JP2020011487A - Laminate - Google Patents
Laminate Download PDFInfo
- Publication number
- JP2020011487A JP2020011487A JP2018136704A JP2018136704A JP2020011487A JP 2020011487 A JP2020011487 A JP 2020011487A JP 2018136704 A JP2018136704 A JP 2018136704A JP 2018136704 A JP2018136704 A JP 2018136704A JP 2020011487 A JP2020011487 A JP 2020011487A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- resin film
- laminate
- photocurable composition
- adhesive layer
- 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.)
- Pending
Links
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 105
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 230000009477 glass transition Effects 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims description 51
- 239000012790 adhesive layer Substances 0.000 claims description 41
- 239000004593 Epoxy Substances 0.000 claims description 28
- 239000000853 adhesive Substances 0.000 claims description 21
- 230000001070 adhesive effect Effects 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 15
- 238000005336 cracking Methods 0.000 abstract description 3
- -1 polyethylene terephthalate Polymers 0.000 description 24
- 238000001723 curing Methods 0.000 description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 238000000576 coating method Methods 0.000 description 14
- 239000002585 base Substances 0.000 description 11
- 238000002845 discoloration Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 7
- 230000008602 contraction Effects 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 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 4
- 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 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- BIDWUUDRRVHZLQ-UHFFFAOYSA-N 3-ethyl-3-(2-ethylhexoxymethyl)oxetane Chemical compound CCCCC(CC)COCC1(CC)COC1 BIDWUUDRRVHZLQ-UHFFFAOYSA-N 0.000 description 3
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-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
- 125000001931 aliphatic group Chemical group 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 230000001678 irradiating effect Effects 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 3
- 150000002921 oxetanes Chemical class 0.000 description 3
- 229920001610 polycaprolactone Polymers 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
- URFNSYWAGGETFK-UHFFFAOYSA-N 1,2-bis(4-hydroxyphenyl)ethane Natural products C1=CC(O)=CC=C1CCC1=CC=C(O)C=C1 URFNSYWAGGETFK-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-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
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 2
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- PQJUJGAVDBINPI-UHFFFAOYSA-N 9H-thioxanthene Chemical compound C1=CC=C2CC3=CC=CC=C3SC2=C1 PQJUJGAVDBINPI-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920004552 POLYLITE® Polymers 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 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 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 150000002605 large molecules Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000003459 sulfonic acid esters Chemical class 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- VMHYWKBKHMYRNF-UHFFFAOYSA-N (2-chlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC=C1C(=O)C1=CC=CC=C1 VMHYWKBKHMYRNF-UHFFFAOYSA-N 0.000 description 1
- SJHPCNCNNSSLPL-CSKARUKUSA-N (4e)-4-(ethoxymethylidene)-2-phenyl-1,3-oxazol-5-one Chemical compound O1C(=O)C(=C/OCC)\N=C1C1=CC=CC=C1 SJHPCNCNNSSLPL-CSKARUKUSA-N 0.000 description 1
- FRLDLFKDZOJRND-UHFFFAOYSA-N 1,1,1,6,6,6-hexaiodohexane Chemical compound IC(CCCCC(I)(I)I)(I)I FRLDLFKDZOJRND-UHFFFAOYSA-N 0.000 description 1
- XHXSXTIIDBZEKB-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octamethylanthracene-9,10-dione Chemical compound CC1=C(C)C(C)=C2C(=O)C3=C(C)C(C)=C(C)C(C)=C3C(=O)C2=C1C XHXSXTIIDBZEKB-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
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- UYFJYGWNYQCHOB-UHFFFAOYSA-N 1-(4-tert-butylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C(C)(C)C)C=C1 UYFJYGWNYQCHOB-UHFFFAOYSA-N 0.000 description 1
- ONCICIKBSHQJTB-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]propan-1-one Chemical compound CCC(=O)C1=CC=C(N(C)C)C=C1 ONCICIKBSHQJTB-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- OAMHTTBNEJBIKA-UHFFFAOYSA-N 2,2,2-trichloro-1-phenylethanone Chemical compound ClC(Cl)(Cl)C(=O)C1=CC=CC=C1 OAMHTTBNEJBIKA-UHFFFAOYSA-N 0.000 description 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- UXMYUFHUUYBDLL-UHFFFAOYSA-N 2,2-dimethyl-3-(oxiran-2-ylmethoxy)propan-1-ol Chemical compound OCC(C)(C)COCC1CO1 UXMYUFHUUYBDLL-UHFFFAOYSA-N 0.000 description 1
- LZWVPGJPVCYAOC-UHFFFAOYSA-N 2,3-diphenylanthracene-9,10-dione Chemical compound C=1C=CC=CC=1C=1C=C2C(=O)C3=CC=CC=C3C(=O)C2=CC=1C1=CC=CC=C1 LZWVPGJPVCYAOC-UHFFFAOYSA-N 0.000 description 1
- MFUCEQWAFQMGOR-UHFFFAOYSA-N 2,4-diethyl-9h-thioxanthene Chemical compound C1=CC=C2CC3=CC(CC)=CC(CC)=C3SC2=C1 MFUCEQWAFQMGOR-UHFFFAOYSA-N 0.000 description 1
- LRPXBHSHSWJFGR-UHFFFAOYSA-N 2-(2-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound COC1=CC=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 LRPXBHSHSWJFGR-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- QTUVQQKHBMGYEH-UHFFFAOYSA-N 2-(trichloromethyl)-1,3,5-triazine Chemical class ClC(Cl)(Cl)C1=NC=NC=N1 QTUVQQKHBMGYEH-UHFFFAOYSA-N 0.000 description 1
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- HIGURUTWFKYJCH-UHFFFAOYSA-N 2-[[1-(oxiran-2-ylmethoxymethyl)cyclohexyl]methoxymethyl]oxirane Chemical compound C1OC1COCC1(COCC2OC2)CCCCC1 HIGURUTWFKYJCH-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
- IMJWYODDPLPNHC-UHFFFAOYSA-N 2-[[2,5-ditert-butyl-4-(oxiran-2-ylmethoxy)phenoxy]methyl]oxirane Chemical compound CC(C)(C)C=1C=C(OCC2OC2)C(C(C)(C)C)=CC=1OCC1CO1 IMJWYODDPLPNHC-UHFFFAOYSA-N 0.000 description 1
- NKANYVMWDXJHLE-UHFFFAOYSA-N 2-[[2-(oxiran-2-ylmethoxy)phenoxy]methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1OCC1CO1 NKANYVMWDXJHLE-UHFFFAOYSA-N 0.000 description 1
- YCQOBQDGSRPAHQ-UHFFFAOYSA-N 2-[[2-tert-butyl-4-(oxiran-2-ylmethoxy)phenoxy]methyl]oxirane Chemical compound C=1C=C(OCC2OC2)C(C(C)(C)C)=CC=1OCC1CO1 YCQOBQDGSRPAHQ-UHFFFAOYSA-N 0.000 description 1
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 description 1
- FSYPIGPPWAJCJG-UHFFFAOYSA-N 2-[[4-(oxiran-2-ylmethoxy)phenoxy]methyl]oxirane Chemical compound C1OC1COC(C=C1)=CC=C1OCC1CO1 FSYPIGPPWAJCJG-UHFFFAOYSA-N 0.000 description 1
- OLKHRYQRCJLWLL-UHFFFAOYSA-N 2-cyclohex-3-en-1-yloxirane Chemical compound C1OC1C1CC=CCC1 OLKHRYQRCJLWLL-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- ATTLFLQPHSUNBK-UHFFFAOYSA-N 2-methyl-9h-thioxanthene Chemical compound C1=CC=C2CC3=CC(C)=CC=C3SC2=C1 ATTLFLQPHSUNBK-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
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- SQAAXANYWPZYJI-UHFFFAOYSA-N 2-propan-2-yl-9h-thioxanthene Chemical class C1=CC=C2CC3=CC(C(C)C)=CC=C3SC2=C1 SQAAXANYWPZYJI-UHFFFAOYSA-N 0.000 description 1
- HRHHFLISYUFQLA-UHFFFAOYSA-N 3,6,9-trioxatetracyclo[9.2.2.02,4.08,10]pentadecane Chemical compound C12CCC(CC1)C1C(COCC3C2O3)O1 HRHHFLISYUFQLA-UHFFFAOYSA-N 0.000 description 1
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- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- KBRQWCWVFNLHPU-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)methyl]-2,3,5,6-tetramethylphenol Chemical compound CC1=C(O)C(C)=C(C)C(CC=2C=CC(O)=CC=2)=C1C KBRQWCWVFNLHPU-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- KSGYKTRNRCPDHT-KVSWJAHQSA-N 4-n-[1-[(3-fluorophenyl)methyl]indazol-5-yl]-5-[(e)-2-methoxyethoxyiminomethyl]pyrimidine-4,6-diamine Chemical compound COCCO\N=C\C1=C(N)N=CN=C1NC1=CC=C(N(CC=2C=C(F)C=CC=2)N=C2)C2=C1 KSGYKTRNRCPDHT-KVSWJAHQSA-N 0.000 description 1
- 229920008790 Amorphous Polyethylene terephthalate Polymers 0.000 description 1
- 101100064324 Arabidopsis thaliana DTX48 gene Proteins 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- GTTDKTULJXVAIZ-UHFFFAOYSA-N BrBr(Br)(Br)(Br)(Br)Br Chemical class BrBr(Br)(Br)(Br)(Br)Br GTTDKTULJXVAIZ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NLVWEAVIFJLVLC-UHFFFAOYSA-N C=[N+]=[N-].FC(F)(F)S.FC(F)(F)S Chemical compound C=[N+]=[N-].FC(F)(F)S.FC(F)(F)S NLVWEAVIFJLVLC-UHFFFAOYSA-N 0.000 description 1
- HEEHKSPBUUYDPX-UHFFFAOYSA-N C=[N+]=[N-].SC1CCCCC1.SC1CCCCC1 Chemical compound C=[N+]=[N-].SC1CCCCC1.SC1CCCCC1 HEEHKSPBUUYDPX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- DKNPRRRKHAEUMW-UHFFFAOYSA-N Iodine aqueous Chemical compound [K+].I[I-]I DKNPRRRKHAEUMW-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
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- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- NIYNIOYNNFXGFN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol;7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound OCC1CCC(CO)CC1.C1C(C(=O)O)CCC2OC21.C1C(C(=O)O)CCC2OC21 NIYNIOYNNFXGFN-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- IPRVKUPKUIJURA-UHFFFAOYSA-N adamantane-1,2,2-triol Chemical compound C1C(C2)CC3CC1C(O)(O)C2(O)C3 IPRVKUPKUIJURA-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- LHMRXAIRPKSGDE-UHFFFAOYSA-N benzo[a]anthracene-7,12-dione Chemical compound C1=CC2=CC=CC=C2C2=C1C(=O)C1=CC=CC=C1C2=O LHMRXAIRPKSGDE-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
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- HGXHJQLDZPXEOG-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,4-dicarboxylate Chemical compound C1CC(C(=O)OCC2OC2)CCC1C(=O)OCC1CO1 HGXHJQLDZPXEOG-UHFFFAOYSA-N 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IFDFMWBBLAUYIW-UHFFFAOYSA-N ethane-1,2-diol;ethyl acetate Chemical compound OCCO.CCOC(C)=O IFDFMWBBLAUYIW-UHFFFAOYSA-N 0.000 description 1
- DRIIOWCRDBYORK-UHFFFAOYSA-N ethane-1,2-diol;methyl acetate Chemical compound OCCO.COC(C)=O DRIIOWCRDBYORK-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 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
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、積層体に関する。詳しくは、基材の膨張や収縮に追従し、接着面のクラックや剥離を防止できる積層体に関する。 The present invention relates to a laminate. More specifically, the present invention relates to a laminate that can follow expansion and contraction of a base material and prevent cracking and peeling of an adhesive surface.
光感受性接着剤は、光の照射により重合が開始され、硬化する接着剤である。具体的には、光重合開始剤に光を照射することにより発生させたラジカルやカチオンを、光硬化性化合物に作用させて重合反応を進行させる。透湿度の低い基材を接着する場合、水系接着剤では溶媒の水が乾燥しにくく硬化しにくいが、光感受性接着剤を用いれば光の照射により硬化を進行させることができる（特許文献１）。 The photosensitive adhesive is an adhesive whose polymerization is started by light irradiation and is cured. Specifically, radicals and cations generated by irradiating the photopolymerization initiator with light act on the photocurable compound to progress the polymerization reaction. In the case of bonding a substrate having low moisture permeability, the water-based adhesive makes it difficult for the solvent water to dry and harden, but when a photosensitive adhesive is used, the curing can be advanced by light irradiation (Patent Document 1). .
しかし、光感受性接着剤で接着した場合、温度変化によって基材にクラックや剥離が生じることがあった。特に、シクロオレフィンポリマー等の収縮応力が大きい被着体と、ポリビニルアルコール等の収縮応力が小さい被着体とを光感受性接着剤で接着した場合には、シクロオレフィンポリマーの膨張・収縮に接着層やポリビニルアルコールが追従できず、ポリビニルアルコールと接着層との間でクラックや剥離が発生することがあった。 However, when adhered with a light-sensitive adhesive, cracks or peeling may occur on the substrate due to a change in temperature. In particular, when an adherend having a large shrinkage stress such as a cycloolefin polymer and an adherend having a small shrinkage stress such as polyvinyl alcohol are bonded with a light-sensitive adhesive, the adhesive layer is not affected by the expansion and contraction of the cycloolefin polymer. And polyvinyl alcohol could not follow, and cracks and peeling sometimes occurred between polyvinyl alcohol and the adhesive layer.
クラックや剥離の防止のためには、硬化時の光照射を増大させ、重合反応を十分進行させて接着強度を向上することが考えられる。しかし、例えば基材としてポリビニルアルコールフィルムを用いた場合には、熱や光による劣化が起きやすく、重合時の光照射量を増大すると変色やシワが生じる傾向がある。過大な光照射を行わなくても、基材の膨張や収縮に追従できる接着層が必要とされている。 In order to prevent cracks and peeling, it is conceivable to increase the light irradiation during curing to sufficiently promote the polymerization reaction to improve the adhesive strength. However, for example, when a polyvinyl alcohol film is used as the base material, deterioration due to heat or light is likely to occur, and discoloration or wrinkling tends to occur when the amount of light irradiation during polymerization is increased. There is a need for an adhesive layer that can follow the expansion and contraction of the substrate without irradiating excessive light.
本発明は、基材の膨張や収縮に追従し、接着面のクラックや剥離を防止できる積層体を提供することを目的とする。 An object of the present invention is to provide a laminate that can follow the expansion and contraction of a base material and prevent cracks and peeling of an adhesive surface.
本発明者らは、接着層のガラス転移温度を特定の範囲に調整した場合には、接着層が基材の膨張や収縮に追従し、接着面のクラックや剥離を防止できることを見出した。 The present inventors have found that when the glass transition temperature of the adhesive layer is adjusted to a specific range, the adhesive layer follows expansion and contraction of the base material, and can prevent cracks and peeling of the adhesive surface.
すなわち、本発明は、
ガラス転移温度がＴｇＡである熱可塑樹脂フィルムＡ、
ガラス転移温度がＴｇＢである熱可塑樹脂フィルムＢ、および、
熱可塑樹脂フィルムＡと熱可塑樹脂フィルムＢとの間に形成され、光硬化性組成物を硬化させてなる、ガラス転移温度がＴｇＣである接着層を有する積層体であって、
ＴｇＡ、ＴｇＢ、およびＴｇＣが下記式（１）および（２）：
（１）ＴｇＢ／ＴｇＡ＋ＴｇＡ／ＴｇＢ≦５
（２）ＴｇＡ×０．２≦ＴｇＣ≦ＴｇＢ＋（ＴｇＢ―ＴｇＡ）×０．９
の関係を満たす、積層体に関する。
That is, the present invention
A thermoplastic resin film A having a glass transition temperature of Tg A,
The thermoplastic resin film B glass transition temperature of Tg B and,
A laminate having an adhesive layer formed between a thermoplastic resin film A and a thermoplastic resin film B and obtained by curing a photocurable composition and having a glass transition temperature of Tg C ,
Tg A , Tg B , and Tg C are represented by the following formulas (1) and (2):
(1) Tg B / Tg A + Tg A / Tg B ≦ 5
(2) Tg A × 0.2 ≦ Tg C ≦ Tg B + (Tg B -Tg A) × 0.9
Which satisfies the following relationship:
熱可塑樹脂フィルムＡの６０℃、９０％Ｒｈ環境における水蒸気透過率が２０００ｇ／ｍ２／日以上であることが好ましい。 It is preferable that the water vapor transmission rate of the thermoplastic resin film A in a 60 ° C., 90% Rh environment is 2000 g / m 2 / day or more.
熱可塑樹脂フィルムＢの６０℃、９０％Ｒｈ環境における水蒸気透過率が１０００ｇ／ｍ２／日以下であることが好ましい。 It is preferable that the water vapor permeability of the thermoplastic resin film B in a 60 ° C., 90% Rh environment is 1000 g / m 2 / day or less.
８５℃、８５％Ｒｈの環境下に１００時間放置した後の接着強度が１．５Ｎ／２０ｍｍ以上であることが好ましい。 It is preferable that the adhesive strength after being left in an environment of 85 ° C. and 85% Rh for 100 hours is 1.5 N / 20 mm or more.
光硬化性組成物がエポキシ化合物および感光性カチオン開始剤を含むことが好ましい。 It is preferred that the photocurable composition contains an epoxy compound and a photosensitive cationic initiator.
光硬化性組成物が芳香族系エポキシ化合物を５０重量％以上の濃度で含むことが好ましい。 It is preferable that the photocurable composition contains the aromatic epoxy compound at a concentration of 50% by weight or more.
接着層が、光硬化性組成物を３０〜５００ｍＪ／ｃｍ２の紫外光の照射により硬化させたものであることが好ましい。 Adhesive layer is preferably a photocurable composition is obtained by curing by irradiation with ultraviolet light 30~500mJ / cm 2.
熱可塑樹脂フィルムＡの厚みが１〜５０μｍであり、
熱可塑樹脂フィルムＢの厚みが５〜１００μｍであり、
接着層の厚みが１〜３μｍであることが好ましい。
The thickness of the thermoplastic resin film A is 1 to 50 μm,
The thickness of the thermoplastic resin film B is 5 to 100 μm,
It is preferable that the thickness of the adhesive layer is 1 to 3 μm.
熱可塑樹脂フィルムＡがポリビニルアルコール樹脂からなることが好ましい。 It is preferable that the thermoplastic resin film A is made of a polyvinyl alcohol resin.
また、本発明は、前記積層体を含む偏光板に関する。 Further, the present invention relates to a polarizing plate including the laminate.
本発明の積層体は、基材の膨張や収縮に追従し、接着面のクラックや剥離を防止できる。 The laminate of the present invention follows expansion and contraction of the base material and can prevent cracks and peeling of the bonding surface.
＜＜積層体＞＞
本発明の積層体は、ガラス転移温度がＴｇＡである熱可塑樹脂フィルムＡ、
ガラス転移温度がＴｇＢである熱可塑樹脂フィルムＢ、および、
熱可塑樹脂フィルムＡと熱可塑樹脂フィルムＢとの間に形成され、光硬化性組成物を硬化させてなる、ガラス転移温度がＴｇＣである接着層を有する積層体であって、
ＴｇＡ、ＴｇＢ、およびＴｇＣが下記式（１）および（２）：
（１）ＴｇＢ／ＴｇＡ＋ＴｇＡ／ＴｇＢ≦５
（２）ＴｇＡ×０．２≦ＴｇＣ≦ＴｇＢ＋（ＴｇＢ−ＴｇＡ）×０．９
の関係を満たす。
<< Laminate >>
The laminate of the invention, the thermoplastic resin film A glass transition temperature of Tg A,
The thermoplastic resin film B glass transition temperature of Tg B and,
A laminate having an adhesive layer formed between a thermoplastic resin film A and a thermoplastic resin film B and obtained by curing a photocurable composition and having a glass transition temperature of Tg C ,
Tg A , Tg B , and Tg C are represented by the following formulas (1) and (2):
(1) Tg B / Tg A + Tg A / Tg B ≦ 5
(2) Tg A × 0.2 ≦ Tg C ≦ Tg B + (Tg B -Tg A) × 0.9
Satisfy the relationship.
＜熱可塑樹脂フィルムＡ＞
熱可塑樹脂フィルムＡは、熱可塑樹脂であればその材質は特に限定されず、例えば、ポリビニルアルコール樹脂や、トリアセチルセルロース樹脂等が挙げられる。熱可塑樹脂フィルムＡのガラス転移温度ＴｇＡは、３０〜１４０℃が好ましく、３５〜１３０℃がより好ましく、４０〜７０℃がさらに好ましい。なお、熱可塑樹脂フィルムＡのガラス転移温度ＴｇＡは実施例記載の手法にて測定される値をいう。
<Thermoplastic resin film A>
The material of the thermoplastic resin film A is not particularly limited as long as it is a thermoplastic resin, and examples thereof include a polyvinyl alcohol resin and a triacetyl cellulose resin. Glass transition temperature Tg A of the thermoplastic resin film A is preferably from 30 to 140 ° C., more preferably from 35 to 130 ° C., more preferably 40 to 70 ° C.. The glass transition temperature Tg A of the thermoplastic resin film A refers to a value measured by the method described in Examples.
熱可塑樹脂フィルムＡとしては、熱可塑樹脂であれば特に限定されず、ポリビニルアルコール樹脂や、トリアセチルセルロース樹脂が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。 The thermoplastic resin film A is not particularly limited as long as it is a thermoplastic resin, and examples thereof include a polyvinyl alcohol resin and a triacetyl cellulose resin. These may be used alone or in combination of two or more.
熱可塑樹脂フィルムＡの厚みは１〜５０μｍが好ましく、２〜３０μｍがより好ましく、３〜２０μｍがさらに好ましい。 The thickness of the thermoplastic resin film A is preferably 1 to 50 μm, more preferably 2 to 30 μm, and still more preferably 3 to 20 μm.
熱可塑樹脂フィルムＡの水蒸気透過率は２０００ｇ／ｍ２／日以上であるが、２１００ｇ／ｍ２／日以上が好ましく、２２００ｇ／ｍ２／日以上がより好ましい。なお、本発明において、水蒸気透過率は、ＪＩＳＺ０２０８の透湿度試験（カップ法）に準拠して６０℃、９０％Ｒｈ環境において測定される値をいう。 The water vapor transmission rate of the thermoplastic resin film A is 2000 g / m 2 / day or more, preferably 2100 g / m 2 / day or more, more preferably 2200 g / m 2 / day or more. In the present invention, the water vapor permeability refers to a value measured in a 60 ° C., 90% Rh environment in accordance with a moisture permeability test (cup method) of JISZ0208.
熱可塑樹脂フィルムＡは、市販のフィルムを使用しても良いし、非晶性ポリエチレンテレフタレート（ＰＥＴ）等の基材上に、コーティングにより熱可塑樹脂を塗布し、乾燥させて熱可塑樹脂層を形成して延伸することにより製造しても良い。熱可塑樹脂の塗布方法としては、例えば、グラビアコーティング法、リバースコーティング法、ダイコート法、カンマコート法、リップコート法、ファウンテンコーティング法等のロールコーティング法、スプレーコーティング法、ディッピング法、スクリーンコーティング法等が挙げられる。熱可塑樹脂層の形成の前に、コロナ処理、フレーム処理、プラズマ処理、プライマー処理等により、基材の表面処理を行っておいてもよい。プライマー処理に用いるプライマー樹脂としては、特に限定されないが、例えば、ポリウレタン系樹脂、ポリエステル系樹脂等が挙げられる。熱可塑樹脂の乾燥は、基材が変形しない限り特に限定されないが、例えば、５０〜２００℃で０．５〜２０分間の条件で行うことができる。熱可塑樹脂が無溶剤系である場合である場合には乾燥工程は省略できる。 As the thermoplastic resin film A, a commercially available film may be used, or a thermoplastic resin is applied on a base material such as amorphous polyethylene terephthalate (PET) by coating and dried to form a thermoplastic resin layer. It may be manufactured by forming and stretching. Examples of the method of applying the thermoplastic resin include a gravure coating method, a reverse coating method, a die coating method, a comma coating method, a lip coating method, a roll coating method such as a fountain coating method, a spray coating method, a dipping method, and a screen coating method. Is mentioned. Before the formation of the thermoplastic resin layer, the surface treatment of the base material may be performed by corona treatment, flame treatment, plasma treatment, primer treatment or the like. The primer resin used for the primer treatment is not particularly limited, and examples thereof include a polyurethane resin and a polyester resin. The drying of the thermoplastic resin is not particularly limited as long as the base material is not deformed. For example, the drying can be performed at 50 to 200 ° C. for 0.5 to 20 minutes. When the thermoplastic resin is a solventless system, the drying step can be omitted.
熱可塑樹脂の延伸処理の方法としては、例えば、ロール延伸法、テンター延伸法等が挙げられる。延伸倍率は、特に限定されないが、通常４〜８倍程度である。延伸温度は、特に限定されず基材の材質に応じて設定することができる。 Examples of the method of stretching the thermoplastic resin include a roll stretching method and a tenter stretching method. The stretching ratio is not particularly limited, but is usually about 4 to 8 times. The stretching temperature is not particularly limited and can be set according to the material of the substrate.
本発明の積層体を偏光板とする場合には、熱可塑樹脂フィルムＡを偏光子として用いることができる。この場合、上記方法により基材上に熱可塑樹脂層を形成して延伸した後、ヨウ素や二色性有機染料等の二色性色素を吸着配向させることにより偏光子を作製できる。 When the laminate of the present invention is used as a polarizing plate, the thermoplastic resin film A can be used as a polarizer. In this case, a polarizer can be produced by forming and stretching a thermoplastic resin layer on a substrate by the above method, and then adsorbing and orienting a dichroic dye such as iodine or a dichroic organic dye.
熱可塑樹脂層に二色性色素を吸着配向させる方法としては、二色性色素を含有する水溶液に、熱可塑樹脂層を有する基材を浸漬する方法が挙げられる。二色性色素としてヨウ素を用いる場合、ヨウ素及びヨウ化カリウムを含有する水溶液を染色浴として用いる。 As a method for adsorbing and orienting the dichroic dye on the thermoplastic resin layer, there is a method of immersing the base material having the thermoplastic resin layer in an aqueous solution containing the dichroic dye. When iodine is used as the dichroic dye, an aqueous solution containing iodine and potassium iodide is used as a dye bath.
＜熱可塑樹脂フィルムＢ＞
熱可塑樹脂フィルムＢは、熱可塑樹脂であればその材質は特に限定されず、例えば、シクロオレフィンポリマー（ＣＯＰ）、ポリメタクリル酸メチル樹脂（ＰＭＭＡ）、ポリビニルアルコール（ＰＶＡ）樹脂、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート、変性ポリエステル等のポリエステル系樹脂、ポリエチレン（ＰＥ）樹脂、ポリプロピレン（ＰＰ）樹脂、ポリスチレン樹脂、環状オレフィン系樹脂等のポリオレフィン類樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン等のビニル系樹脂、ポリエーテルエーテルケトン（ＰＥＥＫ）樹脂、ポリサルホン（ＰＳＦ）樹脂、ポリエーテルサルホン（ＰＥＳ）樹脂、ポリカーボネート（ＰＣ）樹脂、ポリアミド樹脂、ポリイミド樹脂、アクリル樹脂等が挙げられる。これらは単独で用いても良いし、２種以上を混合しても良い。これらの中でもシクロオレフィンポリマー（ＣＯＰ）、ポリメタクリル酸メチル樹脂（ＰＭＭＡ）、ポリエチレンテレフタレート（ＰＥＴ）が好ましい。
<Thermoplastic resin film B>
The material of the thermoplastic resin film B is not particularly limited as long as it is a thermoplastic resin. For example, cycloolefin polymer (COP), polymethyl methacrylate resin (PMMA), polyvinyl alcohol (PVA) resin, polyethylene terephthalate (PET) ), Polyester resins such as polyethylene naphthalate and modified polyester, polyolefin resins such as polyethylene (PE) resin, polypropylene (PP) resin, polystyrene resin and cyclic olefin resin, and vinyl resins such as polyvinyl chloride and polyvinylidene chloride. Resin, polyetheretherketone (PEEK) resin, polysulfone (PSF) resin, polyethersulfone (PES) resin, polycarbonate (PC) resin, polyamide resin, polyimide resin, acrylic resin, and the like. These may be used alone or as a mixture of two or more. Among these, cycloolefin polymer (COP), polymethyl methacrylate resin (PMMA), and polyethylene terephthalate (PET) are preferred.
熱可塑樹脂フィルムＢのガラス転移温度ＴｇＢは、７０〜１８０℃が好ましく、８０〜１７０℃がより好ましく、１００〜１６５℃がさらに好ましい。なお、熱可塑樹脂フィルムＢのガラス転移温度は、実施例記載の手法にて測定される値をいう。 The glass transition temperature Tg B of the thermoplastic resin film B is preferably from 70 to 180 ° C., more preferably from 80 to 170 ° C., more preferably one hundred to one hundred sixty-five ° C.. In addition, the glass transition temperature of the thermoplastic resin film B refers to a value measured by the method described in Examples.
熱可塑樹脂フィルムＢの厚みは５〜１００μｍが好ましく、１０〜８０μｍがより好ましく、１５〜７０μｍがさらに好ましい。特に、熱可塑樹脂フィルムＡの厚みが３〜２０μｍであり、熱可塑樹脂フィルムＢの厚みが１５〜７０μｍであり、かつ、接着層の厚みが１〜３μｍであることが好ましい。 The thickness of the thermoplastic resin film B is preferably 5 to 100 μm, more preferably 10 to 80 μm, and still more preferably 15 to 70 μm. In particular, it is preferable that the thickness of the thermoplastic resin film A is 3 to 20 μm, the thickness of the thermoplastic resin film B is 15 to 70 μm, and the thickness of the adhesive layer is 1 to 3 μm.
熱可塑樹脂フィルムＢの水蒸気透過率は１０００ｇ／ｍ２／日以下であるが、５００ｇ／ｍ２／日以下が好ましく、２５０ｇ／ｍ２／日以下がより好ましく、１００ｇ／ｍ２／日以下がさらに好ましい。 The water vapor transmission rate of the thermoplastic resin film B is 1000 g / m 2 / day or less, preferably 500 g / m 2 / day or less, more preferably 250 g / m 2 / day or less, and 100 g / m 2 / day or less. More preferred.
＜光硬化性組成物＞
積層体における接着層は、光硬化性組成物の硬化物である。光硬化性組成物は、カチオンにより重合する光カチオン硬化性化合物と感光性カチオン開始剤との混合物や、ラジカルにより重合する光ラジカル硬化性化合物と感光性ラジカル開始剤との混合物が挙げられる。
<Photocurable composition>
The adhesive layer in the laminate is a cured product of the photocurable composition. Examples of the photocurable composition include a mixture of a photocationic curable compound polymerized by a cation and a photosensitive cationic initiator, and a mixture of a photoradical curable compound polymerized by a radical and a photosensitive radical initiator.
カチオンにより重合する光カチオン硬化性化合物としては、例えば、エポキシ化合物、オキセタン化合物が挙げられる。これらは、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the photocationically curable compound polymerized by a cation include an epoxy compound and an oxetane compound. These may be used alone or in combination of two or more.
エポキシ化合物としては、例えば、芳香族系エポキシ化合物、脂環式エポキシ化合物、脂肪族エポキシ化合物、エポキシ基を有する重量平均分子量１０００〜１００００００の高分子量体が挙げられる。これらは、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。基材密着性の点から、光硬化性組成物中、芳香族系エポキシ化合物の含有量は５０重量％以上が好ましく、６０重量％以上がより好ましく、７０重量％以上がさらに好ましい。芳香族系エポキシ化合物以外の硬化成分としては、例えば、脂環式エポキシ化合物、脂肪族エポキシ化合物、エポキシ基を有する重量平均分子量１０００〜１００００００の高分子量体といった芳香環を有しないエポキシ化合物に加え、オキセタン化合物、ビニルエーテル化合物といった非エポキシ化合物が挙げられる。芳香族系エポキシ化合物以外の硬化成分は、１種のみを用いてもよいし、２種以上を用いてもよい。 Examples of the epoxy compound include aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, and high molecular weight compounds having an epoxy group and a weight average molecular weight of 1,000 to 1,000,000. These may be used alone or in combination of two or more. In light of the substrate adhesion, the content of the aromatic epoxy compound in the photocurable composition is preferably equal to or greater than 50% by weight, more preferably equal to or greater than 60% by weight, and still more preferably equal to or greater than 70% by weight. As the curing component other than the aromatic epoxy compound, for example, in addition to an epoxy compound having no aromatic ring such as an alicyclic epoxy compound, an aliphatic epoxy compound, and a high molecular weight compound having an epoxy group and a weight average molecular weight of 1,000 to 1,000,000, Non-epoxy compounds such as oxetane compounds and vinyl ether compounds are exemplified. As the curing component other than the aromatic epoxy compound, only one type may be used, or two or more types may be used.
芳香族系エポキシ化合物としては、例えば、ビス（４−ヒドロキシフェニル）エタンジグリシジルエーテル、ビス（４−ヒドロキシフェニル）プロパンジグリシジルエーテル、クレゾールノボラック型エポキシ化合物、レゾルシンジグリシジルエーテル、カテコールジグリシジルエーテル、ヒドロキノンジグリシジルエーテル、ｔ−ブチルフェニルグリシジルエーテル、ｔ−ブチルヒドロキノンジグリシジルエーテル、２，５−ジ−ｔ−ブチルヒドロキノンジグリシジルエーテル、フタル酸ジグリシジルエステル、ビス（４−ヒドロキシフェニル）メタンジグリシジルエーテル、テトラメチルビス（４−ヒドロキシフェニル）メタンジグリシジルエーテル、テトラメチルビス（４−ヒドロキシフェニル）エタンジグリシジルエーテル、テトラメチルビス（４−ヒドロキシフェニル）プロパンジグリシジルエーテル、テトラメチルビス（４−ヒドロキシフェニル）エーテルジグリシジルエーテル、ジメチルジ−ｔ−ブチルビス（４−ヒドロキシフェニル）スルフィドジグリシジルエーテル、ビスフェノールフルオレン型エポキシ樹脂、ビスクレゾールフルオレン型エポキシ樹脂、ビフェニル型又はテトラメチルビフェニル型エポキシ樹脂類、ジヒドロキシナフタレンのジグリシジルエーテル等が挙げられる。これらの中でもビス（４−ヒドロキシフェニル）エタンジグリシジルエーテル、ビス（４−ヒドロキシフェニル）プロパンジグリシジルエーテルが好ましい。これらは、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the aromatic epoxy compound include bis (4-hydroxyphenyl) ethane diglycidyl ether, bis (4-hydroxyphenyl) propane diglycidyl ether, cresol novolak type epoxy compound, resorcin diglycidyl ether, catechol diglycidyl ether, Hydroquinone diglycidyl ether, t-butylphenyl glycidyl ether, t-butylhydroquinone diglycidyl ether, 2,5-di-t-butylhydroquinone diglycidyl ether, phthalic acid diglycidyl ester, bis (4-hydroxyphenyl) methanediglycidyl Ether, tetramethylbis (4-hydroxyphenyl) methane diglycidyl ether, tetramethylbis (4-hydroxyphenyl) ethanediglycidyl ether, tetra Tylbis (4-hydroxyphenyl) propane diglycidyl ether, tetramethylbis (4-hydroxyphenyl) ether diglycidyl ether, dimethyldi-t-butylbis (4-hydroxyphenyl) sulfide diglycidyl ether, bisphenol fluorene epoxy resin, biscresol Examples include fluorene-type epoxy resins, biphenyl-type or tetramethylbiphenyl-type epoxy resins, and diglycidyl ether of dihydroxynaphthalene. Of these, bis (4-hydroxyphenyl) ethane diglycidyl ether and bis (4-hydroxyphenyl) propane diglycidyl ether are preferred. These may be used alone or in combination of two or more.
脂環式エポキシ化合物としては、例えば３’，４’−エポキシシクロヘキシルメチル、３，４−エポキシシクロヘキサンカルボキシレート、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、リモネンジオキシド、ジシクロペンタジエンジオキシド等が挙げられる。 Examples of the alicyclic epoxy compound include 3 ′, 4′-epoxycyclohexylmethyl, 3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, limonenedi Oxide and dicyclopentadiene dioxide.
脂肪族エポキシ化合物としては、例えばネオペンチルグリコールジグリシジルエーテル、ジメチロールシクロヘキサンジグリシジルエーテル、１，４−シクロヘキサンジグリシジルエーテル、１，３−シクロヘキサンジグリシジルエーテル、１，２−シクロヘキサンジグリシジルエーテル、ジメチロールジシクロペンタジエンジグリシジルエーテル、ヘキサヒドロフタル酸ジグリシジルエステル、ヘキサヒドロテレフタル酸ジグリシジルエステル、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等が挙げられる。 Examples of the aliphatic epoxy compound include neopentyl glycol diglycidyl ether, dimethylol cyclohexane diglycidyl ether, 1,4-cyclohexane diglycidyl ether, 1,3-cyclohexane diglycidyl ether, 1,2-cyclohexane diglycidyl ether, Methylol dicyclopentadiene diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hexahydroterephthalic acid diglycidyl ester, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like.
オキセタン化合物は、分子内に４員環エーテルを有する化合物であり、例えば、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、ジ〔（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、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は市販品を容易に入手することが可能であり、例えば、２−ヒドロキシエチルビニルエーテル、ジエチレングリコールモノビニルエーテル、４−ヒドロキシブチルビニルエーテル（丸善石油化学（株）社製）；アロンオキセタンＯＸＴ−１２１、ＯＸＴ−２２１、ＥＸＯＨ、ＰＯＸ、ＯＸＡ、ＯＸＴ−１０１、ＯＸＴ−２１１、ＯＸＴ−２１２（東亞合成（株）社製）、エタナコールＯＸＢＰ、ＯＸＴＰ（宇部興産（株）社製）等が挙げられる。また、これらのオキセタン類は、光硬化性組成物に対して、通常５０重量％以下、好ましくは１０〜４５重量％の割合で使用される。 The oxetane compound is a compound having a 4-membered ring ether in the molecule, for example, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, -Ethyl-3- (phenoxymethyl) oxetane, di [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, phenol novolak oxetane, and the like. Commercially available products of these oxetane compounds can be easily obtained. For example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.); Aron oxetane OXT- 121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.), etanacol OXBP, OXTP (manufactured by Ube Industries). . These oxetanes are generally used in a proportion of 50% by weight or less, preferably 10 to 45% by weight, based on the photocurable composition.
ビニルエーテル化合物としては、２−ヒドロキシエチルビニルエーテル、ジエチレングリコールモノビニルエーテル、４−ヒドロキシブチルビニルエーテル（丸善石油化学（株）社製）、アロンオキセタンＯＸＴ−１２１、ＯＸＴ−２２１、ＥＸＯＨ、ＰＯＸ、ＯＸＡ、ＯＸＴ−１０１、ＯＸＴ−２１１、ＯＸＴ−２１２（東亞合成（株）社製）、エタナコールＯＸＢＰ、ＯＸＴＰ（宇部興産（株）社製）等が挙げられる。 Examples of the vinyl ether compound include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.), Alonoxetane OXT-121, OXT-221, EXOH, POX, OXA, and OXT-101. OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.), etanacol OXBP, OXTP (manufactured by Ube Industries, Ltd.) and the like.
感光性カチオン開始剤は、光等のエネルギー線の照射を受けてカチオン重合を開始させる物質を放出させる化合物をいい、好ましくは、エネルギー照射によりルイス酸を放出するような化合物をいう。このような化合物としては、例えばオニウム塩、ハロゲン含有化合物、ジアゾメタン化合物、スルホン化合物、スルホン酸化合物などの、放射線により酸を発生する光酸発生剤を用いることができる。オニウム塩としては、例えばトリフレートあるいはヘキサフレートとのヨードニウム塩、スルホニウム塩、ジアゾニウム塩、アンモニウム塩、ピリジニウム塩等が挙げられ、ハロゲン含有化合物としては、ハロアルキル基含有炭化水素化合物あるいはハロアルキル基含有複素環式化合物、例えば、フェニル−ビス（トリクロロメチル）−ｓ−トリアジン、メトキシフェニル−ビス（トリクロロメチル）−ｓ−トリアジンなどの（トリクロロメチル）−ｓ−トリアジン誘導体や、トリブロモネオペンチルアルコール、ヘキサブロモヘキサンなどの臭素化合物、ヘキサヨードヘキサンなどのヨウ素化合物などが挙げられる。また、ジアゾメタン化合物としては、例えばビス（トリフルオロメチルスルホニウム）ジアゾメタン、ビス（シクロヘキシルスルホニウム）ジアゾメタンなどが挙げられる。スルホン化合物としては、例えばβ−ケトスルホン、β−スルホニルスルホン等が挙げられ、スルホン酸化合物としては、アルキル（Ｃ１−１２）スルホン酸エステル、ハロアルキル（Ｃ１−１２）スルホン酸エステル、アリールスルホン酸エステル、イミノスルホナート等が挙げられる。これらは、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 The photosensitive cationic initiator refers to a compound that releases a substance that initiates cationic polymerization upon irradiation with energy rays such as light, and preferably a compound that releases a Lewis acid upon energy irradiation. As such a compound, for example, a photoacid generator that generates an acid by irradiation, such as an onium salt, a halogen-containing compound, a diazomethane compound, a sulfone compound, and a sulfonic acid compound, can be used. Examples of the onium salt include an iodonium salt with triflate or hexaflate, a sulfonium salt, a diazonium salt, an ammonium salt, a pyridinium salt, and the like.Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic ring. Formula compounds, for example, (trichloromethyl) -s-triazine derivatives such as phenyl-bis (trichloromethyl) -s-triazine, methoxyphenyl-bis (trichloromethyl) -s-triazine, tribromoneopentyl alcohol, hexabromo Bromine compounds such as hexane and iodine compounds such as hexaiodohexane are exemplified. Examples of the diazomethane compound include bis (trifluoromethylsulfonium) diazomethane and bis (cyclohexylsulfonium) diazomethane. Examples of the sulfone compound include β-ketosulfone and β-sulfonylsulfone. Examples of the sulfonic acid compound include alkyl (C1-12) sulfonic acid ester, haloalkyl (C1-12) sulfonic acid ester, aryl sulfonic acid ester, and the like. And iminosulfonate. These may be used alone or in combination of two or more.
感光性カチオン開始剤の配合量は、硬化成分１００重量部に対して０．００１〜２０重量部が好ましく、０．０１〜１０重量部がより好ましく、０．１〜７重量部がさらに好ましい。 The amount of the photosensitive cationic initiator is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and even more preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the curing component.
ラジカルにより重合する光ラジカル硬化性化合物としては、例えば、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、３−ヒドロキシプロピル（メタ）アクリレートなどの水酸基を有する（メタ）アクリル酸エステル類；エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、テトラメチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、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ヘキサ（メタ）アクリレート、グリセロール（メタ）アクリレートなどの（メタ）アクリル酸エステル類が挙げられる。これらのモノマーあるいはオリゴマーは、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the photo-radical curable compound polymerized by a radical include (meth) acrylic acid having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate. Esters: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythri Rutetora (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (meth) acrylic acid esters such as glycerol (meth) acrylate. One of these monomers or oligomers may be used alone, or two or more thereof may be used in combination.
感光性ラジカル開始剤とは、光重合開始作用を有する化合物をいう。このような化合物としては、例えばアセトフェノン、２，２−ジエトキシアセトフェノン、ｐ−ジメチルアセトフェノン、ｐ−ジメチルアミノプロピオフェノン、ジクロロアセトフェノン、トリクロロアセトフェノン、ｐ−ｔｅｒｔ−ブチルアセトフェノンなどのアセトフェノン類；ベンゾフェノン、２−クロロベンゾフェノン、ｐ，ｐ’−ビスジメチルアミノベンゾフェノンなどのベンゾフェノン類；ベンジル；ベンゾイン；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、ベンゾインイソブチルエーテルなどのベンゾインエーテル類；ベンジルジメチルケタール；チオキサンテン、２−クロロチオキサンテン、２，４−ジエチルチオキサンテン、２−メチルチオキサンテン、２−イソプロピルチオキサンテンなどのイオウ化合物；２−エチルアントラキノン、オクタメチルアントラキノン、１，２−ベンズアントラキノン、２，３−ジフェニルアントラキノンなどのアントラキノン類；アゾビスイソブチロニトリル；ベンゾイルパーオキサイド、クメンパーオキサイドなどの有機過酸化物；および２−メルカプトベンゾイミダゾール、２−メルカプトベンゾオキサゾール、２−メルカプトベンゾチアゾールなどのチオール化合物が挙げられる。これらの光重合開始剤は、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 The photosensitive radical initiator refers to a compound having a photopolymerization initiating action. Examples of such compounds include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; benzophenone, Benzophenones such as 2-chlorobenzophenone and p, p'-bisdimethylaminobenzophenone; benzyl; benzoin; benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzyl dimethyl ketal; thioxanthen; Sulfur such as thioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene and 2-isopropylthioxanthene Compounds; Anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone; Azobisisobutyronitrile; Organic peroxides such as benzoyl peroxide and cumene peroxide And thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole. One of these photopolymerization initiators may be used alone, or two or more thereof may be used in combination.
感光性ラジカル開始剤の配合量は、ラジカルにより硬化する光ラジカル硬化性化合物１００重量部に対して０．００１〜１０重量部が好ましく、０．０１〜７重量部がより好ましく、０．１〜５重量部がさらに好ましい。 The compounding amount of the photosensitive radical initiator is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 7 parts by weight, and more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the photo-radical curable compound which is cured by a radical. 5 parts by weight is more preferred.
光硬化性組成物は、光硬化性化合物と、感光性カチオン開始剤や感光性ラジカル開始剤の他に、水酸基、カルボキシル基、およびスルホ基からなる群から選択される１種以上の親水性基を有し、分子量が１０００以下である化合物を含んでいてもよい。光硬化性組成物が親水性基を有する化合物を含むと、フィルム中の親水性基の近傍にすみやかに集合し、光硬化性組成物がフィルムへ浸透しやすくなる。特に、分子量が１０００以下の比較的小さな分子は、立体障害が小さくフィルム樹脂構造内部に浸透しやすい。このような添加剤としては、ポリエステルポリオール、ポリエーテルポリオール、ポリカプロラクトンポリオール、グリセリン等のポリオール、トリメチロールエタン、トリメチロールプロパン、アダマンタントリオール、ポリカプロラクトントリオール等のトリオール、ポリカーボネートジオール、ポリセステルジオール、ポリエーテルジオール等のジオールが挙げられる。この中でも、ポリカプロラクトンポリオール、ポリエステルポリオール、ポリカーボネートジオールが好ましい。これらの化合物の分子量は１０００以下が好ましく、９００以下がより好ましく、８５０以下がさらに好ましい。これらの化合物の配合量は、硬化成分１００重量部に対して１〜１００重量部が好ましく、５〜５０重量部がより好ましい。 The photocurable composition comprises, in addition to the photocurable compound, a photosensitive cationic initiator and a photosensitive radical initiator, one or more hydrophilic groups selected from the group consisting of a hydroxyl group, a carboxyl group, and a sulfo group. And a compound having a molecular weight of 1,000 or less. When the photocurable composition contains a compound having a hydrophilic group, the photocurable composition quickly aggregates near the hydrophilic group in the film, and the photocurable composition easily penetrates into the film. In particular, relatively small molecules having a molecular weight of 1000 or less have small steric hindrance and easily penetrate into the inside of the film resin structure. Examples of such additives include polyester polyols, polyether polyols, polycaprolactone polyols, polyols such as glycerin, trimethylolethane, trimethylolpropane, adamantanetriol, triols such as polycaprolactonetriol, polycarbonate diols, polyester diols, Diols such as polyether diols are included. Among them, polycaprolactone polyol, polyester polyol and polycarbonate diol are preferred. The molecular weight of these compounds is preferably 1,000 or less, more preferably 900 or less, and even more preferably 850 or less. The compounding amount of these compounds is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the curing component.
光硬化性組成物は、以上に述べた成分の他に、反応性希釈剤、硬化剤、硬化促進剤、添加剤、溶剤等を含んでいてもよい。なお、光硬化性組成物は、シクロヘキサン、トルエン、キシレン等の炭化水素溶剤、メタノール、エタノール、プロパノール、イソプロパノール等のアルコール系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン及びシクロヘキサノン等のケトン系溶剤、酢酸エチル、酢酸ブチル等のエステル系溶剤、エチレングリコールモノメチルアセテート、エチレングリコールモノエチルアセテート、プロピレングリコール−１−モノメチルエーテル−２−アセテート（ＰＧＭＥＡ）、３−メトキシブチルアセテート、エトキシエチルプロピオネート等のエーテルエステル系溶剤、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン、ジメチルスルホキシド等の溶剤を含んでいてもよいが、製造時の熱乾燥工程を省くためには無溶剤であることが好ましい。また、光硬化性組成物は塗工の容易性のために、２５℃でＥ型粘度計を用いて、回転速度１００ｒｐｍで測定した粘度が２００ｍＰａ・ｓ以下であることが好ましい。 The photocurable composition may include a reactive diluent, a curing agent, a curing accelerator, an additive, a solvent, and the like, in addition to the components described above. The photocurable composition includes a hydrocarbon solvent such as cyclohexane, toluene and xylene; an alcohol solvent such as methanol, ethanol, propanol and isopropanol; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and ethyl acetate. , Butyl acetate and other ester solvents, ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), 3-methoxybutyl acetate, ether esters such as ethoxyethyl propionate System solvent, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and other solvents. It is preferable to omit the drying step is solvent-free. The viscosity of the photocurable composition measured at 25 ° C. using an E-type viscometer at a rotation speed of 100 rpm is preferably 200 mPa · s or less for ease of application.
反応性希釈剤は、粘度調整を行うために添加する低粘度なエポキシ化合物であり、特に二官能以上の低粘度エポキシ化合物が好ましい。反応性希釈剤としては、例えば、次の化合物が挙げられる：ジグリシジルエーテル、ブタンジオールジグリシジルエーテル、ジグリシジルアニリン、ネオペンチルグリコールグリシジルエーテル、シクロヘキサンジメタノールジグリシジルエーテル、アルキレンジグリシジルエーテル、ポリグリコールジグリシジルエーテル、ポリプロピレングリコ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、グリセリントリグリシジルエーテル、４−ビニルシクロヘキセンモノオキサイド、ビニルシクロヘキセンジオキサイド、メチル化ビニルシクロヘキセンジオキサイドなど。これら反応性希釈剤は１種のみを単独で使用できる他、２種以上を混合しても使用することができる。反応性希釈剤の配合量は、光硬化性組成物に対して１〜５０重量％であることが好ましい。 The reactive diluent is a low-viscosity epoxy compound added for adjusting the viscosity, and a bifunctional or higher-functional low-viscosity epoxy compound is particularly preferable. Reactive diluents include, for example, the following compounds: diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, neopentyl glycol glycidyl ether, cyclohexane dimethanol diglycidyl ether, alkylene diglycidyl ether, polyglycol Diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, 4-vinylcyclohexene monooxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide and the like. These reactive diluents can be used alone or in combination of two or more. The amount of the reactive diluent is preferably 1 to 50% by weight based on the photocurable composition.
添加剤としては、無機フィラー、有機フィラー、顔料、染料などの着色剤、難燃剤、光増感剤、消泡剤、増粘剤、界面活性剤、増粘剤、可塑剤、重合禁止剤、紫外線吸収剤、酸化防止剤、帯電防止剤、硬化性の化合物（硬化性モノマー、オリゴマー、または樹脂）などが挙げられる。添加剤の配合量は、光硬化性組成物に対して１〜５０重量％であることが好ましい。 Additives include inorganic fillers, organic fillers, pigments, coloring agents such as dyes, flame retardants, photosensitizers, defoamers, thickeners, surfactants, thickeners, plasticizers, polymerization inhibitors, Examples include an ultraviolet absorber, an antioxidant, an antistatic agent, and a curable compound (curable monomer, oligomer, or resin). The amount of the additive is preferably 1 to 50% by weight based on the weight of the photocurable composition.
接着層は、光硬化性組成物を熱可塑樹脂フィルムＢ上に塗布し、後述の方法で硬化させることにより得られる。光硬化性組成物の塗布方法としては、例えば、グラビアコーティング法、リバースコーティング法、ダイコート法、カンマコート法、リップコート法、ファウンテンコーティング法等のロールコーティング法、スプレーコーティング法、ディッピング法、スクリーンコーティング法等が挙げられる。光硬化性組成物の塗布の前に、コロナ処理、フレーム処理、プラズマ処理、プライマー処理等により、熱可塑樹脂フィルムＢの表面処理を行っておいてもよい。プライマー処理に用いるプライマー樹脂としては、特に限定されないが、例えば、ポリウレタン系樹脂、ポリエステル系樹脂等が挙げられる。 The adhesive layer is obtained by applying the photocurable composition on the thermoplastic resin film B and curing it by a method described later. Examples of the application method of the photocurable composition include a gravure coating method, a reverse coating method, a die coating method, a comma coating method, a lip coating method, a roll coating method such as a fountain coating method, a spray coating method, a dipping method, and a screen coating method. And the like. Before the application of the photocurable composition, the surface treatment of the thermoplastic resin film B may be performed by corona treatment, flame treatment, plasma treatment, primer treatment, or the like. The primer resin used for the primer treatment is not particularly limited, and examples thereof include a polyurethane resin and a polyester resin.
＜積層体＞
本発明の積層体は、上記方法により基材上に形成された熱可塑樹脂フィルムＡの上に、後述の光硬化性組成物、熱可塑樹脂フィルムＢを順に積層するか、又は、熱可塑樹脂フィルムＢ上に積層された光硬化性組成物を、熱可塑樹脂フィルムＡと接するように張り合わせ、その後、熱可塑樹脂フィルムＡから基材を剥離し、最後に、光硬化性組成物を硬化させることにより、作製できる。
<Laminate>
The laminate of the present invention is obtained by sequentially laminating a photocurable composition and a thermoplastic resin film B described later on a thermoplastic resin film A formed on a substrate by the above method, or The photocurable composition laminated on the film B is adhered so as to be in contact with the thermoplastic resin film A, and thereafter, the base material is peeled off from the thermoplastic resin film A, and finally, the photocurable composition is cured. Thus, it can be manufactured.
光硬化性組成物は、熱可塑樹脂フィルムＡ、光硬化性組成物の被膜、および熱可塑樹脂フィルムＢからなる積層体に対し、熱可塑樹脂フィルムＡ面、または熱可塑樹脂フィルムＢ面から光照射処理を行うことにより硬化させる。光照射処理には、例えば紫外線、可視光、電子線、電離放射線等を使用する。紫外線硬化の場合には、超高圧水銀灯、高圧水銀灯、低圧水銀灯、カーボンアーク、キセノンアーク、メタルハライドランプ等の光源から発する紫外線等を使用することができる。エネルギー線源の照射量は、紫外線により３０〜５００ｍＪ／ｃｍ２が好ましく、３０〜２００ｍＪ／ｃｍ２がより好ましい。照射量が５００ｍＪ／ｃｍ２を超えると熱可塑樹脂フィルムが変質することがある。本発明では、接着層のガラス転移温度を一定の範囲に設定することにより、３０〜５００ｍＪ／ｃｍ２という比較的少量の紫外線照射によっても十分な接着性を実現できる。 The photocurable composition is applied to the laminate of the thermoplastic resin film A, the coating of the photocurable composition, and the thermoplastic resin film B from the thermoplastic resin film A surface or the thermoplastic resin film B surface. It is cured by performing irradiation treatment. For the light irradiation treatment, for example, ultraviolet light, visible light, electron beam, ionizing radiation, or the like is used. In the case of ultraviolet curing, ultraviolet rays emitted from a light source such as an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used. The irradiation amount of the energy ray source is preferably from 30 to 500 mJ / cm 2 , more preferably from 30 to 200 mJ / cm 2 due to ultraviolet rays. When the irradiation amount exceeds 500 mJ / cm 2 , the thermoplastic resin film may be deteriorated. In the present invention, by setting the glass transition temperature of the adhesive layer within a certain range, sufficient adhesiveness can be realized even with irradiation of a relatively small amount of ultraviolet light of 30 to 500 mJ / cm 2 .
さらに、上記積層体の熱可塑樹脂フィルムＡの上に、第２の接着層、および第２の熱可塑樹脂フィルムＢを積層させることにより、熱可塑樹脂フィルムＢ、接着層、熱可塑樹脂フィルムＡ、第２の接着層、および第２の熱可塑樹脂フィルムＢがこの順に積層された積層体を得ることもできる。このような積層体は、例えば、熱可塑樹脂フィルムＡからなる偏光子が２つの熱可塑樹脂フィルムＢにより挟まれた偏光板となる。第２の接着層および第２の熱可塑樹脂フィルムＢの組成としては、前述した接着層および熱可塑樹脂フィルムＢの組成を用いることができ、２つの接着層、および２つの熱可塑樹脂フィルムＢの組成は同一でもよく、異なってもよい。 Further, by laminating the second adhesive layer and the second thermoplastic resin film B on the thermoplastic resin film A of the laminate, the thermoplastic resin film B, the adhesive layer, the thermoplastic resin film A , A second adhesive layer, and a second thermoplastic resin film B can be obtained in this order. Such a laminate becomes, for example, a polarizing plate in which a polarizer made of a thermoplastic resin film A is sandwiched between two thermoplastic resin films B. As the composition of the second adhesive layer and the second thermoplastic resin film B, the above-described composition of the adhesive layer and the thermoplastic resin film B can be used, and the two adhesive layers and the two thermoplastic resin films B can be used. May be the same or different.
光硬化性組成物を硬化させてなる接着層のガラス転移温度ＴｇＣは、２０〜１００℃が好ましく、３５〜９５℃がより好ましく、４０〜９０℃がさらに好ましい。また、硬化後の積層体の厚みは１〜３μｍが好ましく、１．１〜２．９μｍがより好ましく、１．２〜２．８μｍがさらに好ましい。 Glass transition temperature Tg C of the adhesive layer formed by curing the photocurable composition is preferably from 20 to 100 ° C., more preferably from 35 to 95 ° C., more preferably 40 to 90 ° C.. Further, the thickness of the laminated body after curing is preferably 1 to 3 μm, more preferably 1.1 to 2.9 μm, and still more preferably 1.2 to 2.8 μm.
積層体は、８５℃、８５％Ｒｈの環境下に１００時間放置した後の接着強度が１．５Ｎ／２０ｍｍ以上であることが好ましく、２．０Ｎ／２０ｍｍ以上がより好ましい。なお、この湿熱処理を行う積層体は、熱可塑樹脂フィルムＢに光硬化性組成物を塗布し、熱可塑樹脂フィルムＡを接着層の上に設置した後、３０秒後に熱可塑樹脂フィルムＢの上面から紫外線を照射して得られる積層体をいう。 The laminate preferably has an adhesive strength of 1.5 N / 20 mm or more, more preferably 2.0 N / 20 mm or more, after being left in an environment of 85 ° C. and 85% Rh for 100 hours. The laminate subjected to the wet heat treatment was prepared by applying the photocurable composition to the thermoplastic resin film B and placing the thermoplastic resin film A on the adhesive layer. A laminate obtained by irradiating ultraviolet rays from the upper surface.
＜熱可塑樹脂フィルムと接着層のガラス転移温度の関係＞
熱可塑樹脂フィルムＡのガラス転移温度ＴｇＡ、熱可塑樹脂フィルムＢのガラス転移温度ＴｇＢ、および接着層のガラス転移温度ＴｇＣは、下記式（１）および（２）：
（１）ＴｇＢ／ＴｇＡ＋ＴｇＡ／ＴｇＢ≦５
（２）ＴｇＡ×０．２≦ＴｇＣ≦ＴｇＢ＋（ＴｇＢ−ＴｇＡ）×０．９
の関係を満たす。ガラス転移温度が式（１）および（２）の関係を満たすことにより、接着層が熱可塑樹脂フィルムＡ基材の膨張や収縮に追従できるようになり、接着層と、熱可塑樹脂フィルムＢの接着面のクラックや剥離を防止できる。
<Relationship between glass transition temperature of thermoplastic resin film and adhesive layer>
Glass transition temperature Tg A of the thermoplastic resin film A, the thermoplastic resin film glass transition temperature Tg B of B, and the glass transition temperature Tg C of the adhesive layer, the following equation (1) and (2):
(1) Tg B / Tg A + Tg A / Tg B ≦ 5
(2) Tg A × 0.2 ≦ Tg C ≦ Tg B + (Tg B -Tg A) × 0.9
Satisfy the relationship. When the glass transition temperature satisfies the relations of the formulas (1) and (2), the adhesive layer can follow the expansion and contraction of the thermoplastic resin film A base, and the adhesive layer and the thermoplastic resin film B Cracking and peeling of the bonding surface can be prevented.
式（１）のＴｇＢ／ＴｇＡ＋ＴｇＡ／ＴｇＢは５以下であるが、４以下が好ましく、３．５以下がより好ましい。５より大きいと接着強度が低下する傾向がある。 Tg B / Tg A + Tg A / Tg B in the formula (1) is 5 or less, preferably 4 or less, more preferably 3.5 or less. If it is larger than 5, the adhesive strength tends to decrease.
式（２）においてＴｇＣはＴｇＡ×０．２以上であるが、ＴｇＡ×０．３以上が好ましく、ＴｇＡ×０．４以上がさらに好ましい。ＴｇＣがＴｇＡ×０．２未満では取扱い性が悪くなる傾向がある。 In the formula (2), Tg C is Tg A × 0.2 or more, preferably Tg A × 0.3 or more, and more preferably Tg A × 0.4 or more. If Tg C is less than Tg A × 0.2, handleability tends to be poor.
また、式（２）においてＴｇＣはＴｇＢ＋（ＴｇＢ−ＴｇＡ）×０．９以下であるが、ＴｇＢ＋（ＴｇＢ−ＴｇＡ）×０．８以下が好ましく、ＴｇＢ＋（ＴｇＢ−ＴｇＡ）×０．７以下がより好ましい。ＴｇＣがＴｇＢ＋（ＴｇＢ−ＴｇＡ）×０．９を超えるとクラックが発生する傾向がある。 In the formula (2), Tg C is equal to or less than Tg B + (Tg B −Tg A ) × 0.9, but is preferably equal to or less than Tg B + (Tg B −Tg A ) × 0.8, and more preferably Tg B + (Tg B −Tg A ) × 0.7 or less is more preferable. If Tg C exceeds Tg B + (Tg B −Tg A ) × 0.9, cracks tend to occur.
＜＜偏光板＞＞
本発明の積層体は、偏光板、表示素子の基板、有機ＥＬ素子用の封止材や円偏光板、全面保護板、半導体用・太陽電池用等のパッシベーション膜等の用途に用いることができる。偏光板として用いる場合には、前述のように、１つの熱可塑樹脂フィルムＡが、接着層を介して２つの熱可塑樹脂フィルムＢにより挟まれた形態であってもよい。偏光板として用いる場合には、位相差フィルム、視野角拡大フィルム、輝度向上フィルム、保護フィルム、離型フィルム等と組み合わせてもよい。
<< Polarizing plate >>
The laminate of the present invention can be used for applications such as a polarizing plate, a substrate of a display element, a sealing material for an organic EL element, a circularly polarizing plate, a protective plate for a whole surface, and a passivation film for a semiconductor or a solar cell. . When used as a polarizing plate, as described above, one thermoplastic resin film A may be sandwiched between two thermoplastic resin films B via an adhesive layer. When used as a polarizing plate, it may be combined with a retardation film, a viewing angle widening film, a brightness enhancement film, a protective film, a release film, or the like.
以下、実施例を挙げて本発明を説明するが、本発明は以下の実施例に限定されない。以下、「％」は特記ない限り「重量％」を意味する。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples. Hereinafter, “%” means “% by weight” unless otherwise specified.
１．使用材料
１−１．熱可塑樹脂フィルムＡ
・トリアセチルセルロースフィルム（富士フィルム株式会社製、ＴＪ２５ＵＬ、２５μｍ、Ｔｇ１３０℃）
・ポリビニルアルコールフィルム（株式会社クラレ製、ＶＦ−ＰＥ＃３０００、平均重合度２４００、ケン化度９９．９モル％、厚さ３０μｍ、Ｔｇ４７℃）
1. Materials used 1-1. Thermoplastic resin film A
・ Triacetylcellulose film (Fuji Film Co., Ltd., TJ25UL, 25 μm, Tg130 ° C.)
・ Polyvinyl alcohol film (VF-PE # 3000, manufactured by Kuraray Co., Ltd., average degree of polymerization 2400, degree of saponification 99.9 mol%, thickness 30 μm, Tg 47 ° C.)
１−２．熱可塑樹脂フィルムＢ
ＣＯＰフィルム（日本ゼオン社製、ＺｅｏｎｏｒＦｉｌｍ ＺＦ１４、Ｔｇ１３６℃、膜厚４０μｍ）
・ポリエステル（ＰＥＴ）フィルム（東レ株式会社製、ルミラーＴ６０、２５μｍ、Ｔｇ１００℃）
・アクリル樹脂（ＰＭＭＡ）フィルム（住友化学株式会社製、テクノロイＳ００１Ｇ，７５μｍ、Ｔｇ１０３℃）
1-2. Thermoplastic resin film B
COP film (ZeonorFilm ZF14, Tg136 ° C, film thickness 40 µm, manufactured by Zeon Corporation)
・ Polyester (PET) film (Lumilar T60, 25 µm, Tg100 ° C, manufactured by Toray Industries, Inc.)
Acrylic resin (PMMA) film (Technoloy S001G, 75 μm, Tg103 ° C, manufactured by Sumitomo Chemical Co., Ltd.)
１−３．光硬化性組成物
（硬化成分）
・芳香族系エポキシ化合物（ＤＩＣ株式会社製、ＥＰＩＣＬＯＮ ８５０−ＬＣ）
・芳香族系エポキシ化合物（ＤＩＣ株式会社製、ＥＰＩＣＬＯＮ ＥＸＡ−８３０ＬＶＰ）
・芳香族系エポキシ化合物（ＤＩＣ株式会社製、ＥＰＩＣＬＯＮ ８３５）
・芳香族系エポキシ化合物（ナガセケムテックス株式会社製、デナコールＥＸ１４６）
・脂環式エポキシ化合物（株式会社ダイセル製、セロキサイド２０２１Ｐ）
・オキセタン化合物（東亞合成株式会社製、アロンオキセタンＯＸＴ−２２１）
（開始剤）
・オニウム塩系感光性カチオン開始剤（サンアプロ株式会社製、ＣＰＩ−１００Ｐ）
（親水性基を有する化合物）
・ポリカプロラクトンポリオール（ＤＩＣ株式会社製、ポリライト ＯＤ−Ｘ−２１５５）
・ポリエステルポリオール（ＤＩＣ株式会社製、ポリライト ＯＤ−Ｘ−２５８６）
・ポリカーボネートジオール（ＤＩＣ株式会社製、プラクセルＣＤ２０５ＰＬ）
1-3. Photocurable composition (curing component)
・ Aromatic epoxy compound (DIC Corporation, EPICLON 850-LC)
-Aromatic epoxy compound (DIC Corporation, EPICLON EXA-830LVP)
-Aromatic epoxy compound (DIC Corporation, EPICLON 835)
・ Aromatic epoxy compound (Denacol EX146, manufactured by Nagase ChemteX Corporation)
・ Alicyclic epoxy compound (Ceroxide 2021P, manufactured by Daicel Corporation)
-Oxetane compound (Aron Oxetane OXT-221 manufactured by Toagosei Co., Ltd.)
(Initiator)
・ Onium salt-based photosensitive cation initiator (CPI-100P, manufactured by San Apro Corporation)
(Compound having a hydrophilic group)
・ Polycaprolactone polyol (manufactured by DIC Corporation, Polylite OD-X-2155)
・ Polyester polyol (manufactured by DIC Corporation, Polylite OD-X-2586)
・ Polycarbonate diol (Placcel CD205PL, manufactured by DIC Corporation)
２．評価方法
２−１．ガラス転移温度
熱可塑樹脂フィルムＡと、接着層のガラス転移温度は、ＴＭＡ ＳＳ７１００（株式会社日立ハイテクサイエンス）を使用して測定した。熱可塑樹脂フィルムＢのガラス転移温度は、ＪＩＳ７１２１に準拠し、ＤＳＣ２１０型（セイコー電子工業株式会社製）を使用して測定した。
2. Evaluation method 2-1. Glass transition temperature The glass transition temperatures of the thermoplastic resin film A and the adhesive layer were measured using TMA SS7100 (Hitachi High-Tech Science Co., Ltd.). The glass transition temperature of the thermoplastic resin film B was measured according to JIS7121 using a DSC210 type (manufactured by Seiko Instruments Inc.).
２−２．クラック
無アルカリガラス上に粘着剤を塗布し、乾燥膜厚が３５μｍとなる粘着剤層を形成した。次に、後述する両面積層体を２０ｍｍ×１５０ｍｍの大きさに裁断後、粘着剤層上に設置しラミネートし、冷熱衝撃試験（ヒートショック試験）を行った。冷熱衝撃試験は、−４０℃で３０分間保持し、次に８５℃に昇温して３０分間保持する操作を１サイクルとし、これを合計１００サイクル繰り返すことにより行った。両面積層体の熱可塑樹脂フィルムＡ、熱可塑樹脂フィルムＢ、または接着層におけるクラックの有無を観察し、下記の基準で評価した。
○：クラックの発生は認められなかった。
×：クラックが発生した 。
2-2. An adhesive was applied on the crack-free alkali glass to form an adhesive layer having a dry film thickness of 35 μm. Next, after cutting a double-sided laminate described later into a size of 20 mm × 150 mm, the laminate was placed on an adhesive layer and laminated, and a thermal shock test (heat shock test) was performed. The thermal shock test was performed by maintaining the temperature at -40 ° C for 30 minutes, then increasing the temperature to 85 ° C and maintaining the temperature for 30 minutes as one cycle, and repeating this for a total of 100 cycles. The presence or absence of cracks in the thermoplastic resin film A, the thermoplastic resin film B, or the adhesive layer of the double-sided laminate was observed and evaluated according to the following criteria.
：: No crack was observed.
×: Cracks occurred.
２−３．反り
２−２で使用した粘着剤層上の試験片を、地面に垂直に設置し、中央部の凹み量を定規にて測定し、下記の基準で評価した。
○：１ｍｍ未満
△：１ｍｍ以上３ｍｍ未満
×：３ｍｍ以上
2-3. The test piece on the pressure-sensitive adhesive layer used in the warpage 2-2 was placed vertically on the ground, and the amount of depression at the center was measured with a ruler, and evaluated according to the following criteria.
○: less than 1 mm △: 1 mm or more and less than 3 mm ×: 3 mm or more
２−４．変色
２−２で使用した粘着剤層上の試験片の変色やムラの発生を目視にて確認し、下記の基準で評価した。
○：変化が見られなかった。
△：わずかに変色やムラの発生が見られた。
×：変色やムラの発生が見られた。
2-4. The discoloration and unevenness of the test piece on the pressure-sensitive adhesive layer used in Discoloration 2-2 were visually confirmed and evaluated according to the following criteria.
：: No change was observed.
Δ: Slight discoloration or unevenness was observed.
×: Discoloration or unevenness was observed.
２−５．湿熱処理後の接着強度
実施例および比較例で作製した積層体を２０ｍｍ×１５０ｍｍに裁断したものを試験片として用いた。試験片には、光硬化性組成物が塗工されていない範囲（２０ｍｍ×１０ｍｍ）をあらかじめ用意した。試験片の熱可塑樹脂フィルムＡからなる層を引っ張り試験機（装置名：東洋精機株式会社製ストログラフ試験器）に粘着テープで固定した。熱可塑樹脂フィルムＢからなる層のうち光硬化性組成物が塗工されていない部分を、上部つかみ具で固定し、剥離速度３００ｍｍ／ｍｉｎにて９０°剥離強度（Ｎ／２０ｍｍ）を測定した。なお、湿熱処理後の接着強度は、試験片を恒温恒湿器（ＥＳＰＥＣ社製、ＦＲ−１Ｊ）を用いて温度８５℃、相対湿度８５％の環境下に１００時間保存した後、前記方法で接着強度を測定した。
2-5. Adhesive strength after wet heat treatment The laminate prepared in each of Examples and Comparative Examples was cut into a size of 20 mm x 150 mm and used as a test piece. A range (20 mm × 10 mm) where the photocurable composition was not applied was prepared in advance for the test piece. The layer composed of the thermoplastic resin film A of the test piece was fixed to a tensile tester (device name: Strograph tester manufactured by Toyo Seiki Co., Ltd.) with an adhesive tape. The portion of the layer made of the thermoplastic resin film B, on which the photocurable composition was not applied, was fixed with an upper grip, and the 90 ° peel strength (N / 20 mm) was measured at a peel speed of 300 mm / min. . The adhesive strength after the wet heat treatment was determined by the method described above after the test specimen was stored in an environment of 85 ° C. and 85% relative humidity for 100 hours using a thermo-hygrostat (FR-1J manufactured by ESPEC). The adhesive strength was measured.
（実施例１〜１５、比較例１、２）
表１に記載の各成分を配合し、光硬化性組成物を作製した。
Each component described in Table 1 was blended to prepare a photocurable composition.
各製造例の光硬化性組成物を銅板に塗布し、３０秒後に直接、上面から紫外線を照射（装置：ヘレウス株式会社製、Ｄバルブ（３３０〜３８０ｎｍ）、積算光照射量は表２に記載）して光硬化させた。硬化後、この硬化物（接着層）を銅板からはがし取り、ガラス転移温度を上記に記載の方法により測定した。 The photocurable composition of each production example was applied to a copper plate, and 30 seconds later, ultraviolet light was directly irradiated from the upper surface (apparatus: Heraeus Co., Ltd., D valve (330 to 380 nm), and the integrated light irradiation amount is described in Table 2. ) And light cured. After curing, the cured product (adhesive layer) was peeled off from the copper plate, and the glass transition temperature was measured by the method described above.
次に、表２に記載の熱可塑樹脂フィルムＢに、表１に記載の光硬化性組成物を、表２記載の厚さになるように塗布した後、熱可塑樹脂フィルムＡを各光硬化性組成物層の上に設置し、３０秒後に熱可塑樹脂フィルムＢの上面から紫外線を照射（装置：ヘレウス株式会社製、Ｄバルブ（３３０〜３８０ｎｍ）、積算光照射量は表２に記載）することにより、熱可塑樹脂フィルムＡと熱可塑樹脂フィルムＢとの間に、光硬化性接着剤を硬化させてなる接着層を有する積層体を作製した。この積層体の湿熱処理後の接着強度を測定した。 Next, after applying the photocurable composition shown in Table 1 to the thermoplastic resin film B shown in Table 2 so as to have the thickness shown in Table 2, the thermoplastic resin film A was cured by photocuring. It is placed on the conductive composition layer, and after 30 seconds, it is irradiated with ultraviolet light from the upper surface of the thermoplastic resin film B (apparatus: Heraeus Co., Ltd., D-bulb (330-380 nm), the integrated light irradiation amount is described in Table 2). By doing so, a laminate having an adhesive layer formed by curing the photocurable adhesive between the thermoplastic resin film A and the thermoplastic resin film B was produced. The adhesive strength of the laminate after the wet heat treatment was measured.
さらに、熱可塑樹脂フィルムＡに、上述の方法で各接着剤を塗布後、熱可塑樹脂フィルムＢを設置後、硬化させることで、熱可塑樹脂フィルムＢ／接着層／熱可塑樹脂フィルムＡ／接着層／熱可塑樹脂フィルムＢがこの順に積層されてなる両面積層体を形成した。無アルカリガラス上に粘着剤層を介して両面積層体を設置し、この試験片のクラック、反り、変色を評価した。また、ガラス転移温度ＴｇＡ、ＴｇＢ、ＴｇＣが式（１）および（２）を充足するか検討した。その結果を表２に示す。 Further, after applying each adhesive to the thermoplastic resin film A by the above-described method, and then setting and curing the thermoplastic resin film B, the thermoplastic resin film B / adhesive layer / thermoplastic resin film A / adhesive Layer / thermoplastic resin film B was laminated in this order to form a double-sided laminate. A double-sided laminate was placed on an alkali-free glass via an adhesive layer, and the test piece was evaluated for cracks, warpage, and discoloration. Further, it was examined whether the glass transition temperatures Tg A , Tg B , and Tg C satisfy the equations (1) and (2). Table 2 shows the results.
表２に示すように、ガラス転移温度ＴｇＡ、ＴｇＢ、およびＴｇＣが式（１）および（２）の関係を満たす実施例１〜１５では両面積層体におけるクラック、反りおよび変色の発生が抑制された。特に、光硬化性組成物中に芳香族系エポキシ化合物を５０％以上含む実施例１〜３、５〜７、９〜１１、１３〜１５では両面積層体の反りを大きく抑制できた。ガラス転移温度ＴｇＡ、ＴｇＢ、およびＴｇＣが式（２）の関係を満たさない比較例１、２の両面積層体においてクラック、反り、および変色が発生した。また、比較例１では接着層のガラス転移温度ＴｇＣが相対的に低いため、熱可塑樹脂フィルムＡと接着層との間に湿気がたまり、著しい変色が発生した。比較例２では、接着層のガラス転移温度ＴｇＣが相対的に高いため、柔軟性に乏しく、クラックや反りが発生した。また、硬化時の光照射量が多い影響で、変色が生じた。 As shown in Table 2, in Examples 1 to 15 in which the glass transition temperatures Tg A , Tg B , and Tg C satisfy the relations of the formulas (1) and (2), cracks, warpage, and discoloration occur in the double-sided laminate. Was suppressed. In particular, in Examples 1 to 3, 5 to 7, 9 to 11, and 13 to 15 in which the photocurable composition contained 50% or more of the aromatic epoxy compound, the warpage of the double-sided laminate was significantly suppressed. Cracks, warpage, and discoloration occurred in the double-sided laminates of Comparative Examples 1 and 2 in which the glass transition temperatures Tg A , Tg B , and Tg C did not satisfy the relationship of Expression (2). Further, since a relatively low glass transition temperature Tg C of the adhesive layer in Comparative Example 1, accumulated moisture between the thermoplastic resin film A and the adhesive layer, significant discoloration has occurred. In Comparative Example 2, a glass transition temperature Tg C of the adhesive layer because relatively high, inflexible, cracks or warpage occurs. In addition, discoloration occurred due to the large amount of light irradiation during curing.
Claims (10)
ガラス転移温度がＴｇＢである熱可塑樹脂フィルムＢ、および、
熱可塑樹脂フィルムＡと熱可塑樹脂フィルムＢとの間に形成され、光硬化性組成物を硬化させてなる、ガラス転移温度がＴｇＣである接着層を有する積層体であって、
ＴｇＡ、ＴｇＢ、およびＴｇＣが下記式（１）および（２）：
（１）ＴｇＢ／ＴｇＡ＋ＴｇＡ／ＴｇＢ≦５
（２）ＴｇＡ×０．２≦ＴｇＣ≦ＴｇＢ＋（ＴｇＢ−ＴｇＡ）×０．９
の関係を満たす、積層体。 A thermoplastic resin film A having a glass transition temperature of Tg A,
The thermoplastic resin film B glass transition temperature of Tg B and,
A laminate having an adhesive layer formed between a thermoplastic resin film A and a thermoplastic resin film B and obtained by curing a photocurable composition and having a glass transition temperature of Tg C ,
Tg A , Tg B , and Tg C are represented by the following formulas (1) and (2):
(1) Tg B / Tg A + Tg A / Tg B ≦ 5
(2) Tg A × 0.2 ≦ Tg C ≦ Tg B + (Tg B -Tg A) × 0.9
A laminate that satisfies the relationship.
熱可塑樹脂フィルムＢの厚みが５〜１００μｍであり、
接着層の厚みが１〜３μｍである請求項１〜７のいずれか１項に記載の積層体。 The thickness of the thermoplastic resin film A is 1 to 50 μm,
The thickness of the thermoplastic resin film B is 5 to 100 μm,
The laminate according to any one of claims 1 to 7, wherein the thickness of the adhesive layer is 1 to 3 µm.
請求項１〜８のいずれか１項に記載の積層体。 The thermoplastic resin film A is made of a polyvinyl alcohol resin,
The laminate according to any one of claims 1 to 8.
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| KR20150087752A (en) * | 2014-01-22 | 2015-07-30 | 제일모직주식회사 | Adhesive composition for polarizing plate, adhesive film prepared using the same, polarizing plate comprising the same and optical display apparatus comprising the same |
| US20150315431A1 (en) * | 2014-04-30 | 2015-11-05 | Samsung Sdi Co., Ltd. | Adhesive film for polarizing plate, adhesive composition for the same, polarizing plate comprising the same and optical display comprising the same |
| WO2018025698A1 (en) * | 2016-08-03 | 2018-02-08 | 住友化学株式会社 | Laminate film |
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| KR20150087752A (en) * | 2014-01-22 | 2015-07-30 | 제일모직주식회사 | Adhesive composition for polarizing plate, adhesive film prepared using the same, polarizing plate comprising the same and optical display apparatus comprising the same |
| US20150315431A1 (en) * | 2014-04-30 | 2015-11-05 | Samsung Sdi Co., Ltd. | Adhesive film for polarizing plate, adhesive composition for the same, polarizing plate comprising the same and optical display comprising the same |
| WO2018025698A1 (en) * | 2016-08-03 | 2018-02-08 | 住友化学株式会社 | Laminate film |
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| WO2022055667A1 (en) * | 2020-09-10 | 2022-03-17 | D&K International Inc. | Intrusion resistant thermal laminating film |
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