JP4428470B1 - Polarizing plate and adhesive composition for forming polarizing plate - Google Patents
Polarizing plate and adhesive composition for forming polarizing plate Download PDFInfo
- Publication number
- JP4428470B1 JP4428470B1 JP2009137764A JP2009137764A JP4428470B1 JP 4428470 B1 JP4428470 B1 JP 4428470B1 JP 2009137764 A JP2009137764 A JP 2009137764A JP 2009137764 A JP2009137764 A JP 2009137764A JP 4428470 B1 JP4428470 B1 JP 4428470B1
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polarizing plate
- acrylate
- adhesive layer
- protective film
- 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.)
- Active
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 41
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 230000001681 protective effect Effects 0.000 claims abstract description 71
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 45
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract description 16
- 230000009477 glass transition Effects 0.000 claims abstract description 12
- 239000012790 adhesive layer Substances 0.000 claims description 66
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 55
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 17
- 229920001610 polycaprolactone Polymers 0.000 claims description 17
- 239000004632 polycaprolactone Substances 0.000 claims description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 9
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000004080 punching Methods 0.000 abstract description 16
- 239000000470 constituent Substances 0.000 abstract description 3
- 239000002313 adhesive film Substances 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 22
- 229920005989 resin Polymers 0.000 description 22
- -1 N, N-dimethylaminomethyl Chemical group 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229940113165 trimethylolpropane Drugs 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- HDGYKGLIXMYNBH-UHFFFAOYSA-N 2-hydroxyhept-2-enoic acid Chemical compound CCCCC=C(O)C(O)=O HDGYKGLIXMYNBH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- MPRJFHVZWIKCOO-UHFFFAOYSA-N butyl prop-2-eneperoxoate Chemical compound CCCCOOC(=O)C=C MPRJFHVZWIKCOO-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- PGMMMHFNKZSYEP-UHFFFAOYSA-N 1,20-Eicosanediol Chemical compound OCCCCCCCCCCCCCCCCCCCCO PGMMMHFNKZSYEP-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- GJBXIPOYHVMPQJ-UHFFFAOYSA-N hexadecane-1,16-diol Chemical compound OCCCCCCCCCCCCCCCCO GJBXIPOYHVMPQJ-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000005028 tinplate Substances 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
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- PASIEQDVKZQWRI-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol 3-hydroxy-2,2-dimethylpropanoic acid prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OCC(C)(C)CO.OCC(C)(C)C(O)=O PASIEQDVKZQWRI-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- SEGKJLWPIPSYSC-UHFFFAOYSA-N 3-ethyloctane-1,8-diol Chemical compound OCCC(CC)CCCCCO SEGKJLWPIPSYSC-UHFFFAOYSA-N 0.000 description 1
- XPFCZYUVICHKDS-UHFFFAOYSA-N 3-methylbutane-1,3-diol Chemical compound CC(C)(O)CCO XPFCZYUVICHKDS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- UAKWLVYMKBWHMX-UHFFFAOYSA-N SU4312 Chemical compound C1=CC(N(C)C)=CC=C1C=C1C2=CC=CC=C2NC1=O UAKWLVYMKBWHMX-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 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
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 101150059062 apln gene Proteins 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-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
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 208000028659 discharge Diseases 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
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229940063557 methacrylate Drugs 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- XLKZJJVNBQCVIX-UHFFFAOYSA-N tetradecane-1,14-diol Chemical compound OCCCCCCCCCCCCCCO XLKZJJVNBQCVIX-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000009816 wet lamination Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polarising Elements (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Liquid Crystal (AREA)
- Adhesive Tapes (AREA)
Abstract
【課題】ポリビニルアルコール系偏光子と、アクリル系フィルムやシクロオレフィン系フィルムに代表される難接着性の保護フィルムとを構成層とし、接着力が大きく、耐久性に優れる偏光板小片を形成し得る偏光板であって、打ち抜き加工性に優れる偏光板を提供する。
【解決手段】ポリビニルアルコール系偏光子３の両面が、ラジカル重合性組成物を硬化してなる、ガラス転移温度が−８０℃〜０℃の接着剤層２、４を介して、アクリル系フィルム及びシクロオレフィン系フィルムからなる群より選ばれる保護フィルム１、５でそれぞれ被覆されてなる偏光板。
【選択図】図１[PROBLEMS] To form a polarizing plate piece having a high adhesive force and excellent durability, comprising a polyvinyl alcohol polarizer and a hard-to-adhere protective film typified by an acrylic film or a cycloolefin film as constituent layers. Provided is a polarizing plate which is excellent in punching workability.
SOLUTION: Both surfaces of a polyvinyl alcohol polarizer 3 are obtained by curing an acrylic film and an adhesive film 2 and 4 having a glass transition temperature of −80 ° C. to 0 ° C. formed by curing a radical polymerizable composition. A polarizing plate coated with protective films 1 and 5 selected from the group consisting of cycloolefin-based films.
[Selection] Figure 1
Description
本発明は、液晶表示装置等に用いられる偏光板に関するものである The present invention relates to a polarizing plate used for a liquid crystal display device or the like.
時計、携帯電話、個人用の携帯情報端末（ＰＤＡ）、ノートパソコン、パソコン用モニタ、ＤＶＤプレーヤー、ＴＶなどでは液晶表示装置が急激に市場展開している。液晶表示装置は、液晶のスイッチングによる偏光状態を可視化させたものであり、その表示原理から、偏光子が用いられる。特に、ＴＶ等の用途では、ますます高輝度、高コントラスト、広い視野角が求められ、偏光板においてもまずます高透過率、高偏光度、高い色再現性などが求められている。 Liquid crystal display devices are rapidly developing in watches, mobile phones, personal digital assistants (PDAs), notebook computers, personal computer monitors, DVD players, TVs, and the like. The liquid crystal display device visualizes the polarization state by switching of the liquid crystal, and a polarizer is used from the display principle. In particular, in applications such as TVs, higher brightness, higher contrast, and wider viewing angles are required, and polarizing plates are also required to have higher transmittance, higher degree of polarization, and higher color reproducibility.
液晶表示関連分野などに用いられる偏光フィルムは、通常ポリビニルアルコール（ＰＶＡ）にヨウ素や染料を吸着させたものを一軸延伸して製造される。このポリビニルアルコール系偏光フィルムは熱や水分により収縮し、偏光性能の低下をきたすため、その表面に保護フィルムが貼合されたものが偏光板である。 A polarizing film used in a liquid crystal display-related field or the like is usually produced by uniaxially stretching a polyvinyl alcohol (PVA) adsorbed with iodine or a dye. Since this polyvinyl alcohol-type polarizing film shrinks due to heat or moisture and lowers the polarizing performance, a polarizing plate is a film in which a protective film is bonded to the surface.
偏光フィルムに保護フィルムを貼着するための接着剤としては、従来からポリビニルアルコール系樹脂の水溶液（ＰＶＡ系接着剤）が広く使用されている（特許文献１、２参照）。
ところが、ポリビニルアルコール系接着剤のような水系接着剤は、乾燥に長時間を要するので、偏光板の生産性の点で好ましくない。
特に、偏光フィルムに水系接着剤を塗工し、乾燥せずに保護フィルムを重ね合わせ、その状態で乾燥させる、いわゆるウェットラミネーション法の場合には、接着剤層と偏光フィルムとの接着性を高めるために、偏光フィルムの水分率も相対的に高くしておかないと、接着性が良好な偏光板を得ることができない。
Conventionally, an aqueous solution of a polyvinyl alcohol resin (PVA adhesive) has been widely used as an adhesive for sticking a protective film to a polarizing film (see
However, water-based adhesives such as polyvinyl alcohol-based adhesives are not preferable in terms of productivity of polarizing plates because they take a long time to dry.
In particular, in the case of a so-called wet lamination method in which a water-based adhesive is applied to a polarizing film, a protective film is overlaid without drying, and dried in that state, the adhesiveness between the adhesive layer and the polarizing film is increased. Therefore, a polarizing plate with good adhesion cannot be obtained unless the moisture content of the polarizing film is also relatively high.
特許文献３には、水性ウレタン系接着剤を用いてなる偏光板が開示されている。
しかし、特許文献３に記載される偏光板の場合、透湿性の低い保護フィルムを用いているため、水分の蒸散及び硬化に長時間を要する。しかも、透湿性の低い保護フィルムは疎水性なので、水性接着剤から形成される接着剤層との接着性が不十分であるという問題もある。
However, in the case of the polarizing plate described in
ところで、水系接着剤を用いてなる偏光板は、高温や高温高湿度の環境下に置かれると、寸法が大きく変化してしまうという問題がある。寸法変化を抑えるには、偏光子の水分率を下げたり、透湿度の低い透明保護フィルムを用いたりするという対策が考えられる。
しかし、こうした対策では、乾燥工程における能率が下がったり、偏光特性が下がったり、または外観の不具合が発生し実質上有用な偏光板を得ることができない。
By the way, a polarizing plate made using a water-based adhesive has a problem that the dimensions greatly change when placed in an environment of high temperature or high temperature and high humidity. In order to suppress the dimensional change, measures such as lowering the moisture content of the polarizer or using a transparent protective film with low moisture permeability can be considered.
However, with such measures, the efficiency in the drying process is lowered, the polarization characteristics are lowered, or the appearance is defective, so that a practically useful polarizing plate cannot be obtained.
また、特にＴＶで代表されるように、近年、画像表示装置の大画面化が進むにつれ、偏光板に対しても大型化の要求が高まり、生産性向上が非常に重要な課題になっている。
しかし、前述の水系接着剤を用いた偏光板では、バックライトの熱により偏光板の寸法が変化し、その寸法変化に起因するひずみが画面の一部に局在化し、その結果本来画面全体が黒く表示されるべき場合に、部分的に光がもれてしまう、いわゆる光抜け（ムラ）が顕著になってくるという問題がある。
In addition, as represented by TV in particular, as the screen size of image display devices has been increasing in recent years, there has been a growing demand for larger polarizing plates, and improving productivity has become a very important issue. .
However, in the polarizing plate using the water-based adhesive described above, the size of the polarizing plate changes due to the heat of the backlight, and the distortion caused by the change in size is localized in a part of the screen, and as a result, the entire screen originally becomes There is a problem that so-called light omission (unevenness) in which light is partially leaked when it should be displayed in black becomes noticeable.
上記のような理由から、水系接着剤の代わりに、カチオン重合性紫外線硬化型接着剤を使用することが提案されている（特許文献４参照）。しかし、カチオン重合性紫外線硬化型接着剤は、紫外線照射後に暗反応があるので、長尺の硬化物を巻取りロール状にした場合、保管時に巻き癖がつきやすいという問題がある。しかも、カチオン重合性紫外線硬化型接着剤は、硬化時の湿度の影響を受けやすく、硬化状態がバラつきやすいという問題がある。そこで、均一な硬化状態を発現するためには、環境湿度は言うに及ばず、ＰＶＡ系偏光子の含水率を厳しく管理する必要がある。
ラジカル重合性紫外線硬化型接着剤にはこのような問題が比較的少ないという点で優れる。
For the reasons described above, it has been proposed to use a cationic polymerizable ultraviolet curable adhesive instead of the water-based adhesive (see Patent Document 4). However, since the cationic polymerizable ultraviolet curable adhesive has a dark reaction after being irradiated with ultraviolet rays, there is a problem that when a long cured product is formed into a take-up roll shape, curling tends to occur during storage. In addition, the cationic polymerizable ultraviolet curable adhesive is susceptible to the influence of humidity during curing and has a problem that the cured state tends to vary. Therefore, in order to develop a uniform cured state, it is necessary to strictly control the moisture content of the PVA polarizer, not to mention the environmental humidity.
Radical polymerizable UV curable adhesives are excellent in that these problems are relatively small.
ところで、偏光板は、大画面用ＴＶに利用されるばかりではなく、携帯電話やパソコン等の比較的小さい画面にも利用される。比較的小さい画面用の偏光板は、通常、大きな偏光板を所望の大きさに裁断して製造する。裁断しても偏光板の積層状態が強固に保持されること（打ち抜き加工性）が要求される。以下、裁断後の偏光板を裁断前と区別して「偏光板小片」ということとする。
工業的には、先端に刃を具備する所定の大きさの四辺形の金型枠で偏光板を打ち抜き、「偏光板小片」を得る。
極めて薄く、鋭い刃によって、対向する２辺を順次裁断する場合に比して、「打ち抜き加工」の場合、遥かに大きな負荷が接着剤層にかかる。従って、接着剤層には「打ち抜き加工」に耐える強靭さが求められる。
By the way, the polarizing plate is used not only for a large screen TV but also for a relatively small screen such as a mobile phone or a personal computer. A relatively small polarizing plate for a screen is usually produced by cutting a large polarizing plate into a desired size. Even if it is cut, it is required that the laminated state of the polarizing plate is firmly maintained (punching workability). Hereinafter, the polarizing plate after cutting is referred to as “polarizing plate small piece” to distinguish it from before cutting.
Industrially, a polarizing plate is punched out by a quadrilateral mold frame of a predetermined size having a blade at the tip to obtain a “polarizing plate piece”.
In the case of “punching”, a much larger load is applied to the adhesive layer as compared with the case where two opposing sides are sequentially cut by an extremely thin and sharp blade. Therefore, the adhesive layer is required to have toughness that can withstand “punching”.
そして、裁断前の偏光板と同様に「打ち抜き加工」後の偏光板小片にも、高温下や高温高湿下に置かれても、形状、接着状態、光学特性等を維持することが求められる。
接着剤層が固すぎたり、偏光子や保護フィルムと接着剤層との密着性が良くなかったりすると、裁断によって偏光板小片の端部が剥離することがある。この端部の剥離は、剥離部分の偏光性能を低下させるだけでなく、高温下や高温高湿下に置かれると偏光板小片の変形（主に収縮）のきっかけとなってしまう恐れがある。
つまり、裁断前の偏光板には打ち抜き加工性に優れることが要求され、裁断後の偏光板小片にも耐久性が要求される。
And like the polarizing plate before cutting, the polarizing plate piece after “punching” is required to maintain the shape, adhesion state, optical characteristics, etc. even when placed under high temperature or high temperature and high humidity. .
If the adhesive layer is too hard or the adhesion between the polarizer or the protective film and the adhesive layer is not good, the edge of the polarizing plate piece may be peeled off by cutting. The peeling of the end portion not only deteriorates the polarization performance of the peeling portion, but may be a cause of deformation (mainly shrinkage) of the polarizing plate piece when placed under high temperature or high temperature and high humidity.
That is, the polarizing plate before cutting is required to have excellent punching workability, and the polarizing plate piece after cutting is also required to have durability.
上記したように、ラジカル重合性紫外線硬化型接着剤は、カチオン重合性硬化型接着剤に比して、種々の点で優れる。
しかし、ラジカル重合性紫外線硬化型接着剤を用いた場合、接着剤層が相対的に固いことが多く、耐打ち抜き加工性や耐久性の点で劣っていた。
特許文献５には、接着剤層のガラス転移温度を６０℃以上にコントロールすることによって、耐久性に優れた偏光板を得ることができる旨記載されている。
確かに、接着剤層のガラス転移温度を高くすれば、偏光板が高温に曝され、ＰＶＡ系偏光子が収縮しようとしても、接着剤層がその変形に抗し易くはなる。
しかし、接着剤層のガラス転移温度が高くすると、打ち抜き加工性が低下したり、保護フィルムとＰＶＡ偏光子とを十分な強度で接着できなかったりする。特許文献５の実施例レベルに記載されるアクリル系フィルムを保護フィルムとする偏光板の場合、接着力はいずれも０．７Ｎ／１５ｍｍ（＝１．１７Ｎ／２５ｍｍ）よりも低い値を示す。この程度の接着力では、かろうじて付着しているに程度であり、以下のような問題を有する。
即ち、打ち抜き時に大きな負荷がかかる「打ち抜き加工」に接着剤層が耐えられず、端部が剥離してしまい、欠陥となる。
As described above, the radical polymerizable ultraviolet curable adhesive is superior in various respects as compared with the cationic polymerizable curable adhesive.
However, when a radical polymerizable ultraviolet curable adhesive is used, the adhesive layer is often relatively hard and is inferior in terms of punching resistance and durability.
Certainly, if the glass transition temperature of the adhesive layer is increased, even if the polarizing plate is exposed to a high temperature and the PVA polarizer is about to shrink, the adhesive layer easily resists the deformation.
However, when the glass transition temperature of the adhesive layer is high, the punching processability is lowered, or the protective film and the PVA polarizer cannot be bonded with sufficient strength. In the case of a polarizing plate using an acrylic film described in the example level of
That is, the adhesive layer cannot withstand the “punching process” that requires a large load during punching, and the end part peels off, resulting in a defect.
ところで、偏光板小片は、感圧性接着剤層（＝粘着剤層）によって、ガラスセル部材に貼着され、使用される。ＰＶＡ系偏光子／保護フィルム間の接着力の小ささは、偏光板小片を液晶表示素子用のガラスセル部材に貼着する際に、さらなる問題を引き起こす。
偏光板貼着時に界面に空気が入ってしまったり、ゴミが入ってしまったりするなどの不具合が発生した場合には、偏光板をガラスセル部材から剥がし、新たな偏光板をガラスセル部材に貼り直す。この工程を、「リワーク」という。偏光板内部の力（ＰＶＡ系偏光子／接着剤層間の接着力、接着剤層／保護フィルム間の接着力）が、偏光板とガラスセル部材との間の力（ガラスセル部材／粘着剤層間の接着力、粘着剤層／偏光板間の接着力）よりも小さいと、「リワーク」の際に、ガラスセル部材上に偏光板の一部、具体的には保護フィルムが粘着剤層によって貼着された状態で残ってしまう。偏光板の剥離状態が破壊されるこの現象をデラミネーション（剥離）といい、この偏光板のデラミネーションは、「リワーク」にとって大きな障害である。
従って、保護フィルムとＰＶＡ偏光子とは、粘着剤層／偏光板間の接着力よりも相対的に大きな強度で接着されることが必要となる。しかし、偏光板固定用の粘着剤もさまざまなものがあり、その強度も様々であるが、およその目安としては、３．０Ｎ／２５ｍｍ以上の接着力が、偏光板形成用の接着剤には求められる。
By the way, a polarizing plate piece is stuck and used for a glass cell member by a pressure sensitive adhesive layer (= adhesive layer). The small adhesive force between the PVA polarizer / protective film causes a further problem when the polarizing plate piece is attached to a glass cell member for a liquid crystal display element.
If a problem such as air entering the polarizing plate or dust entering the polarizing plate occurs, remove the polarizing plate from the glass cell member and attach a new polarizing plate to the glass cell member. cure. This process is called “rework”. The force inside the polarizing plate (adhesive strength between the PVA polarizer / adhesive layer, adhesive strength between the adhesive layer / protective film) is the force between the polarizing plate and the glass cell member (glass cell member / adhesive layer) The adhesive force between the pressure-sensitive adhesive layer and the adhesive layer / polarizing plate) is smaller than the adhesive strength between the polarizing plate and the protective film. It remains in a worn state. This phenomenon in which the peeling state of the polarizing plate is destroyed is referred to as delamination (delamination). This delamination of the polarizing plate is a major obstacle to “rework”.
Therefore, it is necessary that the protective film and the PVA polarizer are bonded with a relatively higher strength than the adhesive force between the pressure-sensitive adhesive layer / polarizing plate. However, there are various pressure-sensitive adhesives for fixing the polarizing plate, and the strengths thereof are also various. As a rough guide, an adhesive force of 3.0 N / 25 mm or more is used for the adhesive for forming the polarizing plate. Desired.
本発明は、ポリビニルアルコール系偏光子と、アクリル系フィルムやシクロオレフィン系フィルムに代表される難接着性の保護フィルムとを構成層とし、接着力が大きく、耐久性に優れる偏光板小片を形成し得る偏光板であって、打ち抜き加工性に優れる偏光板を提供することを目的とする。 The present invention comprises a polyvinyl alcohol polarizer and a hard-to-adhere protective film typified by an acrylic film or a cycloolefin film as a constituent layer to form a small polarizing plate having high adhesion and excellent durability. It is an object of the present invention to provide a polarizing plate that is excellent in punching workability.
本発明者らは前記課題を解決すべく鋭意検討を重ねた結果、以下に示す偏光板により前記目的に達成できることを見出し、本発明を完成するに至った。
すなわち、本発明は、ポリビニルアルコール系偏光子（３）の両面が、４−ヒドロキシブチルアクリレート：２０〜９０重量％、ω-カルボキシ-ポリカプロラクトンアクリレート：１〜７０重量％、その他のラジカル重合性化合物：０〜１５重量％、光重合開始剤：０．０１〜２０重量％、シランカップリング剤：０〜１０重量％を含有し、酸価が０．１〜２００ｍｇＫＯＨ／ｇのラジカル重合性組成物を硬化してなる、ガラス転移温度が−８０〜０℃の接着剤層（２）、（４）を介して、アクリル系フィルム及びシクロオレフィン系フィルムからなる群より選ばれる保護フィルム（１）、（５）でそれぞれ被覆されてなる偏光板に関する。
As a result of intensive studies to solve the above problems, the present inventors have found that the object can be achieved by the following polarizing plate, and have completed the present invention.
That is, in the present invention, both sides of the polyvinyl alcohol polarizer (3) are 4-hydroxybutyl acrylate: 20 to 90% by weight, ω-carboxy-polycaprolactone acrylate: 1 to 70% by weight, and other radical polymerizable compounds. : 0 to 15% by weight, photopolymerization initiator: 0.01 to 20% by weight, silane coupling agent: 0 to 10% by weight, radically polymerizable composition having an acid value of 0.1 to 200 mgKOH / g A protective film (1) selected from the group consisting of an acrylic film and a cycloolefin film via an adhesive layer (2), (4) having a glass transition temperature of -80 to 0 ° C, The present invention relates to a polarizing plate coated with (5).
また、本発明は、第１の保護フィルム（１）、第１の接着剤層（２）、ポリビニルアルコール系偏光子（３）、第２の接着剤層（４）及び第２の保護フィルム（５）がこの順序で積層されてなる偏光板の製造方法であって、
アクリル系フィルム及びシクロオレフィン系フィルムからなる群より選ばれる第１の保護フィルム（１）の一方の面に、４−ヒドロキシブチルアクリレート：２０〜９０重量％、ω-カルボキシ-ポリカプロラクトンアクリレート：１〜７０重量％、その他のラジカル重合性化合物：０〜１５重量％、光重合開始剤：０．０１〜２０重量％、シランカップリング剤：０〜１０重量％を含有し、酸価が０．１〜２００ｍｇＫＯＨ／ｇのラジカル重合性組成物を塗工し、第１の硬化性接着剤層（２’）を形成し、
アクリル系フィルム及びシクロオレフィン系フィルムからなる群より選ばれる第２の保護フィルム（５）の一方の面に、４−ヒドロキシブチルアクリレート：２０〜９０重量％、ω-カルボキシ-ポリカプロラクトンアクリレート：１〜７０重量％、その他のラジカル重合性化合物：０〜１５重量％、光重合開始剤：０．０１〜２０重量％、シランカップリング剤：０〜１０重量％を含有し、酸価が０．１〜２００ｍｇＫＯＨ／ｇのラジカル重合性組成物を塗工し、第２の硬化性接着剤層（４’）を形成し、
ポリビニルアルコール系偏光子（３）の各面に、第１の硬化性接着剤層（２’）及び第２の硬化性接着剤層（４’）を、同時に／または順番に重ね合わせ、
第１の保護フィルム（１）及び／または第２の保護フィルム（５）の側から活性エネルギー線を照射することを特徴とする、偏光板の製造方法に関する。
In addition, the present invention provides a first protective film (1), a first adhesive layer (2), a polyvinyl alcohol polarizer (3), a second adhesive layer (4), and a second protective film ( 5) is a method for producing a polarizing plate laminated in this order,
On one surface of the first protective film (1) selected from the group consisting of an acrylic film and a cycloolefin film, 4-hydroxybutyl acrylate: 20 to 90% by weight, ω-carboxy-polycaprolactone acrylate: 1 to 70% by weight, other radical polymerizable compound: 0 to 15% by weight, photopolymerization initiator: 0.01 to 20% by weight, silane coupling agent: 0 to 10% by weight, with an acid value of 0.1 Applying a radically polymerizable composition of ~ 200 mg KOH / g to form a first curable adhesive layer (2 ');
On one surface of the second protective film (5) selected from the group consisting of an acrylic film and a cycloolefin film, 4-hydroxybutyl acrylate: 20 to 90% by weight, ω-carboxy-polycaprolactone acrylate: 1 to 70% by weight, other radical polymerizable compound: 0 to 15% by weight, photopolymerization initiator: 0.01 to 20% by weight, silane coupling agent: 0 to 10% by weight, with an acid value of 0.1 Applying a radically polymerizable composition of ~ 200 mg KOH / g to form a second curable adhesive layer (4 ');
A first curable adhesive layer (2 ′) and a second curable adhesive layer (4 ′) are simultaneously and / or sequentially overlapped on each surface of the polyvinyl alcohol polarizer (3),
The present invention relates to a method for producing a polarizing plate, which comprises irradiating active energy rays from the first protective film (1) and / or the second protective film (5) side.
さらに、本発明は、４−ブチルヒドロキシアクリレート：２０〜９０重量％、ω-カルボキシ-ポリカプロラクトンアクリレート：１〜７０重量％、その他のラジカル重合性化合物：０〜１５重量％、光重合開始剤：０．０１〜２０重量％、シランカップリング剤：０〜１０重量％を含有することを特徴とする、偏光板形成用ラジカル重合性接着剤組成物に関する。 Furthermore, the present invention relates to 4-butylhydroxy acrylate: 20 to 90% by weight, ω-carboxy-polycaprolactone acrylate: 1 to 70% by weight, other radical polymerizable compounds: 0 to 15% by weight, photopolymerization initiator: It is related with the radically polymerizable adhesive composition for polarizing plate formation characterized by containing 0.01-20 weight% and a silane coupling agent: 0-10 weight%.
本発明により、ポリビニルアルコール系偏光子と、アクリル系フィルムやシクロオレフィン系フィルムに代表される難接着性の保護フィルムとを構成層とし、耐久性に優れる偏光板小片を形成し得る偏光板であって、打ち抜き加工性に優れる偏光板を提供することができるようになった。 According to the present invention, a polarizing plate capable of forming a polarizing plate piece having excellent durability, comprising a polyvinyl alcohol polarizer and a hard-to-adhere protective film represented by an acrylic film or a cycloolefin film as constituent layers. Thus, it has become possible to provide a polarizing plate excellent in punching workability.
本発明の偏光板における接着剤層について説明する。
接着剤層は、ラジカル重合性組成物を硬化してなるものであり、−８０〜０℃のガラス転移温度（以下、Ｔｇという）を呈するものであり、打ち抜き加工性の点から、−６０〜−２０℃であることがより好ましく、−６０〜−４０℃であることがさらに好ましい。
ラジカル重合性組成物は、硬化物のＴｇが上記のようになるように、４−ヒドロキシブチルアクリレート：２０〜９０重量％、ω-カルボキシ-ポリカプロラクトンアクリレート：１〜７０重量％、その他のラジカル重合性化合物：０〜１５重量％等の硬化性成分群から、適宜２種類以上の化合物を選択してなるものである。単官能または二官能以上のいずれも用いることができる。（メタ）アクリロイル基を有する化合物が好適であり、アクリロイル基を有する化合物がより好適である。
ＰＶＡ系偏光子との接着性向上の点から、水酸基を有する硬化性成分が好ましく、硬化物のＴｇを低くできるという点で、４−ヒドロキシブチルアクリレートが重要である。
The adhesive layer in the polarizing plate of the present invention will be described.
The adhesive layer is formed by curing a radically polymerizable composition and exhibits a glass transition temperature (hereinafter referred to as Tg) of −80 to 0 ° C. From the point of punching workability, −60 to It is more preferably −20 ° C., and further preferably −60 to −40 ° C.
The radically polymerizable composition was prepared by using 4-hydroxybutyl acrylate: 20 to 90% by weight, ω-carboxy-polycaprolactone acrylate: 1 to 70% by weight, and other radical polymerization so that the Tg of the cured product was as described above. Compound: Two or more compounds are appropriately selected from a curable component group such as 0 to 15% by weight . Either monofunctional or bifunctional or more can be used. A compound having a (meth) acryloyl group is preferred, and a compound having an acryloyl group is more preferred.
From the viewpoint of improving adhesiveness between the PVA-based polarizer, preferably curable component that having a hydroxyl group, in that the Tg of the cured product can be lowered, 4-hydroxybutyl acrylate is important.
（メタ）アクリロイル基を有する化合物のうち、単官能化合物としては、例えばＮ，Ｎ−ジメチルアミノメチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ヒドロキシブチルメタアクリレート、ｎ−ヘキシルアクリレート、シクロヘキシルアクリレート、ｎ−デシルアクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニルオキシエチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、ノニルフェノキシエチル（メタ）アクリレート、ラウリル（メタ）アクリレート、フェニルグリシジルエーテル（メタ）アクリレート、（メタ）アクリル酸、（メタ）アクリル酸ダイマー、ω-カルボキシ-ポリカプロラクトンメタアクリレート、アクリロイルモルホリン等があげられる。
ＰＶＡ系偏光子との接着性向上の点から、水酸基を有するものが好ましいが、硬化物のＴｇを低くしにくいという点で、水酸基を有してはいても、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）アクリレートは使用しないことが好ましい。
Among the compounds having a (meth) acryloyl group, examples of the monofunctional compound include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meta ) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxybutyl methacrylate, n- hexyl acrylate, cyclohexyl acrylate, n- Decyl acrylate, isobornyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, Cycloalkenyl phenoxyethyl (meth) acrylate, lauryl (meth) acrylate, phenyl glycidyl ether (meth) acrylates, (meth) acrylic acid, (meth) acrylic acid dimer, .omega.-carboxy - polycaprolactone meth acrylate, acryloyl morpholine, and the like .
From the viewpoint of improving adhesiveness with a PVA polarizer, those having a hydroxyl group are preferred, but 2-hydroxyethyl (meth) acrylate may be used even if it has a hydroxyl group in that it is difficult to lower the Tg of the cured product. It is preferable not to use 2-hydroxypropyl (meth) acrylate.
本発明において用いられる接着剤を構成するラジカル重合性組成物は、形成される接着剤層の凝集力向上の点から酸価が０．１〜２００ｍｇＫＯＨ／ｇの範囲であることが好ましく、１０〜１５０ｍｇＫＯＨ／ｇの範囲であることがより好ましい。
ラジカル重合性組成物が上記のような酸価を有するようにするためには、（メタ）アクリロイル基を有する化合物としてカルボキシル基を有するものが好適に用いられ、接着剤の高酸価を維持しつつ、Ｔｇを低くできるものとして、（メタ）アクリル酸と６−ヘキサノリドを反応させたアクリル（系）モノマー、即ちω-カルボキシ-ポリカプロラクトン（メタ）アクリレートが好ましく、特にω-カルボキシ-ポリカプロラクトンアクリレートが有用である。
The radical polymerizable composition constituting the adhesive used in the present invention preferably has an acid value in the range of 0.1 to 200 mgKOH / g from the viewpoint of improving the cohesive strength of the formed adhesive layer. More preferably, it is in the range of 150 mgKOH / g.
In order for the radical polymerizable composition to have the acid value as described above, a compound having a carboxyl group is preferably used as the compound having a (meth) acryloyl group, and the high acid value of the adhesive is maintained. On the other hand, an acrylic (based) monomer obtained by reacting (meth) acrylic acid and 6-hexanolide, that is, ω-carboxy-polycaprolactone (meth) acrylate is preferable, and ω-carboxy-polycaprolactone acrylate is particularly preferable. Is useful.
（メタ）アクリロイル基を有する化合物のうち、２官能化合物としては、例えばエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、ポリプロピレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリプロピレングリコールジアクリレート、ビスフェノールＡのアルキレンオキシド付加物のジ（メタ）アクリレート、テトラエチレングリコールジアクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジアクリレート、１，４−ブタンジオールジ（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、１，１２−ドデカンジオールジ（メタ）アクリレート、１，１４−テトラデカンジオールジ（メタ）アクリレート、１，１６−ヘキサデカンジオールジ（メタ）アクリレート、１，２０−エイコサンジオールジ（メタ）アクリレート、イソペンチルジオールジ（メタ）アクリレート、３−エチル−１，８−オクタンジオールジ（メタ）アクリレート、ウレタン基含有ジ（メタ）アクリレート等があげられる。 Among the compounds having a (meth) acryloyl group, examples of the bifunctional compound include ethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, and alkylene oxide of bisphenol A. Adducts di (meth) acrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate hydroxypivalate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1, 12-dodecanediol di (meth) acrylate, 1,14-tetradecanediol di (meth) acrylate, 1,16-hexadecanediol di (meth) Acrylate, 1,20-eicosanediol di (meth) acrylate, isopentyldiol di (meth) acrylate, 3-ethyl-1,8-octanediol di (meth) acrylate, urethane group-containing di (meth) acrylate, etc. can give.
（メタ）アクリロイル基を有する化合物のうち、３官能以上の化合物としては、例えばトリメチロールプロパントリ（メタ）アクリレート、トリメチロールオクタントリ（メタ）アクリレート、トリメチロールプロパンポリエトキシトリ（メタ）アクリレート、トリメチロールプロパンポリプロポキシトリ（メタ）アクリレート、トリメチロールプロパンポリエトキシポリプロポキシトリ（メタ）アクリレート、トリス［（メタ）アクロイルオキシエチル］イソシアヌレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールポリエトキシテトラ（メタ）アクリレート、ペンタエリスリトールポリプロポキシテトラ（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、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリトリトールヘキサ（メタ）アクリレート、カプロラクトン変性トリス［（メタ）アクリロイルオキシエチル］イソシアヌレート等があげられる。 Among the compounds having a (meth) acryloyl group, trifunctional or higher functional compounds include, for example, trimethylolpropane tri (meth) acrylate, trimethyloloctanetri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, tri Methylolpropane polypropoxytri (meth) acrylate, trimethylolpropane polyethoxypolypropoxytri (meth) acrylate, tris [(meth) acryloyloxyethyl] isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol polyethoxytetra ( (Meth) acrylate, pentaerythritol polypropoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropa Tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified tris [(meth) acryloyloxyethyl] isocyanurate .
本発明明における硬化性組成物は、保護フィルムとの接着力を大きくでき、偏光板の収縮を抑制できるという点で、シランカップリング剤を含有することが好ましい。シランカップリング剤をとしては、アクリロイル基を有するものが好ましい。 It is preferable that the curable composition in the present invention contains a silane coupling agent in that the adhesive force with the protective film can be increased and the shrinkage of the polarizing plate can be suppressed. As the silane coupling agent, those having an acryloyl group are preferable.
本発明における硬化性組成物は、さらに必要であれば適宜その他の添加剤を添加してもよい。活性エネルギー線硬化型接着剤は、電子線硬化型、紫外線硬化型の態様で用いることができる。前記接着剤を電子線硬化型で用いる場合には、前記接着剤には光重合開始剤を含有させることは特に必要ではないが、紫外線硬化型で用いる場合には、光重合開始剤が用いられる。
光重合開始剤としては特に制限はなく、例えばイルガキュアー１８４，９０７，６５１，１７００，１８００，８１９，３６９，２６１、ＤＡＲＯＣＵＲ-ＴＰＯ（チバ・スペシャルティ・ケミカルズ社製）、ダロキュア-１１７３（メルク社製）、エザキュアーＫＩＰ１５０、ＴＺＴ（日本シイベルヘグナー社製）、カヤキュアＢＭＳ、カヤキュアＤＭＢＩ、（日本化薬製）等が挙げられる。
If necessary, the curable composition of the present invention may contain other additives as appropriate. The active energy ray curable adhesive can be used in an electron beam curable type or an ultraviolet curable type. When the adhesive is used as an electron beam curable type, it is not particularly necessary for the adhesive to contain a photopolymerization initiator, but when used as an ultraviolet curable type, a photopolymerization initiator is used. .
There is no restriction | limiting in particular as a photoinitiator, For example, Irgacure 184,907,651,1700,1800,819,369,261, DAROCUR-TPO (made by Ciba Specialty Chemicals), Darocur-1173 (made by Merck) ), Ezacure KIP150, TZT (manufactured by Nippon Shibel Hegner), Kayacure BMS, Kayacure DMBI, (Nippon Kayaku Co., Ltd.) and the like.
本発明明における硬化性組成物は、上記したように４−ブチルヒドロキシアクリレート、及びω-カルボキシ-ポリカプロラクトンアクリレートを含有することが好ましく、紫外線硬化型の場合には、光重合開始剤を含有することが好ましい。
シランカップリング剤を含有しない場合には、ラジカル重合性化合物と光重合開始剤との合計１００重量％中に、４−ブチルヒドロキシアクリレート：２０〜９０重量％、ω-カルボキシ-ポリカプロラクトンアクリレート：１〜７０重量％、その他のラジカル重合性化合物：０〜１５重量％、光重合開始剤：０．０１〜２０重量％を含有することが好ましく、４−ブチルヒドロキシアクリレート：３０〜８５重量％、ω-カルボキシ-ポリカプロラクトンアクリレート：５〜６０重量％、その他のラジカル重合性化合物：１〜１０重量％、光重合開始剤：１〜１０重量％を含有することがより好ましい。
シランカップリング剤を含有する場合には、ラジカル重合性化合物と光重合開始剤とシランカップリング剤との合計１００重量％中に、４−ブチルヒドロキシアクリレート：２０〜９０重量％、ω-カルボキシ-ポリカプロラクトンアクリレート：１〜７０重量％、その他のラジカル重合性化合物：０〜１５重量％、光重合開始剤：０．０１〜２０重量％、シランカップリング剤：０．１〜１０重量％を含有することが好ましく、４−ブチルヒドロキシアクリレート：３０〜８５重量％、ω-カルボキシ-ポリカプロラクトンアクリレート：５〜６０重量％、その他のラジカル重合性化合物：１〜１０重量％、光重合開始剤：１〜１０重量％、シランカップリング剤：０．５〜５重量％を含有することがより好ましい。
その他のラジカル重合性化合物としては、ウレタンアクリレートが好ましい。
The curable composition according to the present invention preferably contains 4-butylhydroxyacrylate and ω-carboxy-polycaprolactone acrylate as described above. In the case of an ultraviolet curable type, it contains a photopolymerization initiator. It is preferable.
When no silane coupling agent is contained, 4-butylhydroxy acrylate: 20 to 90% by weight, ω-carboxy-polycaprolactone acrylate: 1% in total of 100% by weight of the radical polymerizable compound and the photopolymerization initiator ~ 70 wt%, other radical polymerizable compounds: 0 to 15 wt%, photopolymerization initiator: preferably 0.01 to 20 wt%, 4-butylhydroxyacrylate: 30 to 85 wt%, ω -Carboxy-polycaprolactone acrylate: More preferably, it contains 5 to 60% by weight, other radical polymerizable compound: 1 to 10% by weight, and photopolymerization initiator: 1 to 10% by weight.
When a silane coupling agent is contained, 4-butylhydroxyacrylate: 20 to 90% by weight, ω-carboxy- in 100% by weight of the total of the radical polymerizable compound, the photopolymerization initiator, and the silane coupling agent. Polycaprolactone acrylate: 1 to 70% by weight, other radical polymerizable compounds: 0 to 15% by weight, photopolymerization initiator: 0.01 to 20% by weight, silane coupling agent: 0.1 to 10% by weight 4-butylhydroxy acrylate: 30 to 85% by weight, ω-carboxy-polycaprolactone acrylate: 5 to 60% by weight, other radical polymerizable compounds: 1 to 10% by weight, photopolymerization initiator: 1 It is more preferable to contain 10 to 10 weight% and a silane coupling agent: 0.5 to 5 weight%.
As other radical polymerizable compounds, urethane acrylate is preferable.
また、その他の添加剤の例としては、カルボニル化合物などで代表される活性エネルギー線による硬化速度や感度を上がる増感剤、シランカップリング剤やエチレンオキシドで代表される接着促進剤、透明保護フィルムとの濡れ性を向上させる添加剤、アクリロキシ基化合物や炭化水素系（天然、合成樹脂）などに代表され、機械的強度や加工性などを向上させる添加剤、紫外線吸収剤、老化防止剤、染料、加工助剤、イオントラップ剤、酸化防止剤、粘着付与剤、充填剤（金属化合物フィラー以外）、可塑剤、レベリング剤、発泡抑制剤、帯電防止割などがあげられる。 Examples of other additives include sensitizers that increase the curing speed and sensitivity by active energy rays typified by carbonyl compounds, adhesion promoters typified by silane coupling agents and ethylene oxide, and transparent protective films. Additives that improve wettability, acryloxy group compounds and hydrocarbons (natural and synthetic resins), and other additives that improve mechanical strength and processability, UV absorbers, anti-aging agents, dyes, Examples thereof include processing aids, ion trapping agents, antioxidants, tackifiers, fillers (other than metal compound fillers), plasticizers, leveling agents, foaming inhibitors, and antistatics.
本発明における硬化性組成物は、活性エネルギー線に反応性を示さない樹脂類（いわゆるイナートポリマー）、たとえばその他のエポキシ樹脂、フェノール樹脂、ウレタン樹脂、ポリエステル樹脂、ケトンホルムアルデヒド樹脂、クレゾール樹脂、キシレン樹脂、ジアリルフタレート樹脂、スチレン樹脂、グアナミン樹脂、天然及び合成ゴム、アクリル樹脂、ポリオレフィン樹脂、及びこれらの変性物を含むこともできる。 The curable composition in the present invention is a resin (so-called inert polymer) that does not react to active energy rays, such as other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins. Diallyl phthalate resin, styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin, and modified products thereof.
［偏光子］
本発明の偏光板に用いられるポリビニルアルコール系偏光子（３）について説明する。
偏光子を形成するポリビニルアルコール系樹脂としては、ポリビニルアルコール、エチレン・ビニルアルコール共重合体などが挙げられるが、耐水性の点から、エチレン・ビニルアルコール共重合体が好ましい。ポリビニルアルコールとしては、酢酸基が数十％残存している部分ケン化ポリビニルアルコールや、酢酸基が残存しない完全ケン化ポリビニルアルコールや、水酸基が変性された変性ポリビニルアルコールなどが挙げられるが、特に限定されるものではない。ポリビニルアルコール系樹脂は、１種単独で使用することも、あるいは２種以上を併用することもできる。
[Polarizer]
The polyvinyl alcohol-type polarizer (3) used for the polarizing plate of this invention is demonstrated.
Examples of the polyvinyl alcohol-based resin that forms the polarizer include polyvinyl alcohol and ethylene / vinyl alcohol copolymer. From the viewpoint of water resistance, an ethylene / vinyl alcohol copolymer is preferable. Examples of polyvinyl alcohol include partially saponified polyvinyl alcohol in which several tens of percent of acetate groups remain, fully saponified polyvinyl alcohol in which acetate groups do not remain, and modified polyvinyl alcohol in which hydroxyl groups have been modified. Is not to be done. A polyvinyl alcohol-type resin can be used individually by 1 type, or can also use 2 or more types together.
上記ポリビニルアルコールの具体例としては、（株）クラレ製のＲＳポリマーであるＲＳ−１１０（ケン化度＝９９％、重合度＝１，０００）、同社製のクラレポバールＬＭ−２０ＳＯ（ケン化度＝４０％、重合度＝２，０００）、日本合成化学工業（株）製のゴーセノールＮＭ−１４（ケン化度＝９９％、重合度＝１，４００）などが挙げられる。ポリビニルアルコールは、例えば、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル等の脂肪酸ビニルエステルの重合体を、アルカリ触媒等を用いてケン化して得られる。 Specific examples of the polyvinyl alcohol include RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (degree of saponification) manufactured by the same company. = 40%, polymerization degree = 2,000), Gohsenol NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, polymerization degree = 1,400), and the like. Polyvinyl alcohol is obtained, for example, by saponifying a polymer of a fatty acid vinyl ester such as vinyl acetate, vinyl propionate or vinyl pivalate using an alkali catalyst or the like.
上記エチレン・ビニルアルコール共重合体は、エチレンと酢酸ビニルとの共重合体のケン化物、すなわち、エチレン−酢酸ビニルランダム共重合体をケン化して得られるものであり、酢酸基が数十モル％残存している部分ケン化物から、酢酸基が数モル％しか残存していないかまたは酢酸基が残存しない完全ケン化物まで含み、特に限定されない。 The ethylene-vinyl alcohol copolymer is obtained by saponifying a copolymer of ethylene and vinyl acetate, that is, an ethylene-vinyl acetate random copolymer, and has an acetate group of several tens mol%. The remaining saponified product is not particularly limited, and includes a partially saponified product in which only a few mol% of acetic acid groups remain or no acetic acid group remains.
偏光子は、上述のポリビニルアルコール系樹脂をキャスティング成形法等の方法によって、成形することにより得られる。前記偏光子は、ホウ酸等による架橋や、延伸をされたものであってもよい。偏光子の形状としては、特に限定されないが、例えば、フィルム等が挙げられる。なお、本明細書において、「フィルム」の語は、厚みが小さいもの（厚みが１ｍｍ未満のもの）の他、厚手のシート（例えば、厚みが１〜５ｍｍのもの）も含むものとする。偏光子の厚さは、特に限定されないが、例えば、１０〜４０μｍ程度が好ましい。 The polarizer is obtained by molding the polyvinyl alcohol-based resin described above by a casting molding method or the like. The polarizer may be cross-linked or stretched with boric acid or the like. Although it does not specifically limit as a shape of a polarizer, For example, a film etc. are mentioned. In this specification, the term “film” includes not only a sheet having a small thickness (thickness of less than 1 mm) but also a thick sheet (for example, having a thickness of 1 to 5 mm). Although the thickness of a polarizer is not specifically limited, For example, about 10-40 micrometers is preferable.
[保護フィルム]
本発明の偏光板に用いられる保護フィルムについて説明する。
保護フィルムを構成する材料としては、例えば透明性、機械的強度、熱安定性、水分遮断性、等方性などに優れる熱可塑性樹脂が用いられる。このような熱可塑性樹脂の具体例としては、アクリル系樹脂、シクロオレフィン系樹脂が挙げられる。これらの樹脂から形成される保護フィルムは、トリアセチルセルロース等のセルロース樹脂、ポリエステル樹脂等から形成される保護フィルムに比して、難接着性である。
[Protective film]
The protective film used for the polarizing plate of this invention is demonstrated.
As a material constituting the protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is used. Specific examples of such thermoplastic resins include acrylic resins and cycloolefin resins. Protective films formed from these resins are less adhesive than protective films formed from cellulose resins such as triacetyl cellulose, polyester resins, and the like.
シクロオレフィン系樹脂は、環状オレフィンを重合単位として重合される樹脂の総称である。具体例としては、環状オレフィンの開環（共）重合体、環状オレフィンの付加重合体、環状オレフィンとエチレン、プロピレン等のα−オレフィンとその共重合体（代表的にはランダム共重合体）、および、これらを不飽和カルボン酸やその誘導体で変性したグラフト重合体、ならびに、それらの水素化物などが挙げられ、ノルボルネン系樹脂が好ましい。ノルボルネン系樹脂フィルムは、特開２００５−１６４６３２号公報、特開２００６−２０１７３６号公報、特開２００８−２３３２７９号公報等に記載された公知の方法により得ることができる。 The cycloolefin-based resin is a general term for resins that are polymerized using a cyclic olefin as a polymerization unit. Specific examples include ring-opening (co) polymers of cyclic olefins, addition polymers of cyclic olefins, cyclic olefins and α-olefins such as ethylene and propylene (typically random copolymers), And a graft polymer obtained by modifying these with an unsaturated carboxylic acid or a derivative thereof, a hydride thereof, or the like, and a norbornene-based resin is preferable. The norbornene resin film can be obtained by a known method described in JP-A No. 2005-164632, JP-A No. 2006-201736, JP-A No. 2008-233279, and the like.
シクロオレフィン系樹脂としては、種々の製品が市販されている。具体例としては、日本ゼオン株式会社製の商品名「ゼオノア」、ＪＳＲ株式会社製の商品名「アートン」、ＴＩＣＯＮＡ社製の商品名「トーパス」、三井化学株式会社製の商品名「ＡＰＥＬ」が挙げられる。 Various products are commercially available as cycloolefin resins. Specific examples include the product name “ZEONOR” manufactured by ZEON CORPORATION, the product name “ARTON” manufactured by JSR Corporation, the product name “TOPAS” manufactured by TICONA, and the product name “APEL” manufactured by Mitsui Chemicals, Inc. Can be mentioned.
アクリル系樹脂は、ポリメチルメタクリレートをはじめ、メチルメタクリレートやブチルメタクリレート等のアルキルエステル類の（メタ）アクリレートを主成分とする樹脂（＝共重合体）である。場合によっては、他の樹脂とブレンドされて、フィルム化される。アクリル系フィルムは、特開２００２−３６１７１２号公報等に記載された公知の方法により得ることができる。
アクリル系フィルムは、種々の製品が市販されている。具体例としては、三菱レイヨン社製の商品名「アクリプレン」や、カネカ社製の商品名「サンデュレン」が挙げられる。
The acrylic resin is a resin (= copolymer) mainly composed of (meth) acrylate of alkyl esters such as methyl methacrylate and butyl methacrylate as well as polymethyl methacrylate. In some cases, it is blended with another resin to form a film. The acrylic film can be obtained by a known method described in JP-A No. 2002-361712.
Various products are commercially available for the acrylic film. Specific examples include the product name “Acryprene” manufactured by Mitsubishi Rayon Co., Ltd. and the product name “Sanduren” manufactured by Kaneka Corporation.
本発明の偏光板に使用される保護フィルムは、（１）、（５）の両面とも同一組成であっても異なっていても良い。例えば、（１）にシクロオレフィン系樹脂フィルムを使用し、（５）に、アクリル系樹脂フィルムを使用しても何ら差し支えは無い。 The protective film used for the polarizing plate of the present invention may be the same or different on both sides of (1) and (5). For example, a cycloolefin resin film can be used for (1) and an acrylic resin film can be used for (5).
保護フィルムの厚さは、適宜に決定しうるが、一般には強度や取扱性等の作業性、薄層性などの点より１〜５００μｍ程度である。特に１〜３００μｍが好ましく、５〜２００μｍがより好ましい。透明保護フィルムは、５〜１５０μｍの場合に特に好適である。
なお、偏光子の両側に保護フィルムを設ける場合、その表裏で同じポリマー材料からなる保護フィルムを用いてもよく、異なるポリマー材料等からなる保護フィルムを用いてもよい。
Although the thickness of a protective film can be determined suitably, generally it is about 1-500 micrometers from points, such as workability | operativity, such as intensity | strength and handleability, and thin layer property. 1-300 micrometers is especially preferable, and 5-200 micrometers is more preferable. The transparent protective film is particularly suitable when the thickness is 5 to 150 μm.
In addition, when providing a protective film in the both sides of a polarizer, the protective film which consists of the same polymer material may be used by the front and back, and the protective film which consists of a different polymer material etc. may be used.
本発明の偏光板は、以下のようにして得ることができる。
即ち、第１の保護フィルム（１）の一方の面に、ガラス転移温度が−８０〜０℃の硬化物を形成し得るラジカル重合性組成物を塗工し、第１の硬化性接着剤層（２’）を形成し、
第２の保護フィルム（５）の一方の面に、ガラス転移温度が−８０〜０℃の硬化物を形成し得るラジカル重合性組成物を塗工し、第２の硬化性接着剤層（４’）を形成し、
次いで、ポリビニルアルコール系偏光子（３）の各面に、第１の硬化性接着剤層（２’）及び第２の硬化性接着剤層（４’）を、同時に／または順番に重ね合わせ、
第２の保護フィルム（５）の側から活性エネルギー線を照射し、第１の硬化性接着剤層（２’）及び第２の硬化性接着剤層（４’）を硬化することによって製造することが好ましい。
The polarizing plate of the present invention can be obtained as follows.
That is, a radically polymerizable composition capable of forming a cured product having a glass transition temperature of −80 to 0 ° C. is applied to one surface of the first protective film (1), and the first curable adhesive layer (2 ')
A radical polymerizable composition capable of forming a cured product having a glass transition temperature of −80 to 0 ° C. is applied to one surface of the second protective film (5), and the second curable adhesive layer (4 ') And form
Next, the first curable adhesive layer (2 ′) and the second curable adhesive layer (4 ′) are simultaneously and / or sequentially overlapped on each surface of the polyvinyl alcohol polarizer (3),
It is produced by irradiating active energy rays from the second protective film (5) side and curing the first curable adhesive layer (2 ′) and the second curable adhesive layer (4 ′). It is preferable.
以下、図２に基づいて、工程ごとに説明する。
［工程（ａ）］
工程（ａ）は、図２の（ａ）に示されるように、保護フィルム（１）および（５）のそれぞれ片面に、接着剤層形成用のラジカル重合性組成物を塗布し、必要に応じて乾燥等を行って、硬化性接着剤層（２’）、（４’）を具備する積層体（１’）、（５’）を得る工程である。
ラジカル重合性組成物の塗布方法としては、特に限定されないが、例えばダイコート法、ロールコート法、グラビアコート法、スピンコート法などが挙げられる。
Hereafter, it demonstrates for every process based on FIG.
[Step (a)]
In step (a), as shown in FIG. 2 (a), a radically polymerizable composition for forming an adhesive layer is applied to one side of each of the protective films (1) and (5). And drying, etc. to obtain laminates (1 ′) and (5 ′) having curable adhesive layers (2 ′) and (4 ′).
The application method of the radically polymerizable composition is not particularly limited, and examples thereof include a die coating method, a roll coating method, a gravure coating method, and a spin coating method.
［工程（ｂ）］
工程（ｂ）は、図２の（ｂ）に示されるように、ポリビニルアルコール系偏光子（３）の一方の面（図では上面）に、保護フィルム（１）と硬化性接着剤層（２’）とを具備する積層体（１’）を、
ポリビニルアルコール系偏光子（３）の他方の面（図では下面）に、保護フィルム（５）と硬化性接着剤層（４’）とを具備する積層体（５’）を、それぞれ重ね合わせる工程である。
[Step (b)]
In step (b), as shown in FIG. 2 (b), the protective film (1) and the curable adhesive layer (2) are formed on one surface (upper surface in the figure) of the polyvinyl alcohol polarizer (3). A laminate (1 ') comprising:
A step of superimposing a laminate (5 ′) comprising a protective film (5) and a curable adhesive layer (4 ′) on the other surface (lower surface in the figure) of the polyvinyl alcohol polarizer (3). It is.
［工程（ｃ）］
工程（ｃ）は、図２の（ｃ）に示されるように、活性エネルギー線（６）を照射することにより、保護フィルム（１）、（５）とポリビニルアルコール系偏光子（３）とに挟まれた硬化性接着剤層（２’）、（４’）を硬化させ、接着剤層（２），（４）を形成させる工程である。
図では、保護フィルム（５）の側から活性エネルギー線（６）を照射する場合を示すが、保護フィルム（１）の側から活性エネルギー線（６）を照射してもよいし、両側から同時に、または順次活性エネルギー線（６）を照射してもよい。
活性エネルギー線の照射量は、特に限定されるものではないが、波長２００〜４５０ｎｍ、照度１〜５００ｍＷ／ｃｍ2の光を、照射量が１０〜１０００ｍＪ／ｃｍ2となるように照射して露光することが好ましい。照射する活性エネルギー線の種類としては、可視光、紫外線、赤外線、Ｘ線、α線、β線、γ線等を用いることができるが、特に紫外線が好ましい。光の照射装置としては、例えば、高圧水銀ランプ、低圧水銀ランプ、メタルハライドランプ、エキシマランプ等を用いることが好ましい。
活性エネルギー線（６）照射後、室温で１週間程度エージングすることもできる。
工程（ｃ）を経ることにより、硬化性接着剤層（２’）、（４’）を硬化させて接着剤層（２），（４）とし、偏光子（３）と保護フィルム（１）および（５）とが接着剤層（２），（４）を介して接着されてなる偏光板が完成する（図１、図２中の（ｄ）参照）。
[Step (c)]
In the step (c), as shown in FIG. 2 (c), the active energy rays (6) are irradiated to the protective films (1) and (5) and the polyvinyl alcohol polarizer (3). This is a step of curing the sandwiched curable adhesive layers (2 ′) and (4 ′) to form adhesive layers (2) and (4).
Although the figure shows the case where the active energy ray (6) is irradiated from the protective film (5) side, the active energy ray (6) may be irradiated from the protective film (1) side or simultaneously from both sides. Alternatively, the active energy ray (6) may be sequentially irradiated.
The irradiation amount of the active energy ray is not particularly limited, but exposure is performed by irradiating light having a wavelength of 200 to 450 nm and an illuminance of 1 to 500 mW / cm 2 so that the irradiation amount is 10 to 1000 mJ / cm 2. It is preferable to do. Visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays and the like can be used as the type of active energy rays to be irradiated, and ultraviolet rays are particularly preferable. As the light irradiation device, for example, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, an excimer lamp, or the like is preferably used.
After irradiation with the active energy ray (6), it can be aged at room temperature for about one week.
Through the step (c), the curable adhesive layers (2 ′) and (4 ′) are cured to form adhesive layers (2) and (4), and the polarizer (3) and the protective film (1). And (5) are bonded through the adhesive layers (2) and (4) to complete a polarizing plate (see (d) in FIGS. 1 and 2).
また、本発明の偏光板は、ポリビニルアルコール系偏光子（３）の一方の面に、ガラス転移温度が−８０〜０℃の硬化物を形成し得るラジカル重合性組成物を塗工し、第１の硬化性接着剤層（２’）を形成し、形成された第１の硬化性接着剤層（２’）の表面を第１の保護フィルム（１）で覆い、次いでポリビニルアルコール系偏光子（３）の他方の面に、ガラス転移温度が−８０〜０℃の硬化物を形成し得るラジカル重合性組成物を塗工し、第２の硬化性接着剤層（４’）を形成し、形成された第２の硬化性接着剤層（４’）の表面を第２の保護フィルム（２）で覆い、それから、第２の保護フィルム（５）の側から活性エネルギー線を照射し、第１の硬化性接着剤層（２’）及び第２の硬化性接着剤層（４’）を硬化することによって製造することもできる。 In the polarizing plate of the present invention, a radically polymerizable composition capable of forming a cured product having a glass transition temperature of −80 to 0 ° C. is applied to one surface of the polyvinyl alcohol polarizer (3). 1 curable adhesive layer (2 ′) is formed, the surface of the formed first curable adhesive layer (2 ′) is covered with a first protective film (1), and then a polyvinyl alcohol polarizer On the other side of (3), a radical polymerizable composition capable of forming a cured product having a glass transition temperature of −80 to 0 ° C. is applied to form a second curable adhesive layer (4 ′). Covering the surface of the formed second curable adhesive layer (4 ′) with the second protective film (2), and then irradiating active energy rays from the side of the second protective film (5), Made by curing the first curable adhesive layer (2 ') and the second curable adhesive layer (4') It is also possible to.
［ポリビニルアルコール系偏光子］の製造例
ホウ酸２０重量部、ヨウ素０．２重量部、ヨウ化カリウム０．５重量部を水４８０重量部に溶解させて染色液を調製した。この染色液にＰＶＡフィルム（ビニロンフィルム＃４０、アイセロ社製）を、３０秒浸漬した後、フィルムを一方向に２倍に延伸し、乾燥させて、膜厚３０μｍのＰＶＡ偏光子を得た。
Production Example of [Polyvinyl Alcohol Polarizer] A dyeing solution was prepared by dissolving 20 parts by weight of boric acid, 0.2 parts by weight of iodine, and 0.5 parts by weight of potassium iodide in 480 parts by weight of water. A PVA film (Vinylon film # 40, manufactured by Aicello) was immersed in this dyeing solution for 30 seconds, and then the film was stretched twice in one direction and dried to obtain a PVA polarizer having a thickness of 30 μm.
[実施例１]
保護フィルム（１）、（５）として、シクロオレフィン系フィルム（ 日本ゼオン社（株）製の商品名「ゼオノアフィルムＺＦ−１４：１００μｍ」 ）を使用し、その表面に、３００Ｗ・ｍｉｎ／ｍ２の放電量でコロナ放電処理を行い、表面処理後１時間以内に、表１に示すラジカル重合組成物をワイヤーバーコーター＃３を用いて塗工し、硬化性接着剤層（２’）、（４’）を形成し、その硬化性接着剤層（２’）と（４’）との間に上記のＰＶＡ偏光子を挟み、保護フィルム（１）／硬化性接着剤層（２’）／ＰＶＡ系偏光子／硬化性接着剤層（４’）／保護フィルム（５）からなる積層体を得た。
保護フィルム（１）がブリキ板に接するように、この積層体の四方をセロハンテープで固定し、ブリキ板に固定した。
ＵＶ照射装置（東芝社製 高圧水銀灯）で最大照度５００ｍＷ／ｃｍ2、積算光量１０００ｍＪ／ｃｍ２の紫外線を保護フィルム（５）側から照射して、偏光板を作製した。
各接着剤層の厚みは、４μｍであり、下記の方法で求めた接着剤層（２）、（４）のＴｇは−４７℃だった。
なお、下記の方法により求めたラジカル重合組成物の酸価は、０（ｍｇＫＯＨ／ｇ）であった。
[Example 1]
As the protective films (1) and (5), a cycloolefin-based film (trade name “Zeonor film ZF-14: 100 μm” manufactured by Nippon Zeon Co., Ltd.) is used, and 300 W · min / m 2 on the surface thereof. The corona discharge treatment was performed at a discharge amount of 1 and within 1 hour after the surface treatment, the radical polymerization composition shown in Table 1 was applied using a wire
Four sides of this laminate were fixed with cellophane tape so that the protective film (1) was in contact with the tin plate, and was fixed to the tin plate.
A polarizing plate was produced by irradiating ultraviolet rays having a maximum illuminance of 500 mW / cm 2 and an integrated light quantity of 1000 mJ / cm 2 from the protective film (5) side with a UV irradiation apparatus (high pressure mercury lamp manufactured by Toshiba Corporation).
The thickness of each adhesive layer was 4 μm, and the Tg of the adhesive layers (2) and (4) determined by the following method was −47 ° C.
The acid value of the radical polymerization composition determined by the following method was 0 (mgKOH / g).
＜Ｔｇ：ガラス転移温度＞
各組成物を適当量プラスチック製の容器に入れ、紫外線を照射し、硬化させたもの、１０ｍｇを測定用試料とし、示差走査熱量計（ＤＳＣ）を用いて、２０℃/分の昇温速度で測定した。
<Tg: Glass transition temperature>
Appropriate amount of each composition is put in a plastic container, irradiated with ultraviolet rays and cured, 10 mg is used as a measurement sample, and a differential scanning calorimeter (DSC) is used at a heating rate of 20 ° C./min. It was measured.
＜酸価＞
共栓三角フラスコ中に試料（各組成物）約１ｇを精密に量り採り、トルエン／エタノール（容量比：トルエン／エタノール＝２／１）混合液１００ｍｌを加えて溶解する。これに、フェノールフタレイン試液を指示薬として加え、３０秒間保持する。その後、溶液が淡紅色を呈するまで０．１Ｎアルコール性水酸化カリウム溶液で滴定する。
酸価は次式により求めた。酸価は樹脂の乾燥状態の数値とした（単位：ｍｇＫＯＨ／ｇ）。
酸価（ｍｇＫＯＨ／ｇ）＝｛（５．６１１×ａ×Ｆ）／Ｓ｝
ただし、Ｓ：試料の採取量（ｇ）
ａ：０．１Ｎアルコール性水酸化カリウム溶液の消費量（ｍｌ）
Ｆ：０．１Ｎアルコール性水酸化カリウム溶液の力価
<Acid value>
About 1 g of a sample (each composition) is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. To this is added phenolphthalein reagent as an indicator and held for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red.
The acid value was determined by the following formula. The acid value was a numerical value of the dry state of the resin (unit: mgKOH / g).
Acid value (mgKOH / g) = {(5.611 × a × F) / S}
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
［実施例２]、［比較例１〜４]
ラジカル重合組成物を表１のように変えた以外は実施例１と同様にして偏光板を作製した。
[Example 2 ], [Comparative Examples 1-4]
A polarizing plate was produced in the same manner as in Example 1 except that the radical polymerization composition was changed as shown in Table 1.
[実施例３]
保護フィルム（１）、（５）として、アクリル系フィルム（三菱レイヨン（株）製の「アクリプレン ＨＢＤ−００２」、５０μｍ）をそれぞれ用いた以外は、実施例１と同様にして、偏光板を得、同様に評価した。
[Example 3 ]
A polarizing plate was obtained in the same manner as in Example 1 except that each of the protective films (1) and (5) was an acrylic film (“Acryprene HBD-002” manufactured by Mitsubishi Rayon Co., Ltd., 50 μm). , Evaluated in the same way.
[実施例４]
保護フィルム（１）として、アクリル系フィルム（三菱レイヨン（株）製の「アクリプレン ＨＢＤ−００２」：５０μｍ）を使用し、保護フィルム（５）として、シクロオレフィン系フィルム（日本ゼオン社（株）製の商品名「ゼオノアフィルムＺＦ−１４」：１００μｍ）をそれぞれ用いた以外は、実施例１と同様にして、偏光板を得、同様に評価した。
[Example 4 ]
An acrylic film (“Acryprene HBD-002” manufactured by Mitsubishi Rayon Co., Ltd . : 50 μm) is used as the protective film (1), and a cycloolefin film (manufactured by Nippon Zeon Co., Ltd.) is used as the protective film (5). A polarizing plate was obtained and evaluated in the same manner as in Example 1 except that the trade name “ZEONOR FILM ZF-14 ”: 100 μm ) was used.
＜接着力＞
得られた偏光板を、２５ｍｍ×１５０ｍｍのサイズにカッターを用いて裁断してサンプルとした。サンプルを両面粘着テープ（東洋インキ製造株式会社製ＤＦ８７１２Ｓ）によりガラス板上に貼り付けた。サンプル（偏光板）には、保護フィルムと偏光子の間に予め剥離のキッカケを設けておき、ピール角度９０度、ピール速度：３００ｍｍ／ｍｉｎ、常温（２３℃）にて測定した。表中の接着力は、
３．０（Ｎ／２５ｍｍ）以上・・・○
１．０（Ｎ／２５ｍｍ）以上〜３（Ｎ／２５ｍｍ）未満・・・△
１．０（Ｎ／２５ｍｍ）未満・・・×
<Adhesive strength>
The obtained polarizing plate was cut into a size of 25 mm × 150 mm using a cutter to obtain a sample. The sample was affixed on the glass plate with the double-sided adhesive tape (DF8712S by Toyo Ink Manufacturing Co., Ltd.). The sample (polarizing plate) was peeled off in advance between the protective film and the polarizer, and measured at a peel angle of 90 degrees, a peel rate of 300 mm / min, and normal temperature (23 ° C.). The adhesive strength in the table is
3.0 (N / 25mm) or more ... ○
1.0 (N / 25mm) or more to less than 3 (N / 25mm) ・ ・ ・ △
Less than 1.0 (N / 25mm) ... ×
＜打ち抜き加工性＞
ダンベル社製の１００ｍｍ×１００ｍｍの刃を用い、作製した偏光板を保護フィルム（１）側から打ち抜いた。
打ち抜いた偏光板の周辺の剥がれ状態を目視で観察した。偏光板の面積（１００ｃｍ２）に対して剥がれた面積の割合（％）が０〜１％未満のものを◎、１〜３％未満のものを○、剥離面積が３％以上のものを×とした。
<Punching workability>
The produced polarizing plate was punched out from the protective film (1) side using a 100 mm × 100 mm blade manufactured by Dumbbell.
The state of peeling around the punched polarizing plate was visually observed. When the ratio (%) of the peeled area to the polarizing plate area (100 cm 2 ) is 0 to less than 1%, ◎, less than 1 to 3% are good, and peeled area is 3% or more. It was.
＜収縮率＞
上記偏光板小片を６０℃−ドライと６０℃−９０ＲＨ％の恒温恒湿機中にそれぞれ６０時間放置した後の延伸方向の縮み量を測定し、元の長さ（１００ｍｍ）に対する縮み量の割合を収縮率とし求めた。
収縮率が０．２％以下のものを◎、０．２％より大きくて０．４％以下ものを○、０．４％を超えるものを×とした。
<Shrinkage rate>
The amount of contraction in the stretching direction after the polarizing plate pieces were left in a constant temperature and humidity chamber of 60 ° C.-dry and 60 ° C.-90 RH% for 60 hours was measured, and the ratio of the contraction amount to the original length (100 mm) Was determined as the shrinkage rate.
A sample having a shrinkage ratio of 0.2% or less was rated as ◎, a sample having a shrinkage rate of more than 0.2% and not more than 0.4% was evaluated as ◯, and a sample having a shrinkage rate exceeding 0.4% was evaluated as ×.
表１から、実施例１〜４の偏光板は、打ち抜き加工性と収縮率が共に優れていることがわかる。一方、比較例１〜４の偏光板は、打ち抜き加工性または収縮率のどちらかが劣る。 From Table 1, it can be seen that the polarizing plates of Examples 1 to 4 are excellent in both punching workability and shrinkage. On the other hand, the polarizing plates of Comparative Examples 1 to 4 are inferior in either punching workability or shrinkage.
（１）第１の保護フィルム
（１’）第１の保護フィルム（１）と硬化性接着剤層（２’）とを具備する積層体
（２）第１の接着剤層
（２’）硬化性組成物（Ａ）から形成された硬化性接着剤層
（３）ポリビニルアルコール系偏光子
（４）第２の接着剤層
（４’）硬化性組成物（Ｂ）から形成された硬化性接着剤層
（５）第２の保護フィルム
（５’）第２の保護フィルム（５）と硬化性接着剤層（４’）とを具備する積層体
（６）活性エネルギー線
(1) First protective film (1 ′) Laminate comprising first protective film (1) and curable adhesive layer (2 ′) (2) First adhesive layer (2 ′) cured Curable Adhesive Layer (3) Polyvinyl Alcohol Polarizer (4) Second Adhesive Layer (4 ′) Curable Adhesive Formed from Curable Composition (B) Laminate (6) Active energy ray comprising agent layer (5) second protective film (5 ′) second protective film (5) and curable adhesive layer (4 ′)
Claims (3)
アクリル系フィルム及びシクロオレフィン系フィルムからなる群より選ばれる第１の保護フィルム（１）の一方の面に、４−ヒドロキシブチルアクリレート：２０〜９０重量％、ω-カルボキシ-ポリカプロラクトンアクリレート：１〜７０重量％、その他のラジカル重合性化合物：０〜１５重量％、光重合開始剤：０．０１〜２０重量％、シランカップリング剤：０〜１０重量％を含有し、酸価が０．１〜２００ｍｇＫＯＨ／ｇのラジカル重合性組成物を塗工し、第１の硬化性接着剤層（２’）を形成し、
アクリル系フィルム及びシクロオレフィン系フィルムからなる群より選ばれる第２の保護フィルム（５）の一方の面に、４−ヒドロキシブチルアクリレート：２０〜９０重量％、ω-カルボキシ-ポリカプロラクトンアクリレート：１〜７０重量％、その他のラジカル重合性化合物：０〜１５重量％、光重合開始剤：０．０１〜２０重量％、シランカップリング剤：０〜１０重量％を含有し、酸価が０．１〜２００ｍｇＫＯＨ／ｇのラジカル重合性組成物を塗工し、第２の硬化性接着剤層（４’）を形成し、
ポリビニルアルコール系偏光子（３）の各面に、第１の硬化性接着剤層（２’）及び第２の硬化性接着剤層（４’）を、同時に／または順番に重ね合わせ、
第１の保護フィルム（１）及び／または第２の保護フィルム（５）の側から活性エネルギー線を照射することを特徴とする、偏光板の製造方法。 The first protective film (1), the first adhesive layer (2), the polyvinyl alcohol polarizer (3), the second adhesive layer (4) and the second protective film (5) are in this order. A method for producing a laminated polarizing plate,
On one surface of the first protective film (1) selected from the group consisting of an acrylic film and a cycloolefin film, 4-hydroxybutyl acrylate: 20 to 90% by weight, ω-carboxy-polycaprolactone acrylate: 1 to 70% by weight, other radical polymerizable compound: 0 to 15% by weight, photopolymerization initiator: 0.01 to 20% by weight, silane coupling agent: 0 to 10% by weight, with an acid value of 0.1 Applying a radically polymerizable composition of ~ 200 mg KOH / g to form a first curable adhesive layer (2 ');
On one surface of the second protective film (5) selected from the group consisting of an acrylic film and a cycloolefin film, 4-hydroxybutyl acrylate: 20 to 90% by weight, ω-carboxy-polycaprolactone acrylate: 1 to 70% by weight, other radical polymerizable compound: 0 to 15% by weight, photopolymerization initiator: 0.01 to 20% by weight, silane coupling agent: 0 to 10% by weight, with an acid value of 0.1 Applying a radically polymerizable composition of ~ 200 mg KOH / g to form a second curable adhesive layer (4 ');
A first curable adhesive layer (2 ′) and a second curable adhesive layer (4 ′) are simultaneously and / or sequentially overlapped on each surface of the polyvinyl alcohol polarizer (3),
A method for producing a polarizing plate, comprising irradiating active energy rays from the first protective film (1) and / or the second protective film (5) side.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009137764A JP4428470B1 (en) | 2009-06-08 | 2009-06-08 | Polarizing plate and adhesive composition for forming polarizing plate |
| TW099106721A TWI348035B (en) | 2009-06-08 | 2010-03-09 | Polarizing plate and adhesive composition for forming polarizing plate |
| KR1020100026128A KR100973677B1 (en) | 2009-06-08 | 2010-03-24 | Polarizing plate and adhesive composition for polarizing plate |
| CN2010101558680A CN101907737B (en) | 2009-06-08 | 2010-04-02 | Polarizing plate and adhesive composition for polarizing plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009137764A JP4428470B1 (en) | 2009-06-08 | 2009-06-08 | Polarizing plate and adhesive composition for forming polarizing plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP4428470B1 true JP4428470B1 (en) | 2010-03-10 |
| JP2010282161A JP2010282161A (en) | 2010-12-16 |
Family
ID=42072732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009137764A Active JP4428470B1 (en) | 2009-06-08 | 2009-06-08 | Polarizing plate and adhesive composition for forming polarizing plate |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4428470B1 (en) |
| KR (1) | KR100973677B1 (en) |
| CN (1) | CN101907737B (en) |
| TW (1) | TWI348035B (en) |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8094034B2 (en) | 2007-09-18 | 2012-01-10 | Georgia Tech Research Corporation | Detecting actuation of electrical devices using electrical noise over a power line |
| US9766277B2 (en) | 2009-09-25 | 2017-09-19 | Belkin International, Inc. | Self-calibrating contactless power consumption sensing |
| JP5881695B2 (en) | 2010-07-02 | 2016-03-09 | ベルキン・インターナショナル・インコーポレイテッド | System and method for measuring power usage in a structure and system and method for calibrating the same |
| US9291694B2 (en) | 2010-07-02 | 2016-03-22 | Belkin International, Inc. | System and method for monitoring electrical power usage in an electrical power infrastructure of a building |
| JP5980223B2 (en) * | 2011-10-21 | 2016-08-31 | 日本化薬株式会社 | UV curable resin composition, cured product and article |
| KR101908290B1 (en) * | 2012-04-03 | 2018-10-16 | 동우 화인켐 주식회사 | Double-sided pressure-sensitive adhesive sheet And Display device comprising the same |
| CN104428331B (en) * | 2012-07-11 | 2019-02-15 | 东洋油墨Sc控股株式会社 | Active energy beam polymer resin composition and the laminated body for using the resin combination |
| CN107286856A (en) * | 2012-10-19 | 2017-10-24 | 琳得科株式会社 | Adhesive composition and bonding sheet |
| KR20140074581A (en) * | 2012-12-10 | 2014-06-18 | 동우 화인켐 주식회사 | Acrylic copolymer and adhesive composition comprising the same and polarising plate using the same |
| WO2014129841A1 (en) * | 2013-02-21 | 2014-08-28 | 주식회사 엘지화학 | Method for manufacturing double-sided polarizing plate and double-sided polarizing plate manufactrured by same |
| KR101627904B1 (en) * | 2013-02-21 | 2016-06-13 | 주식회사 엘지화학 | Method for preparing Polarizer having Protection films in two sides and Polarizer having Protection films in two sides therefrom |
| KR101503216B1 (en) | 2013-06-18 | 2015-03-17 | 주식회사 엘지화학 | Radical Curable Adhesive Composition and Polarizing Plate comprising the same |
| EP2840124B1 (en) * | 2013-06-18 | 2019-01-30 | LG Chem, Ltd. | Radical-curable adhesive composition and polarizing plate comprising same |
| WO2015022825A1 (en) | 2013-08-12 | 2015-02-19 | 日本合成化学工業株式会社 | Adhesive agent composition, adhesive agent composition for polarizing plate, adhesive agent for polarizing plate, and polarizing plate manufactured using said adhesive agent |
| KR101687872B1 (en) * | 2013-09-30 | 2016-12-19 | 주식회사 엘지화학 | Radical curable adhesive composition and polarizing plate comprising the same |
| KR101496617B1 (en) * | 2013-09-30 | 2015-02-25 | 주식회사 엘지화학 | Polarizing Plate |
| WO2015046814A1 (en) * | 2013-09-30 | 2015-04-02 | 주식회사 엘지화학 | Radical curing adhesive composition and polarizing plate comprising same |
| WO2015046816A1 (en) * | 2013-09-30 | 2015-04-02 | 주식회사 엘지화학 | Polarizing plate and image display device comprising same |
| KR101650235B1 (en) * | 2013-09-30 | 2016-08-22 | 주식회사 엘지화학 | Polarizing Plate |
| KR101620164B1 (en) * | 2013-09-30 | 2016-05-12 | 주식회사 엘지화학 | Radical Curable Adhesive Composition And Polarizing Plate Comprising The Same |
| KR101732228B1 (en) * | 2013-09-30 | 2017-05-02 | 주식회사 엘지화학 | Polarizing plate and image display apparatus comprising the same |
| KR101685257B1 (en) | 2013-09-30 | 2016-12-09 | 주식회사 엘지화학 | Radical curable adhesive composition and polarizing plate comprising the same |
| KR101620188B1 (en) | 2013-09-30 | 2016-05-12 | 주식회사 엘지화학 | Polarizing plate and image display apparatus comprising the same |
| KR101666703B1 (en) * | 2013-10-31 | 2016-10-17 | 주식회사 엘지화학 | Polarizing plate and display device comprising the same |
| US20160333234A1 (en) * | 2014-01-30 | 2016-11-17 | Zeon Corporation | Laminate and polarizing plate |
| WO2015182631A1 (en) | 2014-05-27 | 2015-12-03 | 日本合成化学工業株式会社 | Adhesive composition, adhesive composition for polarizing plates, adhesive for polarizing plates, and polarizing plate formed using same |
| CN111458783B (en) * | 2014-07-16 | 2022-02-11 | 日东电工株式会社 | Polarizing film and method for producing same |
| JP6701697B2 (en) * | 2014-12-04 | 2020-05-27 | 三菱ケミカル株式会社 | Adhesive composition for polarizing plate, adhesive for polarizing plate, and polarizing plate using the same |
| JP6868344B2 (en) | 2016-04-20 | 2021-05-12 | 日東電工株式会社 | Polarizing film and its manufacturing method, optical film and image display device |
| JP6868343B2 (en) | 2016-04-20 | 2021-05-12 | 日東電工株式会社 | Polarizing film and its manufacturing method, optical film and image display device |
| CN110462473B (en) * | 2017-03-29 | 2021-12-21 | 日东电工株式会社 | Adhesive layer-attached single-sided protective polarizing film, image display device, and continuous production method therefor |
| US20220229330A1 (en) * | 2019-10-31 | 2022-07-21 | Lg Chem, Ltd. | Polarizing plate laminate and method for preparing same |
| WO2023080517A1 (en) * | 2021-11-05 | 2023-05-11 | 주식회사 엘지화학 | Uv-curable adhesive agent composition, adhesive film including same, polarization film including same, and display device including polarization film |
| JP7491457B1 (en) | 2023-11-24 | 2024-05-28 | ａｒｔｉｅｎｃｅ株式会社 | Active energy ray curable adhesive and laminate |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000098370A (en) * | 1998-09-28 | 2000-04-07 | Bridgestone Corp | Adhesive composition for liquid crystal display device and liquid crystal display device |
| JP2003277697A (en) * | 2002-03-22 | 2003-10-02 | Bridgestone Corp | Photocurable adhesive sheet and method for producing optical information-recording medium using the same |
| JP2005281338A (en) * | 2004-03-26 | 2005-10-13 | Nippon Shokubai Co Ltd | Adhesive composition |
| JP2005344022A (en) * | 2004-06-03 | 2005-12-15 | Emulsion Technology Co Ltd | Aqueous resin emulsion composition for bonding cycloolefinic resin molded product, dry film, method for bonding and cycloolefinic resin laminate |
| JP2006219526A (en) * | 2005-02-08 | 2006-08-24 | Nitto Denko Corp | Adhesive composition for optical members, adhesive layer for optical member and production method thereof, optical member with adhesive, and image display |
| JP2007238853A (en) * | 2006-03-10 | 2007-09-20 | Toyo Ink Mfg Co Ltd | Adhesive composition and adhesive film produced by using the adhesive composition |
| JP2008013634A (en) * | 2006-07-04 | 2008-01-24 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition and surface protective film for optical member |
| JP2008065251A (en) * | 2006-09-11 | 2008-03-21 | Dainippon Printing Co Ltd | Polarizing plate |
| JP2008297363A (en) * | 2007-05-29 | 2008-12-11 | Toyo Ink Mfg Co Ltd | Polyester resin and pressure-sensitive adhesive composition |
| JP2009007544A (en) * | 2007-05-29 | 2009-01-15 | Toyo Ink Mfg Co Ltd | Polyester resin and pressure-sensitive adhesive composition |
| JP2009057550A (en) * | 2007-08-06 | 2009-03-19 | Hitachi Chem Co Ltd | Adhesive material |
| JP2009173877A (en) * | 2007-12-27 | 2009-08-06 | Nippon Synthetic Chem Ind Co Ltd:The | Adhesive for optical member and optical member with adhesive layer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200535517A (en) * | 2003-12-26 | 2005-11-01 | Zeon Corp | Polarizing plate protective film, polarizing plate with reflection preventing function and optical product |
-
2009
- 2009-06-08 JP JP2009137764A patent/JP4428470B1/en active Active
-
2010
- 2010-03-09 TW TW099106721A patent/TWI348035B/en active
- 2010-03-24 KR KR1020100026128A patent/KR100973677B1/en active IP Right Grant
- 2010-04-02 CN CN2010101558680A patent/CN101907737B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000098370A (en) * | 1998-09-28 | 2000-04-07 | Bridgestone Corp | Adhesive composition for liquid crystal display device and liquid crystal display device |
| JP2003277697A (en) * | 2002-03-22 | 2003-10-02 | Bridgestone Corp | Photocurable adhesive sheet and method for producing optical information-recording medium using the same |
| JP2005281338A (en) * | 2004-03-26 | 2005-10-13 | Nippon Shokubai Co Ltd | Adhesive composition |
| JP2005344022A (en) * | 2004-06-03 | 2005-12-15 | Emulsion Technology Co Ltd | Aqueous resin emulsion composition for bonding cycloolefinic resin molded product, dry film, method for bonding and cycloolefinic resin laminate |
| JP2006219526A (en) * | 2005-02-08 | 2006-08-24 | Nitto Denko Corp | Adhesive composition for optical members, adhesive layer for optical member and production method thereof, optical member with adhesive, and image display |
| JP2007238853A (en) * | 2006-03-10 | 2007-09-20 | Toyo Ink Mfg Co Ltd | Adhesive composition and adhesive film produced by using the adhesive composition |
| JP2008013634A (en) * | 2006-07-04 | 2008-01-24 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition and surface protective film for optical member |
| JP2008065251A (en) * | 2006-09-11 | 2008-03-21 | Dainippon Printing Co Ltd | Polarizing plate |
| JP2008297363A (en) * | 2007-05-29 | 2008-12-11 | Toyo Ink Mfg Co Ltd | Polyester resin and pressure-sensitive adhesive composition |
| JP2009007544A (en) * | 2007-05-29 | 2009-01-15 | Toyo Ink Mfg Co Ltd | Polyester resin and pressure-sensitive adhesive composition |
| JP2009057550A (en) * | 2007-08-06 | 2009-03-19 | Hitachi Chem Co Ltd | Adhesive material |
| JP2009173877A (en) * | 2007-12-27 | 2009-08-06 | Nippon Synthetic Chem Ind Co Ltd:The | Adhesive for optical member and optical member with adhesive layer |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201044034A (en) | 2010-12-16 |
| CN101907737A (en) | 2010-12-08 |
| JP2010282161A (en) | 2010-12-16 |
| CN101907737B (en) | 2013-03-27 |
| TWI348035B (en) | 2011-09-01 |
| KR100973677B1 (en) | 2010-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4428470B1 (en) | Polarizing plate and adhesive composition for forming polarizing plate | |
| JP5459128B2 (en) | Polarizing plate and light curable adhesive for polarizing plate formation | |
| KR102309118B1 (en) | Optical film with adhesive on both sides and method for fabrication of image display device employing same, and method of suppressing curling of optical film with adhesive on both sides | |
| KR102249906B1 (en) | Image display device | |
| JP5402419B2 (en) | Ultraviolet curable composition, polarizing plate using the same, and method for producing the same | |
| JP5332599B2 (en) | Polarizing plate, manufacturing method thereof, and composite polarizing plate using the same | |
| JP6122337B2 (en) | Polarizing film and method for manufacturing the same, optical film and image display device | |
| JP5429777B2 (en) | Polarizer | |
| KR102525401B1 (en) | Polarizing plate, liquid crystal panel and liquid crystal display device | |
| JP2010286737A (en) | Polarizing plate and manufacturing method of the same | |
| JP2013072951A (en) | Polarizing plate and method for manufacturing the same | |
| JP2017211434A (en) | Laminate film and image display device | |
| JP6172302B2 (en) | Polarizing plate, liquid crystal panel, and liquid crystal display device | |
| JP6481059B2 (en) | Polarizing film and method for manufacturing the same, optical film and image display device | |
| JP2010197978A (en) | Optical protective film and method of manufacturing the same, and polarizing plate and method of manufacturing the same | |
| JPWO2019003679A1 (en) | Polarizer | |
| JP2008197310A (en) | Thin polarizing plate, composite polarizing plate, image display device, and method for manufacturing composite polarizing plate | |
| WO2014162977A1 (en) | Polarizing plate | |
| JP2021060575A (en) | Flexible image display device and optical laminate used therefor | |
| WO2021131152A1 (en) | Decorative laminated body, optical laminated body, and flexible image display device | |
| JP6825848B2 (en) | Polarizing plate for curved image display panel | |
| JP2013035968A (en) | Photocurable adhesive for forming polarizing plate and polarizing plate | |
| JP2021060576A (en) | Flexible image display device and optical laminate used therefor | |
| JP2017134413A (en) | Polarizing film and production method of the same, optical film, and image display device | |
| JP6903830B1 (en) | Flexible image display device and optical laminate used for it |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121225 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4428470 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20091207 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121225 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121225 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131225 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |