JP2005053976A - Pressure-sensitive adhesive for lowly polar film - Google Patents
Pressure-sensitive adhesive for lowly polar film Download PDFInfo
- Publication number
- JP2005053976A JP2005053976A JP2003206345A JP2003206345A JP2005053976A JP 2005053976 A JP2005053976 A JP 2005053976A JP 2003206345 A JP2003206345 A JP 2003206345A JP 2003206345 A JP2003206345 A JP 2003206345A JP 2005053976 A JP2005053976 A JP 2005053976A
- Authority
- JP
- Japan
- Prior art keywords
- component
- pressure
- film
- sensitive adhesive
- low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 48
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
- 229920006158 high molecular weight polymer Polymers 0.000 claims abstract description 11
- 230000003287 optical effect Effects 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 8
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 239000000853 adhesive Substances 0.000 claims description 29
- 230000001070 adhesive effect Effects 0.000 claims description 29
- 239000012948 isocyanate Substances 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 239000002313 adhesive film Substances 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 27
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 3
- 239000010408 film Substances 0.000 description 38
- 229940048053 acrylate Drugs 0.000 description 26
- -1 2-ethylhexyl Chemical group 0.000 description 11
- 238000007334 copolymerization reaction Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 150000001875 compounds Chemical class 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
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012788 optical film Substances 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 244000062793 Sorghum vulgare Species 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 235000019713 millet Nutrition 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- DKJBREHOVWISMR-UHFFFAOYSA-N 1-chloro-2,3-diisocyanatobenzene Chemical compound ClC1=CC=CC(N=C=O)=C1N=C=O DKJBREHOVWISMR-UHFFFAOYSA-N 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-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
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- ORTNTAAZJSNACP-UHFFFAOYSA-N 6-(oxiran-2-ylmethoxy)hexan-1-ol Chemical compound OCCCCCCOCC1CO1 ORTNTAAZJSNACP-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229940114077 acrylic acid Drugs 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
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- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- SJPFBRJHYRBAGV-UHFFFAOYSA-N n-[[3-[[bis(oxiran-2-ylmethyl)amino]methyl]phenyl]methyl]-1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC=1C=C(CN(CC2OC2)CC2OC2)C=CC=1)CC1CO1 SJPFBRJHYRBAGV-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polarising Elements (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、低極性フィルム用粘着剤に関するものであり、より詳細には、液晶ディスプレイなどに用いられる視野角拡大フィルムや位相差板フィルムなどの低極性フィルムに対しても密着性の良好な粘着剤に関するものである。
【０００２】
【従来の技術】
液晶ディスプレイには、偏光板や位相差板などが積層されているが、近年、ディスプレイの大型化や高性能化の要求が高まり、積層されるフィルムの高機能化が進んでいる。例えば、偏光板に使用されているＰＶＣ層保護フィルムにおいては、トリアセチルセルロースフィルムからノルボルネン樹脂フィルムに代わる動きがあり、位相差板フィルムおいても、ポリカーボネートの低極性変性フィルムやノルボルネン樹脂フィルムへの置き換えが進んでいる。
【０００３】
しかし、これらのフィルムは、極性が低いものが多く、従来用いられてきた粘着剤では、フィルム表面への密着性が悪く、耐久性に問題が生じることがあった。
【０００４】
一方、従来からアクリル系の粘着剤として、脂環式モノマーを共重合させたポリマーを用いることが知られている（特許文献１及び特許文献２）。しかしながら、これらの粘着剤は、再剥離性（一旦接着されたフィルムを再度剥がし易い性能）の向上を目的として、経時での粘着力の上昇を抑制するために開発されたものであるため、経時で発泡やハガレが生じやすく、耐久性が十分でないという問題点があった。また、かかる粘着剤は、経時で粘着力が不充分になるため、高温化や高湿下において、特にハガレが生じる場合があるという問題点があった。
【０００５】
また、光学フィルム用粘着剤として、芳香族含有モノマーを共重合させたポリマーを用いることが知られている（特許文献３及び特許文献４）。しかしながら、これらの粘着剤は、偏光板や位相差板などの光学部材と粘着剤との間及び粘着剤と被着体との間の界面反射を抑制するために、粘着剤の屈折率を調整することを目的とするものであった。また、貼り付け直後から強い接着性を示すように設計されているため、貼り付けミスをしても張り直しができる性能（リワーク性）に劣るという問題点があった。すなわち、これらの粘着剤では、極性の低い光学フィルム表面に対しての密着性やリワーク性を改良することには全く認識がなく、実際これらの粘着剤は、低極性フィルム用粘着剤としては、密着性、リワーク性に問題があるものであった。
【０００６】
【特許文献１】
特開平８−１４３８４２号公報
【特許文献２】
特開２００１−２７９２０８号公報
【特許文献３】
特開２００２−１７３６５６号公報
【特許文献４】
特開２００３− １３０２９号公報
【０００７】
【発明が解決しようとする課題】
従って、本発明は、光学的な機能を有する低極性フィルムに対しても粘着性等の性能が優れた粘着剤の提供をその課題とするものである。
【０００８】
【課題を解決するための手段】
本発明者らは、上記実状において鋭意検討を重ねた結果、脂環式モノマー又は芳香族含有モノマーを共重合成分とする重量平均分子量１００万〜２００万の高分子量ポリマーと架橋剤を粘着剤に含有させることにより、上記課題を解決できることを見出し、本発明を完成した。
【０００９】
すなわち本発明は、次の成分（Ａ）及び成分（Ｂ）
（Ａ）少なくとも次の成分（ａ１）、（ａ２）及び（ａ３）を共重合してなる重量平均分子量が１００万〜２００万の範囲である高分子量ポリマー
（ａ１）（メタ）アクリル酸アルキルエステル ３０〜９０質量％
（ａ２）脂環式モノマー又は芳香環含有モノマー ９〜５０質量％
（ａ３）官能基含有モノマー ０．５〜１０質量％
（Ｂ）架橋剤
を含有する低極性フィルム用粘着剤を提供するものである。
【００１０】
また本発明は、光学的機能を有する低極性フィルムに、上記低極性フィルム用粘着剤を塗工してなる光学機能性粘着フィルムを提供するものである。
【００１１】
【発明の実施の形態】
本明細書において、低極性フィルム用粘着剤とは、低極性フィルム、例えば、視野角拡大フィルム、位相差フィルム、偏光板等のノルボルネン系樹脂やポリカーボネート系樹脂で形成されたフィルムに使用した場合でも良好な密着性を示す粘着剤を意味する。
【００１２】
本発明の低極性フィルム用粘着剤（以下、「本発明粘着剤」という）は、高分子量ポリマー（成分（Ａ））と架橋剤（成分（Ｂ））を含有するものである。
【００１３】
このうち、成分（Ａ）を構成する共重合成分の一つである（メタ）アクリル酸アルキルエステル（成分（ａ１））は、鎖状のアルキル基を有し、脂肪族環も芳香環もその構造中に有さない（メタ）アクリル酸アルキルエステルである。
【００１４】
この（メタ）アクリル酸アルキルエステルの好ましい例としては、炭素数１〜１２の分岐していてもよいアルキル基を有するものが挙げられ、具体的には、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレートが挙げられる。
【００１５】
また、成分（Ａ）の別の必須共重合成分である脂環式モノマー又は芳香環含有モノマー（成分（ａ２））は、その構造中に環状アルキル基又は芳香族基を含む共重合可能な化合物である。
【００１６】
具体的な、脂環式モノマーの例としては、シクロヘキシル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニルオキシ（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンタン（メタ）アクリレート等が挙げられる。特に好ましくは、シクロヘキシルアクリレート又はシクロヘキシルメタクリレート等が挙げられる。また、具体的な、芳香環含有モノマーの例としては、フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、エチレンオキサイド変性ノニルフェノール（メタ）アクリレート、スチレン、ビニルトルエン、α−メチルスチレン等が挙げられる。
【００１７】
更に、成分（Ａ）の他の別の必須共重合成分である官能基含有モノマー（成分（ａ３））は、後記する架橋剤（成分（Ｂ））と反応する官能基をその分子構造中に含み、共重合可能な化合物である。
【００１８】
成分（ａ３）に含まれる官能基のうち、好ましいものとしては、水酸基、カルボキシル基、アミド基又はＮ置換アミド基等が挙げられる。これらの基を含む具体的な成分（ａ３）の例としては、２−ヒドロキシエチル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等の水酸基含有モノマー、（メタ）アクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸等のカルボキシル基含有モノマー、（メタ）アクリルアミド等のアミド基含有モノマー、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メトキシエチル（メタ）アクリルアミド等のＮ置換アミド基含有モノマーが挙げられる。
【００１９】
上記成分（Ａ）は、上記成分（ａ１）、成分（ａ２）及び成分（ａ３）を共重合させることにより製造される。この共重合に当たっての重合方法は、特に限定はされないが、ポリマー設計の容易さの点でラジカル重合が好ましく、汚染性などを考慮すると溶液重合が特に好ましい。
【００２０】
この共重合においては、成分（ａ１）は、成分（Ａ）に対して３０〜９０質量％（以下、単に「％」で示す）の範囲、好ましくは、５０〜８５％の範囲で、成分（ａ２）は、９〜５０％の範囲、好ましくは、９〜３０％の範囲で、成分（ａ３）は、０．５〜１０％の範囲、好ましくは、１〜５％の範囲で使用される。また、成分（ａ１）と成分（ａ２）の合計量が、成分（Ａ）に対して８０％以上であることが基材への密着性や耐久性の面で好ましく、特に好ましくは、９０％以上である。
【００２１】
なお、成分（Ａ）の製造に当たっては、上記必須共重合成分以外に、他の共重合性モノマーを共重合してもよい。他の共重合性モノマーとしては、例えば酢酸ビニル等の脂肪族カルボン酸ビニル化合物等が挙げられる。これらは、成分（Ａ）に対して、０〜１０％の範囲で共重合される。
【００２２】
上記のように重合して得られる成分（Ａ）の分子量は、重量平均分子量として、１００万〜２００万の範囲であることが必須である。分子量が１００万未満の場合は、高温時に発泡する場合があり、２００万より大きい場合は、高温又は高湿熱時にハガレが発生する場合がある。より好ましい重量平均分子量としては、１２０万〜１６０万である。
【００２３】
一方、本発明粘着剤の別の必須成分である架橋剤（成分（Ｂ））は、成分（Ａ）の有する官能基と反応又は相互作用し得る化合物である。この成分（Ｂ）としては、イソシアネート系架橋剤又はエポキシ系架橋剤がリワーク性に優れ、また粘着シートにアワ、ハガレが発生しにくいため、好ましく使用される。
【００２４】
上記成分（Ｂ）のうちイソシアネート系架橋剤は、その分子中に２以上のイソシアネート基を有する化合物であり、具体的には、トリレンジイソシアネート、クロルフェニレンジイソシアネート、ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネート、水添されたジフェニルメタンジイソシアネートなどのイソシアネートモノマーや、それらをトリメチロールプロパンなどの２価以上のアルコール化合物等に付加反応させたイソシアネート化合物ないしイソシアヌレート化物、ビュレット型化合物等が例示される。また、公知のポリエーテルポリオールやポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオールなどにイソシアネート化合物を付加反応させたウレタンプレポリマー型のイソシアネート等も挙げられる。
【００２５】
また、エポキシ系架橋剤は、その分子中に２以上のエポキシ基を有する化合物であり、具体的には、ビスフェノールＡエピクロルヒドリン型のエポキシ系樹脂、エチレングリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１，６−ヘキサンジオールグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、ジアミングリシジルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシリレンジアミン、１，３−ビス（Ｎ，Ｎ’−ジアミングリシジルアミノメチル）シクロヘキサン等が挙げられる。
【００２６】
本発明粘着剤の調製は、上記成分（Ａ）と成分（Ｂ）を常法に従って混合することにより行われる。本発明粘着剤中の成分（Ａ）の量は特に限定されず、他の配合成分のバランス量とすれば良いが、好ましい含有量は粘着剤全体に対して５０％以上、特に好ましくは７０％以上である。
【００２７】
また、本発明粘着剤中の架橋剤（Ｂ）の含有量は、特に制約されるものではないが、成分（Ａ）１００重量部に対して、０．０１〜５重量部の範囲で含有させることが好ましい。さらに、成分（Ｂ）としてイソシアネート系架橋剤を使用する場合は、０．０５〜１重量部の範囲とすることが特に好ましく、エポキシ系架橋剤を使用する場合は、０．０２〜０．２重量部の範囲とすることが特に好ましい。この架橋剤（Ｂ）の含有量が少なすぎると、高温時の耐久性が悪化し、アワ、ハガレが発生する場合があり、多すぎても耐久性が悪化する場合がある。
【００２８】
本発明粘着剤には、上記必須含有成分に加え、更に成分（Ｃ）としてシランカップリング剤を含有させることが、高湿熱時のハガレ防止の点で好ましい。
【００２９】
成分（Ｃ）としては公知のものが使用できるが、エポキシ基、イソシアネート基、メルカプト基、アミノ基、カルボキシル基、アルコキシ基を有するものが特に好ましい。
【００３０】
成分（Ｃ）を使用する場合は、成分（Ａ）１００重量部に対して、０．０５〜０．５重量部の範囲とすることが好ましい。これらシランカップリング剤は、その含有量が少なすぎると、ハガレ防止の効果を発揮できず、多すぎるとブリードしてハガレやアワが発生する場合がある。
【００３１】
本発明粘着剤には、上記必須含有成分に加え、更に成分（Ｄ）として低分子量（メタ）アクリル系ポリマーを含有させることが好ましい。
【００３２】
この成分（Ｄ）を構成する共重合成分としては、特に限定されないが、成分（Ａ）の共重合成分として例示した、（メタ）アクリル酸アルキルエステル（ａ１）や、脂環式モノマー又は芳香環含有モノマー（ａ２）を利用することができる。この際、使用する共重合成分として、成分（Ａ）で使用する共重合成分（ａ１）や（ａ２）と同じ共重合成分を共重合させると、高分子量ポリマー（成分（Ａ））との相溶性が増すので特に好ましく、特に（ａ１）及び（ａ２）の両者とも一致させ、更にこれらの共重合比も、成分（Ａ）のそれとほぼ同じにすることが相溶性の点で好ましい。
【００３３】
上記成分（Ｄ）の重量平均分子量は、１０００〜３００００の範囲であり、好ましくは、１０００〜２００００、特に好ましくは、３０００〜１００００である。１０００未満だと、耐久性が低下する場合があり、３００００より大きいと相溶性が悪くなる場合がある。
【００３４】
上記のように、成分（Ｄ）は、原料であるモノマーが、成分（Ａ）のものとほぼ同一のものであり、分子量が小さいものであり、その製造に当たっては、溶液重合することが特に望ましい。
【００３５】
上記のようにして得られる成分（Ｄ）の配合量は、成分（Ａ）１００重量部に対して、５〜１００重量部の範囲であり、好ましくは、１０〜５０重量部である。
【００３６】
以上のようにして製造される本発明粘着剤を、例えば、偏光板に積層される視野角拡大フィルムや、位相差板フィルム等の光学的機能を有する低極性光学フィルムに塗工し、光学機能性粘着フィルムとするには、常法に従って本発明粘着剤を酢酸エチル、トルエン、メチルエチルケトン等の有機溶剤に溶解し、これを低極性フィルム上に塗布、乾燥させて架橋反応を起こさせ、反対側の粘着面上に剥離フィルムないし剥離紙を貼り合わせればよい。
【００３７】
【作用】
本発明の必須成分である高分子量ポリマー（成分（Ａ））は、重量平均分子量１００万〜２００万と大きな分子量を有しているため、これを含有させて得られた粘着剤は、耐久性に優れている。
【００３８】
また、成分（Ａ）中に、脂環式モノマー又は芳香環含有モノマーが共重合されることにより、低極性フィルムに対する密着性及び耐久性が向上する。この理由は明らかではないが、これらモノマーが低極性の環を有するため、高分子量ポリマー自体の極性が低くなり、同様に極性の低い光学フィルムへの密着性が上昇したものと考えられる。
【００３９】
さらに、本発明粘着剤は貼り付け直後の粘着力が低く、基材への密着力が良いためリワーク性に優れている。さらに、低極性フィルムに適用した場合、特にその特性が生かされる。
【００４０】
【実施例】
次に実施例等を挙げて本発明を更に説明するが、本発明はこれらにより何ら制約されるものではない。
【００４１】
製 造 例 １〜７、９〜１５、１７〜２１
撹拌機、還流冷却器、温度計及び窒素導入管を備えた反応装置に、それぞれ表１に示す重量部（以下、実施例又は表で、「部」と略記することがある）の共重合性モノマーと酢酸エチル及び／又はトルエンを仕込み、アゾビスイソブチロニトリル（ＡＩＢＮ）０．１部を加えた。次いで、窒素ガス気流中、６８℃にて８時間重合を行うことにより、高分子量ポリマー（成分（Ａ））を得た。
【００４２】
製 造 例 ８、１６
撹拌機、還流冷却器、温度計及び窒素導入管を備えた反応装置に、それぞれ表１に示す重量部の共重合性モノマーとトルエンを仕込み、過酸化ベンゾイル３部とα−スチレンダイマー５部を加えた。次いで、窒素ガス気流中、１１０℃にて６時間重合を行うことにより、低分子量（メタ）アクリル系ポリマー（成分（Ｄ）を得た。
【００４３】
なお、各ポリマーの分子量は、反応溶媒の使用量を、１００〜２２０部の範囲で調節することによって変化させた。得られたポリマーの重量平均分子量を表１に併記する。
【００４４】
【表１】
ＢＡ ： ブチルアクリレート
２ＥＨＡ ： ２−エチルヘキシルアクリレート
ＣＨＡ ： シクロヘキシルアクリレート
ＩＢＸＡ ： イソボルニルアクリレート
ＰＨＥＡ ： フェノキシエチルアクリレート
ＢｚＡ ： ベンジルアクリレート
２ＨＥＡ ： ２−ヒドロキシエチルアクリレート
ＡＡ ： アクリル酸
３ＨＰＡ ： ３−ヒドロキシプロピルアクリレート
【００４５】
実 施 例 １〜１３ 及び 比 較 例 １〜１２
製造例１〜７、製造例９〜１５又は製造例１７〜２１で製造した高分子量ポリマーと、製造例８又は製造例１６で製造した低分子量（メタ）アクリレート系ポリマーとを使用し、これらを酢酸エチルに表２に記載した組成と量でそれぞれ混合溶解した。次いで、表２に記載した架橋剤及び／又はシランカップリング剤、をそれぞれ加えて混合し、粘着剤溶液を得た。得られた粘着剤溶液を、厚さ１００μｍのノルボルネン樹脂フィルム上に、乾燥後の厚みが２５μｍになるように塗布し、８０℃で溶媒を除去し乾燥するとともに架橋反応させた。乾燥面に厚み３８μｍのシリコーンコートされたポリエチレンテレフタレートフィルム（ＰＥＴフィルム）を貼り合わせて、２３℃、６５％ＲＨで７日放置し粘着シートを得た。
【００４６】
【表２】
コロネートＬ ：日本ポリウレタン工業社製イソシアネート系架橋剤
テトラッドＸ ：三菱瓦斯化学社製エポキシ系架橋剤
ＫＢＥ−９００７：信越ポリマー社製イソシアネート型シランカップリング剤
ＫＢＥ−４０２ ：信越ポリマー社製エポキシ型シランカップリング剤
【００４７】
試 験 例 １
上記実施例及び比較例で得られた粘着シートについて、その耐久性及び粘着力・リワーク性を以下の評価方法で評価した。この結果を表３にまとめて示す。
【００４８】
（ 耐 久 性 ）
上記粘着シートをそれぞれ６０ｍｍ×１２０ｍｍに裁断し、ＰＥＴフィルムを剥離後、ガラス基板上に貼り付け、８５℃、ドライで５００時間及び６０℃、９５％ＲＨで５００時間放置し、粘着シートに発生するアワ、ハガレの状態を目視で観察し耐久性を評価した。また、観察した後、粘着シート表面を手でこすり密着性を確認した。
【００４９】
＜アワ＞
○：粘着シートに発泡が確認されなかった
△：粘着シートにわずかに発泡が確認された
×：粘着シートに発泡が確認された
＜ハガレ＞
○：粘着シートに剥がれが起こらなかった
△：粘着シートに剥がれがわずかに起こった
×：粘着シートに剥がれが起こった
＜密着性＞
○：強くこすっても剥がれなかった
△：強くこすると剥がれた
×：軽くこすると剥がれた
【００５０】
（ 粘着力・リワーク性 ）
＜初期接着力＞
上記粘着シートをそれぞれ２５ｍｍ×１２０ｍｍに裁断し、ＪＩＳ−Ｚ−０２３７及びＪＩＳ−Ｚ−０２３８に準じて接着力を測定した。被着体としては、ガラス板を使用した。
【００５１】
＜経時接着力＞
上記粘着シートをそれぞれ２５ｍｍ×１５０ｍｍに裁断し、７０℃で６時間放置した後、２３℃まで放冷し、ＪＩＳ−Ｚ−０２３７及びＪＩＳ−Ｚ−０２３８に準じて接着力を測定した。被着体としては、ガラス板を使用した。
【００５２】
【表３】
【００５３】
表３に示した評価結果から明らかなように、本発明の粘着剤を用いた粘着シートには、アワ、ハガレが発生せず、耐久性及び密着性に優れていた。また、経時粘着力が低下することがなく、リワーク性に優れた粘着剤であることも示された。一方、比較例の粘着シートは、密着性、耐久力、リワーク性に劣っており、ガラス基板上に粘着剤の残りが見られるものもあった。
【００５４】
【発明の効果】
本発明の粘着剤は、低極性フィルムに対して使用した場合でも、密着性やリワーク性が優れたものである。
【００５５】
従って、この粘着剤を使用することにより、視野角拡大フィルム、位相差板フィルム、偏光板等の光学的機能を有する低極性フィルムに適度な粘着性を付与することができ、使用しやすい光学機能性粘着フィルムを提供することができる。
以 上[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a low-polarity film pressure-sensitive adhesive, and more specifically, a pressure-sensitive adhesive having good adhesion to a low-polarity film such as a viewing angle widening film or a retardation film used in a liquid crystal display. It relates to the agent.
[0002]
[Prior art]
In liquid crystal displays, polarizing plates and retardation plates are laminated, but in recent years, there has been an increasing demand for larger displays and higher performance of displays, and advanced functions of laminated films have been advanced. For example, in the PVC layer protective film used for the polarizing plate, there is a movement to replace the norbornene resin film from the triacetyl cellulose film, and even in the retardation film, the low polarity modified film of polycarbonate or the norbornene resin film can be used. Replacement is progressing.
[0003]
However, many of these films have a low polarity, and the pressure-sensitive adhesives that have been used conventionally have poor adhesion to the film surface and may have problems with durability.
[0004]
On the other hand, it is conventionally known to use a polymer obtained by copolymerizing an alicyclic monomer as an acrylic adhesive (Patent Document 1 and Patent Document 2). However, these pressure-sensitive adhesives have been developed for the purpose of improving re-peelability (performance that allows a film once adhered to be easily peeled again) to suppress an increase in adhesive strength over time. However, there is a problem that foaming or peeling is likely to occur and durability is not sufficient. Further, such an adhesive has a problem that peeling may occur particularly at high temperatures and high humidity because the adhesive strength becomes insufficient with time.
[0005]
In addition, it is known to use a polymer obtained by copolymerizing an aromatic-containing monomer as an adhesive for an optical film (Patent Document 3 and Patent Document 4). However, these pressure-sensitive adhesives adjust the refractive index of the pressure-sensitive adhesive in order to suppress interfacial reflection between optical members such as polarizing plates and retardation plates, and pressure-sensitive adhesives, and between pressure-sensitive adhesives and adherends. It was intended to do. In addition, since it is designed to exhibit strong adhesiveness immediately after pasting, there is a problem that it is inferior in performance (reworkability) in which re-stripping can be performed even if a pasting mistake is made. That is, with these pressure-sensitive adhesives, there is no recognition in improving the adhesion and reworkability to the optical film surface with low polarity, in fact, these pressure-sensitive adhesives are, as pressure-sensitive adhesives for low-polarity films, There were problems with adhesion and reworkability.
[0006]
[Patent Document 1]
JP-A-8-143842 [Patent Document 2]
Japanese Patent Laid-Open No. 2001-279208 [Patent Document 3]
JP 2002-173656 A [Patent Document 4]
Japanese Patent Laid-Open No. 2003-13029
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a pressure-sensitive adhesive having excellent performance such as adhesiveness even for a low-polarity film having an optical function.
[0008]
[Means for Solving the Problems]
As a result of intensive studies in the above situation, the present inventors have used a high molecular weight polymer having a weight average molecular weight of 1,000,000 to 2,000,000 as a copolymerization component and a crosslinking agent as an adhesive. The present inventors have found that the above-mentioned problems can be solved by the inclusion, and the present invention has been completed.
[0009]
That is, the present invention includes the following components (A) and (B):
(A) High molecular weight polymer (a1) (meth) acrylic acid alkyl ester having a weight average molecular weight in the range of 1,000,000 to 2,000,000 obtained by copolymerizing at least the following components (a1), (a2) and (a3) 30-90% by mass
(A2) Alicyclic monomer or aromatic ring-containing monomer 9 to 50% by mass
(A3) Functional group-containing monomer 0.5 to 10% by mass
(B) A pressure-sensitive adhesive for a low polarity film containing a crosslinking agent is provided.
[0010]
The present invention also provides an optical functional pressure-sensitive adhesive film obtained by coating the above low-polarity film pressure-sensitive adhesive on a low-polarity film having an optical function.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
In the present specification, the low-polarity film pressure-sensitive adhesive is a low-polarity film, for example, when used for a film formed of a norbornene-based resin or a polycarbonate-based resin such as a viewing angle widening film, a retardation film, and a polarizing plate. It means a pressure-sensitive adhesive exhibiting good adhesion.
[0012]
The pressure-sensitive adhesive for low polarity films of the present invention (hereinafter referred to as “the pressure-sensitive adhesive of the present invention”) contains a high molecular weight polymer (component (A)) and a crosslinking agent (component (B)).
[0013]
Among these, the (meth) acrylic acid alkyl ester (component (a1)), which is one of the copolymerization components constituting the component (A), has a chain alkyl group. It is a (meth) acrylic acid alkyl ester not present in the structure.
[0014]
Preferable examples of this (meth) acrylic acid alkyl ester include those having an alkyl group having 1 to 12 carbon atoms, and specifically include methyl (meth) acrylate and ethyl (meth). Acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) Examples include acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, and dodecyl (meth) acrylate.
[0015]
In addition, the alicyclic monomer or aromatic ring-containing monomer (component (a2)), which is another essential copolymerization component of component (A), is a copolymerizable compound containing a cyclic alkyl group or aromatic group in its structure. It is.
[0016]
Specific examples of alicyclic monomers include cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, and isobornyl (meth) acrylate. And adamantane (meth) acrylate. Particularly preferred is cyclohexyl acrylate or cyclohexyl methacrylate. Specific examples of aromatic ring-containing monomers include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, styrene, vinyltoluene, α -Methyl styrene etc. are mentioned.
[0017]
Furthermore, the functional group-containing monomer (component (a3)), which is another essential copolymerization component of component (A), has a functional group that reacts with a crosslinking agent (component (B)) described later in its molecular structure. And a copolymerizable compound.
[0018]
Of the functional groups contained in the component (a3), preferred are a hydroxyl group, a carboxyl group, an amide group, an N-substituted amide group, and the like. Specific examples of the component (a3) containing these groups include hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Carboxylic group-containing monomers such as (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid, amide group-containing monomers such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxyethyl (meth) acrylamide N-substituted amide group-containing monomers such as
[0019]
The said component (A) is manufactured by copolymerizing the said component (a1), a component (a2), and a component (a3). The polymerization method for the copolymerization is not particularly limited, but radical polymerization is preferable from the viewpoint of ease of polymer design, and solution polymerization is particularly preferable in consideration of contamination.
[0020]
In this copolymerization, the component (a1) is in the range of 30 to 90% by mass (hereinafter simply indicated as “%”), preferably in the range of 50 to 85% with respect to the component (A). a2) is used in a range of 9-50%, preferably 9-30%, and component (a3) is used in a range of 0.5-10%, preferably 1-5%. . Further, the total amount of the component (a1) and the component (a2) is preferably 80% or more with respect to the component (A) in terms of adhesion to the substrate and durability, and particularly preferably 90%. That's it.
[0021]
In producing the component (A), other copolymerizable monomers may be copolymerized in addition to the essential copolymerization component. Examples of other copolymerizable monomers include aliphatic vinyl carboxylate compounds such as vinyl acetate. These are copolymerized in the range of 0 to 10% with respect to the component (A).
[0022]
The molecular weight of the component (A) obtained by polymerization as described above must be in the range of 1,000,000 to 2,000,000 as the weight average molecular weight. When the molecular weight is less than 1 million, foaming may occur at high temperatures, and when it is greater than 2 million, peeling may occur at high temperatures or high heat of humidity. A more preferred weight average molecular weight is 1.2 million to 1.6 million.
[0023]
On the other hand, the crosslinking agent (component (B)), which is another essential component of the pressure-sensitive adhesive of the present invention, is a compound that can react or interact with the functional group of the component (A). As this component (B), an isocyanate-based cross-linking agent or an epoxy-based cross-linking agent is preferably used because it has excellent reworkability and hardly generates a flare or peeling on the pressure-sensitive adhesive sheet.
[0024]
Among the components (B), the isocyanate-based crosslinking agent is a compound having two or more isocyanate groups in its molecule, and specifically, tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone. Illustrative examples include isocyanate monomers such as diisocyanate, diphenylmethane diisocyanate and hydrogenated diphenylmethane diisocyanate, and isocyanate compounds or isocyanurates obtained by addition reaction of these with a dihydric or higher alcohol compound such as trimethylolpropane. The Moreover, the urethane prepolymer type isocyanate etc. which made the isocyanate compound addition reaction to well-known polyether polyol, polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol, etc. are mentioned.
[0025]
The epoxy-based crosslinking agent is a compound having two or more epoxy groups in the molecule, and specifically, bisphenol A epichlorohydrin type epoxy-based resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl. Ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamine glycidylamine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diamineglycidylaminomethyl) cyclohexane and the like can be mentioned.
[0026]
The pressure-sensitive adhesive of the present invention is prepared by mixing the component (A) and the component (B) according to a conventional method. The amount of the component (A) in the pressure-sensitive adhesive of the present invention is not particularly limited, and may be a balance amount of other compounding components, but the preferable content is 50% or more, particularly preferably 70% with respect to the whole pressure-sensitive adhesive. That's it.
[0027]
The content of the crosslinking agent (B) in the pressure-sensitive adhesive of the present invention is not particularly limited, but is 0.01 to 5 parts by weight with respect to 100 parts by weight of the component (A). It is preferable. Furthermore, when using an isocyanate type crosslinking agent as a component (B), it is especially preferable to set it as the range of 0.05-1 weight part, and when using an epoxy type crosslinking agent, it is 0.02-0.2. A range of parts by weight is particularly preferable. If the content of the cross-linking agent (B) is too small, durability at high temperatures may be deteriorated, and may cause cracking and peeling, and if too much, durability may be deteriorated.
[0028]
In addition to the above essential components, the pressure-sensitive adhesive of the present invention preferably further contains a silane coupling agent as component (C) from the viewpoint of preventing peeling during high-humidity heat.
[0029]
Although a well-known thing can be used as a component (C), The thing which has an epoxy group, an isocyanate group, a mercapto group, an amino group, a carboxyl group, and an alkoxy group is especially preferable.
[0030]
When using a component (C), it is preferable to set it as the range of 0.05-0.5 weight part with respect to 100 weight part of component (A). If the content of these silane coupling agents is too small, the effect of preventing peeling cannot be exhibited. If the content is too large, bleeding may occur, causing peeling or milling.
[0031]
The pressure-sensitive adhesive of the present invention preferably contains a low molecular weight (meth) acrylic polymer as the component (D) in addition to the above essential components.
[0032]
Although it does not specifically limit as a copolymerization component which comprises this component (D), The (meth) acrylic-acid alkylester (a1) illustrated as a copolymerization component of a component (A), an alicyclic monomer, or an aromatic ring The containing monomer (a2) can be used. At this time, when the same copolymer component as the copolymer component (a1) or (a2) used in the component (A) is copolymerized as a copolymer component to be used, a phase with a high molecular weight polymer (component (A)) is obtained. It is particularly preferable because of increased solubility, and it is particularly preferable from the viewpoint of compatibility that both (a1) and (a2) are made to coincide with each other, and the copolymerization ratio thereof is substantially the same as that of component (A).
[0033]
The weight average molecular weight of the said component (D) is the range of 1000-30000, Preferably it is 1000-20000, Most preferably, it is 3000-10000. If it is less than 1000, the durability may be lowered, and if it is more than 30000, the compatibility may be deteriorated.
[0034]
As described above, the component (D) is such that the raw material monomer is substantially the same as that of the component (A) and has a small molecular weight, and in the production thereof, it is particularly desirable to perform solution polymerization. .
[0035]
The compounding quantity of the component (D) obtained by the above is the range of 5-100 weight part with respect to 100 weight part of component (A), Preferably, it is 10-50 weight part.
[0036]
The pressure-sensitive adhesive of the present invention produced as described above is applied to a low-polarity optical film having an optical function such as a viewing angle widening film laminated on a polarizing plate or a retardation film, for example, and an optical function. In order to obtain a sticky adhesive film, the adhesive of the present invention is dissolved in an organic solvent such as ethyl acetate, toluene, methyl ethyl ketone, etc. according to a conventional method, and this is applied onto a low polarity film and dried to cause a crosslinking reaction. A release film or release paper may be bonded to the adhesive surface.
[0037]
[Action]
The high molecular weight polymer (component (A)), which is an essential component of the present invention, has a large molecular weight such as a weight average molecular weight of 1,000,000 to 2,000,000. Is excellent.
[0038]
Moreover, the adhesiveness and durability with respect to a low-polarity film improve by copolymerizing an alicyclic monomer or an aromatic ring containing monomer in a component (A). The reason for this is not clear, but since these monomers have a low polarity ring, the polarity of the high molecular weight polymer itself is lowered, and it is considered that the adhesion to an optical film having a low polarity is also increased.
[0039]
Furthermore, since the adhesive of the present invention has a low adhesive force immediately after bonding and good adhesion to the substrate, it has excellent reworkability. Furthermore, when applied to a low-polarity film, the characteristics are particularly utilized.
[0040]
【Example】
EXAMPLES Next, although an Example etc. are given and this invention is demonstrated further, this invention is not restrict | limited at all by these.
[0041]
Production Examples 1-7, 9-15, 17-21
Copolymerizability of parts by weight shown in Table 1 (hereinafter sometimes abbreviated as “parts” in Examples or Tables) in a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen introduction tube A monomer and ethyl acetate and / or toluene were charged, and 0.1 part of azobisisobutyronitrile (AIBN) was added. Subsequently, it superposed | polymerized at 68 degreeC in nitrogen gas stream for 8 hours, and the high molecular weight polymer (component (A)) was obtained.
[0042]
Manufacturing Example 8, 16
A reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube was charged with parts by weight of the copolymerizable monomer and toluene shown in Table 1, respectively, and 3 parts of benzoyl peroxide and 5 parts of α-styrene dimer were added. added. Subsequently, it superposed | polymerized at 110 degreeC in nitrogen gas stream, and the low molecular weight (meth) acrylic-type polymer (component (D) was obtained.
[0043]
In addition, the molecular weight of each polymer was changed by adjusting the usage-amount of the reaction solvent in the range of 100-220 parts. The weight average molecular weight of the obtained polymer is also shown in Table 1.
[0044]
[Table 1]
BA: butyl acrylate 2EHA: 2-ethylhexyl acrylate CHA: cyclohexyl acrylate IBXA: isobornyl acrylate PHEA: phenoxyethyl acrylate BzA: benzyl acrylate 2HEA: 2-hydroxyethyl acrylate AA: acrylic acid 3HPA: 3-hydroxypropyl acrylate
Examples 1 to 13 and Comparative Examples 1 to 12
Using the high molecular weight polymer produced in Production Examples 1-7, Production Examples 9-15, or Production Examples 17-21, and the low molecular weight (meth) acrylate polymer produced in Production Example 8 or Production Example 16, these were used. They were mixed and dissolved in ethyl acetate in the compositions and amounts described in Table 2. Subsequently, the crosslinking agent and / or silane coupling agent described in Table 2 were added and mixed to obtain an adhesive solution. The obtained adhesive solution was applied onto a norbornene resin film having a thickness of 100 μm so that the thickness after drying was 25 μm, and the solvent was removed at 80 ° C., followed by drying and a crosslinking reaction. A 38 μm-thick silicone-coated polyethylene terephthalate film (PET film) was bonded to the dried surface, and allowed to stand at 23 ° C. and 65% RH for 7 days to obtain an adhesive sheet.
[0046]
[Table 2]
Coronate L: Nippon Polyurethane Industry Co., Ltd. isocyanate cross-linking agent Tetrad X: Mitsubishi Gas Chemical Co., Ltd. epoxy cross-linking agent KBE-9007: Shin-Etsu Polymer Co., Ltd. isocyanate type silane coupling agent KBE-402: Shin-Etsu Polymer Co., Ltd. epoxy-type silane cup Ring agent [0047]
Test example 1
About the adhesive sheet obtained by the said Example and comparative example, the durability and adhesive force and rework property were evaluated with the following evaluation methods. The results are summarized in Table 3.
[0048]
( durability )
Each of the pressure-sensitive adhesive sheets is cut into 60 mm × 120 mm, and after the PET film is peeled off, it is attached on a glass substrate, left at 85 ° C., dry for 500 hours and at 60 ° C., 95% RH for 500 hours, and is generated on the pressure-sensitive adhesive sheet. The state of millet and peel was visually observed to evaluate the durability. Moreover, after observing, the adhesive sheet surface was rubbed by hand and adhesiveness was confirmed.
[0049]
<Our>
○: Foam was not confirmed on the adhesive sheet. Δ: Foam was confirmed slightly on the adhesive sheet. ×: Foam was confirmed on the adhesive sheet.
○: Peeling did not occur on the adhesive sheet Δ: Peeling occurred slightly on the adhesive sheet ×: Peeling occurred on the adhesive sheet <Adhesion>
○: not peeled off even when rubbed strongly △: peeled off when rubbed strongly ×: peeled off when rubbed lightly
(Adhesive strength / reworkability)
<Initial adhesive strength>
The pressure-sensitive adhesive sheets were each cut into 25 mm × 120 mm, and the adhesive strength was measured according to JIS-Z-0237 and JIS-Z-0238. As the adherend, a glass plate was used.
[0051]
<Adhesive strength over time>
Each of the pressure-sensitive adhesive sheets was cut into 25 mm × 150 mm, allowed to stand at 70 ° C. for 6 hours, allowed to cool to 23 ° C., and the adhesive strength was measured according to JIS-Z-0237 and JIS-Z-0238. As the adherend, a glass plate was used.
[0052]
[Table 3]
[0053]
As is clear from the evaluation results shown in Table 3, the pressure-sensitive adhesive sheet using the pressure-sensitive adhesive of the present invention was free from millet and peeling, and was excellent in durability and adhesion. Moreover, it was also shown that it is an adhesive having excellent reworkability without decreasing the adhesive force with time. On the other hand, the pressure-sensitive adhesive sheet of the comparative example was inferior in adhesion, durability, and reworkability, and some of the pressure-sensitive adhesive remained on the glass substrate.
[0054]
【The invention's effect】
Even when the pressure-sensitive adhesive of the present invention is used for a low-polarity film, it has excellent adhesion and reworkability.
[0055]
Therefore, by using this pressure-sensitive adhesive, it is possible to impart moderate tackiness to low-polarity films having optical functions such as viewing angle widening films, phase difference plate films, polarizing plates, etc. An adhesive film can be provided.
that's all
Claims (6)
（Ａ）少なくとも次の成分（ａ１）、（ａ２）及び（ａ３）を共重合してなる重量平均分子量が１００万〜２００万の範囲である高分子量ポリマー
（ａ１）（メタ）アクリル酸アルキルエステル ３０〜９０質量％
（ａ２）脂環式モノマー又は芳香環含有モノマー ９〜５０質量％
（ａ３）官能基含有モノマー ０．５〜１０質量％
（Ｂ）架橋剤
を含有する低極性フィルム用粘着剤。Next component (A) and component (B)
(A) High molecular weight polymer (a1) (meth) acrylic acid alkyl ester having a weight average molecular weight in the range of 1,000,000 to 2,000,000 obtained by copolymerizing at least the following components (a1), (a2) and (a3) 30-90% by mass
(A2) Alicyclic monomer or aromatic ring-containing monomer 9 to 50% by mass
(A3) Functional group-containing monomer 0.5 to 10% by mass
(B) A low-polarity film pressure-sensitive adhesive containing a crosslinking agent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003206345A JP4521520B2 (en) | 2003-08-06 | 2003-08-06 | Adhesive for low polarity film |
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| JP2003206345A JP4521520B2 (en) | 2003-08-06 | 2003-08-06 | Adhesive for low polarity film |
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| JP2009282479A Division JP2010100857A (en) | 2009-12-14 | 2009-12-14 | Optical function self-adhesive film for pasting glass substrate |
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| JP2005053976A true JP2005053976A (en) | 2005-03-03 |
| JP4521520B2 JP4521520B2 (en) | 2010-08-11 |
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Cited By (42)
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