JP4248019B2 - Polarizing plate with pressure-sensitive adhesive sheet - Google Patents
Polarizing plate with pressure-sensitive adhesive sheet Download PDFInfo
- Publication number
- JP4248019B2 JP4248019B2 JP2003429501A JP2003429501A JP4248019B2 JP 4248019 B2 JP4248019 B2 JP 4248019B2 JP 2003429501 A JP2003429501 A JP 2003429501A JP 2003429501 A JP2003429501 A JP 2003429501A JP 4248019 B2 JP4248019 B2 JP 4248019B2
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive sheet
- polarizing plate
- parts
- 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.)
- Expired - Lifetime
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims description 53
- 239000000178 monomer Substances 0.000 claims description 42
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 27
- 239000011521 glass Substances 0.000 claims description 22
- 229910021647 smectite Inorganic materials 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 13
- 238000002834 transmittance Methods 0.000 claims description 13
- 239000007822 coupling agent Substances 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002734 clay mineral Substances 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 description 20
- 230000001070 adhesive effect Effects 0.000 description 20
- 239000004973 liquid crystal related substance Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 8
- -1 isooctyl group Chemical group 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229910002012 Aerosil® Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000010998 test method Methods 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
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- 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
- MVYVKSBVZFBBPL-UHFFFAOYSA-N 2-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)NC(=O)C=C MVYVKSBVZFBBPL-UHFFFAOYSA-N 0.000 description 1
- LRRQSCPPOIUNGX-UHFFFAOYSA-N 2-hydroxy-1,2-bis(4-methoxyphenyl)ethanone Chemical compound C1=CC(OC)=CC=C1C(O)C(=O)C1=CC=C(OC)C=C1 LRRQSCPPOIUNGX-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-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
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- SQUNKLNGFIILTR-UHFFFAOYSA-N C1(CCCCC1)CO[Si](OC)(OC)CC Chemical compound C1(CCCCC1)CO[Si](OC)(OC)CC SQUNKLNGFIILTR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 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
- 230000007547 defect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- NDMVEPBCXVVMEN-UHFFFAOYSA-N dibenzyl(dioctadecyl)azanium Chemical class C=1C=CC=CC=1C[N+](CCCCCCCCCCCCCCCCCC)(CCCCCCCCCCCCCCCCCC)CC1=CC=CC=C1 NDMVEPBCXVVMEN-UHFFFAOYSA-N 0.000 description 1
- FAMDLVPKRRDPQV-UHFFFAOYSA-N dibenzyl(dioctadecyl)phosphanium Chemical class C=1C=CC=CC=1C[P+](CCCCCCCCCCCCCCCCCC)(CCCCCCCCCCCCCCCCCC)CC1=CC=CC=C1 FAMDLVPKRRDPQV-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 1
- JKODDBUWSNWKJZ-UHFFFAOYSA-N dimethyl(dioctadecyl)phosphanium Chemical class CCCCCCCCCCCCCCCCCC[P+](C)(C)CCCCCCCCCCCCCCCCCC JKODDBUWSNWKJZ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- MIQYOHNNWUEBSP-UHFFFAOYSA-N dodecyl(trimethyl)phosphanium Chemical class CCCCCCCCCCCC[P+](C)(C)C MIQYOHNNWUEBSP-UHFFFAOYSA-N 0.000 description 1
- VZXRCMCRCZBKEZ-UHFFFAOYSA-N dodecyl(triphenyl)phosphonium Chemical class C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCCCCCCCC)C1=CC=CC=C1 VZXRCMCRCZBKEZ-UHFFFAOYSA-N 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical class CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-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
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 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
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- AZFQCTBZOPUVOW-UHFFFAOYSA-N methyl(triphenyl)phosphanium Chemical class C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 AZFQCTBZOPUVOW-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical class CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- OPECTNGATDYLSS-UHFFFAOYSA-N naphthalene-2-sulfonyl chloride Chemical compound C1=CC=CC2=CC(S(=O)(=O)Cl)=CC=C21 OPECTNGATDYLSS-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
- 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
- 230000003287 optical effect Effects 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- IKANSXQHJXBNIN-UHFFFAOYSA-N trimethyl(octadecyl)phosphanium Chemical class CCCCCCCCCCCCCCCCCC[P+](C)(C)C IKANSXQHJXBNIN-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、液晶表示装置に用いられる感圧性接着シート付き偏光板およびその製造方法に関するものである。
The present invention relates to a polarizing plate with a pressure-sensitive adhesive sheet used in a liquid crystal display device and a method for producing the same.
液晶表示装置では、液晶を注入したガラスセルに偏光板を貼り合わせている（特許文献１参照）。液晶は非常に高価であるのに対し、偏光板は比較的安価であるので、液晶表示装置の製造の際に、偏光板の貼り合わせ不良などが発生すると、高価な液晶を注入したガラスセルまで廃棄したり、偏光板を苦労して剥がし取る必要があった。
In a liquid crystal display device, a polarizing plate is bonded to a glass cell into which liquid crystal is injected (see Patent Document 1). While liquid crystals are very expensive, polarizing plates are relatively inexpensive. When a liquid crystal display device is manufactured, if a bonding failure of the polarizing plates occurs, even glass cells filled with expensive liquid crystals are used. It was necessary to discard or peel off the polarizing plate with difficulty.
このような問題に対して、偏光板のガラスセルへの接着力を下げれば、リワーク性は良くなるが、接着力を下げることにより、液晶表示装置が高温や多湿雰囲気に放置された際に、その耐久性が低下するという問題がある。
このように、液晶表示装置を製造する従来の技術では、偏光板のガラスへのリワーク性と耐久性をともに満足させることは難しかった。
本発明は、このような事情に照らし、液晶表示装置を製造するにあたり、偏光板のガラスへのリワーク性にすぐれているとともに、耐久性が良い感圧性接着シート付き偏光板を提供することを目的としている。
As described above, in the conventional technique for manufacturing a liquid crystal display device, it has been difficult to satisfy both the reworkability and durability of the polarizing plate on glass.
In light of such circumstances, an object of the present invention is to provide a polarizing plate with a pressure-sensitive adhesive sheet that is excellent in reworkability of the polarizing plate to glass and has good durability in manufacturing a liquid crystal display device. It is said.
なお、リワーク性とは、偏光板を貼り合わせたガラスセルから偏光板を剥がし取る際の剥がしやすさのことであり、リワーク性にすぐれるとは、簡単に手で剥ぎ取ることができることをいう。また、耐久性とは、偏光板を貼り合わせたガラスセルを高温または高温多湿雰囲気に放置した際、偏光板の端部からの浮きや剥がれの発生のし難さのことであり、耐久性が良いとは、偏光板の端部から浮きや剥がれが発生しないことをいう。
The reworkability refers to the ease of peeling when the polarizing plate is peeled off from the glass cell to which the polarizing plate is bonded, and excellent reworkability means that it can be easily removed by hand. . Durability refers to the difficulty of floating or peeling from the edge of the polarizing plate when the glass cell with the polarizing plate is left in a high temperature or high temperature and humidity atmosphere. “Good” means that no floating or peeling occurs from the end of the polarizing plate.
本発明者らは、上記の目的を達成するため、鋭意検討した結果、アクリル系モノマーを主成分とするビニル系モノマーに、所定量の親油性の層状珪酸塩、カップリング剤、架橋剤としての多官能（メタ）アクリレートおよび光重合開始剤を含ませた光重合性組成物を調製し、これを光重合させることにより、全光線透過率が８５〜１００％、ヘイズ値が０〜５、ガラスへの接着力が０．１〜４Ｎ／２５mm幅である感圧性接着シートを形成することができ、これを偏光板に貼り合わせるための接着シートとして利用することにより、ガラスへのリワーク性にすぐれ、かつ耐久性が良い感圧性接着シート付き偏光板が得られることを知り、本発明を完成するに至ったものである。
As a result of intensive studies to achieve the above-mentioned object, the present inventors have obtained a predetermined amount of lipophilic layered silicate, coupling agent, and crosslinking agent as a vinyl monomer mainly composed of an acrylic monomer. By preparing a photopolymerizable composition containing a polyfunctional (meth) acrylate and a photopolymerization initiator and photopolymerizing it, the total light transmittance is 85 to 100%, the haze value is 0 to 5, glass A pressure-sensitive adhesive sheet with an adhesive strength of 0.1 to 4 N / 25 mm can be formed, and by using this as an adhesive sheet for bonding to a polarizing plate, it has excellent reworkability to glass. The inventors have found that a polarizing plate with a pressure-sensitive adhesive sheet having good durability can be obtained, and have completed the present invention.
すなわち、本発明は、偏光板に感圧性接着シートを貼り合わせた感圧性接着シート付き偏光板の製造において、上記感圧性接着シートの形成にあたり、（Ａ）アルキル基の炭素数が４〜１４個の（メタ）アクリル酸アルキルエステルを主成分とするビニル系モノマー９７〜１００重量％およびこれと共重合可能な極性基含有モノマー３〜０重量％からなるモノマー、（ｂ）上記（Ａ）成分のモノマー１００重量部あたり２〜２０重量部となる割合の親油性の層状珪酸塩として平均長さが１０〜１００ｎｍであるスメクタイト系粘土鉱物、（ｃ）カップリング剤、（ｄ）架橋剤としての多官能（メタ）アクリレート、（ｅ）光重合開始剤を含む光重合性組成物を、光重合させて、全光線透過率が８５〜１００％、ヘイズ値が０〜５、ガラスへの接着力が０．１〜４Ｎ／２５mm幅である感圧性接着シートを形成することを特徴とする感圧性接着シート付き偏光板の製造方法に係るものである。 That is , in the production of a pressure-sensitive adhesive sheet-attached polarizing plate in which a pressure-sensitive adhesive sheet is bonded to a polarizing plate, the present invention provides (A) an alkyl group having 4 to 14 carbon atoms in forming the pressure-sensitive adhesive sheet. A monomer comprising 97 to 100% by weight of a vinyl monomer mainly comprising (meth) acrylic acid alkyl ester and 3 to 0% by weight of a polar group-containing monomer copolymerizable therewith, (b) of the component (A) A smectite clay mineral having an average length of 10 to 100 nm as a lipophilic layered silicate in a proportion of 2 to 20 parts by weight per 100 parts by weight of monomer, (c) a coupling agent, and (d) many as a crosslinking agent A photopolymerizable composition containing a functional (meth) acrylate and (e) a photopolymerization initiator is photopolymerized to give a total light transmittance of 85 to 100%, a haze value of 0 to 5, and glass. Adhesive strength is related to the manufacturing method of the pressure-sensitive adhesive sheet with a polarizing plate and forming a pressure-sensitive adhesive sheet is 0.1~4N / 25mm width.
このように、本発明は、偏光板に貼り合わせる感圧性接着シートをアクリル系の（共）重合体をベースとし、これに親油性の層状珪酸塩、カップリング剤および架橋剤を含ませて、良好な視認性、透明性を有するとともに、ガラスへの接着力を適正範囲に規制して、凝集力が高く保持性にすぐれる構成としたことにより、偏光板のガラスへのリワーク性にすぐれ、かつ耐久性が良い感圧性接着シート付き偏光板を提供できる。
Thus, in the present invention, the pressure-sensitive adhesive sheet to be bonded to the polarizing plate is based on an acrylic (co) polymer, and includes an oleophilic layered silicate, a coupling agent, and a crosslinking agent. With good visibility and transparency, the adhesive strength to the glass is regulated to an appropriate range, and the composition has high cohesive strength and excellent retainability. In addition, a polarizing plate with a pressure-sensitive adhesive sheet having good durability can be provided.
本発明における（Ａ）成分のモノマーは、アルキル基の炭素数が４〜１４個の（メタ）アクリル酸アルキルエステルを主成分とするビニル系モノマー９７〜１００重量％と、これと共重合可能な極性基含有モノマー３〜０重量％とからなり、とくに好ましくは前者のビニル系モノマー９９〜１００重量％と、後者の極性基含有モノマー１〜０重量％とからなるものであるのがよい。後者の極性基含有モノマーが３重量％を超えると、接着力が高くなりすぎて、好ましい特性が得られにくい。
The monomer of the component (A) in the present invention is copolymerizable with 97 to 100% by weight of a vinyl monomer mainly composed of (meth) acrylic acid alkyl ester having 4 to 14 carbon atoms in the alkyl group, and copolymerizable therewith. It is preferably composed of 3 to 0% by weight of a polar group-containing monomer, particularly preferably composed of 99 to 100% by weight of the former vinyl monomer and 1 to 0% by weight of the latter polar group-containing monomer. If the latter polar group-containing monomer exceeds 3% by weight, the adhesive strength becomes too high, and it is difficult to obtain desirable characteristics.
アルキル基の炭素数が４〜１４個の（メタ）アクリル酸アルキルエステルには、ブチル基、イソブチル基、ペンチル基、イソペンチル基、ヘキシル基、ヘプチル基、オクチル基、イソオクチル基、ノニル基、イソノニル基、デシル基、イソデシル基などのアルキル基を有するアクリル酸またはメタクリル酸のアルキルエステルが用いられる。
ビニル系モノマーとしては、上記の（メタ）アクリル酸アルキルエステルを主成分として、モノマー全体の３０重量％以下の割合で、共重合可能な他のモノマーを使用することもできる。具体的には、アルキル基の炭素数が３以下または１５個以上の（メタ）アクリル酸アルキルエステルや、酢酸ビニル、スチレンまたはその誘導体、（メタ）アクリロニトリル、（メタ）アクリルアミドなどが挙げられる。
また、極性基含有モノマーには、（メタ）アクリル酸、イタコン酸などのカルボン酸基含有モノマー、２−アクリルアミドプロパンスルホン酸などのスルホン酸基含有モノマーなどの不飽和酸、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレートなどの水酸基含有モノマーなどが用いられる。
(Meth) acrylic acid alkyl ester having 4 to 14 carbon atoms in alkyl group includes butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, nonyl group, isononyl group An alkyl ester of acrylic acid or methacrylic acid having an alkyl group such as decyl group or isodecyl group is used.
As the vinyl monomer, other monomers that can be copolymerized with the above (meth) acrylic acid alkyl ester as a main component in a proportion of 30% by weight or less of the whole monomer can also be used. Specific examples include (meth) acrylic acid alkyl esters having 3 or less or 15 or more carbon atoms in the alkyl group, vinyl acetate, styrene or derivatives thereof, (meth) acrylonitrile, (meth) acrylamide, and the like.
In addition, polar group-containing monomers include unsaturated acids such as carboxylic acid group-containing monomers such as (meth) acrylic acid and itaconic acid, sulfonic acid group-containing monomers such as 2-acrylamidopropanesulfonic acid, and 2-hydroxyethyl (methacrylate). ) Hydroxyl-containing monomers such as acrylate and 2-hydroxypropyl (meth) acrylate are used.
本発明における（ｂ）成分の親油性の層状珪酸塩は、（ａ）成分の（共）重合体に良好に分散して接着シートの凝集力ひいては耐久性の改善に寄与するものであり、結晶構造中に交換性陽イオンを有する層状珪酸塩を親油化処理したものが用いられる。
層状珪酸塩には、モンモリロナイト、サポナイト、ヘクトライト スチーブンサイトなどのスメクタイト系粘土鉱物、フッ素四ケイ素雲母などのマイカ系粘土鉱物が挙げられ、１種または２種以上を使用できる。とくに好ましくは、平均長さが１０〜１００ｎｍであるスメクタイト系粘土鉱物が用いられる。
The lipophilic layered silicate of the component (b) in the present invention is well dispersed in the (co) polymer of the component (a) and contributes to the improvement of the cohesive strength of the adhesive sheet and thus the durability. A layered silicate having an exchangeable cation in its structure and subjected to lipophilic treatment is used.
Examples of the layered silicate include smectite clay minerals such as montmorillonite, saponite and hectorite stevensite, and mica clay minerals such as fluortetrasilicic mica, and one or more can be used. Particularly preferably, a smectite clay mineral having an average length of 10 to 100 nm is used.
層状珪酸塩の形状は、厚さが約１ｎｍ、縦横がそれぞれ０．０１〜１０μｍの範囲の板状であり、その平均長さとは縦横のうちの長い方の平均長さを意味し、この平均長さは、感圧性接着シートのＴＥＭ写真により、実測することができる。
層状珪酸塩の平均長さは１０〜１００ｎｍ、好ましくは２０〜８０ｎｍ、さらに好ましくは３０〜６０ｎｍであるのがよい。この平均長さが１０ｎｍ未満となると、均一に分散させるのが困難になり、また１００ｎｍを超えると、透明性が低下して、偏光板に貼り合わせたのちの輝度が低下する傾向にある。
The shape of the layered silicate is a plate shape having a thickness of about 1 nm and a length and width in the range of 0.01 to 10 μm, respectively, and the average length means the longer average length of the length and breadth. The length can be measured by a TEM photograph of the pressure-sensitive adhesive sheet.
The average length of the layered silicate is 10 to 100 nm, preferably 20 to 80 nm, and more preferably 30 to 60 nm. When the average length is less than 10 nm, it is difficult to uniformly disperse, and when it exceeds 100 nm, the transparency is lowered and the luminance after being bonded to the polarizing plate tends to be lowered.
結晶構造中に交換性陽イオンを有する層状珪酸塩は、層間の交換性陽イオンを有機カチオンなどでイオン交換処理し、層間を親油化する必要がある。
上記の交換性陽イオンとは、層状珪酸塩の結晶層の表面に存在するナトリウムやカルシウムなどの金属イオンのことである。これらのイオンは親水性であるため、親油性のモノマーは層状珪酸塩の層間に侵入することができず、良好な分散物を得ることができない。モノマーを層間に侵入させるためには、交換性陽イオンを親油性のカチオン性界面活性剤などでイオン交換することが必要である。
In a layered silicate having an exchangeable cation in the crystal structure, the exchangeable cation between layers needs to be subjected to an ion exchange treatment with an organic cation or the like to make the interlayer oleophilic.
The exchangeable cation is a metal ion such as sodium or calcium existing on the surface of the layered silicate crystal layer. Since these ions are hydrophilic, the lipophilic monomer cannot penetrate between the layers of the layered silicate, and a good dispersion cannot be obtained. In order for the monomer to enter between the layers, it is necessary to ion-exchange the exchangeable cation with a lipophilic cationic surfactant or the like.
このような目的で用いられるカチオン性界面活性剤としては、４級アンモニウム塩や４級ホスホニウム塩などを挙げることができる。その１種を単独で使用してもよいし、２種以上を混合して使用してもよい。
４級アンモニウム塩としては、たとえば、ラウリルトリメチルアンモニウム塩、ステアリルトリメチルアンモニウム塩、トリオクチルアンモニウム塩、ジステアリルジメチルアンモニウム塩、ジステアリルジベンジルアンモニウム塩などや、フメチルジエチルプロピレンオキサイド骨格を有するアンモニウム塩などが挙げられる。
４級ホスホニウム塩としては、たとえば、ドデシルトリフェニルホスホニウム塩、メチルトリフェニルホスホニウム塩、ラウリルトリメチルホスホニウム塩、ステアリルトリメチルホスホニウム塩、ジステアリルジメチルホスホニウム塩、ジステアリルジベンジルホスホニウム塩などが挙げられる。
Examples of the cationic surfactant used for such purposes include quaternary ammonium salts and quaternary phosphonium salts. One of them may be used alone, or two or more of them may be mixed and used.
Examples of the quaternary ammonium salt include lauryltrimethylammonium salt, stearyltrimethylammonium salt, trioctylammonium salt, distearyldimethylammonium salt, distearyldibenzylammonium salt, and ammonium salt having a fumethyldiethylpropylene oxide skeleton. Is mentioned.
Examples of the quaternary phosphonium salt include dodecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, distearyldimethylphosphonium salt, distearyldibenzylphosphonium salt, and the like.
このような（ｂ）成分の親油性の層状珪酸塩は、（Ａ）成分のアルキル基の炭素数が４〜１４個の（メタ）アクリル酸アルキルエステルを主成分とするビニル系モノマーとこれと共重合可能な極性基含有モノマーとからなるモノマー１００重量部に対し、つまりは、（ａ）成分としての上記モノマーの（共）重合体１００重量部に対し、２〜２０重量部、好ましくは３〜１５重量部、さらに好ましくは４〜１０重量部の割合で用いられる。この使用量が２重量部未満では、凝集力が低下し、耐久性の改善効果が得られず、２０重量部を超えると、増粘のため、塗布などによるシート成形が難しくなる。
Such a lipophilic layered silicate of component (b) is composed of a vinyl monomer mainly composed of (A) component alkyl group (meth) acrylic acid alkyl ester having 4 to 14 carbon atoms, and 2 to 20 parts by weight, preferably 3 parts per 100 parts by weight of the monomer comprising a copolymerizable polar group-containing monomer, ie, 100 parts by weight of the (co) polymer of the monomer as component (a). -15 parts by weight, more preferably 4-10 parts by weight. If the amount used is less than 2 parts by weight, the cohesive force is reduced, and the effect of improving durability cannot be obtained. If the amount used exceeds 20 parts by weight, it is difficult to form a sheet by coating due to thickening.
本発明に用いられる（ｃ）成分のカップリング剤は、上記（ｂ）成分の親油性の層状珪酸塩と相互作用することにより、接着シートの凝集力を向上させて、せん断保持性を高くするとともに、ガラスとの密着性を向上させる働きも有しており、これらの相乗効果により偏光板の耐久性を大きく向上させるものである。
なお、前記（Ａ）成分のモノマーのうち、極性基含有モノマーも、上記カップリング剤と同様の効果を発揮し、このモノマーを使用することにより偏光板の耐久性を一段と向上させることができる。しかし、極性基含有モノマーを使用しすぎると、接着力が高くなりすぎてリワーク性が低下するため、前記した適量の使用量とする。
The coupling agent of component (c) used in the present invention interacts with the lipophilic layered silicate of component (b), thereby improving the cohesive force of the adhesive sheet and increasing the shear retention. In addition, it also has the function of improving the adhesion to glass, and the synergistic effect of these effects greatly improves the durability of the polarizing plate.
Among the monomers of the component (A), the polar group-containing monomer also exhibits the same effect as the above coupling agent, and the durability of the polarizing plate can be further improved by using this monomer. However, if the polar group-containing monomer is used too much, the adhesive strength becomes too high and the reworkability is lowered.
このようなカップリング剤は、とくに限定されないが、分子中に２個以上の異なる反応基を持つ有機珪素単量体が好ましく用いられる。２個の反応基の一つは無機質と化学結合する反応基であり、もう一つは有機材料と化学結合する反応基である。
上記の無機質と化学結合する反応基としては、メトキシ基、エトキシ基、シラノール基などがあり、また有機材料と化学結合する反応基としては、ビニル基、エポキシ基、メタクリル基、アミノ基、メルカプト基などがある。
Such a coupling agent is not particularly limited, but an organosilicon monomer having two or more different reactive groups in the molecule is preferably used. One of the two reactive groups is a reactive group that chemically bonds with an inorganic substance, and the other is a reactive group that chemically bonds with an organic material.
Examples of reactive groups that chemically bond with the above inorganic materials include methoxy groups, ethoxy groups, and silanol groups, and reactive groups that chemically bond with organic materials include vinyl groups, epoxy groups, methacryl groups, amino groups, and mercapto groups. and so on.
このようなシランカップリング剤としては、ビニルトリクロルシラン、ビニルトリス（β−メトキシエトキシ）シラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、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、γ−グリシド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メチルジエトキシシラン、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、γ−グリシドキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシランなどが挙げられる。
Examples of such silane coupling agents include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- ( Aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ- Glycid Xylpropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, etc. Is mentioned.
本発明においては、このようなカップリング剤の中から、その１種または２種以上を選択して使用することができるが、その選択は、（ａ）成分の（共）重合体との相溶性、増粘性、ゲル化の有無などを考慮して、決定すればよい。
このようなカップリング剤の使用量は、（Ａ）成分のモノマー１００重量部、つまり、その（共）重合体１００重量部に対して、０．０５〜１０重量部、好ましくは０．１〜５重量部、より好ましくは０．２〜２重量部とする。０．０５重量部未満では効果がなく、１０重量部を超えると凝集力が上がりすぎて密着力が低下する傾向がある。
In the present invention, one or two or more of these coupling agents can be selected and used. The selection depends on the phase of the component (a) with the (co) polymer. The determination may be made in consideration of solubility, thickening, and the presence or absence of gelation.
The amount of such a coupling agent used is 0.05 to 10 parts by weight, preferably 0.1 to 100 parts by weight of the monomer (A), that is, 100 parts by weight of the (co) polymer. 5 parts by weight, more preferably 0.2 to 2 parts by weight. If it is less than 0.05 part by weight, there is no effect, and if it exceeds 10 parts by weight, the cohesive force tends to increase too much and the adhesion tends to decrease.
本発明に用いられる（ｄ）成分の架橋剤は、感圧性接着剤の凝集力などを高めて加工性を向上させるためのものであり、分子内に（メタ）アクリロイル基からなる官能基を２個以上有する多官能（メタ）アクリレートが用いられる。このような多官能（メタ）アクリレートとしては、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、１，２−エチレングリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレートなどが挙げられる。
The crosslinking agent of the component (d) used in the present invention is for improving the cohesive force of the pressure-sensitive adhesive and improving processability, and has 2 functional groups composed of (meth) acryloyl groups in the molecule. A polyfunctional (meth) acrylate having at least one is used. Such polyfunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth). ) Acrylate and the like.
これらの多官能（メタ）アクリレートの使用量としては、（Ａ）成分のモノマー１００重量部あたり、０．０２〜５重量部、好ましくは０．０５〜３重量部、さらに好ましくは０．１〜１重量部の範囲とするのがよい。
この範囲内で、２官能の場合は多く、３官能やそれ以上の官能基数の場合は少なくすることができるが、０．０２重量部より少ないと架橋剤としての効果がなく、また５重量部より多いと脆くなり、いずれもシート加工性が低下する。
The polyfunctional (meth) acrylate is used in an amount of 0.02 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 100 parts by weight of the monomer (A). The range is preferably 1 part by weight.
Within this range, the number of bifunctional groups is large, and the number of trifunctional or higher functional groups can be reduced. However, if it is less than 0.02 parts by weight, there is no effect as a crosslinking agent, and 5 parts by weight. If it is more, it becomes brittle, and in any case, the sheet processability decreases.
本発明に用いられる（ｅ）成分の光重合開始剤には、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテルなどのベンゾインエーテル類、アニゾインメチルエーテルなどの置換ベンゾインエーテル類、２，２−ジエトキシアセトフェノン、２，２−ジメトキシ−２−フェノンアセトフェノンなどの置換アセトフェノン類、２−メチル−２−ヒドロキシプロピオフェノンなどの置換α−ケトール類、２−ナフタレンスルホニルクロリドなどの芳香族スルホニルクロリド類、１−フェノン−１，１−プロパンジオン−２−（ｏ−エトキシカルボニル）オキシムなどの光活性オキシム類がある。
Examples of the photopolymerization initiator (e) used in the present invention include benzoin ethers such as benzoin methyl ether and benzoin isopropyl ether, substituted benzoin ethers such as anisoin methyl ether, 2,2-diethoxyacetophenone, Substituted acetophenones such as 2,2-dimethoxy-2-phenone acetophenone, substituted α-ketols such as 2-methyl-2-hydroxypropiophenone, aromatic sulfonyl chlorides such as 2-naphthalenesulfonyl chloride, 1-phenone There are photoactive oximes such as -1,1-propanedione-2- (o-ethoxycarbonyl) oxime.
これらの光重合開始剤は、（ａ）成分のモノマー１００重量部あたり、通常０．００５〜１重量部、好ましくは０．０５〜０．５重量部の割合で用いられる。０．００５重量部より少ないと、光重合後に未反応モノマーが多く残存して、接着界面において気泡の発生などを生じやすい。また、１重量部より多いと、光重合物中にこの光重合開始剤が残存して、黄変などの原因となりやすい。
These photopolymerization initiators are generally used in a proportion of 0.005 to 1 part by weight, preferably 0.05 to 0.5 part by weight, per 100 parts by weight of the monomer (a). When the amount is less than 0.005 parts by weight, a large amount of unreacted monomer remains after photopolymerization, and bubbles are easily generated at the adhesion interface. On the other hand, when the amount is more than 1 part by weight, the photopolymerization initiator remains in the photopolymerization product, which tends to cause yellowing.
本発明においては、上記の（Ａ）成分のモノマー、（ｂ）成分の親油性の層状珪酸塩、（ｃ）成分のシランカップリング剤および（ｅ）成分の光重合開始剤を、前記した割合で混合し、このプレミックスを超音波ホモジナイザーなどを用いて分散させる。このように調製される分散物の粘度が低い場合、部分的に光重合して、粘度が約５００〜５，０００センチポイズのコーティング可能なシロップ状にしてもよい。
つぎに、この分散物に、さらに（ｄ）成分の架橋剤である多官能（メタ）アクリレートを混合し、光重合性組成物を調製する。この組成物には、光重合性を損なわない限り、老化防止剤などの公知の各種の添加剤を、加えてもよい。
In the present invention, the above-mentioned proportions of the monomer of the above component (A), the lipophilic layered silicate of the component (b), the silane coupling agent of the component (c) and the photopolymerization initiator of the component (e) And the premix is dispersed using an ultrasonic homogenizer or the like. If the dispersion thus prepared has a low viscosity, it may be partially photopolymerized into a coatable syrup having a viscosity of about 500 to 5,000 centipoise.
Next, this dispersion is further mixed with a polyfunctional (meth) acrylate which is a crosslinking agent of component (d) to prepare a photopolymerizable composition. Various known additives such as anti-aging agents may be added to the composition as long as the photopolymerizability is not impaired.
本発明においては、このように調製される光重合性組成物を、剥離ライナーとしての剥離処理フィルム上に塗布し、紫外線の照射による光重合処理を施して、光重合物からなる厚さが通常５〜１００μｍの感圧性接着シートを形成する。上記の光重合処理は、窒素ガスなど不活性ガスで置換された酸素の少ない雰囲気中で行われるか、あるいは紫外線透過性のフィルムによる被覆で空気が遮断された状態で行われる。
In the present invention, the photopolymerizable composition thus prepared is applied onto a release-treated film as a release liner, and subjected to a photopolymerization treatment by irradiation with ultraviolet rays. A pressure sensitive adhesive sheet of 5 to 100 μm is formed. The above photopolymerization treatment is performed in an oxygen-reduced atmosphere substituted with an inert gas such as nitrogen gas, or in a state where air is blocked by coating with an ultraviolet light transmissive film.
光重合に使用する紫外線は、波長範囲が約１８０〜４６０ｎｍの電磁放射性であるが、これより長波長または短波長の電磁放射性を用いてもよい。紫外線源としては、水銀アーク、炭素アーク、低圧水銀ランプ、中・高圧水銀ランプ、メタルハライドランプなどの一般の照明装置が用いられる。紫外線の強度は、被照射体までの距離や電圧の調整および照射時間（生産性）との兼ね合いで、適宜設定できる。
このような紫外線の照射後、必要により、臭気低減などを目的として、乾燥工程を設けることもできる。乾燥方法および条件は任意であるが、たとえば、熱風式乾燥炉を用いて１００〜１４０℃程度で１０〜１８０秒程度乾燥すればよい。
The ultraviolet rays used for photopolymerization are electromagnetic radiation having a wavelength range of about 180 to 460 nm, but electromagnetic radiation having a longer wavelength or shorter wavelength may be used. As an ultraviolet ray source, a general lighting device such as a mercury arc, a carbon arc, a low pressure mercury lamp, a medium / high pressure mercury lamp, a metal halide lamp, or the like is used. The intensity of the ultraviolet light can be appropriately set in consideration of the distance to the irradiated object, adjustment of voltage, and irradiation time (productivity).
After such ultraviolet irradiation, if necessary, a drying step can be provided for the purpose of reducing odor. Although a drying method and conditions are arbitrary, what is necessary is just to dry for about 10 to 180 second at about 100-140 degreeC using a hot air type drying furnace, for example.
このようにして剥離ライナー上に形成される感圧性接着シートを偏光板に貼り合わせることにより、本発明の感圧性接着シート付き偏光板を製造する。
また、本発明においては、剥離ライナーである剥離処理フィルムを使用することなく、前記の光重合性組成物を偏光板上に直接塗布し、上記同様に光重合処理することにより、光重合処理と同時に偏光板に感圧性接着シートを貼り合わせることもできる。この場合、感圧性接着シートと偏光板の密着性をより高めることができる。しかし、塗工中に偏光板に傷やしわ、折れなどが発生しないように注意する必要があり、とくに偏光板の変形を防ぐため、乾燥温度は１００℃程度を上限にするのが望ましい。
Thus, the pressure sensitive adhesive sheet with pressure sensitive adhesive sheet of the present invention is manufactured by sticking the pressure sensitive adhesive sheet formed on the release liner to the polarizing plate.
Further, in the present invention, without using a release treatment film as a release liner, the above photopolymerizable composition is directly applied on a polarizing plate and subjected to a photopolymerization treatment in the same manner as described above. At the same time, a pressure-sensitive adhesive sheet can be bonded to the polarizing plate. In this case, the adhesion between the pressure-sensitive adhesive sheet and the polarizing plate can be further enhanced. However, care must be taken so that the polarizing plate is not scratched, wrinkled, broken or the like during coating. In particular, in order to prevent deformation of the polarizing plate, the drying temperature is preferably about 100 ° C. as the upper limit.
このように製造される本発明の感圧性接着シート付き偏光板は、上記の方法で形成される感圧性接着シートが、（ａ）アルキル基の炭素数が４〜１４個の（メタ）アクリル酸アルキルエステルを主成分とするビニル系モノマー９７〜１００重量％およびこれと共重合可能な極性基含有モノマー３〜０重量％の（共）重合体、（ｂ）上記（ａ）成分１００重量部あたり２〜２０重量部となる割合の親油性の層状珪酸塩、（ｃ）カップリング剤、（ｄ）架橋剤を含有するとともに、全光線透過率が８５〜１００％、ヘイズ値が０〜５、ガラスへの接着力が０．１〜４Ｎ／２５mm幅であることを特徴としており、これにより、視認性、透明性、リワーク性および耐久性にすぐれたものとなる。
The pressure-sensitive adhesive sheet with the pressure-sensitive adhesive sheet of the present invention thus produced is a (meth) acrylic acid in which the pressure-sensitive adhesive sheet formed by the above method has (a) an alkyl group having 4 to 14 carbon atoms. 97 to 100% by weight of a vinyl-based monomer having an alkyl ester as a main component and 3 to 0% by weight of a polar group-containing monomer copolymerizable therewith, (b) per 100 parts by weight of the component (a) While containing 2 to 20 parts by weight of a lipophilic layered silicate, (c) a coupling agent, (d) a crosslinking agent, the total light transmittance is 85 to 100%, the haze value is 0 to 5, Adhesive strength to glass is 0.1 to 4 N / 25 mm width, which makes it excellent in visibility, transparency, reworkability and durability.
これに対し、全光線透過率８５％未満となったり、ヘイズ値が５を超えると、液晶表示の輝度が低下する。また、ガラスへの接着力が０．１Ｎ／２５mm幅未満となると、ガラスに対する接着力が低すぎるため、偏光板が剥がれ落ちやすくなり実用上ふさわしくなく、また４Ｎ／２５mm幅を超えると、リワーク性が低下する。
本発明における感圧性接着シートの好適な全光線透過率は９０〜１００％、とくに好適な全光線透過率は９５〜１００％であり、また好適なヘイズ値は０〜３、さらに好適なヘイズ値は０〜１である。また、好適なガラスへの接着力は０．２〜３Ｎ／２５mm幅、さらに好適なガラスへの接着力は０．３〜２Ｎ／２５mm幅である。
On the other hand, when the total light transmittance is less than 85% or the haze value exceeds 5, the luminance of the liquid crystal display decreases. Also, if the adhesive strength to glass is less than 0.1 N / 25 mm width, the adhesive strength to glass is too low, so the polarizing plate is easily peeled off and is not suitable for practical use, and if it exceeds 4 N / 25 mm width, it is reworkable. Decreases.
The preferable total light transmittance of the pressure-sensitive adhesive sheet in the present invention is 90 to 100%, the particularly preferable total light transmittance is 95 to 100%, the preferable haze value is 0 to 3, and the more preferable haze value. Is 0-1. Moreover, the adhesive force to suitable glass is 0.2-3N / 25mm width, and the more suitable adhesive force to glass is 0.3-2N / 25mm width.
なお、本発明において、感圧性接着シートの形成は、上記した光重合法に限定されず、他のいかなる方法で形成してもよい。
たとえば、前記（Ａ）成分のモノマーに、（ｂ）成分の親油性の層状珪酸塩、（ｃ）成分のカップリング剤、（ｄ）成分の架橋剤および熱重合開始剤を、必要により適宜の溶剤を用いて混合し、これを剥離ライナー上に塗布するか、または偏光板上に直接塗布し、加熱乾燥後、熱重合処理して、感圧性接着シートを形成してもよい。
In the present invention, the formation of the pressure-sensitive adhesive sheet is not limited to the above-described photopolymerization method, and may be formed by any other method.
For example, the monomer of component (A) may be added with a lipophilic layered silicate of component (b), a coupling agent of component (c), a crosslinking agent of component (d), and a thermal polymerization initiator as necessary. It mixes using a solvent, and this may be apply | coated on a peeling liner, or it apply | coats directly on a polarizing plate, and may heat-process after heat drying, and may form a pressure-sensitive adhesive sheet.
上記の熱重合処理を採用するときは、架橋剤として、前記した多官能（メタ）アクリレートを使用する代わりに、外部架橋剤であるポリイソシアネート化合物などの多官能性化合物を添加して、架橋処理するようにしてもよい。
なお、上記の熱重合処理などの方法では、形成される感圧性接着シート中に揮発成分が残存しやすく、これが偏光板をガラスセルに貼り合わせたのちに、高温に保存されると、揮発してボイドの原因となることがある。これに対して、前記の光重合法ではこのような揮発成分が残存しにくく、本発明の目的にとくに適している。
When employing the above thermal polymerization treatment, instead of using the above-mentioned polyfunctional (meth) acrylate as a crosslinking agent, a polyfunctional compound such as a polyisocyanate compound that is an external crosslinking agent is added to the crosslinking treatment. You may make it do.
In the above-described method such as thermal polymerization treatment, volatile components are likely to remain in the pressure-sensitive adhesive sheet to be formed, and when this is stored at a high temperature after the polarizing plate is bonded to the glass cell, it volatilizes. May cause voids. On the other hand, such a volatile component hardly remains in the photopolymerization method, and is particularly suitable for the purpose of the present invention.
本発明の感圧性接着シート付き偏光板において、感圧性接着シートを貼り合わせる偏光板には、従来公知ものをいずれも使用できる。
たとえば、親水性高分子フィルムにヨウ素および／または二色性染料を吸着させて延伸したものやポリエン配向フィルムなどの偏光子の片面または両面にトリアセチルモルロースなどの各種のポリマーからなる保護フィルムを設けてなる公知の偏光板が挙げられる。また、この偏光板に位相差板を積層して楕円偏光板や円偏光板としたもの、さらに上記の偏光板に反射板、半透過反射板、視覚補償フィルム、輝度向上フィルムなどの光学層を、１層または２層以上積層したものなどが挙げられる。
In the polarizing plate with a pressure-sensitive adhesive sheet of the present invention, any conventionally known polarizing plate can be used for bonding the pressure-sensitive adhesive sheet.
For example, a protective film made of various polymers such as triacetylmorulose on one or both sides of a polarizer such as a film made by adsorbing iodine and / or a dichroic dye on a hydrophilic polymer film or a polyene oriented film A known polarizing plate is provided. In addition, a retardation plate is laminated on this polarizing plate to form an elliptical polarizing plate or a circular polarizing plate, and an optical layer such as a reflection plate, a transflective reflection plate, a visual compensation film, or a brightness enhancement film is added to the above polarizing plate. Examples thereof include one layer or a laminate of two or more layers.
以下に、本発明の実施例として「実施例１〜５」を記載し、これと「比較例１〜４」と対比して、本発明を具体的に説明する。ただし、本発明は、以下の実施例にのみ限定されるものではない。なお、以下において、部とあるのは重量部を意味する。
Hereinafter, "Examples 1 to 5" are described as examples of the present invention, and the present invention will be specifically described in comparison with "Comparative Examples 1 to 4". However, the present invention is not limited only to the following examples. In the following, “parts” means parts by weight.
２−エチルヘキシルアクリレート１００部、光重合開始剤としての２，２−ジメトキシ−２−フェニルアセトフェノン（チバガイギーコーポレーション製の「イルガキュアー６５１」）０．１部、親油性の層状珪酸塩であるスメクタイト（コープケミカル社製の「ルーセンタイトＳＰＮ」、平均長さ５０ｎｍ）５部、カップリング剤としてのγ−グリシドキシプロピルトリメトキシシラン（信越シリコーン社製の「ＫＢＭ４０３」）０．２部を用いて、プレミックスを調製した。
このプレミックスを、超音波ホモジナイザー（Ｎｉｓｓｅｉ社製の「ＵＳ−６００Ｔ」）にて、スメクタイトの粒が見えなくなるまで分散させ、コーティング可能な組成物としたのち、これに架橋剤としてのトリメチロールプロパントリアクリレート（日本化薬社製の「ＴＭＰＴＡ」）０．２部を、混合して、光重合性組成物とした。
100 parts of 2-ethylhexyl acrylate, 0.1 part of 2,2-dimethoxy-2-phenylacetophenone (“Irgacure 651” manufactured by Ciba Geigy Corporation) as a photopolymerization initiator, smectite (corpe) which is a lipophilic layered silicate Using 5 parts of “Lucentite SPN” (average length: 50 nm) manufactured by Chemical Co., Ltd., 0.2 parts of γ-glycidoxypropyltrimethoxysilane (“KBM403” manufactured by Shin-Etsu Silicone Co., Ltd.) as a coupling agent, A premix was prepared.
This premix was dispersed with an ultrasonic homogenizer (“US-600T” manufactured by Nissei) until smectite grains disappeared to form a coatable composition, which was then trimethylolpropane as a cross-linking agent. 0.2 parts of triacrylate (“TMPTA” manufactured by Nippon Kayaku Co., Ltd.) was mixed to obtain a photopolymerizable composition.
この光重合性組成物を、剥離ライナーとしてシリコーン離型処理した厚さが５０μｍのポリエチレンテレフタレートフィルムからなる離型処理フィルム上に塗布したのち、上記と同様の離型処理フィルムでカバーして、酸素による重合阻害が起こらないようにし、光強度１００ｍｗ／cm2 の高圧水銀ランプにより、６０秒間、紫外線を照射して、光重合させた。その後、離型処理フィルムのカバーを剥がし、１３０℃で１８０秒間、加熱乾燥を行い、厚さが３０μｍの光重合物からなる感圧性接着シートを形成した。
このように剥離ライナー上に形成した感圧性接着シートを、ラミネータにより、偏光板に貼り合わせて、感圧性接着シート付き偏光板を作製した。
After coating this photopolymerizable composition on a release treatment film made of a polyethylene terephthalate film having a thickness of 50 μm and subjected to a silicone release treatment as a release liner, it was covered with a release treatment film similar to the above, and oxygen In this way, the polymerization was inhibited by UV irradiation for 60 seconds with a high-pressure mercury lamp having a light intensity of 100 mw / cm 2 . Thereafter, the cover of the release treatment film was peeled off and heat-dried at 130 ° C. for 180 seconds to form a pressure-sensitive adhesive sheet made of a photopolymer having a thickness of 30 μm.
The pressure-sensitive adhesive sheet thus formed on the release liner was bonded to the polarizing plate with a laminator to prepare a polarizing plate with a pressure-sensitive adhesive sheet.
親油性の層状珪酸塩であるスメクタイト（コープケミカル社製の「ルーセンタイトＳＰＮ」）の量を、５部から８部に変更した以外は、実施例１と同様にして、感圧性接着シート付き偏光板を作製した。
Polarized light with pressure-sensitive adhesive sheet in the same manner as in Example 1 except that the amount of smectite (“Lucentite SPN” manufactured by Co-op Chemical), which is a lipophilic layered silicate, was changed from 5 parts to 8 parts. A plate was made.
親油性の層状珪酸塩であるスメクタイト（コープケミカル社製の「ルーセンタイトＳＰＮ」）の量を、５部から１５部に変更した以外は、実施例１と同様にして、感圧性接着シート付き偏光板を作製した。
Polarized light with pressure-sensitive adhesive sheet in the same manner as in Example 1 except that the amount of smectite (“Lucentite SPN” manufactured by Coop Chemical Co.), which is a lipophilic layered silicate, was changed from 5 parts to 15 parts. A plate was made.
２−エチルヘキシルアクリレート１００部を、２−エチルヘキシルアクリレート９９部およびアクリル酸１部に変更し、かつ親油性の層状珪酸塩であるスメクタイト（コープケミカル社製の「ルーセンタイトＳＰＮ」）の量を、５部から８部に変更した以外は、実施例１と同様にして、感圧性接着シート付き偏光板を作製した。
100 parts of 2-ethylhexyl acrylate is changed to 99 parts of 2-ethylhexyl acrylate and 1 part of acrylic acid, and the amount of smectite (“Lucentite SPN” manufactured by Coop Chemical Co.), which is a lipophilic layered silicate, is 5 A polarizing plate with a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the part was changed from 8 parts to 8 parts.
２−エチルヘキシルアクリレート１００部を、２−エチルヘキシルアクリレート９７部およびアクリル酸３部に変更し、かつ親油性の層状珪酸塩であるスメクタイト（コープケミカル社製の「ルーセンタイトＳＰＮ」）の量を、５部から８部に変更した以外は、実施例１と同様にして、感圧性接着シート付き偏光板を作製した。
100 parts of 2-ethylhexyl acrylate is changed to 97 parts of 2-ethylhexyl acrylate and 3 parts of acrylic acid, and the amount of smectite (“Lucentite SPN” manufactured by Corp Chemical), which is a lipophilic layered silicate, is 5 A polarizing plate with a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the part was changed from 8 parts to 8 parts.
比較例１
２−エチルヘキシルアクリレート１００部を、２−エチルヘキシルアクリレート９５部およびアクリル酸５部に変更し、かつ親油性の層状珪酸塩であるスメクタイト（コープケミカル社製の「ルーセンタイトＳＰＮ」）の量を、５部から８部に変更した以外は、実施例１と同様にして、感圧性接着シート付き偏光板を作製した。
Comparative Example 1
100 parts of 2-ethylhexyl acrylate is changed to 95 parts of 2-ethylhexyl acrylate and 5 parts of acrylic acid, and the amount of smectite (“Lucentite SPN” manufactured by Coop Chemical Co.), which is a lipophilic layered silicate, is 5 A polarizing plate with a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the part was changed from 8 parts to 8 parts.
比較例２
親油性の層状珪酸塩であるスメクタイト（コープケミカル社製の「ルーセンタイトＳＰＮ」）の量を、５部から１部に変更した以外は、実施例１と同様にして、感圧性接着シート付き偏光板を作製した。
Comparative Example 2
Polarized light with pressure-sensitive adhesive sheet in the same manner as in Example 1 except that the amount of smectite (“Lucentite SPN” manufactured by Coop Chemical Co.), which is a lipophilic layered silicate, was changed from 5 parts to 1 part. A plate was made.
比較例３
親油性の層状珪酸塩であるスメクタイト（コープケミカル社製の「ルーセンタイトＳＰＮ」）の量を、５部から８部に変更し、かつカップリング剤としてのγ−グリシドキシプロピルトリメトキシシラン（信越シリコーン社製の「ＫＢＭ４０３」）を配合しなかった以外は、実施例１と同様にして、感圧性接着シート付き偏光板を作製した。
Comparative Example 3
The amount of smectite (“Lucentite SPN” manufactured by Coop Chemical Co.), which is a lipophilic layered silicate, was changed from 5 parts to 8 parts, and γ-glycidoxypropyltrimethoxysilane ( A polarizing plate with a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that “KBM403” manufactured by Shin-Etsu Silicone Co., Ltd. was not blended.
比較例４
親油性の層状珪酸塩であるスメクタイト（コープケミカル社製の「ルーセンタイトＳＰＮ」）５部を、シリカ充填材（日本アエロジル社の「アエロジルＲ９７２」）８部に変更した以外は、実施例１と同様にして、感圧性接着シート付き偏光板を作製した。
Comparative Example 4
Example 1 except that 5 parts of smectite (“Lucentite SPN” manufactured by Corp Chemical Co.), which is a lipophilic layered silicate, was changed to 8 parts of silica filler (“Aerosil R972” manufactured by Nippon Aerosil Co., Ltd.). Similarly, a polarizing plate with a pressure-sensitive adhesive sheet was produced.
上記の実施例１〜５および比較例１〜４の各感圧性接着シート付き偏光板について、以下の方法により、全光線透過率、ヘイズ値および接着力を測定し、また、破断強度および耐久性の試験を行った。これらの結果は、表１（実施例１〜５）および表２（比較例１〜４）に示されるとおりであった。
About each polarizing plate with a pressure sensitive adhesive sheet of said Examples 1-5 and Comparative Examples 1-4, a total light transmittance, a haze value, and adhesive force are measured with the following method, Moreover, breaking strength and durability The test was conducted. These results were as shown in Table 1 (Examples 1 to 5) and Table 2 (Comparative Examples 1 to 4).
なお、表１および表２には、参考のために、光重合に用いた原料組成を示した。両表中の各表示は、下記のとおりである。
２ＥＨＡ：２エチルヘキシルアクリレート
ＡＡ：アクリル酸
ルーセンタイトＳＰＮ：親油性の層状珪酸塩であるスメクタイト
アエロジル：日本アエロジル社の「アエロジルＲ９７２」
ＫＢＭ４０３：γ−グリシドキシプロピルトリメトキシシラン
ＴＭＰＴＡ：トリメチロールプロパントリアクリレート
Ｉｒｇ６５１：チバガイギーコーポレーション製の「イルガキュアー６５１」
In Tables 1 and 2, the raw material compositions used for photopolymerization are shown for reference. Each indication in both tables is as follows.
2EHA: 2-ethylhexyl acrylate AA: Acrylic acid Lucentite SPN: Smectite, a lipophilic layered silicate Aerosil: “Aerosil R972” manufactured by Nippon Aerosil Co., Ltd.
KBM403: γ-glycidoxypropyltrimethoxysilane TMPTA: trimethylolpropane triacrylate Irg651: “Irgacure 651” manufactured by Ciba Geigy Corporation
＜全光線透過率＞
感圧性接着シートのみについて、フィルム濁度計（日本電色工業社製の「ＮＤＭ−２０Ｄ」）を用いて、全光線透過率を測定した。
<Total light transmittance>
Only for the pressure-sensitive adhesive sheet, the total light transmittance was measured using a film turbidimeter (“NDM-20D” manufactured by Nippon Denshoku Industries Co., Ltd.).
＜ヘイズ値＞
感圧性接着シートのみについて、フィルム濁度計（日本電色工業社製の「ＮＤＭ−２０Ｄ」）を用いて、ヘイズ値を測定した。
<Haze value>
For only the pressure-sensitive adhesive sheet, the haze value was measured using a film turbidimeter (“NDM-20D” manufactured by Nippon Denshoku Industries Co., Ltd.).
＜接着力＞
ＪＩＳ Ｃ２１０７の接着力試験法（１８０度引き剥がし法）に準じ、測定した。ただし、試験片は、感圧性接着シート付き偏光板を幅２５mm、長さ１２０mmにカットし、離型処理フィルムを剥がしたのち、動式圧着装置を使用して、ガラス板に貼り合わせた。その他は、上記の接着力試験法と同様にして、測定した。
<Adhesive strength>
The measurement was performed according to the adhesion test method (180 degree peeling method) of JIS C2107. However, the test piece was bonded to a glass plate using a dynamic pressure bonding apparatus after the polarizing plate with a pressure-sensitive adhesive sheet was cut into a width of 25 mm and a length of 120 mm, and the release treatment film was peeled off. Others were measured in the same manner as the above-described adhesion test method.
＜破断強度＞
凝集力・保持性の目安として、破断強度の測定を行った。測定は、ＪＩＳ Ｃ２１０７の引張り強さおよび伸び試験法に準じて、行った。ただし、試験片は、感圧性接着シートのみを５０mm角に切り出し、塗工の幅方向に丸めたものを使用した。
また、つかみの間隔を１０mmにし、引張り速度は５０mm／分にし、試験片破断時の最大荷重を測定した。その他は、上記の試験法と同様にして、測定した。
<Breaking strength>
Break strength was measured as a measure of cohesive strength and retention. The measurement was performed according to the tensile strength and elongation test method of JIS C2107. However, as the test piece, only a pressure-sensitive adhesive sheet was cut into a 50 mm square and rounded in the coating width direction.
Further, the distance between the grips was set to 10 mm, the pulling speed was set to 50 mm / min, and the maximum load when the test piece was broken was measured. Others were measured in the same manner as the above test method.
＜耐久性＞
試験片は、感圧性接着シート付き偏光板を幅５０mm、長さ１５０mmにカットし、離型処理フィルムを剥がしたのち、ガラス板に貼り合わせ、５０℃，５気圧のオートクレーブ中に３０分間放置して接着させた。
この偏光板を貼り合わせたガラス板を、６０℃，９０％ＲＨに３日間放置後、外観を目視にてチェックし、以下の判断基準で評価した。
○：外観良好（貼り合わせた偏光板の端部に浮きや剥がれが発生していない）
×：外観不良（貼り合わせた偏光板の端部に浮きや剥がれが発生した）
<Durability>
For the test piece, a polarizing plate with a pressure-sensitive adhesive sheet was cut to a width of 50 mm and a length of 150 mm, the release-treated film was peeled off, and then bonded to a glass plate and left in an autoclave at 50 ° C. and 5 atm for 30 minutes. And bonded.
The glass plate to which this polarizing plate was bonded was allowed to stand at 60 ° C. and 90% RH for 3 days, and then the appearance was visually checked and evaluated according to the following criteria.
○: Appearance is good (no floating or peeling at the end of the bonded polarizing plate)
X: Appearance defect (floating or peeling occurred at the end of the bonded polarizing plate)
表１ ┌──────────┬───────────────────┐
│ │ 実施例 │
│ ├───┬───┬───┬───┬───┤
│ │ １ │ ２ │ ３ │ ４ │ ５ │
├──────────┼───┼───┼───┼───┼───┤
│２ＥＨＡ │１００│１００│１００│ ９９│ ９７│
│ │ │ │ │ │ │
│ＡＡ │ ０ │ ０ │ ０ │ １ │ ３ │
│ │ │ │ │ │ │
│ルーセンタイトＳＰＮ│ ５ │ ８ │ １５│ ８ │ ８ │
│ │ │ │ │ │ │
│アエロジル │ − │ − │ − │ − │ − │
│ │ │ │ │ │ │
│ＫＢＭ４０３ │０．２│０．２│０．２│０．２│０．２│
│ │ │ │ │ │ │
│ＴＭＰＴＡ │０．２│０．２│０．２│０．２│０．２│
│ │ │ │ │ │ │
│Ｉｒｇ６５１ │０．１│０．１│０．１│０．１│０．１│
├──────────┼───┼───┼───┼───┼───┤
│全光線透過率（％） │ ９０│ ９０│ ９０│ ９０│ ９０│
│ │ │ │ │ │ │
│ヘイズ値 │０．７│０．７│０．７│０．７│０．７│
│ │ │ │ │ │ │
│接着力（Ｎ／25mm幅）│０．７│０．２│０．１│ ２ │ ４ │
├──────────┼───┼───┼───┼───┼───┤
│破断強度（Ｎ／cm2 ）│ ３０│ ３５│ ３７│ ４０│ ４５│
│ │ │ │ │ │ │
│耐久性 │ ○ │ ○ │ ○ │ ○ │ ○ │
└──────────┴───┴───┴───┴───┴───┘
Table 1 ┌──────────┬───────────────────┐
│ │ Examples │
│ ├───┬───┬───┬───┬───┤
│ │ 1 │ 2 │ 3 │ 4 │ 5 │
├──────────┼───┼───┼───┼───┼───┤
│2EHA │100│100│100│ 99│ 97│
│ │ │ │ │ │ │
│AA │ 0 │ 0 │ 0 │ 1 │ 3 │
│ │ │ │ │ │ │
│Lucentite SPN│ 5 │ 8 │ 15│ 8 │ 8 │
│ │ │ │ │ │ │
│Aerosil │-│-│-│-│-│
│ │ │ │ │ │ │
│KBM403 │0.2│0.2│0.2│0.2│0.2│
│ │ │ │ │ │ │
│TMPTA │0.2│0.2│0.2│0.2│0.2│
│ │ │ │ │ │ │
│Irg651 │0.1│0.1│0.1│0.1│0.1│
├──────────┼───┼───┼───┼───┼───┤
│Total light transmittance (%) │ 90│ 90│ 90│ 90│ 90│
│ │ │ │ │ │ │
│Haze value │0.7│0.7│0.7│0.7│0.7│
│ │ │ │ │ │ │
│Adhesive strength (N / 25mm width) │0.7│0.2│0.1│ 2 │ 4 │
├──────────┼───┼───┼───┼───┼───┤
│ Breaking strength (N / cm 2 ) │ 30│ 35│ 37│ 40│ 45│
│ │ │ │ │ │ │
│ Durability │ ○ │ ○ │ ○ │ ○ │ ○ │
└──────────┴───┴───┴───┴───┴───┘
表２ ┌──────────┬───────────────┐
│ │ 比較例 │
│ ├───┬───┬───┬───┤
│ │ １ │ ２ │ ３ │ ４ │
├──────────┼───┼───┼───┼───┤
│２ＥＨＡ │ ９５│１００│１００│１００│
│ │ │ │ │ │
│ＡＡ │ ５ │ ０ │ ０ │ ０ │
│ │ │ │ │ │
│ルーセンタイトＳＰＮ│ ８ │ １ │ ８ │ − │
│ │ │ │ │ │
│アエロジル │ − │ − │ − │ ８ │
│ │ │ │ │ │
│ＫＢＭ４０３ │０．２│０．２│ − │０．２│
│ │ │ │ │ │
│ＴＭＰＴＡ │０．２│０．２│０．２│０．２│
│ │ │ │ │ │
│Ｉｒｇ６５１ │０．１│０．１│０．１│０．１│
├──────────┼───┼───┼───┼───┤
│全光線透過率（％） │ ９０│ ９０│ ９０│ ８５│
│ │ │ │ │ │
│ヘイズ値 │０．７│０．７│０．７│１．２│
│ │ │ │ │ │
│接着力（Ｎ／25mm幅）│ ９ │０．２│ 0.08 │０．２│
├──────────┼───┼───┼───┼───┤
│破断強度（Ｎ／cm2 ）│ ５０│ １０│ １５│ １５│
│ │ │ │ │ │
│耐久性 │ ○ │ × │ × │ × │
└──────────┴───┴───┴───┴───┘
Table 2 ┌──────────┬───────────────┐
│ │ Comparative Example │
│ ├───┬───┬───┬───┤
│ │ 1 │ 2 │ 3 │ 4 │
├──────────┼───┼───┼───┼───┤
│2EHA │ 95│100│100│100│
│ │ │ │ │ │
│AA │ 5 │ 0 │ 0 │ 0 │
│ │ │ │ │ │
│Lucentite SPN│ 8 │ 1 │ 8 │ − │
│ │ │ │ │ │
│Aerosil │-│-│-│ 8 │
│ │ │ │ │ │
│KBM403 │0.2│0.2│ − │0.2│
│ │ │ │ │ │
│TMPTA │0.2│0.2│0.2│0.2│
│ │ │ │ │ │
│Irg651 │0.1│0.1│0.1│0.1│
├──────────┼───┼───┼───┼───┤
│Total light transmittance (%) │ 90│ 90│ 90│ 85│
│ │ │ │ │ │
│Haze value │0.7│0.7│0.7│1.2│
│ │ │ │ │ │
│Adhesive strength (N / 25mm width) │ 9 │0.2│ 0.08 │0.2│
├──────────┼───┼───┼───┼───┤
│ Breaking strength (N / cm 2 ) │ 50│ 10│ 15│ 15│
│ │ │ │ │ │
│ Durability │ ○ │ × │ × │ × │
└──────────┴───┴───┴───┴───┘
上記の表１および表２の結果から明らかなように、本発明の実施例１〜５の感圧性接着シート付き偏光板は、感圧性接着シートの全光線透過率が９０％、ヘイズ値が０．７、接着力が０．１〜４Ｎ／２５mm幅の範囲にあり、視認性、透明性、リワーク性にすぐれるとともに、破断強度が３０〜４５Ｎ／cm2 で、耐久性に格段にすぐれていることがわかる。これに対して、本発明とは異なる比較例１〜４の感圧性接着シート付き偏光板は、上記特性のいずれか、とくにリワーク性か耐久性かのいずれかに劣っている。
As is clear from the results of Tables 1 and 2, the polarizing plates with pressure-sensitive adhesive sheets of Examples 1 to 5 of the present invention have a total light transmittance of 90% and a haze value of 0. .7, Adhesive strength is in the range of 0.1 to 4 N / 25 mm width, excellent visibility, transparency, reworkability, and break strength of 30 to 45 N / cm 2. I understand that. On the other hand, the polarizing plates with pressure-sensitive adhesive sheets of Comparative Examples 1 to 4, which are different from the present invention, are inferior in any of the above characteristics, particularly in either reworkability or durability.
Claims (1)
In producing a polarizing plate with a pressure-sensitive adhesive sheet, in which a pressure-sensitive adhesive sheet is bonded to a polarizing plate, (A) (meth) acrylic acid having 4 to 14 carbon atoms in the alkyl group in forming the pressure-sensitive adhesive sheet. A monomer comprising 97 to 100% by weight of a vinyl monomer having an alkyl ester as a main component and 3 to 0% by weight of a polar group-containing monomer copolymerizable therewith, (b) 2 per 100 parts by weight of the monomer of the component (A) A smectite clay mineral having an average length of 10 to 100 nm as a lipophilic layered silicate in a proportion of ˜20 parts by weight, (c) a coupling agent, (d) a polyfunctional (meth) acrylate as a crosslinking agent, (E) A photopolymerizable composition containing a photopolymerization initiator is photopolymerized so that the total light transmittance is 85 to 100%, the haze value is 0 to 5, and the adhesion to glass is 0.1 to 4N. Method for producing a pressure-sensitive adhesive sheet with a polarizing plate and forming a pressure-sensitive adhesive sheet is 25mm wide.
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| JP5588626B2 (en) | 2008-08-04 | 2014-09-10 | 富士フイルム株式会社 | Optical film, polarizing plate, optical compensation film, antireflection film, and liquid crystal display device |
| JP5544858B2 (en) * | 2009-12-11 | 2014-07-09 | サイデン化学株式会社 | Adhesive composition for polarizing plate |
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|---|---|---|---|---|
| JP3022993B2 (en) * | 1990-12-25 | 2000-03-21 | 日本合成化学工業株式会社 | Polarizing plate having an adhesive layer |
| JPH0720314A (en) * | 1993-06-30 | 1995-01-24 | Sekisui Chem Co Ltd | Polarizing plate fixing structure |
| JP4803524B2 (en) * | 2001-05-15 | 2011-10-26 | 綜研化学株式会社 | Optical member pressure-sensitive adhesive and optical member provided with the pressure-sensitive adhesive |
| JP2002363522A (en) * | 2001-06-06 | 2002-12-18 | Nitto Denko Corp | Clear pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet thereof |
| JP2002365522A (en) * | 2001-06-06 | 2002-12-18 | Ricoh Co Ltd | Focus controller |
| JP2003183457A (en) * | 2001-12-18 | 2003-07-03 | Nitto Denko Corp | Transparent self-adhesive composition excellent in external shock-absorbing property |
| JP4062668B2 (en) * | 2002-05-15 | 2008-03-19 | 日東電工株式会社 | Adhesive optical film, optical film adhesive composition and image display device |
-
2003
- 2003-12-25 JP JP2003429501A patent/JP4248019B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JP2005189437A (en) | 2005-07-14 |
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