JP3896119B2 - Photocurable resin composition for display element and display element - Google Patents
Photocurable resin composition for display element and display element Download PDFInfo
- Publication number
- JP3896119B2 JP3896119B2 JP2004004853A JP2004004853A JP3896119B2 JP 3896119 B2 JP3896119 B2 JP 3896119B2 JP 2004004853 A JP2004004853 A JP 2004004853A JP 2004004853 A JP2004004853 A JP 2004004853A JP 3896119 B2 JP3896119 B2 JP 3896119B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- photocurable resin
- group
- polymerization initiator
- photocationic polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000011342 resin composition Substances 0.000 title claims description 82
- 239000003505 polymerization initiator Substances 0.000 claims description 70
- 150000001875 compounds Chemical class 0.000 claims description 55
- 238000012663 cationic photopolymerization Methods 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- -1 —OH group Chemical group 0.000 claims description 21
- 125000002091 cationic group Chemical group 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 150000001450 anions Chemical class 0.000 claims description 7
- 125000003566 oxetanyl group Chemical group 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims 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 claims 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 claims description 4
- VMJFYMAHEGJHFH-UHFFFAOYSA-M triphenylsulfanium;bromide Chemical compound [Br-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 VMJFYMAHEGJHFH-UHFFFAOYSA-M 0.000 claims description 4
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000000047 product Substances 0.000 description 29
- 238000001723 curing Methods 0.000 description 26
- 229920000647 polyepoxide Polymers 0.000 description 26
- 239000003822 epoxy resin Substances 0.000 description 22
- 239000003504 photosensitizing agent Substances 0.000 description 20
- 230000009477 glass transition Effects 0.000 description 19
- 238000010538 cationic polymerization reaction Methods 0.000 description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 12
- 229910052753 mercury Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 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 10
- 238000004383 yellowing Methods 0.000 description 10
- 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 9
- 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 9
- 230000003287 optical effect Effects 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000035699 permeability Effects 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229910052787 antimony Inorganic materials 0.000 description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000565 sealant Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 3
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002998 adhesive polymer Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- 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
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-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
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical class N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 description 1
- IITAGOPHHFGANB-UHFFFAOYSA-N 2-(phenoxymethyl)oxetane Chemical compound C1COC1COC1=CC=CC=C1 IITAGOPHHFGANB-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
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-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
- 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
- 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
- NDRGXRWCWFISPL-UHFFFAOYSA-N 3,3-bis(methoxymethyl)oxetane Chemical compound COCC1(COC)COC1 NDRGXRWCWFISPL-UHFFFAOYSA-N 0.000 description 1
- QSWTVVHEQUBIET-UHFFFAOYSA-N 3,3-bis(phenoxymethyl)oxetane Chemical compound C1OCC1(COC=1C=CC=CC=1)COC1=CC=CC=C1 QSWTVVHEQUBIET-UHFFFAOYSA-N 0.000 description 1
- BIDWUUDRRVHZLQ-UHFFFAOYSA-N 3-ethyl-3-(2-ethylhexoxymethyl)oxetane Chemical compound CCCCC(CC)COCC1(CC)COC1 BIDWUUDRRVHZLQ-UHFFFAOYSA-N 0.000 description 1
- JUXZNIDKDPLYBY-UHFFFAOYSA-N 3-ethyl-3-(phenoxymethyl)oxetane Chemical compound C=1C=CC=CC=1OCC1(CC)COC1 JUXZNIDKDPLYBY-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
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- ZVXSDRDGBCJPEQ-UHFFFAOYSA-N ON=P(O)O Chemical compound ON=P(O)O ZVXSDRDGBCJPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 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
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical class [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229920006000 epoxidized styrene-butadiene-styrene block copolymer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- GAMLUOSQYHLFCT-UHFFFAOYSA-N triethoxy-[3-[(3-ethyloxetan-3-yl)methoxy]propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1(CC)COC1 GAMLUOSQYHLFCT-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 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
- 239000004034 viscosity adjusting agent Substances 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
Description
本発明は、表示素子光硬化性樹脂組成物、ならびに、それを用いた表示素子に関する。中でも、エレクトロルミネッセンス素子（以下、「ＥＬ素子」と記す）に好適に用いられる。 The present invention relates to a display element photocurable resin composition and a display element using the same. Among these, it is preferably used for an electroluminescence element (hereinafter referred to as “EL element”).
光カチオン重合開始剤などの光カチオン系触媒は、通常の熱ラジカル重合温度程度の高温の熱を加えることができない用途において非常に有用である。その中でも、下記式（７）で表される光カチオン重合開始剤は、アニオンに由来する酸が強いことから、硬化塗膜などの硬化物の物性が非常に優れたものとなることが知られている。
このような光カチオン重合開始剤を用いた光硬化性樹脂組成物、例えば、ビスフェノールＡ型エポキシ樹脂（例えば、商品名「エピコート８２８」、ジャパンエポキシレジン社製）１００重量部、上記式（７）で表される光カチオン重合開始剤（例えば、商品名「Ｒｈｏｔｏｉｎｉｔｉａｔｏｒ２０７４」、Ｒｈｏｄｉａ社製）１重量部および光増感剤（例えば、商品名「ＤＥＴＸ−Ｓ」、日本化薬社製）１重量部を含有してなる光硬化性樹脂組成物は、厚み１００μｍに塗工した後、２０ｍＷの光を１００秒間（２０００ｍＪ）照射し、さらに８０℃で３０分間後硬化（後養生）させた後の硬化塗膜（硬化フィルム）のＤＭＡによるガラス転移温度（Ｔｇ）を測定すると、上記ガラス転移温度は１６０℃以上となる。 A photocurable resin composition using such a cationic photopolymerization initiator, for example, bisphenol A type epoxy resin (for example, trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.) 100 parts by weight, the above formula (7) 1 part by weight of a photocationic polymerization initiator (for example, trade name “Rhotoinitiator 2074”, manufactured by Rhodia) and 1 part by weight of a photosensitizer (for example, trade name “DETX-S”, manufactured by Nippon Kayaku Co., Ltd.) After the photocurable resin composition containing the composition is applied to a thickness of 100 μm, it is irradiated with 20 mW of light for 100 seconds (2000 mJ) and further post-cured (post-cured) for 30 minutes at 80 ° C. When the glass transition temperature (Tg) by DMA of the coating film (cured film) is measured, the glass transition temperature is 160 ° C. or higher.
しかし、上記式（７）で表される光カチオン重合開始剤を用いた光硬化性樹脂組成物は、光カチオン重合開始剤がヨウ素（Ｉ）を含有しているため、光照射後にヨウ素ラジカルが発生し、このヨウ素ラジカルにより、硬化が進行する過程で塗膜が黄変などの着色を起こすという問題点がある。また、このような光カチオン重合開始剤は、そのカチオン構造に由来する光の吸収波長が２５０ｎｍ未満と短いため、例えば高圧水銀灯や超高圧水銀灯などを光源とする通常の光を使用する場合には、例えばアントラセン系やチオキサントン系などの光増感剤を併用する必要があり、これらの光増感剤自体やその反応物等により着色が生じうるという問題点もある。 However, in the photocurable resin composition using the photocationic polymerization initiator represented by the above formula (7), the photocationic polymerization initiator contains iodine (I). This iodine radical causes a problem that the coating film is colored such as yellowing in the process of curing. In addition, since such a photocationic polymerization initiator has a short absorption wavelength of light derived from its cationic structure of less than 250 nm, for example, when using ordinary light using a high pressure mercury lamp or an ultrahigh pressure mercury lamp as a light source, for example. For example, it is necessary to use a photosensitizer such as anthracene or thioxanthone, and there is a problem that coloring may occur due to the photosensitizer itself or a reaction product thereof.
一方、リン（Ｐ）系光カチオン重合開始剤（例えば、商品名「Ｕｖａｃｕｒｅ１５９１」、ダイセルＵＣＢ社製）やアンチモン（Ｓｂ）系光カチオン重合開始剤（例えば、商品名「アデカオプトマーＳＰ１７０」、旭電化工業社製）を用いた光硬化性樹脂組成物は、硬化が進行する過程において黄変などの着色は起こさない。しかし、リン系光カチオン重合開始剤やアンチモン系光カチオン重合開始剤を用いた光硬化性樹脂組成物の上記Ｔｇは１００℃前後であるので、上記式（７）で表される光カチオン重合開始剤を用いた光硬化性樹脂組成物は、リン系光カチオン重合開始剤やアンチモン系光カチオン重合開始剤を用いた光硬化性樹脂組成物に比較して、非常に高いガラス転移温度を有する硬化物となる。これは、上記式（７）で表される光カチオン重合開始剤が発生する酸の強さにより、エポキシ樹脂の硬化が十分に行われていることによるものと考えられる。 On the other hand, phosphorus (P) photocationic polymerization initiator (for example, trade name “Uvacure 1591”, manufactured by Daicel UCB) and antimony (Sb) photocationic polymerization initiator (for example, trade name “Adekaoptomer SP170”, Asahi The photo-curable resin composition using Denka Kogyo Co., Ltd. does not cause yellowing or the like in the process of curing. However, since the Tg of the photocurable resin composition using a phosphorous photocationic polymerization initiator or an antimony photocationic polymerization initiator is around 100 ° C., the photocationic polymerization initiation represented by the above formula (7) is initiated. The photo-curable resin composition using an agent has a very high glass transition temperature compared to the photo-curable resin composition using a phosphoric photocationic polymerization initiator or an antimony photocationic polymerization initiator. It becomes a thing. This is considered due to the fact that the epoxy resin is sufficiently cured by the strength of the acid generated by the photocationic polymerization initiator represented by the above formula (7).
本発明の目的は、上記問題点に鑑み、硬化進行過程において黄変などの着色を起こすことがなく、かつ、高いガラス転移温度を有するため透湿性が低く、透明性にも優れる硬化物となる表示素子用光硬化性樹脂組成物、ならびに、この表示素子用光硬化性樹脂組成物を用いた表示素子を提供することにある。 In view of the above problems, the object of the present invention is a cured product that does not cause yellowing or the like in the course of curing and has a high glass transition temperature, and thus has low moisture permeability and excellent transparency. It is providing the photocurable resin composition for display elements , and the display element using this photocurable resin composition for display elements.
請求項１に記載の発明（本発明）による表示素子用光硬化性樹脂組成物は、下記一般式（４）または下記一般式（５）で表される光カチオン重合開始剤と、分子内に少なくとも１個のエポキシ基を有する光カチオン重合性化合物及び／又は分子内に少なくとも１個のオキセタニル基を有する光カチオン重合性化合物と、硬化制御剤としてのポリエーテル化合物とを含有することを特徴とする。
請求項２に記載の発明（本発明）による表示素子用光硬化性樹脂組成物は、トリフェニルスルホニウムブロマイドとソジウムテトラキス（ペンタフルオロフェニル）ボレートとを反応させることにより得られた光カチオン重合開始剤と、分子内に少なくとも１個のエポキシ基を有する光カチオン重合性化合物及び／又は分子内に少なくとも１個のオキセタニル基を有する光カチオン重合性化合物と、硬化制御剤としてのポリエーテル化合物とを含有することを特徴とする。 The photocurable resin composition for a display element according to the invention according to claim 2 is a photocationic polymerization start obtained by reacting triphenylsulfonium bromide with sodium tetrakis (pentafluorophenyl) borate. An agent, a photocationically polymerizable compound having at least one epoxy group in the molecule and / or a photocationically polymerizable compound having at least one oxetanyl group in the molecule, and a polyether compound as a curing control agent and it features that you contain.
請求項３に記載の発明（本発明）による表示素子は、上記請求項１又は２に記載の表示素子用光硬化性樹脂組成物を用いてなることを特徴とする。 Display device according to the invention (the present invention) according to claim 3, characterized by comprising using the above claim 1 or 2 display elements photocurable resin composition according to.
本発明で用いられる光カチオン重合開始剤は、下記一般式（４）または下記一般式（５）で表され、スルホニウムカチオン部分を有する。 The photocationic polymerization initiator used in the present invention is represented by the following general formula ( 4 ) or the following general formula ( 5 ), and has a sulfonium cation moiety.
上記一般式（４）および一般式（５）中、Ｒ1 〜Ｒ ４ は、互いに同一であっても良いし異なっていても良く、直鎖状または分枝鎖状Ｃ1〜Ｃ12アルキル基、直鎖状または分枝鎖状Ｃ1 〜Ｃ12アルコキシル基、ハロゲン原子、−ＯＨ基、−ＣＯＯＨ基および−ＣＯＯ−アルキルエステル基（ここで、アルキル部分は直鎖状または分枝鎖状Ｃ1〜Ｃ12残基である）から選択される基を示す。Ｘ − は、下記式（６）で表されるアニオンを示す。 The general formula (4) and the general formula (5), R 1 to R 4 may be different or may be the same as each other, linear or branched C 1 -C 12 alkyl group A linear or branched C 1 -C 12 alkoxyl group, a halogen atom, —OH group, —COOH group and —COO-alkyl ester group (wherein the alkyl moiety is a linear or branched C 1 1 to C 12 residues) . X − represents an anion represented by the following formula (6) .
また、上記光カチオン重合開始剤は、下記一般式（６）で表される硼素中心アニオン部分を有する。 Moreover, the said photocationic polymerization initiator has a boron center anion part represented by the following general formula ( 6 ).
このように中心アニオンが硼素であると、光カチオン重合開始剤の酸強度が強くなるため、この光カチオン重合開始剤を用いた光硬化性樹脂組成物の硬化性が向上し、高いガラス転移温度を有する硬化物を得ることができる。その結果、光硬化性樹脂組成物の硬化物の透湿性（透湿度）が低下するため、この光硬化性樹脂組成物を用いて作製した例えばＥＬ素子の寿命を長くすることができ、信頼性を高めることができる。 When the center anion as this is a boron, since the acid strength of the photo-cationic polymerization initiator is increased, to improve the curability of the photocurable resin composition using the cationic photopolymerization initiator, a high glass transition A cured product having a temperature can be obtained. As a result, since the moisture permeability (moisture permeability) of the cured product of the photocurable resin composition is lowered, the lifetime of, for example, an EL element produced using this photocurable resin composition can be extended, and the reliability Can be increased.
上記光カチオン重合開始剤は、前記一般式（４）、前記一般式（５）および前記一般式（６）から明らかなように、ヨウ素（Ｉ）を含有していないので、光照射後にヨウ素ラジカルを発生しない。従って、上記光カチオン重合開始剤を用いた光硬化性樹脂組成物は、硬化進行過程においてヨウ素ラジカルに起因する塗膜の黄変などの着色を起こすことがない。 As is apparent from the general formula ( 4 ), the general formula ( 5 ), and the general formula ( 6 ), the photocationic polymerization initiator does not contain iodine (I). Does not occur. Thus, photo-curable resin composition using the cationic photopolymerization initiator is never cause coloration such as yellowing of the paint film due to iodine radicals in curing progression.
また、上記光カチオン重合開始剤は、前記一般式（４）または前記一般式（５）で表されるカチオン部分（カチオン構造）に由来する光の吸収を波長３００ｎｍ以上の光に有するため、高圧水銀灯や超高圧水銀灯などを光源とする通常の光を使用する場合でも、必ずしも光増感剤を併用する必要はない。従って、上記光カチオン重合開始剤を用いた光硬化性樹脂組成物は、光増感剤自体やその反応物等に起因する着色も防止することができる。 Moreover, since the said photocationic polymerization initiator has absorption of the light originating in the cation part (cation structure) represented by the said General formula ( 4 ) or the said General formula ( 5 ) in the light of wavelength 300nm or more, it is high pressure Even when using ordinary light using a mercury lamp or an ultrahigh pressure mercury lamp as a light source, it is not always necessary to use a photosensitizer together. Therefore, the photocurable resin composition using the above-mentioned photocationic polymerization initiator can also prevent coloring caused by the photosensitizer itself or a reaction product thereof.
さらに、上記光カチオン重合開始剤は、リン系光カチオン重合開始剤やアンチモン系光カチオン重合開始剤とは異なり、光硬化性樹脂組成物の硬化物のガラス転移温度を著しく高める機能を有する。従って、上記光カチオン重合開始剤を用いた光硬化性樹脂組成物の硬化物は、透湿性の低いものとなり、例えばＥＬ素子の寿命を長期間にわたって保つことができる。 Furthermore, the cationic photopolymerization initiator is different from the phosphorus-based cationic photopolymerization initiator and antimony-based cationic photopolymerization initiator has a function of increasing significantly the glass transition temperature of the cured product of the photocurable resin composition. Therefore, the cured product of a photocurable resin composition using the cationic photopolymerization initiator, becomes low in moisture permeability, for example it is possible to maintain the lifetime of the EL element over a long period of time.
また、上記光カチオン重合開始剤の光の吸収が波長３００ｎｍ未満の光であると、高圧水銀灯や超高圧水銀灯などを光源とする通常の光を使用する場合に、光カチオン重合開始剤を用いた光硬化性樹脂組成物の硬化が不十分となることがあり、逆に光カチオン重合開始剤の光の吸収が波長４００ｎｍを超える光であると、光カチオン重合開始剤を用いた光硬化性樹脂組成物が硬化進行過程において着色を起こすことがある。 Also, use the absorption of light of the optical cationic polymerization initiator is light having a wavelength less than 300 nm, in the case of using an ordinary light as a light source such as a high pressure mercury lamp and ultra-high pressure mercury lamp, a cationic photopolymerization initiator it may cure the photocurable resin composition had become insufficient, when the absorption of light conversely cationic photopolymerization initiator is light exceeding a wavelength 400 nm, light-curable using cationic photopolymerization initiator The resin composition may be colored in the course of curing.
光硬化性樹脂組成物の硬化進行過程における着色防止効果や硬化物のガラス転移温度上昇効果等に優れることから、下記一般式（４）または下記一般式（５）で表される光カチオン重合開始剤が用いられる。これら光カチオン重合開始剤は、単独で用いられても良いし、２種類以上が併用されても良い。 Because of excellent glass transition temperature increasing effect of the anti-coloring effect and cured in the curing course of the photocurable resin composition or the like, photoinitiated cationic polymerization represented by the following general formula (4) or the following general formula (5) An agent is used . This Stanislaus Lo Kuang cationic polymerization initiator may be used alone, or two or more kinds may be used in combination.
上記一般式（４）および一般式（５）中、Ｘ- は、下記式（６）で表されるアニオンを示す。 In the general formula (4) and the general formula (5), X − represents an anion represented by the following formula (6).
本発明で用いられる光カチオン重合開始剤は、特に限定されるものではないが、例えば、トリフェニルスルホニウムブロマイドなどのスルホニウム化合物とソジウムテトラキス（ペンタフルオロフェニル）ボレートなどのフッ化ホウ素化合物とを反応させることにより、合成することができる。 The cationic photopolymerization initiator used in the present invention is not particularly limited. For example, a reaction between a sulfonium compound such as triphenylsulfonium bromide and a boron fluoride compound such as sodium tetrakis (pentafluorophenyl) borate is performed. Can be synthesized.
次に、本発明の光硬化性樹脂組成物は、光カチオン重合性化合物、および、上述した光カチオン重合開始剤が含有されてなる。 Next, the photocurable resin composition of the present invention contains a photocationically polymerizable compound and the above-described photocationic polymerization initiator.
本発明の光硬化性樹脂組成物に用いられる光カチオン重合性化合物としては、光カチオン重合性が高く、少ない光量でも効率的に光硬化が進行することから、分子内に少なくとも１個のエポキシ基を有する化合物（以下、「エポキシ系化合物」と記す）または分子内に少なくとも１個のオキセタニル基を有する化合物（以下、「オキセタニル系化合物」と記す）が用いられる。これらの光カチオン重合性化合物の性状（分子量）は、特に限定されるものではなく、モノマー、オリゴマー、ポリマーのいずれであっても良い。また、これらの光カチオン重合性化合物は、単独で用いられても良いし、２種類以上が併用されても良い。 As the photo cationic polymerizable compound used in the photocurable resin composition of the present invention, high cationic photopolymerizable, since efficient light curing proceeds even with a small amount of light, at least one epoxy group in the molecule compounds having a (hereinafter, referred to as "epoxy compound") a compound having at least one oxetanyl group or in the molecule (hereinafter, referred to as "oxetanyl compound") is needed use. The properties (molecular weight) of these photocationically polymerizable compounds are not particularly limited, and any of monomers, oligomers, and polymers may be used. Moreover, these photocationic polymerizable compounds may be used independently and 2 or more types may be used together.
上記エポキシ系化合物としては、特に限定されるものではないが、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂などのビスフェノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂などのノボラック型エポキシ樹脂、脂肪族エポキシ樹脂、脂環式エポキシ樹脂、異節環状型エポキシ樹脂、多官能性エポキシ樹脂、ビフェニル型エポキシ樹脂、グリシジルエーテル型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、例えば水添ビスフェノールＡ型エポキシ樹脂などのアルコール型エポキシ樹脂、例えば臭素化エポキシ樹脂などのハロゲン化エポキシ樹脂、ゴム変性エポキシ樹脂、ウレタン変性エポキシ樹脂、エポキシ化ポリブタジエン、エポキシ化スチレン−ブタジエン−スチレンブロック共重合体、エポキシ基含有ポリエステル樹脂、エポキシ基含有ポリウレタン樹脂、エポキシ基含有アクリル樹脂等が挙げられる。これらのエポキシ系化合物は、単独で用いられても良いし、２種類以上が併用されても良い。 The epoxy compound is not particularly limited, and examples thereof include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, novolaks such as phenol novolac type epoxy resins and cresol novolac type epoxy resins. Type epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, multifunctional epoxy resin, biphenyl type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin Alcohol type epoxy resins such as hydrogenated bisphenol A type epoxy resins, halogenated epoxy resins such as brominated epoxy resins, rubber modified epoxy resins, urethane modified epoxy resins, epoxidized polymers Butadiene, epoxidized styrene - butadiene - styrene block copolymer, epoxy group-containing polyester resin, epoxy group-containing polyurethane resins, epoxy group-containing acrylic resins. These epoxy compounds may be used alone or in combination of two or more.
上記エポキシ系化合物の市販品としては、特に限定されるものではないが、例えば、ジャパンエポキシレジン社製の商品名「エピコート８０６」、「エピコート８２８」、「エピコート１００１」、「エピコート１００２」などの「エピコート」シリーズや、ダイセル化学工業社製の商品名「セロキサイド２０２１」などの「セロキサイド」シリーズ等が挙げられる。 Although it does not specifically limit as a commercial item of the said epoxy-type compound, For example, brand name "Epicoat 806", "Epicoat 828", "Epicoat 1001", "Epicoat 1002" by Japan Epoxy Resin Co., Ltd. etc. “Epicoat” series, “Celoxide” series such as “Celoxide 2021” manufactured by Daicel Chemical Industries, Ltd.
上記オキセタニル系化合物としては、特に限定されるものではないが、例えば、フェノキシメチルオキセタン、３，３−ビス（メトキシメチル）オキセタン、３，３−ビス（フェノキシメチル）オキセタン、３−エチル−３−（フェノキシメチル）オキセタン、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−｛［３−（トリエトキシシリル）プロポキシ］メチル｝オキセタン、ジ［１−エチル（３−オキセタニル）］メチルエーテル、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、１，４−ビス｛［（３−エチル−３−オキセタニル）メトキシ］メチル｝ベンゼン等が挙げられる。これらのオキセタニル系化合物は、単独で用いられても良いし、２種類以上が併用されても良い。 The oxetanyl-based compound is not particularly limited, and examples thereof include phenoxymethyl oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, and 3-ethyl-3- (Phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, di [1-ethyl (3 -Oxetanyl)] methyl ether, oxetanylsilsesquioxane, phenol novolac oxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene and the like. These oxetanyl compounds may be used alone or in combination of two or more.
上記エポキシ系化合物およびオキセタニル系化合物は、それぞれ単独で用いられても良いし、両者が併用されても良い。 The epoxy compound and the oxetanyl compound may be used alone or in combination.
さらに、他の光カチオン重合性化合物としては、例えば、エポキシド類、環状エーテル類、ビニルエーテル類、ビニルアミン類、不飽和炭化水素類、ラクトン類および他の環状エステル類、ラクタム類、環状カーボネート類、環状アセタール類、アルデヒド類、環状アミン類、環状スルフィド類、シクロシロキサン類、シクロトリホスファゼン類および他の光カチオン重合可能な基やモノマーなどの少なくとも１個の光カチオン重合可能基を有している光カチオン重合性化合物が挙げられ、中でも、エポキシドモノマーなどの環状エーテルモノマーやビニル有機モノマー等が好適に用いられる。これらの他の光カチオン重合性化合物は、単独で用いられても良いし、２種類以上が併用されても良い。 Furthermore, as other photocationically polymerizable compounds, for example, epoxides, cyclic ethers, vinyl ethers, vinylamines, unsaturated hydrocarbons, lactones and other cyclic esters, lactams, cyclic carbonates, cyclic Light having at least one photocationically polymerizable group such as acetals, aldehydes, cyclic amines, cyclic sulfides, cyclosiloxanes, cyclotriphosphazenes and other photocationically polymerizable groups or monomers Examples thereof include cationic polymerizable compounds, among which cyclic ether monomers such as epoxide monomers, vinyl organic monomers, and the like are preferably used. These other photocationically polymerizable compounds may be used alone or in combination of two or more.
本発明の光硬化性樹脂組成物中における上記光カチオン重合開始剤の含有量は、特に限定されるものではないが、前記光カチオン重合性化合物１００重量部に対し、上記光カチオン重合開始剤０．１〜１０重量部であることが好ましい。 Although content of the said photocationic polymerization initiator in the photocurable resin composition of this invention is not specifically limited, The said photocationic polymerization initiator 0 with respect to 100 weight part of said photocationic polymerizable compounds. It is preferable that it is 1-10 weight part.
光カチオン重合性化合物１００重量部に対する上記光カチオン重合開始剤の含有量が０．１重量部未満であると、光カチオン重合性化合物の光カチオン重合が十分に進行しなかったり、光硬化性樹脂組成物の光硬化が遅くなりすぎることがあり、逆に光カチオン重合性化合物１００重量部に対する上記光カチオン重合開始剤の含有量が１０重量部を超えると、光硬化性樹脂組成物の光硬化が速くなりすぎて、作業性が低下したり、不均一な硬化物となりやすくなることがある。 When the content of the photocationic polymerization initiator is less than 0.1 parts by weight based on 100 parts by weight of the photocationic polymerizable compound, the photocationic polymerization of the photocationic polymerizable compound does not proceed sufficiently, or the photocurable resin The photocuring of the composition may be too slow. Conversely, when the content of the photocationic polymerization initiator exceeds 100 parts by weight with respect to 100 parts by weight of the photocationic polymerizable compound, the photocuring of the photocurable resin composition is performed. May become too fast and workability may be reduced, or a non-uniform cured product may be easily obtained.
本発明の光硬化性樹脂組成物には、必須成分である光カチオン重合性化合物および上記光カチオン重合開始剤に加えるに、本発明の課題達成を阻害しない範囲で必要に応じて、上記光カチオン重合開始剤以外の光カチオン重合開始剤（以下、「他の光カチオン重合開始剤」と記す）が含有されていても良い。即ち、必須成分である上記光カチオン重合開始剤と他の光カチオン重合開始剤とが併用されても良い。 The photocurable resin composition of the present invention, in addition to the photo cationic polymerizable compound and the cationic photopolymerization initiator is an essential component, if necessary in a range that does not inhibit the assignment achievement of the present invention, the optical cationic Photocationic polymerization initiators other than the polymerization initiator (hereinafter referred to as “other photocationic polymerization initiators”) may be contained. That is, the optical cationic polymerization initiator and another cationic photopolymerization initiator may be used in combination is an essential component.
上記光カチオン重合開始剤と他の光カチオン重合開始剤とを併用する場合の併用割合は、特に限定されるものではないが、上記光カチオン重合開始剤が５０重量％を超える量であり、他の光カチオン重合開始剤が５０重量％未満の量であることが好ましい。 Combination ratio of the case of using the above photo cationic polymerization initiator and other cationic photopolymerization initiator is not particularly limited, an amount of the cationic photopolymerization initiator is more than 50 wt%, other The photocationic polymerization initiator is preferably in an amount of less than 50% by weight.
また、本発明の光硬化性樹脂組成物中における上記光カチオン重合開始剤および他の光カチオン重合開始剤の含有量は、特に限定されるものではないが、上記光カチオン重合開始剤のみが用いられる場合と同様の上記理由により、前記光カチオン重合性化合物１００重量部に対し、上記光カチオン重合開始剤および他の光カチオン重合開始剤の合計量０．１〜１０重量部であることが好ましい。 The content of the cationic photopolymerization initiator and other cationic photoinitiator in the photocurable resin composition of the present invention is not particularly limited, only the optical cationic polymerization initiator is used the same the reason as to be, relative to the cationic photopolymerizable compound 100 parts by weight, it is preferable that the total amount of 0.1 to 10 parts by weight of the photo cationic polymerization initiator and other cationic photopolymerization initiator .
上記他の光カチオン重合開始剤は、イオン性光酸発生型の光カチオン重合開始剤であっても良いし、非イオン性光酸発生型の光カチオン重合開始剤であっても良い。 The other photocationic polymerization initiator may be an ionic photoacid-generating photocationic polymerization initiator or a nonionic photoacid-generating photocationic polymerization initiator.
上記イオン性光酸発生型の光カチオン重合開始剤としては、特に限定されるものではないが、例えば、芳香族ジアゾニウム塩、芳香族ハロニウム塩、芳香族スルホニウム塩などのオニウム塩や、鉄−アレン錯体、チタノセン錯体、アリールシラノール−アルミニウム錯体などの有機金属錯体等が挙げられる。これらのイオン性光酸発生型の光カチオン重合開始剤は、単独で用いられても良いし、２種類以上が併用されても良い。 The ionic photoacid-generating photocationic polymerization initiator is not particularly limited, and examples thereof include onium salts such as aromatic diazonium salts, aromatic halonium salts, aromatic sulfonium salts, and iron-allene. And organometallic complexes such as complexes, titanocene complexes, and arylsilanol-aluminum complexes. These ionic photoacid-generating photocationic polymerization initiators may be used alone or in combination of two or more.
上記オニウム塩の具体例としては、特に限定されるものではないが、例えば、（Ｃ6 Ｈ5 ）2 Ｉ［Ｂ（Ｃ6 Ｆ5 ）4 ］、（ＣＨ3 Ｃ6 Ｈ4 ）2 Ｉ［Ｂ（Ｃ6 Ｆ5 ）4 ］、（Ｃ6 Ｈ5 ）3 Ｓ［Ｂ（Ｃ6 Ｆ5 ）4 ］、（Ｃ6 Ｈ5 ）3 Ｃ［Ｂ（Ｃ6 Ｆ5 ）4 ］、（Ｃ6 Ｈ5 ）3 Ｓ［ＢＦ（Ｃ6 Ｆ5 ）3 ］、（Ｃ2 Ｈ5 ）3 ＮＨ［ＢＦ（Ｃ6 Ｆ5 ）3 ］、（Ｃ2 Ｈ5 ）ＯＨ［Ｂ（Ｃ6 Ｆ5 ）4 ］、（Ｃ2 Ｈ5 ）3 ＮＨ［Ｂ（Ｃ6 Ｆ5 ）4 ］、（Ｃ6 Ｈ5 ）2 Ｉ［Ｂ〔３，５−（ＣＦ3 ）2 Ｃ6 Ｈ3 〕4 ］、（Ｃ6 Ｈ5 ）3 Ｓ［Ｂ〔３，５−（ＣＦ3 ）2 Ｃ6 Ｈ3 〕4 ］、（Ｃ2 Ｈ5 ）2 ＯＨ［Ｂ〔３，５−（ＣＦ3 ）2 Ｃ6 Ｈ3 〕4 ］、（Ｃ6 Ｈ5 Ｓ）Ｃ6 Ｈ4 Ｓ（Ｃ6 Ｈ5 ）2 ［Ｂ〔３，５−（ＣＦ3 ）2 Ｃ6 Ｈ3 〕4 ］、（Ｃ2 Ｈ5 ）3 ＮＨ［Ｂ〔３，５−（ＣＦ3 ）2 Ｃ6 Ｈ3 〕4 ］、Ｃ6 Ｈ5 Ｎ2 ［Ｂ〔３，５−（ＣＦ3 ）2 Ｃ6 Ｈ3 〕4 ］、（Ｃ6 Ｈ5 ）3 Ｐ［ＢＦ（ＣＨ3 ）［Ｂ〔３，５−（ＣＦ3 ）2 Ｃ6 Ｈ3 〕4 ］、（Ｃ2 Ｈ5 ）3 ＮＨ［Ｂ（ＣＨ3 ）（Ｃ6 Ｆ5 ）3 ］、（Ｃ6 Ｈ5 ）2 Ｉ［Ｂ（ＣＨ3 ）（Ｃ6 Ｆ5 ）3 ］、（Ｃ6 Ｈ5 ）3 Ｓ［Ｂ（ＣＨ3 ）（Ｃ6 Ｆ5 ）3 ］、（Ｃ6 Ｈ5 ）3 Ｓ［Ｂ（ｎ−Ｃ4 Ｈ9 ）（Ｃ6 Ｆ5 ）3 ］、Ｃ6 Ｈ5 Ｎ（ＣＨ3 ）2 Ｈ［Ｂ〔３，５−（ＣＦ3 ）2 Ｃ6 Ｈ3 〕4 ］、Ｃ6 Ｈ5 ＮＨ［Ｂ〔３，５−（ＣＦ3 ）2 Ｃ6 Ｈ3 〕4 ］、Ｃ6 Ｈ5 Ｎ（ＣＨ3 ）2 Ｈ［Ｂ（Ｃ6 Ｆ5 ）4 ］、Ｃ6 Ｈ5 Ｎ（ＣＨ3 ）2 Ｈ［Ｂ（ＣＨ3 ）（Ｃ6 Ｆ5 ）3 ］等が挙げられる。これらのオニウム塩は、単独で用いられても良いし、２種類以上が併用されても良い。 Specific examples of the onium salt are not particularly limited. For example, (C 6 H 5 ) 2 I [B (C 6 F 5 ) 4 ], (CH 3 C 6 H 4 ) 2 I [ B (C 6 F 5 ) 4 ], (C 6 H 5 ) 3 S [B (C 6 F 5 ) 4 ], (C 6 H 5 ) 3 C [B (C 6 F 5 ) 4 ], (C 6 H 5) 3 S [BF (C 6 F 5) 3], (C 2 H 5) 3 NH [BF (C 6 F 5) 3], (C 2 H 5) OH [B (C 6 F 5 ) 4], (C 2 H 5) 3 NH [B (C 6 F 5) 4], (C 6 H 5) 2 I [B [3,5- (CF 3) 2 C 6 H 3 ] 4] , (C 6 H 5) 3 S [B [3,5- (CF 3) 2 C 6 H 3 ] 4], (C 2 H 5 ) 2 OH [B [3,5- (CF 3) 2 C 6 H 3] 4], (C 6 H 5 S) C 6 H 4 S (C 6 H 5) 2 [B [3,5- (CF 3) 2 C 6 H 3 ] 4], (C 2 H 5) 3 NH [B 3,5- (CF 3) 2 C 6 H 3 ] 4], C 6 H 5 N 2 [B [3,5- (CF 3) 2 C 6 H 3 ] 4], (C 6 H 5 ) 3 P [BF (CH 3 ) [B [3,5- (CF 3 ) 2 C 6 H 3 ] 4 ], (C 2 H 5 ) 3 NH [B (CH 3 ) (C 6 F 5 ) 3 ], (C 6 H 5 ) 2 I [B (CH 3 ) (C 6 F 5 ) 3 ], (C 6 H 5 ) 3 S [B (CH 3 ) (C 6 F 5 ) 3 ], (C 6 H 5 ) 3 S [B (n-C 4 H 9 ) (C 6 F 5 ) 3 ], C 6 H 5 N (CH 3 ) 2 H [B [3,5- (CF 3 ) 2 C 6 H 3 4 ], C 6 H 5 NH [B [3,5- (CF 3 ) 2 C 6 H 3 ] 4 ], C 6 H 5 N (CH 3 ) 2 H [B (C 6 F 5 ) 4 ] , C 6 H 5 N (CH 3 ) 2 H [B (CH 3 ) (C 6 F 5 ) 3 ] and the like. These onium salts may be used alone or in combination of two or more.
上記イオン性光酸発生型の光カチオン重合開始剤の市販品としては、特に限定されるものではないが、例えば、旭電化工業社製の商品名「アデカオプトマーＳＰ１５０」、「アデカオプトマーＳＰ１７０」などの「アデカオプトマー」シリーズや、ゼネラルエレクトロニクス社の商品名「ＵＶＥ−１０１４」、サートマー社製の商品名「ＣＤ−１０１２」等が挙げられる。 The commercial product of the ionic photoacid-generating photocationic polymerization initiator is not particularly limited. For example, trade names “Adekaoptomer SP150” and “Adekaoptomer SP170” manufactured by Asahi Denka Kogyo Co., Ltd. "Adekaoptomer" series such as "Product name" UVE-1014 "of General Electronics Co., Ltd., and" CD-1012 "product name of Sartomer.
また、上記非イオン性光酸発生型の光カチオン重合開始剤としては、特に限定されるものではないが、例えば、ニトロベンジルエステル、スルホン酸誘導体、リン酸エステル、フェノールスルホン酸エステル、ジアゾナフトキノン、Ｎ−ヒドロキシイミドホスホナート等が挙げられる。これらの非イオン性光酸発生型の光カチオン重合開始剤は、単独で用いられても良いし、２種類以上が併用されても良い。 Further, the nonionic photoacid-generating photocationic polymerization initiator is not particularly limited, and examples thereof include nitrobenzyl ester, sulfonic acid derivative, phosphoric ester, phenol sulfonic acid ester, diazonaphthoquinone, Examples thereof include N-hydroxyimidophosphonate. These nonionic photoacid-generating photocationic polymerization initiators may be used alone or in combination of two or more.
上記イオン性光酸発生型の光カチオン重合開始剤および非イオン性光酸発生型の光カチオン重合開始剤は、それぞれ単独で用いられても良いし、両者が併用されても良い。 The ionic photoacid-generating photocationic polymerization initiator and the nonionic photoacid-generating photocationic polymerization initiator may be used alone or in combination.
本発明の光硬化性樹脂組成物には、本発明の課題達成を阻害しない範囲で必要に応じて、必須成分である上記光カチオン重合開始剤および必要に応じて併用されても良い上記他の光カチオン重合開始剤の効率をより向上させて、前記光カチオン重合性化合物の光カチオン重合をより促進させるために、光増感剤が含有されていても良い。 In the photocurable resin composition of the present invention, the above-described photocationic polymerization initiator that is an essential component and the above-described other components that may be used together as necessary, as long as they do not hinder achievement of the problems of the present invention. In order to further improve the efficiency of the photocationic polymerization initiator and further promote the photocationic polymerization of the photocationic polymerizable compound, a photosensitizer may be contained.
上記光増感剤としては、特に限定されるものではないが、例えば、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、アゾ化合物、ジアゾ化合物、ハロゲン化合物、光還元性色素等が挙げられ、その具体例としては、特に限定されるものではないが、例えば、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテルなどのベンゾイン誘導体、ベンゾフェノン、２，４−ジクロルベンゾフェノン、ｏ−ベンゾイル安息香酸メチル、４，４’−ビス（ジメチルアミノ）ベンゾフェノンなどのベンゾフェノン誘導体、２−クロルチオキサントン、２−イソプロピルチオキサントンなどのチオキサントン誘導体、２−クロルアントラキノン、２−メチルアントラキノンなどのアントラキノン誘導体等が挙げられる。これらの光増感剤は、単独で用いられても良いし、２種類以上が併用されても良い。 The photosensitizer is not particularly limited, and examples thereof include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo compounds, diazo compounds, halogen compounds, and photoreducible dyes. Specific examples thereof include, but are not limited to, for example, benzoin derivatives such as benzoin methyl ether and benzoin isopropyl ether, benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4, Examples thereof include benzophenone derivatives such as 4′-bis (dimethylamino) benzophenone, thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropylthioxanthone, and anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone. These photosensitizers may be used independently and 2 or more types may be used together.
本発明の光硬化性樹脂組成物中における上記光増感剤の含有量は、特に限定されるものではないが、上記光カチオン重合開始剤１００重量部に対し、光増感剤１〜５００重量部であることが好ましい。 Although content of the said photosensitizer in the photocurable resin composition of this invention is not specifically limited, 1-500 weight of photosensitizers with respect to 100 weight part of said photocationic polymerization initiators. Part.
本発明の光硬化性樹脂組成物には、硬化制御剤が含有される。上記硬化制御剤は、光硬化性樹脂組成物の光カチオン重合反応を阻害することから、光硬化性樹脂組成物中に適当量の硬化制御剤を含有させることにより、光照射後の使用可能時間および硬化時間を制御する反応調節剤としての機能を果たし、光硬化性樹脂組成物の作業性を大幅に向上させることができる。 The photocurable resin composition of the present invention, hardening control agent is Ru are contained. Since the above-mentioned curing control agent inhibits the photocationic polymerization reaction of the photocurable resin composition, the useable time after light irradiation can be obtained by including an appropriate amount of the curing control agent in the photocurable resin composition. In addition, it functions as a reaction regulator for controlling the curing time, and the workability of the photocurable resin composition can be greatly improved.
上記硬化制御剤としては、特に限定されるものではないが、例えば、水酸基を有する脂肪族炭化水素やポリエーテル化合物等が挙げられる。本発明では、ポリエーテル化合物が用いられる。これらの硬化制御剤は、単独で用いられても良いし、２種類以上が併用されても良い。 Although it does not specifically limit as said hardening control agent, For example, the aliphatic hydrocarbon which has a hydroxyl group, a polyether compound, etc. are mentioned. In the present invention, a polyether compound is used. These curing control agents may be used alone or in combination of two or more.
上記水酸基を有する脂肪族炭化水素としては、特に限定されるものではないが、例えば、グリセリンやペンタエリスリトールなどの多官能水酸基含有化合物等が挙げられる。 The aliphatic hydrocarbon having a hydroxyl group is not particularly limited, and examples thereof include polyfunctional hydroxyl group-containing compounds such as glycerin and pentaerythritol.
また、上記ポリエーテル化合物としては、特に限定されるものではないが、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリオキシテトラメチレングリコールなどのポリアルキレンオキサイド等が挙げられる。 The polyether compound is not particularly limited, and examples thereof include polyalkylene oxides such as polyethylene glycol, polypropylene glycol, and polyoxytetramethylene glycol.
上記、硬化制御剤の中でも、ポリアルキレンオキサイドが好適に用いられ、とりわけ、ポリオキシテトラメチレングリコールがより好適に用いられる。 Among the above-mentioned curing control agents, polyalkylene oxide is preferably used, and in particular, polyoxytetramethylene glycol is more preferably used.
上記ポリアルキレンオキサイドの末端は、特に限定されるものではなく、水酸基であっても良いし、他の化合物によりエーテル化やエステル化されていても良いし、エポキシ基などの官能基であっても良く、中でも、前記光カチオン重合性化合物との反応性を有することから、水酸基やエポキシ基が好適に用いられる。 The terminal of the polyalkylene oxide is not particularly limited, and may be a hydroxyl group, may be etherified or esterified with another compound, or may be a functional group such as an epoxy group. Among them, among them, a hydroxyl group or an epoxy group is preferably used because it has reactivity with the photocationically polymerizable compound.
上記ポリエーテル化合物としては、ポリアルキレンオキサイド付加ビスフェノール誘導体も好適に用いられ、特に末端に水酸基またはエポキシ基を有する化合物がより好適に用いられる。これらのうち市販品としては、特に限定されるものではないが、例えば、新日本理化社製の商品名「リカレジンＢＰＯ−２０Ｅ」、「リカレジンＢＥＯ−６０Ｅ」、「リカレジンＰＯ−２０」などの「リカレジン」シリーズ等が挙げられる。 As the polyether compound, a polyalkylene oxide-added bisphenol derivative is also preferably used, and in particular, a compound having a hydroxyl group or an epoxy group at the terminal is more preferably used. Among these, although it does not specifically limit as a commercial item, For example, brand names "Lika Resin BPO-20E", "Lika Resin BEO-60E", "Lika Resin PO-20", etc. made by Shin Nippon Rika Co., Ltd. "Recar Resin" series and the like.
本発明の光硬化性樹脂組成物中における上記硬化制御剤の含有量は、要求される光照射後の使用可能時間および硬化時間に対応して適宜設定されれば良く、特に限定されるものではないが、一般的には、前記光カチオン重合性化合物１００重量部に対し、硬化制御剤０．１〜３０重量部であることが好ましく、より好ましくは０．５〜２０重量部である。 The content of the curing control agent in the photocurable resin composition of the present invention may be appropriately set corresponding to the required usable time and curing time after light irradiation, and is not particularly limited. In general, however, it is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the cationic photopolymerizable compound.
本発明の光硬化性樹脂組成物には、本発明の課題達成を阻害しない範囲で必要に応じて、例えば、粘接着性をより向上させるための粘接着性ポリマーや粘接着性付与剤（タッキファイヤー）、力学的物性や耐久性をより向上させるための充填剤、粘度を調整するための粘度調整剤、揺変性（チキソトロープ性）を付与するための揺変性付与剤（チキソトロープ剤）、力学的物性を改善するための物性調整剤、カップリング剤、補強剤、増量剤、軟化剤（可塑剤）、タレ防止剤、酸化防止剤（老化防止剤）、熱安定剤、難燃剤、帯電防止剤、有機溶剤等の公知の各種添加剤の１種類もしくは２種類以上が含有されていても良い。 In the photocurable resin composition of the present invention, if necessary, for example, an adhesive polymer or an adhesive agent for further improving the adhesiveness within a range that does not hinder the achievement of the present invention. Agent (tackifier), filler for further improving mechanical properties and durability, viscosity modifier for adjusting viscosity, thixotropic agent for imparting thixotropic properties (thixotropic property) , Physical property modifiers, coupling agents, reinforcing agents, extenders, softeners (plasticizers), sagging agents, antioxidants (anti-aging agents), heat stabilizers, flame retardants, One kind or two or more kinds of various known additives such as an antistatic agent and an organic solvent may be contained.
本発明の光硬化性樹脂組成物の製造方法は、特に限定されるものではなく、例えば、万能ミキサー、バンバリーミキサー、ニーダー、２本ロール、３本ロール、押出機等の公知の各種混練機を単独で用いるかまたは併用して、必須成分である光カチオン重合性化合物、ポリエーテル化合物および光カチオン重合開始剤の各所定量と、必要に応じて含有されていても良い他の光カチオン重合開始剤、光増感剤、硬化制御剤および各種添加剤の１種類もしくは２種類以上の各所定量とを、常温下もしくは加熱下で、常圧下、減圧下、加圧下もしくは不活性ガス気流下等の条件下で均一に混練することにより、所望の光硬化性樹脂組成物を得ることができる。 The method for producing the photocurable resin composition of the present invention is not particularly limited. For example, various known kneaders such as a universal mixer, a Banbury mixer, a kneader, two rolls, three rolls, and an extruder are used. alone or in combination is used, cationic photopolymerizable compound is an essential component, and predetermined amounts of a polyether compound and cationic photopolymerization initiators, other cationic photopolymerization may be contained as needed One or two or more predetermined amounts of an initiator, a photosensitizer, a curing control agent, and various additives, at normal temperature or under heating, under normal pressure, under reduced pressure, under pressure, or under an inert gas stream The desired photocurable resin composition can be obtained by uniformly kneading under the conditions.
本発明の光硬化性樹脂組成物は、硬化物における波長３５０〜７００ｎｍの光の吸収率が８０％以上であり、かつ、硬化物の全光線透過率が８０％以上であることが好ましい。 The photocurable resin composition of the present invention preferably has a light absorption rate of 350 to 700 nm in the cured product of 80% or more and a total light transmittance of the cured product of 80% or more.
上記波長３５０〜７００ｎｍの光の吸収率とは、色度計｛例えば、「ＣＯＬＯＲ ＡＮＡＬＹＺＥＲ ＴＣ−１８００Ｍ」（東京電色社製）｝を用いて測定した上記波長領域における光の吸収率を意味する。また、上記硬化物の全光線透過率とは、分光計｛例えば、「ＡＵＴＯＭＡＴＩＣ ＨＡＺＥ ＭＡＴＥＲ ＭＯＤＥＬ ＴＣ−III ＤＰＫ」（東京電色社製）｝を用いて測定した硬化塗膜の全光線透過率（％）を意味する。 The absorptance of light having a wavelength of 350 to 700 nm means the absorptance of light in the wavelength region measured using a chromaticity meter {for example, “COLOR ANALYZER TC-1800M” (manufactured by Tokyo Denshoku)}. . The total light transmittance of the cured product is the total light transmittance of a cured coating film measured using a spectrometer {for example, “AUTOMATIC HAZE MATER MODEL TC-III DPK” (manufactured by Tokyo Denshoku Co., Ltd.)}. %).
本発明の光硬化性樹脂組成物の上記波長３５０〜７００ｎｍの光の吸収率が８０％未満であるか、および／または、本発明の光硬化性樹脂組成物の上記硬化物の全光線透過率が８０％未満であると、本発明の光硬化性樹脂組成物を用いて例えばＥＬ素子を作製した場合に、得られるＥＬ素子の例えば透明性などの光学的特性が不十分となることがある。 The light curable resin composition of the present invention has an absorbance of light having a wavelength of 350 to 700 nm of less than 80%, and / or the total light transmittance of the cured product of the photocurable resin composition of the present invention. If it is less than 80%, for example, when an EL element is produced using the photocurable resin composition of the present invention, the optical characteristics such as transparency of the obtained EL element may be insufficient. .
本発明の光硬化性樹脂組成物は、好ましくは波長３００ｎｍ以上、より好ましくは波長３００〜４００ｎｍの光を含む光を照射して、必須成分である上記光カチオン重合開始剤、必要に応じて含有されていても良い他の光カチオン重合開始剤および光増感剤を活性化することにより、前記光カチオン重合性化合物の光カチオン重合が進行して、硬化する。 The photocurable resin composition of the present invention, containing preferably longer than the wavelength 300 nm, more preferably by irradiating light including light of wavelength 300 to 400 nm, which is an essential component the photo cationic polymerization initiator, if necessary By activating other photocationic polymerization initiators and photosensitizers that may have been prepared, photocationic polymerization of the photocationically polymerizable compound proceeds and cures.
上記光を照射するための光源としては、好ましくは波長３００ｎｍ以上、より好ましくは波長３００〜４００ｎｍの光を含む光を照射しうるものであればどのような光源であっても良く、特に限定されるものではないが、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、エキシマレーザー、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプ、ナトリウムランプ、ハロゲンランプ、キセノンランプ、蛍光灯、太陽光、電子線照射装置等が挙げられる。これらの光源の使用に際しては、例えば光カットフィルター等を用いて、熱線や波長３００ｎｍ未満の光を除去することが好ましい。また、上記各種光源は、単独で用いられても良いし、２種類以上が併用されても良い。さらに、上記各種光源の光硬化性樹脂組成物への照射手順としては、例えば、各種光源の同時照射、時間差をおいての逐次照射、同時照射と逐次照射との組み合わせ照射等が挙げられ、いずれの照射手順を採っても良い。 The light source for irradiating the light may be any light source as long as it can irradiate light including light having a wavelength of 300 nm or more, more preferably 300 to 400 nm, and is particularly limited. For example, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, excimer laser, chemical lamp, black light lamp, microwave excitation mercury lamp, metal halide lamp, sodium lamp, halogen lamp, xenon lamp, fluorescent A lamp, sunlight, an electron beam irradiation apparatus, etc. are mentioned. When using these light sources, it is preferable to remove heat rays or light having a wavelength of less than 300 nm using, for example, a light cut filter or the like. The various light sources may be used alone or in combination of two or more. Furthermore, examples of the irradiation procedure of the various light sources to the photocurable resin composition include simultaneous irradiation of various light sources, sequential irradiation with a time difference, combined irradiation of simultaneous irradiation and sequential irradiation, etc. The irradiation procedure may be taken.
また、本発明の光硬化性樹脂組成物の硬化に際しては、光カチオン重合性化合物の光カチオン重合をより促進して、硬化時間をより短縮するために、好ましくは波長３００ｎｍ以上、より好ましくは波長３００〜４００ｎｍの光を含む光の照射に加えるに、光硬化性樹脂組成物が適用される材料（被着体）を劣化させない範囲で必要に応じて、例えば、加熱硬化等の他の硬化手段を併用しても良い。上記加熱硬化を併用する場合の加熱温度は、特に限定されるものではないが、５０〜１００℃であることが好ましい。 In curing the photocurable resin composition of the present invention, in order to further accelerate the photocationic polymerization of the photocationically polymerizable compound and further shorten the curing time, the wavelength is preferably 300 nm or more, more preferably the wavelength. In addition to irradiation with light including light of 300 to 400 nm, other curing means such as heat curing, for example, within a range that does not deteriorate the material (adhered body) to which the photocurable resin composition is applied. May be used in combination. Although the heating temperature in the case of using together the said heat curing is not specifically limited, It is preferable that it is 50-100 degreeC.
本発明の光硬化性樹脂組成物は、その用途を特に限定されるものではなく、例えば、接着剤、封止剤、片面テープ、両面テープ、封止フィルム、シーリング剤、コーティング剤、ライニング剤、印刷インキ、エレクトロニクス材料等の種々の用途に好適に用いることができ、中でも、接着剤や封止剤として用いることが好ましい。また、これら接着剤、封止剤、片面テープ、両面テープ、封止フィルム等を用いて、ディスプレイ表示部のような透明または半透明の構造体に好適に用いることができ、中でも、ＥＬ素子に用いることが好ましい。 The use of the photocurable resin composition of the present invention is not particularly limited. For example, an adhesive, a sealing agent, a single-sided tape, a double-sided tape, a sealing film, a sealing agent, a coating agent, a lining agent, It can be suitably used for various applications such as printing inks and electronic materials, and among them, it is preferably used as an adhesive or sealant. In addition, these adhesives, sealants, single-sided tapes, double-sided tapes, sealing films, etc. can be used suitably for transparent or semi-transparent structures such as display display parts. It is preferable to use it.
上記接着剤や封止剤の作製方法は、特に限定されるものではなく、例えば、前記光カチオン重合性化合物、ポリエーテル化合物、および、光カチオン重合開始剤、ならびに、必要に応じて含有させる、例えば、粘接着性ポリマー、粘接着性付与剤、充填剤、その他の各種添加剤等の種類を適宜選択し、量を適宜調整して、前記本発明の光硬化性樹脂組成物の製造方法と同様の方法で、これらの各成分を均一に混練することにより、所望の接着剤や封止剤を得ることができる。 The method for producing the adhesive or sealant is not particularly limited, and for example, the photocationic polymerizable compound, the polyether compound, and the photocationic polymerization initiator, and contained as necessary. For example, the photocurable resin composition of the present invention is produced by appropriately selecting the type of adhesive polymer, adhesive agent, filler, other various additives, etc., and adjusting the amount appropriately. A desired adhesive or sealant can be obtained by uniformly kneading these components in the same manner as the above method.
次に、本発明の表示素子は、上述した本発明の光硬化性樹脂組成物を用いてなる。上記表示素子としては、特に限定されるものではないが、例えば、ＥＬ素子や液晶表示素子等が挙げられ、ＥＬ素子としては、有機ＥＬ素子や無機ＥＬ素子等が挙げられる。 Next, the display element of this invention uses the photocurable resin composition of this invention mentioned above. Although it does not specifically limit as said display element, For example, an EL element, a liquid crystal display element, etc. are mentioned, As an EL element, an organic EL element, an inorganic EL element, etc. are mentioned.
光カチオン重合開始剤は、前記一般式（４）または前記一般式（５）および前記一般式（６）から明らかなように、リン系光カチオン重合開始剤やアンチモン系光カチオン重合開始剤ではなく、かつ、ヨウ素（Ｉ）を含有していないので、硬化進行過程において黄変などの着色を起こすことがなく、かつ、高いガラス転移温度を有するため透湿性が低く、透明性にも優れる硬化物となる光硬化性樹脂組成物を得ることができる。 As is clear from the general formula ( 4 ) or the general formula ( 5 ) and the general formula ( 6 ), the photocationic polymerization initiator is not a phosphorus-based photocationic polymerization initiator or an antimony-based photocationic polymerization initiator. In addition, since it does not contain iodine (I), it does not cause yellowing or the like in the course of curing, and has a high glass transition temperature, so it has low moisture permeability and excellent transparency. The photocurable resin composition which becomes can be obtained.
本発明の光硬化性樹脂組成物は、前記光カチオン重合性化合物および上記光カチオン重合開始剤が含有されてなるので、硬化進行過程において黄変などの着色を起こすことがなく、かつ、高いガラス転移温度を有するため透湿性が低く、透明性にも優れる硬化物となる。 The photocurable resin composition of the present invention, since the optical cationic polymerizable compound and the above Symbol photo cationic polymerization initiator, which are contained, without causing coloration, such as yellowing in the cured progression, and high Since it has a glass transition temperature, it becomes a cured product with low moisture permeability and excellent transparency.
また、本発明の光硬化性樹脂組成物では、光カチオン重合性化合物としてエポキシ系化合物やオキセタニル系化合物を用いたり、硬化制御剤を含有させたり、硬化物における波長３５０〜７００ｎｍの光の吸収率が８０％以上であり、かつ、硬化物の全光線透過率が８０％以上であるものとなすことにより、上記効果がより確実なものとなる。 Further, in the photocurable resin composition of the present invention, or an epoxy compound or an oxetanyl compound as a cationic photopolymerizable compound, or contain a hardening control agent, a light having a wavelength 350~700nm in the cured product By making the absorption rate 80% or more and making the total light transmittance of the cured product 80% or more, the above-mentioned effect is more certain.
本発明の表示素子は、上記本発明の光硬化性樹脂組成物を用いて作製されるので、硬化進行過程において黄変などの着色を起こすことがなく、かつ、高いガラス転移温度を有するため透湿性が低く、透明性などの光学的特性にも優れる。 Since the display element of the present invention is produced using the above-mentioned photocurable resin composition of the present invention, it does not cause yellowing or other coloring in the course of curing, and has a high glass transition temperature. Low wettability and excellent optical properties such as transparency.
本発明をさらに詳しく説明するため以下に実施例を挙げるが、本発明はこれらの実施例のみに限定されるものではない。 In order to describe the present invention in more detail, examples will be given below, but the present invention is not limited to these examples.
（参考例１）
常温下で、トリフェニルスルホニウムブロマイド２００ｍｇを含有する水溶液に対して、ソジウムテトラキス（ペンタフルオロフェニル）ボレートの１０重量％水分散液５ｇを滴下した。その後、遠心分離を５回行って、生成した沈殿物を濾別し、精製した後、乾燥して、光カチオン重合開始剤（ａ）を合成した。なお、上記光カチオン重合開始剤（ａ）は、波長３００ｎｍ以上の光を吸収した。
( Reference Example 1)
Under normal temperature, 5 g of a 10 wt% aqueous dispersion of sodium tetrakis (pentafluorophenyl) borate was added dropwise to an aqueous solution containing 200 mg of triphenylsulfonium bromide. Then, centrifugation was performed 5 times, the produced | generated deposit was separated by filtration, and after refine | purifying, it dried and synthesize | combined the photocationic polymerization initiator (a). The cationic photopolymerization initiator (a) absorbed light having a wavelength of 300 nm or more.
ビスフェノールＡ型エポキシ樹脂（商品名「エピコート８２８」、ジャパンエポキシレジン社製）１００重量部に対して、上記で得られた光カチオン重合開始剤（ａ）０．６重量部および光増感剤（商品名「ＤＥＴＸ−Ｓ」、日本化薬社製）０．１重量部を添加し、均一に攪拌混練した後、脱泡して、光硬化性樹脂組成物を製造した。 0.6 parts by weight of the photocationic polymerization initiator (a) obtained above and a photosensitizer (100 parts by weight) with respect to 100 parts by weight of a bisphenol A type epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.) 0.1 part by weight of a trade name “DETX-S” (manufactured by Nippon Kayaku Co., Ltd.) was added, and the mixture was uniformly stirred and kneaded, and then defoamed to produce a photocurable resin composition.
（参考例２）
ビスフェノールＦ型エポキシ樹脂（商品名「エピコート８０６」、ジャパンエポキシレジン社製）１００重量部に対して、参考例１で得られた光カチオン重合開始剤（ａ）０．６重量部および光増感剤「ＤＥＴＸ−Ｓ」０．１重量部を添加し、均一に攪拌混練した後、脱泡して、光硬化性樹脂組成物を製造した。
( Reference Example 2)
0.6 parts by weight of the photocationic polymerization initiator (a) obtained in Reference Example 1 and photosensitization with respect to 100 parts by weight of bisphenol F type epoxy resin (trade name “Epicoat 806”, manufactured by Japan Epoxy Resin Co., Ltd.) 0.1 parts by weight of the agent “DETX-S” was added, stirred and kneaded uniformly, and then defoamed to produce a photocurable resin composition.
（参考例３）
参考例１で得られた光カチオン重合開始剤（ａ）の添加量を０．３重量部としたこと以外は参考例２の場合と同様にして、光硬化性樹脂組成物を製造した。
( Reference Example 3)
Except that the cationic photopolymerization initiator obtained in Reference Example 1 the amount of (a) was 0.3 part by weight in the same manner as in Reference Example 2, to produce a photo-curable resin composition.
（参考例４）
ビスフェノールＦ型エポキシ樹脂「エピコート８０６」１００重量部に対して、前記一般式（４）で表される光カチオン重合開始剤（ｂ）１重量部および光増感剤「ＤＥＴＸ−Ｓ」０．１重量部を添加し、均一に攪拌混練した後、脱泡して、光硬化性樹脂組成物を製造した。なお、上記光カチオン重合開始剤（ｂ）は、波長３００ｎｍ以上の光を吸収した。
( Reference Example 4)
Relative to bisphenol F type epoxy resin "Epikote 806" 100 parts by weight, the formula (4) represented Ru cationic photopolymerization initiator (b) 1 part by weight of photosensitizer agent "DETX-S" 0.1 Part by weight was added, and the mixture was uniformly stirred and kneaded, and then defoamed to produce a photocurable resin composition. The cationic photopolymerization initiator (b) absorbed light having a wavelength of 300 nm or more.
（参考例５）
光増感剤「ＤＥＴＸ−Ｓ」を添加しなかったこと以外は参考例４の場合と同様にして、光硬化性樹脂組成物を製造した。
( Reference Example 5)
A photocurable resin composition was produced in the same manner as in Reference Example 4 except that the photosensitizer “DETX-S” was not added.
（参考例６）
前記一般式（４）で表される光カチオン重合開始剤（ｂ）の添加量を５重量部とし、かつ、光増感剤「ＤＥＴＸ−Ｓ」を添加しなかったこと以外は参考例４の場合と同様にして、光硬化性樹脂組成物を製造した。
( Reference Example 6)
The amount of the general formula (4) represented Ru cationic photopolymerization initiator (b) and 5 parts by weight, and, except for not adding the photosensitizer "DETX-S" is in reference example 4 In the same manner as in the case, a photocurable resin composition was produced.
（実施例１）
さらに、硬化制御剤としてポリエーテル化合物（商品名「リカレジンＢＥＯ−６０Ｅ」、新日本理化社製）５重量部を添加したこと以外は参考例６の場合と同様にして、光硬化性樹脂組成物を製造した。
(Example 1 )
Furthermore, a photocurable resin composition was prepared in the same manner as in Reference Example 6 except that 5 parts by weight of a polyether compound (trade name “Rikaresin BEO-60E”, manufactured by Shin Nippon Rika Co., Ltd.) was added as a curing control agent. Manufactured.
（比較例１）
ビスフェノールＦ型エポキシ樹脂「エピコート８０６」１００重量部に対して、前記式（７）で表されるヨウ素（Ｉ）を含有する光カチオン重合開始剤（ｃ）（商品名「Ｒｈｏｔｏｉｎｉｔｉａｔｏｒ２０７４」、Ｒｈｏｄｉａ社製）０．６重量部および光増感剤「ＤＥＴＸ−Ｓ」０．１重量部を添加し、均一に攪拌混練した後、脱泡して、光硬化性樹脂組成物を製造した。なお、上記光カチオン重合開始剤（ｃ）は、波長３００ｎｍ以上の光を吸収しなかった。
(Comparative Example 1)
Photocationic polymerization initiator (c) containing iodine (I) represented by the above formula (7) with respect to 100 parts by weight of the bisphenol F type epoxy resin “Epicoat 806” (trade name “Rhotoinitiator 2074”, manufactured by Rhodia) ) 0.6 part by weight and 0.1 part by weight of photosensitizer “DETX-S” were added, and the mixture was uniformly stirred and kneaded, and then defoamed to produce a photocurable resin composition. In addition, the said photocationic polymerization initiator (c) did not absorb light with a wavelength of 300 nm or more.
（比較例２）
前記式（７）で表されるヨウ素（Ｉ）を含有する光カチオン重合開始剤（ｃ）「Ｒｈｏｔｏｉｎｉｔｉａｔｏｒ２０７４」の添加量を０．３重量部としたこと以外は比較例１の場合と同様にして、光硬化性樹脂組成物を製造した。
(Comparative Example 2)
Except that the addition amount of the photocationic polymerization initiator (c) “Rhotoinitiator 2074” containing iodine (I) represented by the formula (7) was 0.3 parts by weight, it was the same as in Comparative Example 1. A photocurable resin composition was produced.
（比較例３）
ビスフェノールＦ型エポキシ樹脂「エピコート８０６」１００重量部に対して、リン系光カチオン重合開始剤（ｄ）（商品名「ＵＶＩ６９９０」、ユニオンカーバイド社製）０．６重量部および光増感剤「ＤＥＴＸ−Ｓ」０．１重量部を添加し、均一に攪拌混練した後、脱泡して、光硬化性樹脂組成物を製造した。なお、上記光カチオン重合開始剤（ｄ）は、波長３００ｎｍ以上の光を吸収しなかった。
(Comparative Example 3)
Phosphoric photocationic polymerization initiator (d) (trade name “UVI6990”, manufactured by Union Carbide) 0.6 parts by weight and photosensitizer “DETX” with respect to 100 parts by weight of bisphenol F type epoxy resin “Epicoat 806” -S "0.1 part by weight was added and stirred and kneaded uniformly, and then defoamed to produce a photocurable resin composition. The cationic photopolymerization initiator (d) did not absorb light having a wavelength of 300 nm or more.
（比較例４）
光増感剤「ＤＥＴＸ−Ｓ」を添加しなかったこと以外は比較例１の場合と同様にして、光硬化性樹脂組成物を製造した。
(Comparative Example 4)
A photocurable resin composition was produced in the same manner as in Comparative Example 1 except that the photosensitizer “DETX-S” was not added.
実施例１、参考例１〜６、および、比較例１〜比較例４で得られた光硬化性樹脂組成物の性能（１．硬化物のガラス転移温度、２．硬化物のイエローインデックス）を以下の方法で評価した。その結果は表１に示すとおりであった。 The performances (1. glass transition temperature of cured product, 2. yellow index of cured product) of the photocurable resin compositions obtained in Example 1 , Reference Examples 1-6 , and Comparative Examples 1 to 4 were as follows. Evaluation was made by the following method. The results are shown in Table 1.
１．硬化物のガラス転移温度
アプリケーターを用いて、離型処理が施されたポリエステルフィルム（商品名「＃５０１１」、リンテック社製）の離型処理面に光硬化性樹脂組成物を塗膜の厚みが１５０μｍとなるように塗工した後、超高圧水銀灯を用いて、２０ｍＷの光を１００秒間（光照射量２０００ｍＪ）照射して、塗膜を硬化させた。次いで、上記で得られた光硬化性樹脂組成物の硬化塗膜を所定の大きさに切断した後、昇温速度１０℃／分で３０〜２５０℃まで温度上昇させた時の動的粘弾性スペクトルの測定を行って、ｔａｎδのピークより硬化物のガラス転移温度（℃）を求めた。
1. Glass transition temperature of cured product Using an applicator, the photocurable resin composition was applied to the release-treated surface of the polyester film (trade name “# 5011”, manufactured by Lintec Corporation) subjected to the release treatment. After coating to 150 μm, the coating film was cured by irradiating 20 mW of light for 100 seconds (light irradiation amount: 2000 mJ) using an ultrahigh pressure mercury lamp. Next, after cutting the cured coating film of the photocurable resin composition obtained above to a predetermined size, the dynamic viscoelasticity when the temperature is increased from 30 to 250 ° C. at a temperature rising rate of 10 ° C./min. The spectrum was measured, and the glass transition temperature (° C.) of the cured product was determined from the tan δ peak.
２．硬化物のイエローインデックス
１．の場合と同様にして得られた光硬化性樹脂組成物の硬化塗膜を８０℃の雰囲気下に１５０時間放置した後、色差計「ＣＯＬＯＲ ＡＮＡＬＹＺＥＲ ＴＣ−１８００Ｍ」を用いて、硬化物のイエローインデックスを測定した。
2. Yellow index of cured product After leaving the cured coating film of the photocurable resin composition obtained in the same manner as in the above for 150 hours in an atmosphere of 80 ° C., using a color difference meter “COLOR ANALYZER TC-1800M”, the yellow index of the cured product Was measured.
表１から明らかなように、光カチオン重合開始剤（ａ）および光カチオン重合開始剤（ｂ）を用いて製造した実施例１、及び参考例１〜６の光硬化性樹脂組成物は、いずれも硬化物のガラス転移温度が高かった。また、上記実施例１、及び参考例１〜６の光硬化性樹脂組成物は、いずれも硬化物を８０℃の雰囲気下に１５０時間放置した後のイエローインデックスが低く、ほとんど着色していなかった。 As apparent from Table 1, the cationic photopolymerization initiator (a) and a cationic photopolymerization initiator (b) the actual Example 1 was prepared using, and photocurable resin composition of Reference Example 1-6 In both cases, the glass transition temperature of the cured product was high. In addition, the photocurable resin compositions of Example 1 and Reference Examples 1 to 6 were low in yellow index after leaving the cured product in an atmosphere of 80 ° C. for 150 hours, and were hardly colored. .
これに対し、前記式（７）で表されるヨウ素（Ｉ）を含有する光カチオン重合開始剤（ｃ）を用いて製造した比較例１および比較例２の光硬化性樹脂組成物、および、リン系光カチオン重合開始剤（ｄ）を用いて製造した比較例３の光硬化性樹脂組成物は、いずれも硬化物のガラス転移温度は高かったものの、硬化物を８０℃の雰囲気下に１５０時間放置した後のイエローインデックスが極めて高く、着色が激しかった。また、前記式（７）で表されるヨウ素（Ｉ）を含有する光カチオン重合開始剤（ｃ）を用い、光増感剤を添加することなく製造した比較例４の光硬化性樹脂組成物は、硬化物のガラス転移温度が低く、しかも硬化物を８０℃の雰囲気下に１５０時間放置した後のイエローインデックスが高く、かなり着色していた。 On the other hand, the photocurable resin composition of Comparative Example 1 and Comparative Example 2 produced using the photocationic polymerization initiator (c) containing iodine (I) represented by the formula (7), and Although all the photocurable resin compositions of Comparative Example 3 produced using the phosphorous photocationic polymerization initiator (d) had a high glass transition temperature, the cured product was 150 ° C. in an atmosphere of 80 ° C. The yellow index after standing for a long time was extremely high and the coloring was intense. Moreover, the photocurable resin composition of the comparative example 4 manufactured without adding a photosensitizer using the photocationic polymerization initiator (c) containing the iodine (I) represented by the said Formula (7). The cured product had a low glass transition temperature, and the cured product had a high yellow index after being left in an atmosphere of 80 ° C. for 150 hours.
以上述べたように、光カチオン重合開始剤は、前記一般式（４）または前記一般式（５）および前記一般式（６）から明らかなように、リン系光カチオン重合開始剤やアンチモン系光カチオン重合開始剤ではなく、かつ、ヨウ素（Ｉ）を含有していないので、硬化進行過程において黄変などの着色を起こすことがなく、かつ、高いガラス転移温度を有するため透湿性が低く、透明性にも優れる硬化物となる光硬化性樹脂組成物を得ることができる。 As described above, the photocationic polymerization initiator is a phosphoric photocationic polymerization initiator or an antimony based photocatalyst, as is apparent from the general formula ( 4 ) or the general formula ( 5 ) and the general formula ( 6 ). Since it is not a cationic polymerization initiator and does not contain iodine (I), it does not cause coloring such as yellowing in the course of curing, and has a high glass transition temperature, so it has low moisture permeability and is transparent. Ru can be obtained a photocurable resin composition comprising a cured product excellent in resistance.
本発明の光硬化性樹脂組成物は、前記光カチオン重合性化合物および上記光カチオン重合開始剤が含有されてなるので、硬化進行過程において黄変などの着色を起こすことがなく、かつ、高いガラス転移温度を有するため透湿性が低く、透明性にも優れる硬化物となるものであり、例えば、接着剤、封止剤、片面テープ、両面テープ、封止フィルム、シーリング剤、コーティング剤、ライニング剤、印刷インキ、エレクトロニクス材料、ひいては、有機ＥＬ素子や無機ＥＬ素子などのＥＬ素子等を始め、各種用途に好適に用いられる。 The photocurable resin composition of the present invention, since the optical cationic polymerizable compound and the above Symbol photo cationic polymerization initiator, which are contained, without causing coloration, such as yellowing in the cured progression, and high Since it has a glass transition temperature, it becomes a cured product with low moisture permeability and excellent transparency. For example, adhesive, sealant, single-sided tape, double-sided tape, sealing film, sealing agent, coating agent, lining It is suitably used for various applications including agents, printing inks, electronic materials, and eventually EL elements such as organic EL elements and inorganic EL elements.
中でも、本発明の光硬化性樹脂組成物を接着剤や封止剤として用いると、硬化後は優れた接着力や高いガラス転移温度などの優れた物性を発現するとともに、硬化進行過程において黄変などの着色を起こすこともないので、例えば、有機ＥＬ素子や無機ＥＬ素子などのＥＬ素子等を始め、各種用途に好適に用いられる。 Among them, when the photocurable resin composition of the present invention is used as an adhesive or sealant, it exhibits excellent physical properties such as excellent adhesive strength and high glass transition temperature after curing, and yellowing in the course of curing. For example, EL elements such as organic EL elements and inorganic EL elements are suitably used for various applications.
本発明の表示素子、特に有機ＥＬ素子は、上記本発明の光硬化性樹脂組成物を用いてなるので、例えば透明性などの優れた光学的特性と優れた物性とを発現する。
Since the display element of the present invention, particularly the organic EL element, is formed using the photocurable resin composition of the present invention, it exhibits excellent optical properties such as transparency and excellent physical properties.
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