, for example, an atom transfer radical polymerization method using an atom transfer radical polymerization agent (ATRP polymerization method) as a polymerization control agent, a reversible addition-cleavage chain using a reversible addition-cleavage chain transfer agent. A polymerization method by transfer (RAFT polymerization method), a polymerization method using an organic tellurium compound as a polymerization initiator, and the like can be employed. Among these living radical polymerization methods, a method using an organic tellurium compound as a polymerization initiator is preferable because of controllability of molecular weight and polymerization in an aqueous system. Below, the method of using an organic tellurium compound as a polymerization initiator is shown.
《有機テルル化合物を用いるリビングラジカル重合》
当該第２の(メタ)アクリル酸エステル重合体（Ｂ）［トリブロック共重合体］は、例えば下記一般式（１）で表されるリビングラジカル重合開始剤（以下、有機テルル化合物と称することがある。）を用いて、反応性官能基を有しない(メタ)アクリレート系モノマーと、水酸基含有(メタ)アクリレート系モノマーとを、所定の順で共重合させることにより、製造することができる。
The second (meth) acrylic acid ester polymer (B) [triblock copolymer] is, for example, a living radical polymerization initiator (hereinafter, referred to as an organic tellurium compound) represented by the following general formula (1). And a (meth) acrylate monomer having no reactive functional group and a hydroxyl group-containing (meth) acrylate monomer are copolymerized in a predetermined order.
Ｒ1で示される基は、具体的には次の通りである。
炭素数１〜８のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、シクロプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、シクロブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基等の炭素数１〜８の直鎖状、分岐鎖状又は環状のアルキル基を挙げることができる。好ましいアルキル基としては、炭素数１〜４の直鎖状又は分岐鎖状のアルキル基、より好ましくはメチル基又はエチル基が良い。
アリール基としては、フェニル基、ナフチル基等、置換アリール基としては置換基を有しているフェニル基、置換基を有しているナフチル基等、芳香族へテロ環基としてはピリジル基、フリル基、チエニル基等を挙げることができる。上記置換基を有しているアリール基の置換基としては、例えば、ハロゲン原子、水酸基、アルコキシ基、アミノ基、ニトロ基、シアノ基、−ＣＯＲ5で示されるカルボニル含有基（Ｒ5＝炭素数１〜８のアルキル基、アリール基、炭素数１〜８のアルコキシ基、アリーロキシ基）、スルホニル基、トリフルオロメチル基等を挙げることができる。好ましいアリール基としては、フェニル基、トリフルオロメチル置換フェニル基が良い。また、これら置換基は、１個又は２個置換しているのが良く、パラ位若しくはオルト位が好ましい。
Specific examples of the group represented by R 1 are as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclobutyl group, and n-pentyl. Examples thereof include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms such as a group, n-hexyl group, n-heptyl group and n-octyl group. A preferable alkyl group is a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.
As the aryl group, a phenyl group, a naphthyl group, etc., as a substituted aryl group, a phenyl group having a substituent, a naphthyl group having a substituent, etc., as an aromatic heterocyclic group, a pyridyl group, furyl Group, thienyl group and the like. Examples of the substituent of the aryl group having the above substituent include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by —COR 5 (R 5 = carbon number). 1-8 alkyl groups, aryl groups, C1-C8 alkoxy groups, aryloxy groups), sulfonyl groups, trifluoromethyl groups, and the like. Preferred aryl groups are a phenyl group and a trifluoromethyl-substituted phenyl group. These substituents may be substituted one or two, and the para position or ortho position is preferable.
Ｒ2及びＲ3で示される各基は、具体的には次の通りである。
炭素数１〜８のアルキル基としては、上記Ｒ1で示したアルキル基と同様のものを挙げることができる。
Ｒ4で示される各基は、具体的には次の通りである。
アリール基、置換アリール基、芳香族へテロ環基としては上記Ｒ1で示した基と同様のものを挙げることができる。
アシル基としては、ホルミル基、アセチル基、ベンゾイル基等を挙げることができる。
オキシカルボニル基としては、−ＣＯＯＲ6（Ｒ6＝Ｈ、炭素数１〜８のアルキル基、アリール基）で示される基が好ましく、例えばカルボキシル基、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ｎ−ブトキシカルボニル基、ｓｅｃ−ブトキシカルボニル基、ｔｅｒ−ブトキシカルボニル基、ｎ−ペントキシカルボニル基、フェノキシカルボニル基等を挙げることができる。好ましいオキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基が良い。
Each group represented by R 2 and R 3 is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as those described above for R 1 .
Each group represented by R 4 is specifically as follows.
Examples of the aryl group, substituted aryl group, and aromatic heterocyclic group include the same groups as those described above for R 1 .
Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group.
As the oxycarbonyl group, a group represented by —COOR 6 (R 6 ═H, alkyl group having 1 to 8 carbon atoms, aryl group) is preferable, and examples thereof include a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, An n-butoxycarbonyl group, a sec-butoxycarbonyl group, a ter-butoxycarbonyl group, an n-pentoxycarbonyl group, a phenoxycarbonyl group, and the like can be given. Preferred oxycarbonyl groups are a methoxycarbonyl group and an ethoxycarbonyl group.
好ましいＲ4で示される各基としては、アリール基、置換アリール基、オキシカルボニル基が良い。好ましいアリール基としては、フェニル基が良い。好ましい置換アリール基としては、ハロゲン原子置換フェニル基、トリフルオロメチル置換フェニル基が良い。また、これら置換基は、ハロゲン原子の場合は、１〜５個置換しているのが良い。アルコキシ基やトリフルオロメチル基の場合は、１個又は２個置換しているのが良く、１個置換の場合は、パラ位若しくはオルト位が好ましく、２個置換の場合は、メタ位が好ましい。好ましいオキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基が良い。 Preferred groups represented by R 4 are an aryl group, a substituted aryl group, and an oxycarbonyl group. A preferred aryl group is a phenyl group. Preferred examples of the substituted aryl group include a halogen atom substituted phenyl group and a trifluoromethyl substituted phenyl group. In addition, in the case of a halogen atom, these substituents are preferably substituted by 1-5. In the case of an alkoxy group or a trifluoromethyl group, one or two substituents may be substituted. In the case of one substitution, the para position or the ortho position is preferable, and in the case of two substitutions, the meta position is preferable. . Preferred oxycarbonyl groups are a methoxycarbonyl group and an ethoxycarbonyl group.
好ましい一般式（１）で示される有機テルル化合物Ｉとしては、Ｒ1が、炭素数１〜４のアルキル基を示し、Ｒ2及びＲ3が、水素原子又は炭素数１〜４のアルキル基を示し、Ｒ4が、アリール基、置換アリール基、オキシカルボニル基で示される化合物が良い。特に好ましくは、Ｒ1が、炭素数１〜４のアルキル基を示し、Ｒ2及びＲ3が、水素原子又は炭素数１〜４のアルキル基を示し、Ｒ4が、フェニル基、置換フェニル基、メトキシカルボニル基、エトキシカルボニル基が良い。 As the organic tellurium compound I represented by the general formula (1), R 1 represents an alkyl group having 1 to 4 carbon atoms, and R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 4 is preferably an aryl group, a substituted aryl group, or an oxycarbonyl group. Particularly preferably, R 1 represents an alkyl group having 1 to 4 carbon atoms, R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 4 represents a phenyl group or a substituted phenyl group. A methoxycarbonyl group and an ethoxycarbonyl group are preferable.
一般式（１）で示される有機テルル化合物は、具体的には次の通りである。
有機テルル化合物としては、(メチルテラニル−メチル)ベンゼン、(１−メチルテラニル−エチル)ベンゼン、(２−メチルテラニル−プロピル)ベンゼン、１−クロロ−４−(メチルテラニル−メチル)ベンゼン、１−ヒドロキシ−４−(メチルテラニル−メチル)ベンゼン、１−メトキシ−４−(メチルテラニル−メチル)ベンゼン、１−アミノ−４−(メチルテラニル−メチル)ベンゼン、１−ニトロ−４−(メチルテラニル−メチル)ベンゼン、１−シアノ−４−(メチルテラニル−メチル)ベンゼン、１−メチルカルボニル−４−(メチルテラニル−メチル)ベンゼン、１−フェニルカルボニル−４−(メチルテラニル−メチル)ベンゼン、１−メトキシカルボニル−４−(メチルテラニル−メチル)ベンゼン、１−フェノキシカルボニル−４−(メチルテラニル−メチル)ベンゼン、１−スルホニル−４−(メチルテラニル−メチル)ベンゼン、１−トリフルオロメチル−４−(メチルテラニル−メチル)ベンゼン、１−クロロ−４−(１−メチルテラニル−エチル)ベンゼン、１−ヒドロキシ−４−(１−メチルテラニル−エチル)ベンゼン、１−メトキシ−４−(１−メチルテラニル−エチル)ベンゼン、１−アミノ−４−(１−メチルテラニル−エチル)ベンゼン、１−ニトロ−４−(１−メチルテラニル−エチル)ベンゼン、１−シアノ−４−(１−メチルテラニル−エチル)ベンゼン、１−メチルカルボニル−４−(１−メチルテラニル−エチル)ベンゼン、１−フェニルカルボニル−４−(１−メチルテラニル−エチル)ベンゼン、１−メトキシカルボニル−４−(１−メチルテラニル−エチル)ベンゼン、１−フェノキシカルボニル−４−(１−メチルテラニル−エチル)ベンゼン、１−スルホニル−４−(１−メチルテラニル−エチル)ベンゼン、１−トリフルオロメチル−４−(１−メチルテラニル−エチル)ベンゼン[１−(１−メチルテラニル−エチル)−４−トリフルオロメチルベンゼン]、１−(１−メチルテラニル−エチル)−３,５−ビス−トリフルオロメチルベンゼン、１,２,３,４,５−ペンタフルオロ−６−(１−メチルテラニル−エチル)ベンゼン、１−クロロ−４−(２−メチルテラニル−プロピル)ベンゼン、１−ヒドロキシ−４−(２−メチルテラニル−プロピル)ベンゼン、１−メトキシ−４−(２−メチルテラニル−プロピル)ベンゼン、１−アミノ−４−(２−メチルテラニル−プロピル)ベンゼン、１−ニトロ−４−(２−メチルテラニル−プロピル)ベンゼン、１−シアノ−４−(２−メチルテラニル−プロピル)ベンゼン、１−メチルカルボニル−４−(２−メチルテラニル−プロピル)ベンゼン、１−フェニルカルボニル−４−(２−メチルテラニル−プロピル)ベンゼン、１−メトキシカルボニル−４−(２−メチルテラニル−プロピル)ベンゼン、１−フェノキシカルボニル−４−(２−メチルテラニル−プロピル)ベンゼン、１−スルホニル−４−(２−メチルテラニル−プロピル)ベンゼン、１−トリフルオロメチル−４−(２−メチルテラニル−プロピル)ベンゼン、２−(メチルテラニル−メチル)ピリジン、２−(１−メチルテラニル−エチル)ピリジン、２−(２−メチルテラニル−プロピル)ピリジン、２−メチル−２−メチルテラニル−プロパナール、３−メチル−３−メチルテラニル−２−ブタノン、２−メチルテラニル−エタン酸メチル、２−メチルテラニル−プロピオン酸メチル、２−メチルテラニル−２−メチルプロピオン酸メチル、２−メチルテラニル−エタン酸エチル、２−メチルテラニル−プロピオン酸エチル、２−メチルテラニル−２−メチルプロピオン酸エチル[エチル−２−メチル−２−メチルテラニル−プロピオネート]、２−(ｎ−ブチルテラニル)−２−メチルプロピオン酸エチル[エチル−２−メチル−２−ｎ−ブチルテラニル−プロピオネート]、２−メチルテラニルアセトニトリル、２−メチルテラニルプロピオニトリル、２−メチル−２−メチルテラニルプロピオニトリル、(フェニルテラニル−メチル)ベンゼン、(１−フェニルテラニル−エチル)ベンゼン、(２−フェニルテラニル−プロピル)ベンゼン等を挙げることができる。
The organic tellurium compound represented by the general formula (1) is specifically as follows.
Examples of the organic tellurium compound include (methylterranyl-methyl) benzene, (1-methylterranyl-ethyl) benzene, (2-methylterranyl-propyl) benzene, 1-chloro-4- (methylterranyl-methyl) benzene, 1-hydroxy-4- (Methylterranyl-methyl) benzene, 1-methoxy-4- (methylterranyl-methyl) benzene, 1-amino-4- (methylterranyl-methyl) benzene, 1-nitro-4- (methylterranyl-methyl) benzene, 1-cyano- 4- (methylterranyl-methyl) benzene, 1-methylcarbonyl-4- (methylterranyl-methyl) benzene, 1-phenylcarbonyl-4- (methylterranyl-methyl) benzene, 1-methoxycarbonyl-4- (methylterranyl-methyl) benzene 1-phenoxycarbonyl-4- (methylterranyl- Methyl) benzene, 1-sulfonyl-4- (methylterranyl-methyl) benzene, 1-trifluoromethyl-4- (methylterranyl-methyl) benzene, 1-chloro-4- (1-methylterranyl-ethyl) benzene, 1-hydroxy -4- (1-methylteranyl-ethyl) benzene, 1-methoxy-4- (1-methylterranyl-ethyl) benzene, 1-amino-4- (1-methylterranyl-ethyl) benzene, 1-nitro-4- (1 -Methyl terranyl-ethyl) benzene, 1-cyano-4- (1-methyl teranyl-ethyl) benzene, 1-methylcarbonyl-4- (1-methyl teranyl-ethyl) benzene, 1-phenylcarbonyl-4- (1-methyl terranyl- Ethyl) benzene, 1-methoxycarbonyl-4- (1-methylterranyl-ethyl) benzene, 1-phenoxy Rubonyl-4- (1-methylterranyl-ethyl) benzene, 1-sulfonyl-4- (1-methylterranyl-ethyl) benzene, 1-trifluoromethyl-4- (1-methylterranyl-ethyl) benzene [1- (1- Methylteranyl-ethyl) -4-trifluoromethylbenzene], 1- (1-methylterranyl-ethyl) -3,5-bis-trifluoromethylbenzene, 1,2,3,4,5-pentafluoro-6- ( 1-methylterranyl-ethyl) benzene, 1-chloro-4- (2-methylterranyl-propyl) benzene, 1-hydroxy-4- (2-methylterranyl-propyl) benzene, 1-methoxy-4- (2-methylterranyl-propyl) ) Benzene, 1-amino-4- (2-methylterranyl-propyl) benzene, 1-nitro-4- (2-methylterranyl-propyl) benzene 1-cyano-4- (2-methylterranyl-propyl) benzene, 1-methylcarbonyl-4- (2-methylterranyl-propyl) benzene, 1-phenylcarbonyl-4- (2-methylterranyl-propyl) benzene, 1-methoxy Carbonyl-4- (2-methylterranyl-propyl) benzene, 1-phenoxycarbonyl-4- (2-methylterranyl-propyl) benzene, 1-sulfonyl-4- (2-methylterranyl-propyl) benzene, 1-trifluoromethyl- 4- (2-methylterranyl-propyl) benzene, 2- (methylterranyl-methyl) pyridine, 2- (1-methylterranyl-ethyl) pyridine, 2- (2-methylterranyl-propyl) pyridine, 2-methyl-2-methylterranyl- Propanal, 3-methyl-3-methylteranyl-2-butanone, 2-methyl terranyl-methyl ethanoate, 2-methyl teranyl-methyl propionate, 2-methyl teranyl-2-methyl propionate, 2-methyl teranyl-ethyl ethanoate, 2-methyl terranyl-ethyl propionate, 2-methyl teranyl-2-methyl Ethyl propionate [ethyl-2-methyl-2-methylterranyl-propionate], 2- (n-butylterranyl) -2-methylpropionate [ethyl-2-methyl-2-n-butylterranyl-propionate], 2-methyl Terranylacetonitrile, 2-methylterranylpropionitrile, 2-methyl-2-methylterranylpropionitrile, (phenylterranyl-methyl) benzene, (1-phenylterranyl-ethyl) benzene, (2-phenyl) Terranyl-propyl) benzene etc. Can.
また上記において、メチルテラニル、１−メチルテラニル、２−メチルテラニルの部分がそれぞれエチルテラニル、１−エチルテラニル、２−エチルテラニル、ブチルテラニル、１−ブチルテラニル、２−ブチルテラニルと変更した化合物も全て含まれる。好ましくは、(メチルテラニル−メチル)ベンゼン、(１−メチルテラニル−エチル)ベンゼン、(２−メチルテラニル−プロピル)ベンゼン、１−クロロ−４−(１−メチルテラニル−エチル)ベンゼン、１−トリフルオロメチル−４−(１−メチルテラニル−エチル)ベンゼン[１−(１−メチルテラニル−エチル)−４−トリフルオロメチルベンゼン]、２−メチルテラニル−２−メチルプロピオン酸メチル、２−メチルテラニル−２−メチルプロピオン酸エチル[エチル−２−メチル−２−メチルテラニル−プロピオネート]、２−(ｎ−ブチルテラニル)−２−メチルプロピオン酸エチル[エチル−２−メチル−２−ｎ−ブチルテラニル−プロピオネート]、１−(１−メチルテラニル−エチル)−３,５−ビス−トリフルオロメチルベンゼン、１,２,３,４,５−ペンタフルオロ−６−(１−メチルテラニル−エチル)ベンゼン、２−メチルテラニルプロピオニトリル、２−メチル−２−メチルテラニルプロピオニトリル、(エチルテラニル−メチル)ベンゼン、(１−エチルテラニル−エチル)ベンゼン、(２−エチルテラニル−プロピル)ベンゼン、２−エチルテラニル−２−メチルプロピオン酸メチル、２−エチルテラニル−２−メチルプロピオン酸エチル、２−エチルテラニルプロピオニトリル、２−メチル−２−エチルテラニルプロピオニトリル、(ｎ−ブチルテラニル−メチル)ベンゼン、(１−ｎ−ブチルテラニル−エチル)ベンゼン、(２−ｎ−ブチルテラニル−プロピル)ベンゼン、２−ｎ−ブチルテラニル−２−メチルプロピオン酸メチル、２−ｎ−ブチルテラニル−２−メチルプロピオン酸エチル、２−ｎ−ブチルテラニルプロピオニトリル、２−メチル−２−ｎ−ブチルテラニルプロピオニトリルが良い。
これらの一般式（１）で表される有機テルル化合物は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
Further, in the above, all compounds in which methyl teranyl, 1-methyl terranyl and 2-methyl terranyl are changed to ethyl teranyl, 1-ethyl teranyl, 2-ethyl terranyl, butyl terranyl, 1-butyl terranyl and 2-butyl terranyl, respectively, are included. Preferably, (methylterranyl-methyl) benzene, (1-methylterranyl-ethyl) benzene, (2-methylterranyl-propyl) benzene, 1-chloro-4- (1-methylterranyl-ethyl) benzene, 1-trifluoromethyl-4 -(1-methylteranyl-ethyl) benzene [1- (1-methylterranyl-ethyl) -4-trifluoromethylbenzene], methyl 2-methylterranyl-2-methylpropionate, ethyl 2-methylterranyl-2-methylpropionate [ Ethyl-2-methyl-2-methylterranyl-propionate], 2- (n-butylterranyl) -2-methylpropionate [ethyl-2-methyl-2-n-butylterranyl-propionate], 1- (1-methylterranyl- Ethyl) -3,5-bis-trifluoromethylbenzene, 1,2,3,4,5-pe Tafluoro-6- (1-methylterranyl-ethyl) benzene, 2-methylterranylpropionitrile, 2-methyl-2-methylterranylpropionitrile, (ethylterranyl-methyl) benzene, (1-ethylterranyl-ethyl) benzene , (2-ethylteranyl-propyl) benzene, methyl 2-ethylteranyl-2-methylpropionate, ethyl 2-ethylteranyl-2-methylpropionate, 2-ethylterranylpropionitrile, 2-methyl-2-ethylterranyl Propionitrile, (n-butylteranyl-methyl) benzene, (1-n-butylteranyl-ethyl) benzene, (2-n-butylteranyl-propyl) benzene, 2-n-butylteranyl-2-methylpropionate methyl, 2- n-butyl terranyl-2-methylpropionate ethyl, 2- n-Butyl teranyl propionitrile and 2-methyl-2-n-butyl terranyl propionitrile are preferable.
These organic tellurium compounds represented by the general formula (1) may be used singly or in combination of two or more.
本発明における重合工程においては、上記の有機テルル化合物に加え、重合促進剤としてアゾ系重合開始剤を添加してもよい。アゾ系重合開始剤としては、通常のラジカル重合に用いる開始剤であれば特に限定されないが、例示するなら２,２'−アゾビス(イソブチロニトリル)（ＡＩＢＮ）、２,２'−アゾビス(２−メチルブチロニトリル)（ＡＭＢＮ）、２,２'−アゾビス(２,４−ジメチルバレロニトリル)（ＡＤＶＮ）、１,１'−アゾビス(１−シクロヘキサンカルボニトリル)（ＡＣＨＮ）、ジメチル−２,２'−アゾビスイソブチレート（ＭＡＩＢ）、４,４'−アゾビス(４−シアノバレリアン酸)（ＡＣＶＡ）、１,１'−アゾビス(１−アセトキシ−１−フェニルエタン)、２,２'−アゾビス(２−メチルブチルアミド)、２,２'−アゾビス(４−メトキシ−２,４−ジメチルバレロニトリル)、２,２'−アゾビス(２−メチルアミジノプロパン)二塩酸塩、２,２'−アゾビス[２−(２−イミダゾリン−２−イル)プロパン]、２,２'−アゾビス[２−メチル−Ｎ−(２−ヒドロキシエチル)プロピオンアミド]、２,２'−アゾビス(２,４,４−トリメチルペンタン)、２−シアノ−２−プロピルアゾホルムアミド、２,２'−アゾビス(Ｎ−ブチル−２−メチルプロピオンアミド)、２,２'−アゾビス(Ｎ−シクロヘキシル−２−メチルプロピオンアミド)等が挙げられる。
上記アゾ系重合開始剤を使用する場合、重合開始剤として用いた式（１）の有機テルル化合物１ｍｏｌに対して好ましくは０.０１〜１００ｍｏｌ、より好ましくは０.１〜１００ｍｏｌ、さらに好ましくは０.１〜５ｍｏｌの割合で使用されることが望ましい。
In the polymerization step in the present invention, an azo polymerization initiator may be added as a polymerization accelerator in addition to the organic tellurium compound. The azo polymerization initiator is not particularly limited as long as it is an initiator used for ordinary radical polymerization. However, for example, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis ( 2-methylbutyronitrile) (AMBN), 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN), 1,1′-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2 2,2′-azobisisobutyrate (MAIB), 4,4′-azobis (4-cyanovaleric acid) (ACVA), 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2 '-Azobis (2-methylbutyramide), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylamidinopropane) dihydrochloride, 2, 2'-azobis [2- (2-imi Zolin-2-yl) propane], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2,4,4-trimethylpentane), 2 -Cyano-2-propylazoformamide, 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide) and the like.
When the azo polymerization initiator is used, it is preferably 0.01 to 100 mol, more preferably 0.1 to 100 mol, still more preferably 0 with respect to 1 mol of the organic tellurium compound of the formula (1) used as the polymerization initiator. It is desirable to be used at a ratio of 0.1 to 5 mol.
当該第２の(メタ)アクリル酸エステル重合体（Ｂ）［トリブロック共重合体］を、リビングラジカル重合によって形成する方法は、具体的には次の通りである。
不活性ガスで置換した容器で、前述した水酸基含有(メタ)アクリレート系モノマーと一般式（１）で示されるリビングラジカル重合開始剤及び所望によりアゾ系重合開始剤を混合し、重合反応を行う。この時、不活性ガスとしては、窒素、アルゴン、ヘリウム等を挙げることができる。好ましくは、アルゴン、窒素が良い。特に好ましくは、窒素が良い。
次に、反応系に架橋点となる官能基を有しない(メタ)アクリレート系モノマーを加え、重合反応を行ったのち、水酸基含有(メタ)アクリレート系モノマーを加え、重合反応を行うことにより、ｂ２−ｂ１−ｂ２型（ただし、ｂ１は架橋点となる官能基を有しない(メタ)アクリレート系モノマー単位からなるブロックを示し、ｂ２は水酸基含有(メタ)アクリレート系モノマー単位からなるブロックを示す。）のトリブロック共重合体が得られる。
また、重合反応の順番を、反応性官能基を有しない(メタ)アクリレート系モノマー、水酸基含有(メタ)アクリレート系モノマー、反応性官能基を有しない(メタ)アクリレート系モノマーとすることにより、ｂ１−ｂ２−ｂ１型のトリブロック共重合体が得られる。
The method for forming the second (meth) acrylic acid ester polymer (B) [triblock copolymer] by living radical polymerization is specifically as follows.
In a container substituted with an inert gas, the hydroxyl group-containing (meth) acrylate monomer described above, the living radical polymerization initiator represented by the general formula (1) and, if desired, an azo polymerization initiator are mixed to perform a polymerization reaction. At this time, examples of the inert gas include nitrogen, argon, helium, and the like. Argon and nitrogen are preferable. Nitrogen is particularly preferable.
Next, a (meth) acrylate monomer that does not have a functional group serving as a crosslinking point is added to the reaction system, and a polymerization reaction is performed. Then, a hydroxyl group-containing (meth) acrylate monomer is added, and the polymerization reaction is performed, whereby b2 -B1-b2 type (where b1 represents a block composed of a (meth) acrylate monomer unit having no functional group serving as a crosslinking point, and b2 represents a block composed of a hydroxyl group-containing (meth) acrylate monomer unit) The triblock copolymer is obtained.
Further, b1 is obtained by changing the order of the polymerization reaction to a (meth) acrylate monomer having no reactive functional group, a hydroxyl group-containing (meth) acrylate monomer, and a (meth) acrylate monomer having no reactive functional group. A -b2-b1 type triblock copolymer is obtained.
重合は、通常、無溶媒で行うが、ラジカル重合で一般に使用される有機溶媒を使用しても構わない。使用できる溶媒としては、例えば、ベンゼン、トルエン、Ｎ,Ｎ−ジメチルホルムアミド（ＤＭＦ）、ジメチルスルホキシド（ＤＭＳＯ）、アセトン、クロロホルム、四塩化炭素、テトラヒドロフラン（ＴＨＦ）、酢酸エチル、トリフルオロメチルベンゼン等が挙げられる。また、水性溶媒も使用でき、例えば、水、メタノール、エタノール、イソプロパノール、ｎ−ブタノール、エチルセロソルブ、ブチルセロソルブ、１−メトキシ−２−プロパノール等が挙げられる。溶媒の使用量としては適宜調節すればよいが、例えば、単量体１ｇに対して、溶媒を０.０１〜１００ｍｌ、好ましくは、０.０５〜１０ｍｌ、特に好ましくは０.０５〜０.５ｍｌが良い。 The polymerization is usually performed without a solvent, but an organic solvent generally used in radical polymerization may be used. Examples of the solvent that can be used include benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, trifluoromethylbenzene, and the like. Can be mentioned. Moreover, an aqueous solvent can also be used, for example, water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, etc. are mentioned. The amount of the solvent used may be appropriately adjusted. For example, the solvent is 0.01 to 100 ml, preferably 0.05 to 10 ml, particularly preferably 0.05 to 0.5 ml per 1 g of the monomer. Is good.
得られるトリブロック共重合体の分子量は、反応温度、反応時間及び式（１）の有機テルル化合物の量により調整可能である。反応温度、反応時間は、得られるトリブロック共重合体の分子量あるいは分子量分布により適宜調節すればよいが、通常、６０〜１５０℃で、全反応時間は５〜１００時間程度である。好ましくは、８０〜１２０℃で、全反応時間は１０〜３０時間程度である。この時、圧力は、通常、常圧で行われるが、加圧あるいは減圧しても構わない。
反応終了後、常法により使用溶媒や残存モノマーを減圧下除去したり、沈殿ろ過、再沈殿したり、あるいはカラム分離等をして目的のトリブロック共重合体を精製する。
The molecular weight of the obtained triblock copolymer can be adjusted by the reaction temperature, the reaction time, and the amount of the organic tellurium compound of the formula (1). The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the resulting triblock copolymer, but are usually 60 to 150 ° C. and the total reaction time is about 5 to 100 hours. Preferably, at 80 to 120 ° C., the total reaction time is about 10 to 30 hours. At this time, the pressure is usually a normal pressure, but may be increased or decreased.
After completion of the reaction, the intended triblock copolymer is purified by removing the solvent and residual monomer under reduced pressure, precipitation filtration, reprecipitation, column separation or the like by a conventional method.
本発明の粘着剤組成物においては、成分（Ｂ）として、第２の(メタ)アクリル酸エステル重合体［トリブロック共重合体］は、１種を単独で含有してもよいし、２種以上を組み合わせて含有していてもよい。成分（Ｂ）の含有量は、前述した第１の(メタ)アクリル酸エステル重合体（Ａ）１００質量部に対して、４０質量部未満であることを要する。４０質量部以上であると応力緩和性が阻害される場合があるからである。前記応力緩和性の観点に加え、得られる粘着剤に十分な凝集力を与える観点から、前記重合体（Ａ）１００質量部に対する成分（Ｂ）の含有量は、好ましくは５〜３０質量部、より好ましくは１０〜２５質量部である。
また、当該トリブロック共重合体における水酸基含有(メタ)アクリレート系モノマー単位の含有量は、得られる粘着剤組成物の性能の観点から、１.５〜２０質量％であることが好ましく、５〜１５質量％であることがより好ましい。
In the pressure-sensitive adhesive composition of the present invention, as the component (B), the second (meth) acrylic acid ester polymer [triblock copolymer] may contain one kind alone or two kinds. You may contain combining the above. Content of a component (B) needs to be less than 40 mass parts with respect to 100 mass parts of 1st (meth) acrylic acid ester polymers (A) mentioned above. It is because stress relaxation property may be inhibited as it is 40 mass parts or more. From the viewpoint of giving sufficient cohesive force to the obtained pressure-sensitive adhesive in addition to the stress relaxation viewpoint, the content of the component (B) with respect to 100 parts by mass of the polymer (A) is preferably 5 to 30 parts by mass, More preferably, it is 10-25 mass parts.
In addition, the content of the hydroxyl group-containing (meth) acrylate monomer unit in the triblock copolymer is preferably 1.5 to 20% by mass from the viewpoint of the performance of the obtained pressure-sensitive adhesive composition. More preferably, it is 15 mass%.
（イソシアネート系架橋剤（Ｃ））
本発明の粘着剤組成物において、成分（Ｃ）として含有するイソシアネート系架橋剤は、前述した第２の(メタ)アクリル酸エステル重合体（Ｂ）［トリブロック共重合体］における水酸基含有(メタ)アクリレート系モノマー単位の水酸基を架橋点として、低分子量の前記トリブロック共重合体を架橋し、三次元の網目構造を形成させるためのものである。
なお、第１の(メタ)アクリル酸エステル重合体が、カルボキシル基含有(メタ)アクリレート系モノマー単位を有する場合には、該カルボキシル基を架橋点として、前記高分子量である第１の(メタ)アクリル酸エステル重合体の架橋にも寄与することも考えられる。しかし、イソシアネート系架橋剤（Ｃ）は、水酸基との反応性がカルボキシル基との反応性よりも高いため、後述の架橋剤（Ｃ）の配合量では、重合体（Ｂ）の水酸基との反応で大半が消費され、重合体（Ａ）のカルボキシル基と反応するものは極めて少量と推定される。
(Isocyanate-based crosslinking agent (C))
In the pressure-sensitive adhesive composition of the present invention, the isocyanate-based crosslinking agent contained as the component (C) is a hydroxyl group-containing (meta) group in the second (meth) acrylic acid ester polymer (B) [triblock copolymer] described above. ) The triblock copolymer having a low molecular weight is cross-linked using a hydroxyl group of an acrylate monomer unit as a cross-linking point to form a three-dimensional network structure.
In addition, when the first (meth) acrylic acid ester polymer has a carboxyl group-containing (meth) acrylate monomer unit, the first (meth) having a high molecular weight with the carboxyl group as a crosslinking point. It is also considered that it contributes to the crosslinking of the acrylate polymer. However, since the isocyanate-based crosslinking agent (C) has a higher reactivity with a hydroxyl group than a reactivity with a carboxyl group, the reaction with the hydroxyl group of the polymer (B) in the blending amount of the crosslinking agent (C) described later. Most of them are consumed, and it is estimated that only a small amount reacts with the carboxyl group of the polymer (A).
イソシアネート系架橋剤（Ｃ）は、ポリイソシアネート化合物を含むものであって、該ポリイソシアネート化合物の例としては、ト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、キシリレンジイソシアネートなどの芳香族ポリイソシアネート、ヘキサメチレンジイソシアネートなどの脂肪族ポリイソシアネート、イソホロンジイソシアネート、水素添加ジフェニルメタンジイソシアネートなどの脂環式ポリイソシアネートなど、及びそれらのビウレット体、イソシアヌレート体、さらにはエチレングリコール、プロピレングリコール、ネオペンチルグリコール、トリメチロールプロパン、ヒマシ油などの低分子活性水素含有化合物との反応物であるアダクト体などを挙げることができる。 The isocyanate-based crosslinking agent (C) contains a polyisocyanate compound, and examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, and hexamethylene diisocyanate. Alicyclic polyisocyanates such as aliphatic polyisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, etc., and their biurets, isocyanurates, ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. The adduct body which is a reaction product with the low molecular active hydrogen-containing compound can be used.
本発明においては、このイソシアネート系架橋剤（Ｃ）は１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。また、その使用量は、前記第２の(メタ)アクリル酸エステル重合体（Ｂ）［トリブロック共重合体］１００質量部に対し、ポリイソシアネート化合物として２〜３０質量部の範囲であることが好ましい。この使用量が、２質量部未満ではトリブロック共重合体の熱架橋が不充分となり、所望の性能を有する粘着剤組成物が得られず、一方、３０質量部を超えると、ポットライフが短くなるため、安定的な塗工が困難となる。このような観点から、当該イソシアネート系架橋剤（Ｃ）の使用量は、重合体（Ｂ）１００質量部に対して、ポリイソシアネート化合物として、好ましくは５〜２０質量部、より好ましくは７〜１５質量部である。なお、上述の通り架橋剤（Ｃ）を重合体（Ｂ）の水酸基のみと反応させる観点から、重合体（Ｂ）中の水酸基１００ｍｏｌに対して、架橋剤（Ｃ）の架橋点となる部位が１００ｍｏｌ以下となるのが好ましく、８０ｍｏｌ以下となるのが特に好ましい。また、重合体（Ｂ）との架橋構造により十分な凝集力を得る観点から、重合体（Ｂ）中の水酸基１００ｍｏｌに対して、架橋剤（Ｃ）の架橋点となる部位が３０ｍｏｌ以上であることが好ましく、４０ｍｏｌ以上であることがより好ましく、５０ｍｏｌ以上であることが特に好ましい。 In this invention, this isocyanate type crosslinking agent (C) may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, the usage-amount is a range of 2-30 mass parts as a polyisocyanate compound with respect to 100 mass parts of said 2nd (meth) acrylic ester polymers (B) [triblock copolymer]. preferable. If the amount used is less than 2 parts by mass, thermal crosslinking of the triblock copolymer becomes insufficient, and an adhesive composition having the desired performance cannot be obtained. On the other hand, if it exceeds 30 parts by mass, the pot life is short. Therefore, stable coating becomes difficult. From such a viewpoint, the amount of the isocyanate-based crosslinking agent (C) used is preferably 5 to 20 parts by mass, more preferably 7 to 15 as a polyisocyanate compound with respect to 100 parts by mass of the polymer (B). Part by mass. In addition, from the viewpoint of reacting the crosslinking agent (C) with only the hydroxyl group of the polymer (B) as described above, the site serving as a crosslinking point of the crosslinking agent (C) with respect to 100 mol of the hydroxyl group in the polymer (B). The amount is preferably 100 mol or less, and particularly preferably 80 mol or less. Further, from the viewpoint of obtaining a sufficient cohesive force due to the cross-linking structure with the polymer (B), the cross-linking site of the cross-linking agent (C) is 30 mol or more with respect to 100 mol of the hydroxy group in the polymer (B). It is preferably 40 mol or more, more preferably 50 mol or more.
（シラン系カップリング剤）
本発明の粘着剤組成物には、さらにシラン系カップリング剤を含有させることができる。このシラン系カップリング剤は、例えば本発明の粘着剤を介して、偏光板などの光学部材を液晶セルのガラス基板に、湿熱条件下でも接着性よく貼着するために用いられる。
このシラン系カップリング剤としては、例えば、トリエトキシシラン、ビニルトリス(β−メトキシエトキシ)シラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、β−(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、Ｎ−β−(アミノエチル)−γ−アミノプロピルトリメトキシシラン、Ｎ−β−(アミノエチル)−γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシランなどが挙げられる。
(Silane coupling agent)
The pressure-sensitive adhesive composition of the present invention can further contain a silane coupling agent. This silane coupling agent is used, for example, to adhere an optical member such as a polarizing plate to a glass substrate of a liquid crystal cell with good adhesion even under wet heat conditions via the pressure-sensitive adhesive of the present invention.
Examples of the silane coupling agent include triethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, Examples thereof include N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-chloropropyltrimethoxysilane.
さらに、３−イソシアナトプロピルトリエトキシシラン、３−イソシアナトプロピル(メチル)ジエトキシシラン、２−イソシアナトエチルトリエトキシシラン、２−イソシアナトエチル(メチル)ジエトキシシラン、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)ジエトキシシラン、２−グリシドキシエチルトリエトキシシラン、２−グリシドキシエチル(メチル)ジエトキシシラン、３−(３,４−エポキシシクロヘキシル)プロピルトリエトキシシラン、３−(３,４−エポキシシクロヘキシル)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)エチルトリエトキシシラン、２−(３,４−エポキシシクロヘキシル)エチル(メチル)ジエトキシシランなど、及びこれらのシラン化合物のエトキシ基をメトキシ基に置き換えたシラン化合物を用いることもできる。
これらのシラン系カップリング剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。またその添加量は、本発明の粘着剤組成物の固形分１００質量部に対し、通常０.００１〜１０質量部程度、好ましくは０.１〜７質量部である。
Further, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyl (methyl) diethoxysilane, 2-isocyanatoethyltriethoxysilane, 2-isocyanatoethyl (methyl) diethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 2-glycidoxyethyltriethoxysilane, 2-glycidoxyethyl (methyl) diethoxysilane, 3- (3,4-epoxycyclohexyl) Propyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyl (methyl) diethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl ( Methyl) diethoxysilane, etc., and ethoxy of these silane compounds It can also be used a silane compound obtained by replacing the methoxy group.
These silane coupling agents may be used singly or in combination of two or more. Moreover, the addition amount is about 0.001-10 mass parts normally with respect to 100 mass parts of solid content of the adhesive composition of this invention, Preferably it is 0.1-7 mass parts.
（粘着剤組成物を含む塗工液の調製）
本発明の粘着剤組成物を含む塗工液の調製方法に特に制限はなく、例えば溶媒中に、前述した第１の(メタ)アクリル酸エステル重合体（Ａ）、第２の(メタ)アクリル酸エステル重合体（Ｂ）［トリブロック共重合体］、イソシアネート系架橋剤（Ｃ）及び必要に応じて用いられるシラン系カップリング剤、さらには各種添加剤、例えば酸化防止剤、紫外線吸収剤、光安定剤、レベリング剤、帯電防止剤、屈折率調整剤、難燃剤、消泡剤などを加え、撹拌混合することにより、本発明の粘着剤組成物を含む塗工液を調製することができる。
前記溶媒としては、例えばヘキサン、ヘプタンなどの脂肪族炭化水素、トルエン、キシレンなどの芳香族炭化水素、塩化メチレン、塩化エチレンなどのハロゲン化炭化水素、メタノール、エタノール、プロパノール、ブタノールなどのアルコール、アセトン、メチルエチルケトン、２−ペンタノン、イソホロン、シクロヘキサノンなどのケトン、酢酸エチル、酢酸ブチルなどのエステル、エチルセロソルブなどのセロソルブ系溶媒、プロピレングリコールモノメチルエーテルなどのグリコールエーテル系溶媒などが挙げられる。これらの溶媒は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。
この塗工液中の固形分濃度としては、該塗工液が塗工に適した粘度であればよく、特に制限はない。
(Preparation of coating solution containing pressure-sensitive adhesive composition)
There is no restriction | limiting in particular in the preparation method of the coating liquid containing the adhesive composition of this invention, For example, the 1st (meth) acrylic acid ester polymer (A) mentioned above and the 2nd (meth) acryl in solvent. Acid ester polymer (B) [triblock copolymer], isocyanate crosslinking agent (C) and silane coupling agent used as necessary, and various additives such as antioxidants, ultraviolet absorbers, A coating liquid containing the pressure-sensitive adhesive composition of the present invention can be prepared by adding a light stabilizer, a leveling agent, an antistatic agent, a refractive index adjusting agent, a flame retardant, an antifoaming agent, and the like, followed by stirring and mixing. .
Examples of the solvent include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, alcohols such as methanol, ethanol, propanol, and butanol, acetone. , Ketones such as methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, cellosolv solvents such as ethyl cellosolve, glycol ether solvents such as propylene glycol monomethyl ether, and the like. These solvents may be used alone or in a combination of two or more.
The solid content concentration in the coating solution is not particularly limited as long as the coating solution has a viscosity suitable for coating.
次に、本発明の粘着剤について説明する。
［粘着剤］
本発明の粘着剤は、前記のようにして得られた粘着剤組成物を含む塗工液を用いて得られた粘着剤組成物を、熱架橋してなるものである。
熱架橋は、例えば、前記粘着剤組成物を含む塗工液を後述の方法により剥離シート上に塗布し、６０〜１１０℃、１〜１０分間程度乾燥させ、その後、２３〜３０℃、１〜２週間程度の養生期間をとることにより完了させることができる。
本発明の粘着剤は、ゲル分率が４０％以上であることを要する。このゲル分率が４０％未満であると、高温・高湿下での耐久性が悪く、かつヒートショック試験においても不充分である。さらに、リワーク性と耐久性の観点から、このゲル分率は、好ましくは４０〜８５％、より好ましくは４０〜７０％である。
なお、上記ゲル分率は、下記の方法で測定した値である。
＜ゲル分率の測定＞
粘着剤のみを取り出して秤量し、この時の重さをＭ１とする。これを酢酸エチル中に投入し、ソックスレー抽出装置を用いて１６時間以上還流を行った後、不溶分のみを取り出し、不溶分に含まれている溶剤を乾燥除去した後、秤量し、この時の重さをＭ２とする。ゲル分率は、(Ｍ２／Ｍ１)×１００で表される（％）。
Next, the pressure-sensitive adhesive of the present invention will be described.
[Adhesive]
The pressure-sensitive adhesive of the present invention is obtained by thermally crosslinking a pressure-sensitive adhesive composition obtained by using a coating liquid containing the pressure-sensitive adhesive composition obtained as described above.
In the thermal crosslinking, for example, a coating liquid containing the pressure-sensitive adhesive composition is applied onto a release sheet by the method described later, dried at 60 to 110 ° C. for about 1 to 10 minutes, and thereafter 23 to 30 ° C., 1 to It can be completed by taking a curing period of about 2 weeks.
The pressure-sensitive adhesive of the present invention requires a gel fraction of 40% or more. If the gel fraction is less than 40%, the durability under high temperature and high humidity is poor, and the heat shock test is insufficient. Furthermore, from the viewpoint of reworkability and durability, the gel fraction is preferably 40 to 85%, more preferably 40 to 70%.
The gel fraction is a value measured by the following method.
<Measurement of gel fraction>
Only the adhesive is taken out and weighed, and the weight at this time is M1. This was put into ethyl acetate and refluxed for 16 hours or more using a Soxhlet extraction apparatus. Then, only the insoluble matter was taken out, the solvent contained in the insoluble matter was dried and removed, and weighed. The weight is M2. The gel fraction is expressed as (M2 / M1) × 100 (%).
（粘着シート）
剥離シートの剥離層上に、前述した粘着剤組成物を含む塗工液を、例えばバーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法などを用いて塗工し、加熱乾燥して熱架橋を行い粘着剤層を形成させる。次いで、この粘着剤層上に、前記剥離シートとは剥離強度の異なる別の剥離シートを、その剥離層が接するように貼付することにより、２枚の剥離シートで粘着剤層を挟持してなる粘着シートとすることができる。
なお、この粘着シートの厚さ（剥離シートは含まず）は、通常５〜１００μｍ程度、好ましくは１０〜５０μｍである。
(Adhesive sheet)
On the release layer of the release sheet, the coating liquid containing the pressure-sensitive adhesive composition described above is applied using, for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like. Then, it is heat-dried and thermally crosslinked to form an adhesive layer. Then, another adhesive sheet having a different peel strength from that of the release sheet is stuck on the adhesive layer so that the release layer is in contact, and the adhesive layer is sandwiched between the two release sheets. It can be set as an adhesive sheet.
In addition, the thickness (excluding the release sheet) of this pressure-sensitive adhesive sheet is usually about 5 to 100 μm, preferably 10 to 50 μm.
前記剥離シートとしては、ポリエチレンテレフタレート（以下、ＰＥＴと称する場合がある）、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等のポリエステルフィルム、ポリプロピレンやポリエチレン等のポリオレフィンフィルムなどのプラスチックフィルムに、シリコーン樹脂などの剥離剤を塗布し剥離層を設けたものなどが挙げられる。この剥離シートの厚さについては特に制限はないが、通常２０〜１５０μｍ程度である。 Examples of the release sheet include polyethylene terephthalate (hereinafter sometimes referred to as PET), polybutylene terephthalate, polyester films such as polyethylene naphthalate, plastic films such as polyolefin films such as polypropylene and polyethylene, and release agents such as silicone resin. The thing etc. which apply | coated and provided the peeling layer are mentioned. Although there is no restriction | limiting in particular about the thickness of this peeling sheet, Usually, it is about 20-150 micrometers.
次に、本発明の粘着剤層付き光学部材について説明する。
［粘着剤層付き光学部材］
本発明は、光学部材上に、前述した本発明の粘着剤からなる層を有する、粘着剤層付き光学部材をも提供する。
前記光学部材としては、例えば偏光板、位相差板、光学補償フィルム、反射シート、輝度向上フィルムなどを挙げることができるが、これらの中で偏光板及び位相差板が好ましく用いられる。また、本発明の粘着剤からなる粘着剤層の厚さは、通常５〜１００μｍ程度、好ましくは１０〜５０μｍ、より好ましくは１０〜３０μｍである。
この粘着剤層付き光学部材は、例えば以下のようにして作製することができる。
剥離シートの剥離層上に、前述した方法に従って、粘着剤組成物層を設け、加熱・乾燥して熱架橋を行い、粘着剤層を形成したのち、この上に光学部材を貼合することにより、粘着剤層付き光学部材を作製することができる。
Next, the optical member with an adhesive layer of the present invention will be described.
[Optical member with adhesive layer]
This invention also provides the optical member with an adhesive layer which has a layer which consists of an adhesive of this invention mentioned above on an optical member.
Examples of the optical member include a polarizing plate, a retardation plate, an optical compensation film, a reflection sheet, and a brightness enhancement film. Among these, a polarizing plate and a retardation plate are preferably used. Moreover, the thickness of the adhesive layer which consists of an adhesive of this invention is about 5-100 micrometers normally, Preferably it is 10-50 micrometers, More preferably, it is 10-30 micrometers.
This optical member with an adhesive layer can be produced, for example, as follows.
By providing a pressure-sensitive adhesive composition layer on the release layer of the release sheet according to the method described above, heating and drying to perform thermal crosslinking, forming an adhesive layer, and then bonding an optical member thereon An optical member with a pressure-sensitive adhesive layer can be produced.
本発明の粘着剤は、偏光フィルム単独からなる偏光板に適用して、該偏光板を、例えば液晶ガラスセルに接着させるのに用いることができるが、特に偏光フィルムと視野角拡大フィルムとが一体化してなる偏光板に適用し、この偏光板を、例えば液晶ガラスセルに接着させるのに、好ましく用いることができる。
前記偏光フィルムと視野角拡大フィルムとが一体化してなる偏光板としては、例えばポリビニルアルコール系偏光子の両面に、それぞれトリアセチルセルロース（ＴＡＣ）フィルムを貼り合わせてなる偏光フィルムの片面に、例えばディスコティック液晶からなる視野角拡大機能層を塗布により設けたもの、あるいは視野角拡大フィルムを接着剤で貼り合わせたものなどを挙げることができる。この場合、本発明の粘着剤は、前記視野角拡大機能層又は視野角拡大フィルム側に設ける。
本発明の粘着剤を用いて、前記のようにして液晶ガラスセルに偏光板を接着させることにより作製した液晶表示装置は、高温高湿環境下でも光漏れが生じにくい上、偏光板と液晶ガラスセルとの接着耐久性に優れている。
The pressure-sensitive adhesive of the present invention can be applied to a polarizing plate made of a polarizing film alone and used to adhere the polarizing plate to, for example, a liquid crystal glass cell. In particular, a polarizing film and a viewing angle widening film are integrated. For example, the polarizing plate can be preferably used for bonding to a liquid crystal glass cell.
As the polarizing plate in which the polarizing film and the viewing angle widening film are integrated, for example, on one side of a polarizing film obtained by bonding a triacetyl cellulose (TAC) film to each side of a polyvinyl alcohol polarizer, for example, disco Examples thereof include those provided by applying a viewing angle widening functional layer made of a tick liquid crystal, and those obtained by bonding a viewing angle widening film with an adhesive. In this case, the adhesive of the present invention is provided on the viewing angle widening functional layer or viewing angle widening film side.
A liquid crystal display device produced by adhering a polarizing plate to a liquid crystal glass cell as described above using the pressure-sensitive adhesive of the present invention is less susceptible to light leakage even in a high-temperature and high-humidity environment. Excellent adhesion durability with cells.
また、本発明の粘着剤は、視野角特性の改善を図るため、偏光板と液晶セルの間に粘着剤を介して位相差板が配置される場合においても好適に使用し得る。すなわち、偏光フィルム単独からなる偏光板と位相差板を本発明の粘着剤で貼合して光学フィルムを製造し、該光学フィルムの位相差板と液晶ガラスセルを粘着剤で貼合すればよい。ここで位相差板と液晶ガラスセルを貼合する粘着剤としては特に限定されず、通常偏光板と液晶ガラスセルの貼合に用いられる粘着剤を使用することができる。 In addition, the pressure-sensitive adhesive of the present invention can be suitably used even when a retardation plate is disposed between a polarizing plate and a liquid crystal cell via a pressure-sensitive adhesive in order to improve viewing angle characteristics. That is, a polarizing plate and a retardation plate made of a polarizing film alone are bonded with the pressure-sensitive adhesive of the present invention to produce an optical film, and the retardation film of the optical film and the liquid crystal glass cell are bonded with the pressure-sensitive adhesive. . Here, the pressure-sensitive adhesive for bonding the retardation plate and the liquid crystal glass cell is not particularly limited, and a pressure-sensitive adhesive usually used for bonding the polarizing plate and the liquid crystal glass cell can be used.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、粘着剤の諸特性は、下記の方法に従って求めた。
＜加工方法＞
第１表に示す配合組成になるように調製された粘着剤組成物を含む塗工液を、厚さ３８μｍのＰＥＴからなる剥離シート［リンテック社製、「ＳＰ−ＰＥＴ３８２０５０」］上に乾燥後の粘着剤層の厚さが２５μｍになるようナイフ式塗工機で塗布した。乾燥温度は９０℃、乾燥時間は１分間とした。
その後ディスコティック液晶層付偏光フィルムを、前記粘着剤層とディスコティック液晶層が接するように貼合した。貼合後、２３℃、５０％Ｒｈで１週間の養生期間をとることにより粘着剤層付き偏光板を得た。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The various properties of the pressure-sensitive adhesive were determined according to the following method.
<Processing method>
The coating liquid containing the pressure-sensitive adhesive composition prepared so as to have the composition shown in Table 1 was dried on a release sheet made of PET having a thickness of 38 μm [“SP-PET 382050”, manufactured by Lintec Corporation]. The adhesive layer was coated with a knife coater so that the thickness of the adhesive layer was 25 μm. The drying temperature was 90 ° C. and the drying time was 1 minute.
Thereafter, the polarizing film with a discotic liquid crystal layer was bonded so that the pressure-sensitive adhesive layer and the discotic liquid crystal layer were in contact with each other. After bonding, a polarizing plate with an adhesive layer was obtained by taking a curing period of 1 week at 23 ° C. and 50% Rh.
＜粘着力＞
前記粘着剤層付き偏光板を２５ｍｍ幅×１００ｍｍ長にサンプリングして、剥離フィルムを剥がして無アルカリガラス［コーニング社製、「Ｅａｇｌｅ ＸＧ」］に貼付した。貼付後［栗原製作所社製、「オートクレーブ」］に０.５ＭＰａ、５０℃、２０分間の条件で加圧した。
その後２３℃・５０％Ｒｈ環境下で２４時間放置し、［オリエンテック社製、「テンシロン」］を用いて下記の条件で粘着力を測定した。
剥離速度：３００ｍｍ／ｍｉｎ、剥離角度：１８０°
また、粘着力測定前の放置条件（２３℃・５０％Ｒｈ環境下２４時間）を、２３℃・５０％Ｒｈ環境下で１４日間、及び５０℃・５０％Ｒｈ環境下で２日間とそれぞれ変更し、上記同様な粘着力の測定を併せて行った。
<Adhesive strength>
The polarizing plate with the pressure-sensitive adhesive layer was sampled to a width of 25 mm × 100 mm, the release film was peeled off, and affixed to non-alkali glass [Corning Co., Ltd., “Eagle XG”]. After pasting, [Kurihara Seisakusho, “Autoclave”] was pressurized under conditions of 0.5 MPa, 50 ° C., and 20 minutes.
Then, it was allowed to stand in an environment of 23 ° C. and 50% Rh for 24 hours, and the adhesive strength was measured under the following conditions using [Tensilon] manufactured by Orientec Corporation.
Peeling speed: 300 mm / min, peeling angle: 180 °
In addition, the standing conditions (24 hours under 23 ° C and 50% Rh) are changed to 14 days under 23 ° C and 50% Rh and 2 days under 50 ° C and 50% Rh. And the measurement of adhesive force similar to the above was also performed.
＜耐久性評価＞
前記粘着剤層付き偏光板をスーパーカッター［荻野製作所社製］を用いて２３３ｍｍ×３０９ｍｍサイズに調整した。そして、剥離シートを剥がし、露出した粘着剤層を無アルカリガラス［コーニング社製、「Ｅａｇｌｅ ＸＧ」］に貼合後、［栗原製作所社製、「オートクレーブ」］に０.５ＭＰａ、５０℃、２０分間の条件で加圧した。その後各耐久条件下に投入を行い、２００時間後に１０倍率ルーペを用いて観察を行った。外観変化は以下の基準とした。
○：４辺において外周端部０.６ｍｍ以上に欠点がないもの。
△：４辺のいずれか１辺に外周から０.６ｍｍ以上に浮き・剥がれ・発泡・スジなどの
０.５ｍｍ以下の粘着剤の外観異常、欠点があるもの。
×：４辺のいずれか１辺に外周から０.６ｍｍ以上に浮き・剥がれ・発泡・スジなどの
０.６ｍｍ以上の粘着剤の外観異常、欠点があるもの。
耐久条件
６０℃・９０％Ｒｈ環境
８０℃・Ｄｒｙ環境
ＨＳ：−３５℃⇔７０℃各３０分のヒートショック試験機 ２００サイクル
<Durability evaluation>
The polarizing plate with an adhesive layer was adjusted to a size of 233 mm × 309 mm using a super cutter (manufactured by Hadano Seisakusho). Then, the release sheet was peeled off, and the exposed adhesive layer was bonded to an alkali-free glass [Corning, “Eagle XG”], then [Kurihara Seisakusho, “Autoclave”] to 0.5 MPa, 50 ° C., 20 Pressurization was performed under conditions of minutes. Thereafter, the batteries were charged under each durability condition, and were observed after 200 hours using a 10 magnification loupe. Appearance changes were based on the following criteria.
○: There are no defects at the outer edge of 0.6 mm or more on the four sides.
Δ: Appearance abnormality or defect of adhesive of 0.5 mm or less such as floating, peeling, foaming, streaks, etc. on any one of the 4 sides from 0.6 mm or more from the outer periphery.
X: Any one of the four sides has an appearance abnormality or a defect of an adhesive of 0.6 mm or more such as floating, peeling, foaming, or streaks from the outer periphery to 0.6 mm or more.
Endurance conditions 60 ° C / 90% Rh environment 80 ° C / Dry environment HS: -35 ° C⇔70 ° C 30 minutes heat shock tester 200 cycles
＜光漏れ防止性＞
前記粘着剤層付き偏光板をスーパーカッター［荻野製作所社製］を用いて２３３ｍｍ×３０９ｍｍサイズに調整した。そして、剥離シートを剥がし、露出した粘着剤層を無アルカリガラス［コーニング社製、「Ｅａｇｌｅ ＸＧ」］に貼合後、［栗原製作所社製、「オートクレーブ」］に０.５ＭＰａ、５０℃、２０分間の条件で加圧した。貼合時はガラスの表裏に剥離シートを剥がした前記粘着剤層付き偏光板を偏光軸がクロスニコル状態になるように貼合した。この状態で８０℃・Ｄｒｙ環境下２００時間放置後以下に示す方法で光漏れ防止性を評価した。［大塚電子社製、「ＭＣＰＤ」］を用いて図１に示す各領域の明度を測定して明度差：ΔＬ＊を、式
ΔＬ＊＝[(Ｂ＋Ｃ＋Ｄ＋Ｅ)／４]−Ａ
（ただし、Ａ、Ｂ、Ｃ、Ｄ及びＥは、それぞれＡ領域、Ｂ領域、Ｃ領域、Ｄ領域及びＥ領域のあらかじめ定められた測定点（各領域の中央部１箇所）における明度である。）で求め、光漏れ防止性とする。また、最大明度をＬ＊ｍａｘとして記載した。
なお、光漏れ防止性は、下記の判定基準で評価した。
◎：ΔＬ＊≦１.０
○：１.０≪ΔＬ＊≦２.０
×：ΔＬ＊＞２.０
<Light leakage prevention>
The polarizing plate with an adhesive layer was adjusted to a size of 233 mm × 309 mm using a super cutter (manufactured by Hadano Seisakusho). Then, the release sheet was peeled off, and the exposed adhesive layer was bonded to an alkali-free glass [Corning, “Eagle XG”], then [Kurihara Seisakusho, “Autoclave”] to 0.5 MPa, 50 ° C., 20 Pressurization was performed under the condition of minutes. At the time of pasting, the polarizing plate with the pressure-sensitive adhesive layer obtained by peeling the release sheet on the front and back of the glass was pasted so that the polarization axis was in a crossed Nicols state. In this state, the light leakage prevention property was evaluated by the following method after being left in an 80 ° C./Dry environment for 200 hours. The brightness difference of each region shown in FIG. 1 is measured using [MCPD, manufactured by Otsuka Electronics Co., Ltd.], and the difference in brightness: ΔL * is expressed by the equation: ΔL * = [(B + C + D + E) / 4] −A
(However, A, B, C, D, and E are the lightnesses at predetermined measurement points (one central portion of each region) in the A region, B region, C region, D region, and E region, respectively. ) To obtain the light leakage prevention property. The maximum brightness is described as L * max.
The light leakage prevention property was evaluated according to the following criteria.
A: ΔL * ≦ 1.0
○: 1.0 << ΔL * ≦ 2.0
×: ΔL *> 2.0
＜ゲル分率＞
明細書本文記載の方法に従って、ゲル分率を測定した。
＜ヘーズ値＞
厚さ２５μｍの粘着剤層のヘーズ値を、以下に示す方法により測定した。
前記加工方法において述べた前記粘着剤層付き偏光板の作製工程において、ディスコティック液晶層付偏光フィルムの代わりに別の剥離シート［リンテック社製、「ＳＰ−ＰＥＴ３８１１３０」］を貼合することにより、剥離シート／粘着剤層／剥離シートの構成体を作製した。そして、前記粘着剤層付き偏光板の場合と同じ条件の養生期間をとった。その後、前記構成体の剥離シート［リンテック社製、「ＳＰ−ＰＥＴ３８１１３０」］を剥がし、露出した粘着剤層面をソーダライムガラス（日本板ガラス製）に貼合し、ソーダライムガラス／粘着剤／剥離フィルムを作製した。その後、もう一方の剥離シート［リンテック社製、「ＳＰ−ＰＥＴ３８２０５０」］を剥がし、ヘーズメーター［日本電色工業社製、「ＮＤＨ−２０００」］を用いて、ＪＩＳ Ｋ ７１３６に準じてヘーズ値を測定した。偏光板用粘着剤として使用する場合は、ヘーズ値は小さい方が好ましい。
<Gel fraction>
The gel fraction was measured according to the method described in the specification text.
<Haze value>
The haze value of the adhesive layer having a thickness of 25 μm was measured by the following method.
In the production process of the polarizing plate with the pressure-sensitive adhesive layer described in the processing method, by bonding another release sheet [manufactured by Lintec Corporation, “SP-PET381130”] instead of the polarizing film with a discotic liquid crystal layer, A component of release sheet / adhesive layer / release sheet was prepared. And the curing period of the same conditions as the case of the said polarizing plate with an adhesive layer was taken. Thereafter, the release sheet [SP-PET381130, manufactured by LINTEC Co., Ltd.] is peeled off, and the exposed adhesive layer surface is bonded to soda lime glass (made by Japanese plate glass), soda lime glass / adhesive / release film. Was made. Then, the other release sheet [Lintec Co., Ltd., “SP-PET382020”] is peeled off, and the haze value is measured according to JIS K 7136 using a haze meter [Nippon Denshoku Industries Co., Ltd., “NDH-2000”]. It was measured. When using as an adhesive for polarizing plates, a smaller haze value is preferable.
実施例１〜１０及び比較例１〜５
（１）アクリル酸エステル共重合体（Ａ）の製造
アクリル酸ブチル（ＢＡ）及びアクリル酸（ＡＡ）を第１表に示す割合（質量比）で用い、常法に従い共重合を行い、第１表に示す重量平均分子量（Ｍｗ）のアクリル酸ブチル／アクリル酸ランダム共重合体を製造した。
（２）アクリル酸エステル共重合体（Ｂ）の製造
（イ）リビングラジカル重合による、トリブロック共重合体の製造
実施例１〜１０及び比較例４、５においては、アクリル酸ブチル、及びアクリル酸２−ヒドロキシエチル（ＨＥＡ）又はアクリル酸４−ヒドロキシブチル（４ＨＢＡ）を用い、リビングラジカル重合開始剤として、下記のようにして合成された有機テルル化合物（エチル−２−メチル−２−ｎ−ブチルテラニル−プロピオネート）と、２,２'−アゾビスイソブチロニトリルを使用して、第１表に示す重量平均分子量（Ｍｗ）と分子量分布（ＰＤＩ）を有し、かつ第１表に示す形態のトリブロック共重合体を製造した。
Examples 1-10 and Comparative Examples 1-5
(1) Production of Acrylate Ester Copolymer (A) Using butyl acrylate (BA) and acrylic acid (AA) in the proportions (mass ratio) shown in Table 1, copolymerization is carried out according to a conventional method. A butyl acrylate / acrylic acid random copolymer having a weight average molecular weight (Mw) shown in the table was produced.
(2) Production of acrylic ester copolymer (B) (a) Production of triblock copolymer by living radical polymerization In Examples 1 to 10 and Comparative Examples 4 and 5, butyl acrylate and acrylic acid An organic tellurium compound (ethyl-2-methyl-2-n-butylterranil) synthesized as follows using 2-hydroxyethyl (HEA) or 4-hydroxybutyl acrylate (4HBA) as a living radical polymerization initiator -Propionate) and 2,2'-azobisisobutyronitrile, having the weight average molecular weight (Mw) and molecular weight distribution (PDI) shown in Table 1, and having the form shown in Table 1 A triblock copolymer was produced.
＜エチル−２−メチル−２−ｎ−ブチルテラニル−プロピオネートの合成＞
金属テルル［Ａｌｄｒｉｃｈ製、製品名：Ｔｅｌｌｕｒｉｕｍ（−４０ｍｅｓｈ）]６.３８ｇ（５０ｍｍｏｌ）をテトラハイドロフラン（ＴＨＦ）５０ｍｌに懸濁させ、これにｎ−ブチルリチウム［Ａｌｄｒｉｃｈ製、１.６ｍｏｌ／Ｌヘキサン溶液］３４.４ｍｌ（５５ｍｍｏｌ）を、室温でゆっくり滴下した。この反応溶液を金属テルルが完全に消失するまで撹拌した。この反応溶液に、エチル−２−ブロモ−イソブチレート１０.７ｇ（５５ｍｍｏｌ）を室温で加え、２時間撹拌した。反応終了後、減圧下で溶媒を濃縮し、続いて減圧蒸留して、黄色油状物のエチル−２−メチル−２−ｎ−ブチルテラニル−プロピオネート８.９８ｇ（収率５９.５％）を得た。
<Synthesis of ethyl-2-methyl-2-n-butylteranyl-propionate>
Metal tellurium [product of Aldrich, product name: Tellurium (−40 mesh)] 6.38 g (50 mmol) was suspended in 50 ml of tetrahydrofuran (THF), and n-butyllithium [manufactured by Aldrich, 1.6 mol / L hexane]. Solution] 34.4 ml (55 mmol) was slowly added dropwise at room temperature. The reaction solution was stirred until the metal tellurium disappeared completely. To this reaction solution, 10.7 g (55 mmol) of ethyl-2-bromo-isobutyrate was added at room temperature and stirred for 2 hours. After completion of the reaction, the solvent was concentrated under reduced pressure, followed by distillation under reduced pressure to obtain 8.98 g (yield 59.5%) of ethyl-2-methyl-2-n-butylteranyl-propionate as a yellow oil. .
（ロ）比較例２は、フリーラジカル重合法によるアクリル酸ブチルの単独重合体、比較例３は、リビングラジカル重合法によるアクリル酸ブチルとアクリル酸ラウリルとのランダム共重合体、比較例１はアクリル酸エステル共重合体（Ａ）のみで、アクリル酸エステル共重合体（Ｂ）は用いていない。
（３）粘着剤組成物の調製
第１表に示す配合組成（固形分換算）の粘着剤組成物を調製し、前述した加工方法に従って、粘着剤層付き偏光板を作製し、前述した方法で粘着剤の諸特性を評価すると共に、粘着剤のゲル分率を求めた。その結果を第２表に示す。
(B) Comparative Example 2 is a homopolymer of butyl acrylate by free radical polymerization, Comparative Example 3 is a random copolymer of butyl acrylate and lauryl acrylate by living radical polymerization, and Comparative Example 1 is acrylic. Only the acid ester copolymer (A) is used, and the acrylic acid ester copolymer (B) is not used.
(3) Preparation of pressure-sensitive adhesive composition A pressure-sensitive adhesive composition having the composition shown in Table 1 (in terms of solid content) was prepared, and a polarizing plate with a pressure-sensitive adhesive layer was prepared according to the processing method described above. While evaluating various properties of the pressure-sensitive adhesive, the gel fraction of the pressure-sensitive adhesive was determined. The results are shown in Table 2.
［注］
ＢＡ：アクリル酸ブチル
ＡＡ：アクリル酸
ＨＥＡ：アクリル酸２−ヒドロキシエチル
４ＨＢＡ：アクリル酸４−ヒドロキシブチル
ＬＡ：アクリル酸ラウリル
ＴＤＩ（Ｃ）：トリメチロールプロパン変性トリレンジイソシアネート［日本ポリウレタン社製、「コローネートＬ」］
ＫＢＭ−４０３：３−グリシドキシプロピルトリメトキシシラン［信越化学工業社製、「ＫＢＭ−４０３」］
[note]
BA: butyl acrylate AA: acrylic acid HEA: 2-hydroxyethyl acrylate 4HBA: 4-hydroxybutyl acrylate LA: lauryl acrylate TDI (C): trimethylolpropane-modified tolylene diisocyanate [manufactured by Nippon Polyurethane Co., Ltd. L "]
KBM-403: 3-glycidoxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-403”]
第２表から分かるように、本発明の粘着剤（実施例１〜１０）は、耐久性及び光漏れ防止性の評価において、いずれも「△」以上であるが、比較例１〜５の粘着剤は、前記評価において、いずれも、少なくとも１つの「×」を有している。 As can be seen from Table 2, the pressure-sensitive adhesives (Examples 1 to 10) of the present invention are both “Δ” or more in evaluation of durability and light leakage prevention properties, but the pressure-sensitive adhesives of Comparative Examples 1 to 5 Each of the agents has at least one “x” in the evaluation.
本発明の粘着剤組成物は、液晶表示装置を構成する偏光板などに好適に用いられ、偏光板の伸縮に起因する白抜け現象の発生を防止し得る粘着剤層を形成することができる。 The pressure-sensitive adhesive composition of the present invention is suitably used for a polarizing plate constituting a liquid crystal display device, and can form a pressure-sensitive adhesive layer that can prevent the occurrence of white spots due to expansion and contraction of the polarizing plate.
Claims (9)
（１）前記第２の(メタ)アクリル酸エステル重合体（Ｂ）が、水酸基含有(メタ)アクリレート系モノマー単位を１．５質量％以上有するトリブロック共重合体であること、
（２）前記第２の(メタ)アクリル酸エステル重合体（Ｂ）の含有量が、前記第１の(メタ)アクリル酸エステル重合体（Ａ）１００質量部に対して、４０質量部未満であること、及び
（３）粘着剤組成物から形成される粘着剤のゲル分率が４０％以上であること、
を特徴とするアクリル系粘着剤組成物。 A first (meth) acrylic acid ester polymer (A) having a weight average molecular weight of 1,000,000 to 2.5 million, and a second (meth) acrylic acid ester polymer (B) having a weight average molecular weight of 20,000 to 150,000 And an adhesive composition containing an isocyanate-based crosslinking agent (C),
(1) The second (meth) acrylic acid ester polymer (B) is a triblock copolymer having a hydroxyl group-containing (meth) acrylate monomer unit of 1.5% by mass or more ,
(2) The content of the second (meth) acrylic acid ester polymer (B) is less than 40 parts by mass with respect to 100 parts by mass of the first (meth) acrylic acid ester polymer (A). And (3) the gel fraction of the pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition is 40% or more,
An acrylic pressure-sensitive adhesive composition characterized by the above.
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| JP6412453B2 (en) * | 2015-03-26 | 2018-10-24 | 積水化学工業株式会社 | Adhesive composition and adhesive tape |
| JP6560022B2 (en) * | 2015-05-08 | 2019-08-14 | 積水化学工業株式会社 | Adhesive tape |
| JP6607718B2 (en) * | 2015-07-15 | 2019-11-20 | 綜研化学株式会社 | Adhesive composition for polarizing plate |
| KR102047288B1 (en) * | 2015-12-10 | 2019-11-21 | 주식회사 엘지화학 | Pressure sensitive adhesive composition |
| KR102024256B1 (en) * | 2016-09-23 | 2019-11-04 | 주식회사 엘지화학 | Pressure sensitive adhsive composition |
| US20200032116A1 (en) * | 2016-09-30 | 2020-01-30 | Nitto Denko Corporation | Polarizing film adhesive composition, manufacturing method of polarizing film adhesive layer, polarizing film with adhesive layer, and image display device |
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