JP5221893B2 - Method for producing laminated film - Google Patents
Method for producing laminated film Download PDFInfo
- Publication number
- JP5221893B2 JP5221893B2 JP2007122698A JP2007122698A JP5221893B2 JP 5221893 B2 JP5221893 B2 JP 5221893B2 JP 2007122698 A JP2007122698 A JP 2007122698A JP 2007122698 A JP2007122698 A JP 2007122698A JP 5221893 B2 JP5221893 B2 JP 5221893B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- epoxy resin
- light
- laminated
- films
- 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
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- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 229920000647 polyepoxide Polymers 0.000 claims description 58
- 239000003822 epoxy resin Substances 0.000 claims description 57
- 239000000853 adhesive Substances 0.000 claims description 53
- 230000001070 adhesive effect Effects 0.000 claims description 53
- 238000010438 heat treatment Methods 0.000 claims description 25
- 230000003287 optical effect Effects 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 4
- -1 Triphenylsulfonium hexafluorophosphate Chemical compound 0.000 description 26
- 239000000126 substance Substances 0.000 description 8
- 125000003700 epoxy group Chemical group 0.000 description 7
- 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 7
- 238000000034 method Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 229910001507 metal halide Inorganic materials 0.000 description 6
- 150000005309 metal halides Chemical class 0.000 description 6
- 239000003504 photosensitizing agent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 5
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 4
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 4
- BIDWUUDRRVHZLQ-UHFFFAOYSA-N 3-ethyl-3-(2-ethylhexoxymethyl)oxetane Chemical compound CCCCC(CC)COCC1(CC)COC1 BIDWUUDRRVHZLQ-UHFFFAOYSA-N 0.000 description 4
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000004844 aliphatic epoxy resin Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 150000002921 oxetanes Chemical class 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- JTINZFQXZLCHNS-UHFFFAOYSA-N 2,2-bis(oxiran-2-ylmethoxymethyl)butan-1-ol Chemical compound C1OC1COCC(CO)(CC)COCC1CO1 JTINZFQXZLCHNS-UHFFFAOYSA-N 0.000 description 3
- FNYWFRSQRHGKJT-UHFFFAOYSA-N 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane Chemical compound C1OCC1(CC)COCC1(CC)COC1 FNYWFRSQRHGKJT-UHFFFAOYSA-N 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
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- 230000006866 deterioration Effects 0.000 description 3
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XUVKSPPGPPFPQN-UHFFFAOYSA-N 10-Methyl-9(10H)-acridone Chemical compound C1=CC=C2N(C)C3=CC=CC=C3C(=O)C2=C1 XUVKSPPGPPFPQN-UHFFFAOYSA-N 0.000 description 2
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 2
- JUXZNIDKDPLYBY-UHFFFAOYSA-N 3-ethyl-3-(phenoxymethyl)oxetane Chemical compound C=1C=CC=CC=1OCC1(CC)COC1 JUXZNIDKDPLYBY-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 2
- KSMGAOMUPSQGTB-UHFFFAOYSA-N 9,10-dibutoxyanthracene Chemical compound C1=CC=C2C(OCCCC)=C(C=CC=C3)C3=C(OCCCC)C2=C1 KSMGAOMUPSQGTB-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 1
- VLTYTTRXESKBKI-UHFFFAOYSA-N (2,4-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 VLTYTTRXESKBKI-UHFFFAOYSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- QFDDZIRGHKFRMR-UHFFFAOYSA-N 10-butylacridin-9-one Chemical compound C1=CC=C2N(CCCC)C3=CC=CC=C3C(=O)C2=C1 QFDDZIRGHKFRMR-UHFFFAOYSA-N 0.000 description 1
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- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- FVCHRIQAIOHAIC-UHFFFAOYSA-N 2-[1-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COC(C)COCC1CO1 FVCHRIQAIOHAIC-UHFFFAOYSA-N 0.000 description 1
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- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- FPKCTSIVDAWGFA-UHFFFAOYSA-N 2-chloroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3C(=O)C2=C1 FPKCTSIVDAWGFA-UHFFFAOYSA-N 0.000 description 1
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- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- LMIOYAVXLAOXJI-UHFFFAOYSA-N 3-ethyl-3-[[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(CC)COC2)C=CC=1COCC1(CC)COC1 LMIOYAVXLAOXJI-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
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- 239000002841 Lewis acid Substances 0.000 description 1
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- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- UUJZSXVOPPFFOT-UHFFFAOYSA-N bis(4-methylphenyl)-(9-oxo-7-propan-2-ylthioxanthen-2-yl)sulfanium Chemical compound C1=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=CC=C1[S+](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 UUJZSXVOPPFFOT-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- OHZRFQFGSXWZPT-UHFFFAOYSA-N methyl-[3-(oxiran-2-ylmethoxy)propyl]-silylsilane Chemical compound C(C1CO1)OCCC[SiH]([SiH3])C OHZRFQFGSXWZPT-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 125000005440 p-toluyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C(*)=O)C([H])([H])[H] 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- KEDGSDIAPIAOGT-UHFFFAOYSA-N triethoxy-[3-[(3-ethyloxetan-2-yl)methoxy]propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1OCC1CC KEDGSDIAPIAOGT-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- 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
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
Description
本発明は、広い分野において使用できる積層フィルムの製造方法、詳細には、光硬化型エポキシ樹脂系接着剤を用いたフィルムの貼り合わせからなる積層フィルムの製造方法に関する。 The present invention relates to a method for producing a laminated film that can be used in a wide range of fields, and more particularly, to a method for producing a laminated film comprising laminating films using a photocurable epoxy resin adhesive.
積層フィルムは、自動車、航空機、電気・電子機器を含む広い分野において用いられている。特に、近年では、電気・電子機器における積層フィルムは、ますます多様で高度化している。積層フィルムの多様化、高度化とともに、積層フィルムの製造方法に関しても、製造される積層フィルムの品質を維持しながら、生産性の向上、歩留りの向上、装置の簡略化、自動化などが求められている。 Laminated films are used in a wide range of fields including automobiles, aircraft, and electrical / electronic devices. In particular, in recent years, laminated films in electrical and electronic equipment have become increasingly diverse and sophisticated. With the diversification and sophistication of laminated films, the production method of laminated films is also required to improve productivity, improve yield, simplify equipment, and automate while maintaining the quality of the produced laminated films. Yes.
例えば、光学部材や液晶表示装置において用いられる偏光板は、ポリビニルアルコール(PVA)系偏光子フィルムの両面に保護フィルムもしくは光学補償フィルムを接着剤で貼り合せて製造されるのが一般的である。かかる接着剤として、水系接着剤や有機溶剤系の接着剤が使用されてきたが、これらに代わりに、近年、非水系、非有機溶剤系である非溶剤系接着剤、特に光硬化型エポキシ樹脂系接着剤が使用されるようになってきている。 For example, a polarizing plate used in an optical member or a liquid crystal display device is generally manufactured by bonding a protective film or an optical compensation film with an adhesive on both surfaces of a polyvinyl alcohol (PVA) polarizer film. As such adhesives, water-based adhesives and organic solvent-based adhesives have been used. However, in recent years, non-solvent-based adhesives that are non-aqueous and non-organic solvent-based, in particular, photo-curable epoxy resins. System adhesives have been used.
従来、接着剤として光硬化型エポキシ樹脂系接着剤を用いる積層フィルムの製造においては、光硬化型エポキシ樹脂系接着剤を十分に硬化するために、強い照度の光を照射して照射熱や反応熱で硬化反応を加速するか、あるいは、光照射後にオーブン等により加熱して硬化反応を完結(アフターキュア)する必要があった。光硬化型エポキシ樹脂系接着剤は光照射されると、それに含まれる光重合開始剤(触媒)が活性化し、酸を発生する。この酸が光硬化型エポキシ樹脂のエポキシ基と反応し、エポキシ基が開環してカルボカチオンが生成する。このカルボカチオンが次々とエポキシ樹脂のエポキシ基と反応してエポキシ樹脂系接着剤が硬化する。ところが、カルボカチオンとエポキシ基の反応は常温では起こりにくい反応であるため、強い照度の光を照射するか、あるいは、光照射後にオーブン等により加熱して、カルボカチオンとエポキシ基の反応を加速又は完結する必要があった。 Conventionally, in the production of laminated films that use a photo-curable epoxy resin adhesive as an adhesive, in order to sufficiently cure the photo-curable epoxy resin adhesive, irradiation with intense illumination and irradiation heat and reaction It was necessary to accelerate the curing reaction with heat, or to complete the curing reaction (after cure) by heating in an oven after light irradiation. When the photocurable epoxy resin adhesive is irradiated with light, the photopolymerization initiator (catalyst) contained therein is activated to generate an acid. This acid reacts with the epoxy group of the photocurable epoxy resin, and the epoxy group is ring-opened to generate a carbocation. This carbocation reacts with the epoxy group of the epoxy resin one after another to cure the epoxy resin adhesive. However, since the reaction between the carbocation and the epoxy group is difficult to occur at room temperature, the reaction between the carbocation and the epoxy group is accelerated or accelerated by irradiating light with strong illuminance or by heating in an oven after the light irradiation. It was necessary to complete.
強い照度の光を照射すると、光が熱に変り、例えば、偏光子フィルムの場合には、ヨウ素などで染色したポリビニルアルコールフィルム(偏向子フィルム)からヨウ素抜けが起こったり、あるいは偏光子フィルムや保護フィルム又は光学補償フィルムが変形したりして、品質が劣化する。 When light with strong illuminance is irradiated, the light changes to heat. For example, in the case of a polarizer film, iodine loss occurs from a polyvinyl alcohol film (polarizer film) dyed with iodine, or the polarizer film or protection. The film or the optical compensation film is deformed and the quality is deteriorated.
また、光照射後にオーブン等で加熱する場合には、加熱オーブン等の加熱装置が必要となり、特にラインスピードが速い場合には、加熱オーブンが非常に長くなり、ランニングコストが上昇し、設備投資費用がかさんでくる。 In addition, when heating in an oven after light irradiation, a heating device such as a heating oven is required. Especially when the line speed is high, the heating oven becomes very long, the running cost increases, and the capital investment cost increases. Come in.
本発明の目的は、光硬化型エポキシ樹脂系接着剤を十分に硬化するために強い照度の光を照射したり、光照射後に加熱(アフターキュア)をしたりする必要がない、光硬化型エポキシ樹脂系接着剤を用いたフィルムの貼り合わせからなる積層フィルムの製造方法を提供することである。 The object of the present invention is to provide a photo-curable epoxy that does not require irradiation with strong illuminance light or sufficient heating (after-cure) after light irradiation to sufficiently cure the photo-curable epoxy resin adhesive. It is providing the manufacturing method of the laminated | multilayer film which consists of bonding of the film using a resin adhesive.
本発明者等は、上述した課題を解決すべく鋭意検討したところ、光を照射する前に光硬化型エポキシ樹脂系接着剤を特定の温度に加温することにより前記課題を達成できることを見出し、これらの知見に基づいて本発明を完成するに至った。 The present inventors have intensively studied to solve the above-mentioned problems, and found that the problems can be achieved by heating the photocurable epoxy resin adhesive to a specific temperature before irradiating with light. The present invention has been completed based on these findings.
本発明によれば、以下の1〜4の発明が提供される。 According to the present invention, the following inventions 1 to 4 are provided.
(1)光硬化型エポキシ樹脂系接着剤を用いたフィルムの貼り合わせからなる積層フィルムの製造方法であって、フィルム間に存在する光硬化型エポキシ樹脂系接着剤を40℃以上の温度に加温し、これに光を照射して硬化させてフィルムを接着することを含む方法。 (1) A method for producing a laminated film comprising laminating films using a photocurable epoxy resin adhesive, wherein the photocurable epoxy resin adhesive existing between the films is added to a temperature of 40 ° C. or higher. Heating and irradiating it with light to cure and bonding the film.
(2)光カチオン硬化型エポキシ樹脂系接着剤を用いて偏光子フィルムと保護フィルム及び/又は光学補償フィルムとを貼り合わせてなるフィルムの接着方法であって、フィルム間に存在する光カチオン硬化型エポキシ樹脂系接着剤を40℃以上でかつ前記フィルムの耐熱温度以下の温度に加温し、これに光を照射して硬化させてフィルムを接着することを含む方法。 (2) A method of adhering a film obtained by laminating a polarizer film and a protective film and / or an optical compensation film using a photocationic curable epoxy resin adhesive, wherein the photocationic curable type exists between the films. A method comprising heating an epoxy resin adhesive to a temperature not lower than 40 ° C. and not higher than a heat resistant temperature of the film, and irradiating the resin with light to cure the adhesive.
(3)加温温度が40〜120℃である、(1)又は(2)に記載の方法。 (3) The method according to (1) or (2), wherein the heating temperature is 40 to 120 ° C.
(4)光が400nm以下の波長の光の少なくとも一部がカットされた紫外線である、(1)〜(3)のいずれか1項に記載の方法。 (4) The method according to any one of (1) to (3), wherein the light is ultraviolet light obtained by cutting at least part of light having a wavelength of 400 nm or less.
本発明の製造方法によれば、光硬化型エポキシ樹脂系接着剤を十分に硬化させるために強い照度の光を照射したり、あるいは、光照射後に加熱(アフターキュア)をしたりする必要がないので、品質が良好な偏光板のような積層フィルムを、簡便かつ効率的に製造できる。 According to the production method of the present invention, it is not necessary to irradiate light with strong illuminance in order to sufficiently cure the photocurable epoxy resin adhesive, or to perform heating (after cure) after light irradiation. Therefore, a laminated film such as a polarizing plate with good quality can be easily and efficiently produced.
以下に本発明を詳細に説明する。 The present invention is described in detail below.
本発明で使用する光硬化型エポキシ樹脂系接着剤は、光硬化型エポキシ樹脂と光重合開始剤を含むが、その他に慣用の添加成分を含んでもよい。 The photocurable epoxy resin-based adhesive used in the present invention contains a photocurable epoxy resin and a photopolymerization initiator, but may contain other conventional additive components.
光硬化型エポキシ樹脂は、一般に使用される光硬化型エポキシ樹脂であれば特に限定されず、例えば、芳香族エポキシ樹脂、脂肪族エポキシ樹脂、脂環式エポキシ樹脂等が含まれる。 The photocurable epoxy resin is not particularly limited as long as it is a commonly used photocurable epoxy resin, and examples thereof include aromatic epoxy resins, aliphatic epoxy resins, and alicyclic epoxy resins.
芳香族エポキシ樹脂としては、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ナフタレン骨格エポキシ樹脂、フェノールノボラック型エポキシ樹脂等が挙げられる。 Examples of the aromatic epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, naphthalene skeleton epoxy resin, phenol novolac type epoxy resin and the like.
脂肪族エポキシ樹脂としては、脂肪族多価アルコール又はそのアルキレンオキサイド付加物のポリグリシジルエーテルを用いることができる。脂肪族エポキシ樹脂の例として、エチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,4−ブタンジオールジグリシジルエーテル、1,6−ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリメチロールプロパンジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテルなどが挙げられる。また、ブタジエン系エポキシ樹脂、イソプレン系エポキシ樹脂などの不飽和脂肪酸エポキシも用いることができる。トリメチロールプロパントリグリシジルエーテル、トリメチロールプロパンジグリシジルエーテルは、粘度が低い点で好ましい。脂肪族エポキシ樹脂の市販品には、例えば、共栄社化学(株)製エポライト100MF(トリメチロールプロパントリグリシジルエーテル)、ナガセケムテックス(株)製EX−321L(トリメチロールプロパンジグリシジルエーテル)がある。 As the aliphatic epoxy resin, an aliphatic polyhydric alcohol or an alkylene oxide adduct polyglycidyl ether can be used. Examples of aliphatic epoxy resins include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane diglycidyl ether, polyethylene glycol diglycidyl ether, and the like. In addition, unsaturated fatty acid epoxies such as butadiene-based epoxy resins and isoprene-based epoxy resins can also be used. Trimethylolpropane triglycidyl ether and trimethylolpropane diglycidyl ether are preferable in terms of low viscosity. Commercially available products of aliphatic epoxy resins include, for example, Epolite 100MF (trimethylolpropane triglycidyl ether) manufactured by Kyoeisha Chemical Co., Ltd. and EX-321L (trimethylolpropane diglycidyl ether) manufactured by Nagase ChemteX Corporation.
脂環式エポキシ樹脂は、脂環式環に結合したエポキシ基を分子内に1個以上有する化合物であり、その例として、ビニルシクロヘキセンモノオキサイド、1,2−エポキシ−4−ビニルシクロヘキサン、1,2:8,9ジエポキシリモネン、3、4−エポキシシクロヘキセニルメチル−3、’4’−エポキシシクロヘキセンカルボキシレートなどが挙げられる。これらは、ダイセル化学工業(株)より、商品名CEL2000、CEL3000、CEL2021Pで市販されている。 The alicyclic epoxy resin is a compound having at least one epoxy group bonded to the alicyclic ring in the molecule. Examples thereof include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 1, 2: 8,9 diepoxy limonene, 3,4-epoxycyclohexenylmethyl-3, '4'-epoxycyclohexene carboxylate and the like. These are commercially available from Daicel Chemical Industries, Ltd. under the trade names CEL2000, CEL3000, and CEL2021P.
本発明における光硬化型エポキシ樹脂として、上記したエポキシ樹脂を単独で用いてもよいし、複数種のエポキシ樹脂を任意の配合割合で混合して用いてもよい。 As the photocurable epoxy resin in the present invention, the above-described epoxy resin may be used alone, or a plurality of types of epoxy resins may be mixed and used in an arbitrary blending ratio.
本発明における光重合開始剤は、可視光線、紫外線、X線、電子線などの活性エネルギー線の照射によって、カチオン又はルイス酸を発生し、エポキシ基の重合を開始するものであれば、特に限定されない。光重合開始剤の例として、スルホニウム塩、ヨウドニウム塩、ジアゾニウム塩が挙げられる。 The photopolymerization initiator in the present invention is particularly limited as long as it generates a cation or a Lewis acid by irradiation of active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and initiates polymerization of an epoxy group. Not. Examples of the photopolymerization initiator include sulfonium salts, iodonium salts, and diazonium salts.
スルホニウム系の例として、例えば、
トリフェニルスルホニウム ヘキサフルオロホスフェート、
トリフェニルスルホニウム ヘキサフルオロアンチモネート、
トリフェニルスルホニウム テトラキス(ペンタフルオロフェニル)ボレート、
4,4’−ビス〔ジフェニルスルホニオ〕ジフェニルスルフィド ビスヘキサフルオロホスフェート、
4,4’−ビス〔ジ(β−ヒドロキシエトキシ)フェニルスルホニオ〕ジフェニルスルフィド ビスヘキサフルオロアンチモネート、
4,4’−ビス〔ジ(β−ヒドロキシエトキシ)フェニルスルホニオ〕ジフェニルスルフィド ビスヘキサフルオロホスフェート、
7−〔ジ(p−トルイル)スルホニオ〕−2−イソプロピルチオキサントン ヘキサフルオロアンチモネート、
7−〔ジ(p−トルイル)スルホニオ〕−2−イソプロピルチオキサントン テトラキス(ペンタフルオロフェニル)ボレート、
4−フェニルカルボニル−4’−ジフェニルスルホニオ−ジフェニルスルフィド ヘキサフルオロホスフェート、
4−(p−tert−ブチルフェニルカルボニル)−4’−ジフェニルスルホニオ−ジフェニルスルフィド ヘキサフルオロアンチモネート、
4−(p−tert−ブチルフェニルカルボニル)−4’−ジ(p−トルイル)スルホニオ−ジフェニルスルフィド テトラキス(ペンタフルオロフェニル)ボレート
などが挙げられる。
As an example of a sulfonium system, for example,
Triphenylsulfonium hexafluorophosphate,
Triphenylsulfonium hexafluoroantimonate,
Triphenylsulfonium tetrakis (pentafluorophenyl) borate,
4,4′-bis [diphenylsulfonio] diphenyl sulfide bishexafluorophosphate,
4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluoroantimonate,
4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluorophosphate,
7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate,
7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate,
4-phenylcarbonyl-4′-diphenylsulfonio-diphenyl sulfide hexafluorophosphate,
4- (p-tert-butylphenylcarbonyl) -4′-diphenylsulfonio-diphenyl sulfide hexafluoroantimonate,
4- (p-tert-butylphenylcarbonyl) -4′-di (p-toluyl) sulfonio-diphenyl sulfide tetrakis (pentafluorophenyl) borate and the like.
ヨードニウム塩系の例として、例えば、
ジフェニルヨードニウム テトラキス(ペンタフルオロフェニル)ボレート、
ジフェニルヨードニウム ヘキサフルオロホスフェート、
ジフェニルヨードニウム ヘキサフルオロアンチモネート、
ジ(4−ノニルフェニル)ヨードニウム ヘキサフルオロホスフェート
などが挙げられる。
As an example of an iodonium salt system, for example,
Diphenyliodonium tetrakis (pentafluorophenyl) borate,
Diphenyliodonium hexafluorophosphate,
Diphenyliodonium hexafluoroantimonate,
Examples include di (4-nonylphenyl) iodonium hexafluorophosphate.
ジアゾニウム塩の例として、例えば
ベンゼンジアゾニウム ヘキサフルオロアンチモネート、
ベンゼンジアゾニウム ヘキサフルオロホスフェート
などが挙げられる。
Examples of diazonium salts include benzenediazonium hexafluoroantimonate,
Examples thereof include benzenediazonium hexafluorophosphate.
光重合開始剤の市販品として、旭電化工業(株)製のアデカオプトマーSP−150及びSP−170、ロディア(株)製のPI2074、日本化薬(株)のカヤラッドPCI−220等が挙げられる。 As commercial products of the photopolymerization initiator, Adeka optomer SP-150 and SP-170 manufactured by Asahi Denka Kogyo Co., Ltd., PI 2074 manufactured by Rhodia Co., Ltd., Kayrad PCI-220 manufactured by Nippon Kayaku Co., Ltd., and the like are listed. It is done.
これらの光重合開始剤は、光硬化型エポキシ樹脂100質量部に対して、0.5〜20質量部、好ましくは1〜10質量部を使用する。光重合開始剤は、それぞれ単独で使用しても、又は二種以上を使用してもよい。 These photoinitiators use 0.5-20 mass parts with respect to 100 mass parts of photocurable epoxy resins, Preferably 1-10 mass parts is used. A photoinitiator may be used individually, respectively, or may use 2 or more types.
本発明における光硬化型エポキシ樹脂系接着剤は、必要によりオキセタン化合物を含むことができる。オキセタン化合物は、分子内に4員環エーテル、すなわちオキセタン環を有する化合物である。オキセタン化合物の例として、3−エチル−3−ヒドロキシメチルオキセタン、1,4−ビス〔{(3−エチル−3−オキセタニル)メトキシ}メチル〕ベンゼン、3−エチル−3−(フェノキシメチル)オキセタン、ビス(3−エチル−3−オキセタニルメチル)エーテル、3−エチル−3−(2−エチルヘキシロキシメチル)オキセタン)、3−エチル−〔{(3−トリエトキシシリルプロポキシ)メチル}オキセタン、オキセタニルシルセスキオキサン、フェノールノボラックオキセタンなどが挙げられる。これらのオキセタン化合物の中でも、3−エチル−3−ヒドロキシメチルオキセタン、ビス(3−エチル−3−オキセタニルメチル)エーテル、3−エチル−3−(2−エチルヘキシロキシメチル)オキセタンが好ましい。オキセタン化合物の市販品には、例えば、東亞合成(株)から市販されている、商品名OXT−101(3−エチル−3−ヒドロキシメチルオキセタン)、OXT−211(3−エチル−3−(フェノキシメチル)オキセタン)、OXT−221(ジ[1−エチル(3−オキセタニル)]メチルエーテル)、OXT−212(3−エチル−3−(2−エチルヘキシロキシメチル)オキセタン)がある。 The photocurable epoxy resin adhesive in the present invention may contain an oxetane compound as necessary. The oxetane compound is a compound having a 4-membered ring ether, that is, an oxetane ring in the molecule. Examples of oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, Bis (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane), 3-ethyl-[{(3-triethoxysilylpropoxy) methyl} oxetane, oxetanylsil Examples thereof include sesquioxane and phenol novolac oxetane. Among these oxetane compounds, 3-ethyl-3-hydroxymethyloxetane, bis (3-ethyl-3-oxetanylmethyl) ether, and 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane are preferable. Commercially available products of oxetane compounds include, for example, trade names OXT-101 (3-ethyl-3-hydroxymethyloxetane) and OXT-211 (3-ethyl-3- (phenoxy) commercially available from Toagosei Co., Ltd. Methyl) oxetane), OXT-221 (di [1-ethyl (3-oxetanyl)] methyl ether), OXT-212 (3-ethyl-3- (2-ethylhexyloxymethyl) oxetane).
本発明において、オキセタン化合物は、光硬化型エポキシ樹脂100質量部に対して、50質量部以下の量で使用する。オキセタン化合物は、それぞれ単独で使用しても、又は二種以上を使用してもよい。 In the present invention, the oxetane compound is used in an amount of 50 parts by mass or less with respect to 100 parts by mass of the photocurable epoxy resin. The oxetane compounds may be used alone or in combination of two or more.
本発明における光硬化型エポキシ樹脂系接着剤は、更に、必要に応じて光増感剤を併用することができる。光増感剤を使用することで、反応性が向上し、硬化物の機械強度や接着強度を向上させることができる。光増感剤としては、カルボニル化合物、有機硫黄化合物、過硫化物、レドックス系化合物、アゾ及びジアゾ化合物、ハロゲン化合物、光還元性色素などが挙げられる。光増感剤の例として、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル、α,α−ジメトキシ−α−フェニルアセトフェノンのようなベンゾイン誘導体;ベンゾフェノン、2,4−ジクロロベンゾフェノン、o−ベンゾイル安息香酸メチル、4,4’−ビス(ジエチルアミノ)ベンゾフェノンのようなベンゾフェノン誘導体;2−クロロチオキサントン、2−イソプロピルチオキサントン、2,4−ジエチルチオキサントンのようなチオキサントン誘導体;2−クロロアントラキノン、2−メチルアントラキノンのようなアントラキノン誘導体;N−メチルアクリドン、N−ブチルアクリドンのようなアクリドン誘導体;9,10−ジブトキシアントラセンのようなアントラセン誘導体;その他、α,α−ジエトキシアセトフェノン、ベンジル、フルオレノン、キサントン、ウラニル化合物、ハロゲン化合物、光還元性色素などが挙げられるが、これらに限定されない。また、これらは、単独で使用しても、又は二種以上を使用してもよい。光増感剤の市販品には、例えばカヤキュアDETX−S(日本化薬(株)製)などが挙げられる。光増感剤の量は、光硬化型エポキシ樹脂系接着剤100質量部に対して、0.01〜20質量部、好ましくは0.1〜5質量部である。 The photocurable epoxy resin adhesive in the present invention can be used in combination with a photosensitizer as necessary. By using a photosensitizer, the reactivity is improved, and the mechanical strength and adhesive strength of the cured product can be improved. Examples of the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreductive dyes. Examples of photosensitizers include benzoin methyl ether, benzoin isopropyl ether, benzoin derivatives such as α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4, Benzophenone derivatives such as 4′-bis (diethylamino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone, 2-isopropylthioxanthone and 2,4-diethylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone An acridone derivative such as N-methylacridone and N-butylacridone; an anthracene derivative such as 9,10-dibutoxyanthracene; and other α, α-diethoxyacetophenone , Benzyl, fluorenone, xanthone, uranyl compound, halogen compound, photoreducible dye, and the like. Moreover, these may be used independently or may use 2 or more types. Examples of commercially available photosensitizers include Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.). The quantity of a photosensitizer is 0.01-20 mass parts with respect to 100 mass parts of photocurable epoxy resin adhesives, Preferably it is 0.1-5 mass parts.
本発明における光硬化型エポキシ樹脂系接着剤には、更に、本発明の効果を損なわない限り、上記以外の添加剤、例えばフィラー、酸化防止剤、シランカップリング剤を配合することできる。 The photo-curable epoxy resin adhesive in the present invention may further contain additives other than those described above, for example, fillers, antioxidants, and silane coupling agents, as long as the effects of the present invention are not impaired.
フィラーの例として、タルク、シリカ、マイカ等の無機フィラーや、ポリプロピレン、ポリエチレン等の樹脂フィラーが挙げられる。 Examples of the filler include inorganic fillers such as talc, silica and mica, and resin fillers such as polypropylene and polyethylene.
酸化防止剤としては、例えばジブチルヒドロキシトルエン(BHT)、イルガノックス1010、イルガノックス1035FF、イルガノックス565などが挙げられる。 Examples of the antioxidant include dibutylhydroxytoluene (BHT), Irganox 1010, Irganox 1035FF, Irganox 565, and the like.
シランカップリング剤としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルメチルジエトキシシラン、3−グリシドキシプロピルトリエトキシシラン、p−スチリルトリメトキシシラン、3−メタクリロキシプロピルメチルジメトキシシラン、3−メタクリロキシプロピルトリメトキシシラン、3−メタクリロキシプロピルメチルジエトキシシラン、3−メタクリロキシプロピルトリエトキシシラン、3−メタクリロキシプロピルトリメトキシシラン、3−トリエトキシシリル−N−(1,3−ジメチル−ブチリデン)プロピルアミン等が挙げられる。 Examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldisilane. Ethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- Examples include methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine.
シランカップリング剤の市販品には、例えばエポキシ系(例KBM403、KBM303)、ビニル系(KBM1003)、アクリル系シランカップリング剤(KBM503)、3−エチル(トリエトキシシリルプロポキシメチル)オキセタン(TESOX(東亞合成(株)製))などが挙げられる。 Examples of commercially available silane coupling agents include epoxy (eg, KBM403, KBM303), vinyl (KBM1003), acrylic silane coupling agent (KBM503), 3-ethyl (triethoxysilylpropoxymethyl) oxetane (TESOX ( Toagosei Co., Ltd.)).
本発明における光硬化型エポキシ樹脂系接着剤は、好ましくは、粘度が200mPa・s(25℃)以下、さらに好ましくは150mPa・s(25℃)以下である。粘度が低い程、塗布が行い易く、また接着剤層の塗布厚みが薄くでき、例えば偏光板に保護フィルムまたは光学補償フィルムを貼り付けるのに使用した場合には、偏光板の外観も良好なものになる。高粘度の接着剤も使用できるが、その場合には塗布量を少なくする。 The photocurable epoxy resin adhesive in the present invention preferably has a viscosity of 200 mPa · s (25 ° C.) or less, more preferably 150 mPa · s (25 ° C.) or less. The lower the viscosity, the easier it is to apply, and the thinner the adhesive layer can be applied. For example, when used to attach a protective film or optical compensation film to a polarizing plate, the polarizing plate has a good appearance. become. High-viscosity adhesives can also be used, but in that case the coating amount is reduced.
本発明で使用するフィルムは、少なくとも1つのフィルムが光を透過するフィルムでなければならない。このような光透過性フィルムとして、ポリエステル系フィルム、ポリカーボネート系フィルム、アクリル系フィルム、ポリアミド系フィルム、ポリイミド系フィルム、非結晶性ポリオレフィン系フィルム、シクロオレフィン系フィルム、PVA系フィルム、セルロース系フィルム等が挙げられる。 The film used in the present invention must be a film in which at least one film transmits light. Examples of such light transmissive films include polyester films, polycarbonate films, acrylic films, polyamide films, polyimide films, amorphous polyolefin films, cycloolefin films, PVA films, and cellulose films. Can be mentioned.
非結晶性ポリオレフィン系樹脂は、通常、ノルボルネンや多環ノルボルネン系モノマーのような環状ポリオレフィンの重合単位を有するものであり、環状オレフィンと鎖状環状オレフィンとの共重合体であってもよい。市販されている非結晶性ポリオレフィン系樹脂として、JSR(株)の商品名アートン、日本ゼオン(株)のZEONEX、ZEONOR、三井化学(株)のAPO、アペルなどがある。 The amorphous polyolefin-based resin usually has a polymerization unit of a cyclic polyolefin such as norbornene or a polycyclic norbornene-based monomer, and may be a copolymer of a cyclic olefin and a chain cyclic olefin. Examples of commercially available non-crystalline polyolefin resins include JSR Corporation's trade name Arton, Nippon Zeon Corporation's ZEONEX, ZEONOR, Mitsui Chemicals, Inc. APO, and Appel.
本発明において、光を透過しないフィルムと組み合わせて、光を透過しないフィルムも、例えば積層フィルムの基材フィルムとして使用できる。このような光を透過しないフィルムとして、例えば着色や遮光のために、着色顔料、着色染料、カーボンブラック、無機粒子又は高分子微粒子を含有しているような樹脂、450nm以下の波長領域で光透過性のないポリイミドフィルムなどが挙げられる。 In the present invention, a film that does not transmit light in combination with a film that does not transmit light can also be used as a base film of a laminated film, for example. As such a film that does not transmit light, for example, for coloring and light shielding, a resin containing a coloring pigment, a coloring dye, carbon black, inorganic particles or polymer fine particles, light transmission in a wavelength region of 450 nm or less Non-functional polyimide film.
本発明における各フィルムの厚みは特に限定されず、用途に応じて、各種の厚みのフィルムを使用できる。 The thickness of each film in this invention is not specifically limited, According to a use, the film of various thickness can be used.
積層フィルムが偏光板の場合、PVA系の偏光子フィルムや、トリアセチルセルロース等のセルロース系フィルム、シクロオレフィン系フィルムなど保護フィルム又は光学補償フィルムが使用できる。 When the laminated film is a polarizing plate, a protective film or an optical compensation film such as a PVA polarizer film, a cellulose film such as triacetyl cellulose, and a cycloolefin film can be used.
本発明において、基材フィルムへの光硬化型エポキシ樹脂系接着剤の塗工方法は、特に限定されず、例えば、ドクターブレード、ワイヤーバー、ダイコーター、カンマコーター、グラビアコーターなどを用いた方法を含む。また、本発明におけるフィルムのラミネートは、金属ロール、ゴムロール等を用いて行うことができ、その際のラミネート圧力は、0〜5Mpaであり得る。 In the present invention, the method of applying the photocurable epoxy resin adhesive to the base film is not particularly limited, and for example, a method using a doctor blade, a wire bar, a die coater, a comma coater, a gravure coater, or the like. Including. Moreover, the film lamination in the present invention can be performed using a metal roll, a rubber roll, or the like, and the lamination pressure at that time can be 0 to 5 MPa.
本発明における積層フィルムは、2層、3層、4層、5層、6層又はそれ以上のフィルムからなる積層構造を有し得る。 The laminated film in the present invention may have a laminated structure composed of two, three, four, five, six, or more films.
本発明においては、フィルムの貼り合わせ側の面にコロナ処理、プラズマ処理、エキシマ処理、UV処理などを施したものを使用してもよい。 In this invention, you may use what gave the surface of the bonding side of a film a corona treatment, a plasma processing, an excimer processing, UV processing.
本発明における光硬化型エポキシ樹脂系接着剤の加温温度は、40℃以上であることが必要である。加温温度の上限は、被着体フィルムの耐熱温度であり、被着体フィルムの耐熱性に依存するので一概に限定できないが、例えば120℃である。ここで、フィルムの耐熱温度は、フィルムを60秒間、ある温度下に置いたときに、加熱前と比べて、実質的に、フィルムの変形(反り、変形)がなくかつフィルムの光学的特性(透過率、偏光度)が劣化しないような温度のうち最高の温度をいう。接着剤の加温温度が40℃以下では、光照射による光硬化型エポキシ樹脂の硬化が十分ではなく、本発明の効果を達成できない。接着剤の加温温度は、好ましくは50〜100℃、より好ましくは60〜80℃である。 The heating temperature of the photocurable epoxy resin adhesive in the present invention is required to be 40 ° C. or higher. The upper limit of the heating temperature is the heat resistance temperature of the adherend film and depends on the heat resistance of the adherend film, and thus cannot be generally limited, but is 120 ° C., for example. Here, the heat-resistant temperature of the film is that when the film is placed at a certain temperature for 60 seconds, there is substantially no deformation (warping or deformation) of the film and optical characteristics of the film ( The highest temperature among the temperatures at which the transmittance and polarization degree do not deteriorate. When the heating temperature of the adhesive is 40 ° C. or lower, the photocurable epoxy resin is not sufficiently cured by light irradiation, and the effects of the present invention cannot be achieved. The heating temperature of the adhesive is preferably 50 to 100 ° C, more preferably 60 to 80 ° C.
本発明における光硬化型エポキシ樹脂系接着剤の加温は、例えば、近赤外線ハロゲンランプ、遠赤外線ヒーター、熱風、ホットプレート、加熱ローラーなどが挙げられるが、これらに限定されない。 Examples of the heating of the photocurable epoxy resin adhesive in the present invention include, but are not limited to, a near-infrared halogen lamp, a far-infrared heater, hot air, a hot plate, and a heating roller.
本発明における光とは、可視光線、紫外線、X線、電子線などの活性エネルギー線をいい、好ましくは紫外線である。光照射は、メタルハライドランプ、高圧水銀ランプ、キセノンランプ、ハロゲンランプ等を用いて行うことができる。紫外線を用いる場合には、フィルムの劣化を最少とするため、400nm以下、好ましくは390nm以下の波長の光の少なくとも一部、より好ましくは400nm以下、好ましくは390nm以下の波長の光の全部を含まない紫外線が好ましい。このような紫外線は、例えば、紫外線ランプと被着体フィルムの間に近赤外線カットフィルタや310又は390nm以下の波長の光をカットする光学フィルタを用いることにより得ることができる。かかる光学フィルタとしては、石英ガラス、熱線カットフィルタ(IRCF)、310nm以下カットフィルタ、320nmカットフィルタ、340nmカットフィルタ、390nmカットフィルタ、ソーダライムガラス、400〜450nmバンドパスフィルタ等が挙げられる。 The light in the present invention refers to active energy rays such as visible light, ultraviolet rays, X-rays and electron beams, preferably ultraviolet rays. The light irradiation can be performed using a metal halide lamp, a high-pressure mercury lamp, a xenon lamp, a halogen lamp, or the like. In the case of using ultraviolet rays, in order to minimize deterioration of the film, at least a part of light having a wavelength of 400 nm or less, preferably 390 nm or less, more preferably 400 nm or less, preferably 390 nm or less is included. No ultraviolet light is preferred. Such ultraviolet rays can be obtained, for example, by using a near-infrared cut filter or an optical filter that cuts light having a wavelength of 310 or 390 nm or less between the ultraviolet lamp and the adherend film. Examples of the optical filter include quartz glass, heat ray cut filter (IRCF), 310 nm or less cut filter, 320 nm cut filter, 340 nm cut filter, 390 nm cut filter, soda lime glass, 400 to 450 nm band pass filter, and the like.
本発明における光の照射は、光硬化型エポキシ樹脂系接着剤の温度が40℃以上を有しているときに行う。本発明における光の照射強度は、目的とする接着剤や樹脂フィルムによって異なり、限定されないが、光重合開始剤の活性化に有効な波長領域の照射強度が10〜500mW/cm2であるのが好ましい。光の照射時間は、使用する光硬化性エポキシ樹脂の種類やフィルムの材質によって異なり、限定されないが、照射強度と照射時間との積として表される積算光量が100〜3000mJ/cm2(波長405nm)、好ましくは700〜2000mJ/cm2(波長405nm)となるようにする。 The light irradiation in the present invention is performed when the temperature of the photocurable epoxy resin adhesive is 40 ° C. or higher. The light irradiation intensity in the present invention varies depending on the target adhesive or resin film, and is not limited. However, the irradiation intensity in the wavelength region effective for activating the photopolymerization initiator is 10 to 500 mW / cm 2. preferable. The light irradiation time varies depending on the type of the photocurable epoxy resin used and the material of the film, and is not limited. However, the integrated light amount expressed as the product of the irradiation intensity and the irradiation time is 100 to 3000 mJ / cm 2 (wavelength 405 nm). ), Preferably 700 to 2000 mJ / cm 2 (wavelength 405 nm).
以下に、本発明を実施例により示すが、本発明はこれらの実施例によって限定されるものではない。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
製造例A〜F 光硬化型エポキシ樹脂系接着剤の調製
以下の原材料をポリエチレン製容器に計量して加え、攪拌機で混合・攪拌して均一な光硬化型エポキシ樹脂系接着剤(粘度:150mPa/s(25℃))を得た。
Production Examples A to F Preparation of Photocurable Epoxy Resin Adhesive The following raw materials were weighed and added to a polyethylene container, mixed and stirred with a stirrer to obtain a uniform photocurable epoxy resin adhesive (viscosity: 150 mPa / s). s (25 ° C.)).
100MF:トリメチロールプロパントリグリシジルエーテル、共栄社化学(株)
エピクロンEXA−850S:4,4’−ジグリシジルオキシ−2,2’−ジフェニルプロパン、大日本インキ化学(株)
エピクロンN740:フェノールノボラック型エポキシオリゴマー、大日本インキ化学(株)
CEL2000:1,2−エポキシ−4−ビニルシクロヘキサン、ダイセル化学工業(株)
CEL3000:1,2:8,9ジエポキシリモネン、ダイセル化学工業(株)
CEL2021P:3,4−エポキシシクロヘキセニルメチル−3’,4’−エポキシシクロヘキセンカルボキシレート、ダイセル化学工業(株)
CPI−101A:光重合触媒、サンアプロ(株)
SP−172:光重合触媒、(株)ADEKA
KBM403:3−グリシドキシプロピルトリメトキシシラン、信越化学工業(株)
DBA:9,10−ジブトキシアントラセン、川崎化成工業(株)
100MF: Trimethylolpropane triglycidyl ether, Kyoeisha Chemical Co., Ltd.
Epicron EXA-850S: 4,4′-diglycidyloxy-2,2′-diphenylpropane, Dainippon Ink and Chemicals, Inc.
Epicron N740: Phenol novolac type epoxy oligomer, Dainippon Ink and Chemicals, Inc.
CEL2000: 1,2-epoxy-4-vinylcyclohexane, Daicel Chemical Industries, Ltd.
CEL3000: 1, 2: 8,9 diepoxy limonene, Daicel Chemical Industries, Ltd.
CEL2021P: 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, Daicel Chemical Industries, Ltd.
CPI-101A: Photopolymerization catalyst, Sun Apro Co., Ltd.
SP-172: Photopolymerization catalyst, ADEKA Corporation
KBM403: 3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.
DBA: 9,10-dibutoxyanthracene, Kawasaki Chemical Industry Co., Ltd.
実施例1〜6及び比較例1〜3 積層フィルム(偏光板)の製造
一軸延伸し、ヨウ素で染色したポリビニルアルコール偏光子フィルムの片面にトリアセチルセルロースフィルムを、他の片面に非結晶性ポリオレフィン系樹脂フィルム(日本ゼオン(株)製のゼオノアフィルム)を製造例で調製した光硬化性エポキシ樹脂系接着剤(記号:A)を介して貼り合わせて、3層構造のフィルムを得た。得られた3層構造のフィルムを、赤外線ランプを用いて、室温(25℃)、30℃、40℃、50℃、60℃、70℃、80℃、100℃、120℃及び140℃に加温した後、直ちにメタルハライドランプ(アイグラフィックス社製)を用いて、照射強度200mW/cm2(405nm)、積算光量1000mJ/cm2(405nm)で光の照射を行って積層フィルムを得た。積層フィルム間の接着剤層は、1〜3μm程度の厚みで均一であった。これらは電子顕微鏡によって確認した。
Examples 1 to 6 and Comparative Examples 1 to 3 Production of laminated film (polarizing plate) Triacetyl cellulose film on one side of uniaxially stretched and dyed with iodine, triacetyl cellulose film on one side, amorphous polyolefin based A resin film (ZEONOR film manufactured by Nippon Zeon Co., Ltd.) was bonded through a photocurable epoxy resin adhesive (symbol: A) prepared in Production Example to obtain a film having a three-layer structure. The resulting three-layer film was heated to room temperature (25 ° C.), 30 ° C., 40 ° C., 50 ° C., 60 ° C., 70 ° C., 80 ° C., 100 ° C., 120 ° C. and 140 ° C. using an infrared lamp. Immediately after heating, a metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used to irradiate light with an irradiation intensity of 200 mW / cm 2 (405 nm) and an integrated light quantity of 1000 mJ / cm 2 (405 nm) to obtain a laminated film. The adhesive layer between the laminated films was uniform with a thickness of about 1 to 3 μm. These were confirmed by an electron microscope.
表2に、材料温度、UV照射後の接着剤の状態、UV照射後の積層フィルムの変形、積層フィルムの耐久特性、耐湿試験後の光学特性を示す。 Table 2 shows the material temperature, the state of the adhesive after UV irradiation, the deformation of the laminated film after UV irradiation, the durability characteristics of the laminated film, and the optical characteristics after the moisture resistance test.
材料温度:UV照射直前の接着剤の温度(加温温度)
UV照射後の接着剤の状態:
以下の基準で評価した。
液状で硬化不十分:液体状態で硬化が不十分であり、接着していない
剥がれ:フィルムが剥がれている
△:接着しているが強度はやや弱い。(〜100g/25mm)
○:接着しており、強度も中程度(100〜200g/25mm)
◎:接着しており、強度も十分(200g/25mm〜)
Material temperature: Adhesive temperature just before UV irradiation (heating temperature)
Adhesive state after UV irradiation:
Evaluation was made according to the following criteria.
Liquid and insufficiently cured: Insufficiently cured in liquid state and not bonded. Peeling: The film is peeled. Δ: Bonded but slightly weak in strength. (~ 100g / 25mm)
○: Adhesive, medium strength (100-200g / 25mm)
◎: Adhesive and strong enough (200g / 25mm ~)
UV照射後のフィルムの変形:肉眼で観察した。 Film deformation after UV irradiation: Observed with the naked eye.
耐湿試験後の耐久特性:
積層フィルムを60℃−90%の条件の耐湿試験槽に500時間放置した後の外観(色抜けやフィルム変性)を以下の基準で評価した。
×:はがれや変形、偏光子部分の色抜けが強く起きる。
△:はがれや変形、偏光子部分の色抜けが起きる。
○:偏光子部分の色抜けが極くわずかに起きるが、はがれや変形が起きない。
◎:はがれや変形、偏光子部分の色抜けが起きない。
Durability characteristics after moisture resistance test:
The appearance (color loss and film modification) after leaving the laminated film in a humidity resistance test tank at 60 ° C.-90% for 500 hours was evaluated according to the following criteria.
X: Peeling and deformation, and color loss at the polarizer portion occur strongly.
Δ: Peeling and deformation, and color loss of the polarizer portion occurs.
○: Color loss of the polarizer portion occurs very slightly, but no peeling or deformation occurs.
A: No peeling, deformation, or color loss of the polarizer part occurs.
耐湿試験後の光学特性:
耐湿試験前及び後の積層フィルムについて、偏光度と透過率を測定し、それらの劣化(耐湿試験前の積層フィルムの値からの低下)で評価した。
*被着体材料の変性(変形、耐久特性、光学特性)については熱のみならず、紫外線によっても劣化を生じた。
Optical properties after moisture resistance test:
About the laminated | multilayer film before and after a moisture resistance test, the polarization degree and the transmittance | permeability were measured, and those deterioration (decrease from the value of the laminated film before a moisture resistance test) evaluated.
* Deterioration (deformation, durability characteristics, optical characteristics) of the adherend material was deteriorated not only by heat but also by ultraviolet rays.
表2から、40〜70℃に加温したのち光照射して硬化すると、光硬化型エポキシ樹脂系接着剤が十分に硬化して良好な接着性を示すとともに、フィルムの変形もほとんどないことが分かる。一方、加温温度が25℃、30℃の場合には、フィルムの変形はないものの、光硬化型エポキシ樹脂系接着剤が硬化不十分もしくは未硬化で、接着性が極不良であった。また、材料温度が80〜100℃以上の場合には、光硬化型エポキシ樹脂系接着剤が十分に硬化して良好な接着性を示すが、フィルムがわずかに反った。また100℃超の場合には、光硬化型エポキシ樹脂系接着剤が十分に硬化して良好な接着性を示すが、フィルムが大きく変性した。 From Table 2, when heated to 40-70 ° C. and then cured by light irradiation, the photo-curable epoxy resin adhesive is sufficiently cured to exhibit good adhesiveness, and there is almost no deformation of the film. I understand. On the other hand, when the heating temperature was 25 ° C. or 30 ° C., the film was not deformed, but the photocurable epoxy resin adhesive was insufficiently cured or uncured, and the adhesion was extremely poor. In addition, when the material temperature was 80 to 100 ° C. or higher, the photocurable epoxy resin adhesive was sufficiently cured and exhibited good adhesion, but the film was slightly warped. On the other hand, when the temperature exceeds 100 ° C., the photocurable epoxy resin adhesive is sufficiently cured and exhibits good adhesiveness, but the film is greatly modified.
光硬化性樹脂接着剤B〜Fについて同様の検討を行ったところ、接着性に多少の相違はあるものの、ほぼ同様の結果が得られた。 When the same examination was performed on the photocurable resin adhesives B to F, almost the same results were obtained although there were some differences in the adhesiveness.
なお、加温を赤外線ランプに代えてホットプレートで行った場合、又は熱風で行った場合にも、上記と同様な性能の積層フィルムが得られた。 Note that a laminated film having the same performance as described above was obtained when the heating was performed with a hot plate instead of the infrared lamp or with hot air.
実施例7〜13及び比較例4〜6 積層フィルムの製造
実施例1〜6及び比較例1〜3の積層フィルムの製造において、メタルハライドランプと被着体フィルムの間に、波長390nm以下の光をカットする光学フィルタ(アイグラフィックス社製)を配置して光を照射した。実施例1〜6及び比較例1〜3と同様にして、それぞれ実施例7〜13及び比較例4〜6の積層フィルムを得た。
Examples 7 to 13 and Comparative Examples 4 to 6 Manufacture of laminated films In the production of laminated films of Examples 1 to 6 and Comparative Examples 1 to 3, light having a wavelength of 390 nm or less was applied between the metal halide lamp and the adherend film. An optical filter (made by Eye Graphics Co., Ltd.) to be cut was placed and irradiated with light. In the same manner as in Examples 1 to 6 and Comparative Examples 1 to 3, laminated films of Examples 7 to 13 and Comparative Examples 4 to 6 were obtained.
表3から、波長390nm以下の光をカットする光学フィルタをメタルハライドランプと被着体の間に配置すると、これを配置しない場合に比べ、偏光子およびフィルムの変性も少なく、良好な接着性と耐久特性をもつ積層フィルムが得られた。390nm以下の波長カットフィルタに代えて、320nm以下の波長カットフィルタ、340nm以下の波長カットフィルタ又は370nm以下の波長カットフィルタを使用しても同様の結果が得られたが、390nm以下の波長カットフィルタの使用が最も構成フィルムへの影響が少なかった。光学フィルターの使用により、120℃に加温した場合のフィルムの変形は抑制できたが、140℃に加温した場合のフィルムの変形は抑制できなかった。 From Table 3, when an optical filter that cuts light with a wavelength of 390 nm or less is placed between the metal halide lamp and the adherend, the polarizer and film are less modified and better adhesion and durability than when not placed. A laminated film with properties was obtained. The same result was obtained by using a wavelength cut filter of 320 nm or less, a wavelength cut filter of 340 nm or less, or a wavelength cut filter of 370 nm or less instead of the wavelength cut filter of 390 nm or less. The use of No. had the least effect on the constituent film. By using an optical filter, deformation of the film when heated to 120 ° C. could be suppressed, but deformation of the film when heated to 140 ° C. could not be suppressed.
比較例7〜12 積層フィルムの製造
実施例1と同様にして、3層構造のフィルムを得た。得られた3層構造フィルムを、加温せずに、メタルハライドランプ(アイグラフィックス社製)を用いて、照射強度500mW/cm2(405nm)、積算光量500、1000、2000及び3000mJ/cm2(405nm)で光の照射を行って積層フィルムを得た。さらに、積算光量2000及び3000mJ/cm2(405nm)の場合には、メタルハライドランプと被着体フィルムの間に配置した波長390nm以下の光をカットする光学フィルタ(アイグラフィックス社製)を用いて光照射を行い、積層フィルムを得た。
Comparative Examples 7 to 12 Production of laminated film A film having a three-layer structure was obtained in the same manner as in Example 1. The obtained three-layer structure film was heated without using a metal halide lamp (manufactured by Eye Graphics Co., Ltd.), with an irradiation intensity of 500 mW / cm 2 (405 nm), an integrated light quantity of 500, 1000, 2000 and 3000 mJ / cm 2. (405 nm) was irradiated with light to obtain a laminated film. Furthermore, in the case of an integrated light quantity of 2000 and 3000 mJ / cm 2 (405 nm), an optical filter (made by Eye Graphics Co., Ltd.) that cuts light with a wavelength of 390 nm or less arranged between the metal halide lamp and the adherend film is used. Light irradiation was performed to obtain a laminated film.
表4から、光照射前に加温をしない場合には、光の照射光量を増減しても、接着性に優れかつフィルムの変形のない積層フィルムを得ることはできなかった。 From Table 4, when heating was not performed before light irradiation, it was not possible to obtain a laminated film having excellent adhesion and no film deformation even when the amount of light irradiation was increased or decreased.
本発明は、自動車、航空機、電気・電子機器を含む広い産業分野において使用される積層フィルムの製造に用いることができる。また、速硬化性・速接着性を有したプロセスであるため、製造速度の向上や、加熱プロセスの削減に大きく寄与する。 The present invention can be used for the production of laminated films used in a wide range of industrial fields including automobiles, aircraft, and electrical / electronic devices. In addition, since the process has fast curability and fast adhesiveness, it greatly contributes to the improvement of the production speed and the reduction of the heating process.
Claims (6)
前記フィルム間に存在する光硬化型エポキシ樹脂系接着剤を40〜120℃の温度に加温し、これに光を照射して硬化させて前記フィルムを接着する工程を含み、
前記積層フィルムが偏光板である積層フィルムの製造方法。 A method for producing a laminated film comprising laminating films using a photocurable epoxy resin adhesive,
A step of heating the photocurable epoxy resin adhesive existing between the films to a temperature of 40 to 120 ° C., irradiating and curing the light, and bonding the film;
A method for producing a laminated film, wherein the laminated film is a polarizing plate.
前記偏光子フィルムがポリビニルアルコールである請求項1記載の製造方法。 At least one of the films is a polarizer film;
The manufacturing method according to claim 1, wherein the polarizer film is polyvinyl alcohol.
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JP5677883B2 (en) * | 2011-03-29 | 2015-02-25 | 住友化学株式会社 | Photo-curable adhesive, polarizing plate and laminated optical member |
JP6308721B2 (en) | 2012-03-30 | 2018-04-11 | 日東電工株式会社 | Polarizing film, optical film, and image display device |
KR20130134236A (en) * | 2012-05-30 | 2013-12-10 | 삼성디스플레이 주식회사 | Display device |
JP6296701B2 (en) * | 2012-10-15 | 2018-03-20 | 住友化学株式会社 | Manufacturing method of electronic device |
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CN106569296B (en) * | 2015-10-07 | 2020-08-14 | 住友化学株式会社 | Polarizing plate |
JP6335360B2 (en) * | 2017-04-27 | 2018-05-30 | 日東電工株式会社 | Polarizing plate, method for producing the polarizing plate, optical film, and image display device |
KR102649217B1 (en) * | 2021-11-03 | 2024-03-20 | 정낙군 | Method for fabricating x-ray grids and x-ray grids |
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JP2000109780A (en) * | 1998-10-07 | 2000-04-18 | Dainippon Ink & Chem Inc | Ultraviolet-hardening type adhesive composition for optical member |
JP2001247834A (en) * | 2000-03-02 | 2001-09-14 | Sekisui Chem Co Ltd | Curable pressure-sensitive adhesive composition, curable pressure-sensitive adhesive sheet, and bonding method of optical or electronic substrate |
US6949297B2 (en) * | 2001-11-02 | 2005-09-27 | 3M Innovative Properties Company | Hybrid adhesives, articles, and methods |
JP2003246970A (en) * | 2001-12-21 | 2003-09-05 | Sekisui Chem Co Ltd | Apparatus and method for producing structure adhered by photoreactive adhesive |
JP4276407B2 (en) * | 2002-05-08 | 2009-06-10 | ヘンケル コーポレイション | Photocationically curable epoxy resin composition |
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