WO2023054561A1 - Curable resin composition, coating layer, and film - Google Patents
Curable resin composition, coating layer, and film Download PDFInfo
- Publication number
- WO2023054561A1 WO2023054561A1 PCT/JP2022/036375 JP2022036375W WO2023054561A1 WO 2023054561 A1 WO2023054561 A1 WO 2023054561A1 JP 2022036375 W JP2022036375 W JP 2022036375W WO 2023054561 A1 WO2023054561 A1 WO 2023054561A1
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- WO
- WIPO (PCT)
- Prior art keywords
- curable resin
- resin composition
- weight
- cationically polymerizable
- examples
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 75
- 239000011247 coating layer Substances 0.000 title claims abstract description 12
- 239000010408 film Substances 0.000 title 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000003505 polymerization initiator Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 7
- 239000013008 thixotropic agent Substances 0.000 claims description 6
- -1 silane compound Chemical class 0.000 description 60
- 239000000975 dye Substances 0.000 description 16
- 125000002091 cationic group Chemical group 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 8
- 238000010538 cationic polymerization reaction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical class CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- PFHLXMMCWCWAMA-UHFFFAOYSA-N [4-(4-diphenylsulfoniophenyl)sulfanylphenyl]-diphenylsulfanium Chemical compound C=1C=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1SC(C=C1)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 PFHLXMMCWCWAMA-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010943 off-gassing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FCKXGFANXSHGAW-DTXPUJKBSA-N (2s)-n,n'-bis[(2s)-1-(2-chloro-4-nitroanilino)-1-oxo-3-phenylpropan-2-yl]-2-hydroxybutanediamide Chemical compound C([C@H](NC(=O)C[C@H](O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(=O)NC=1C(=CC(=CC=1)[N+]([O-])=O)Cl)C(=O)NC=1C(=CC(=CC=1)[N+]([O-])=O)Cl)C1=CC=CC=C1 FCKXGFANXSHGAW-DTXPUJKBSA-N 0.000 description 2
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 2
- RRXFVFZYPPCDAW-UHFFFAOYSA-N 4-(7-oxabicyclo[4.1.0]heptan-4-ylmethoxymethyl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2OC2CC1COCC1CC2OC2CC1 RRXFVFZYPPCDAW-UHFFFAOYSA-N 0.000 description 2
- 102100033806 Alpha-protein kinase 3 Human genes 0.000 description 2
- 101710082399 Alpha-protein kinase 3 Proteins 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 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
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 125000003566 oxetanyl group Chemical group 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical class CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- HIYIGPVBMDKPCR-UHFFFAOYSA-N 1,1-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1(COC=C)CCCCC1 HIYIGPVBMDKPCR-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- LFKLPJRVSHJZPL-UHFFFAOYSA-N 1,2:7,8-diepoxyoctane Chemical compound C1OC1CCCCC1CO1 LFKLPJRVSHJZPL-UHFFFAOYSA-N 0.000 description 1
- BMSRLPMIICHPCT-UHFFFAOYSA-N 1,3-bis(oxiran-2-yl)-1,3-dihydro-2-benzofuran Chemical compound C1OC1C1C2=CC=CC=C2C(C2OC2)O1 BMSRLPMIICHPCT-UHFFFAOYSA-N 0.000 description 1
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- RQJCIXUNHZZFMB-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxypropoxy)propane Chemical compound C=COCC(C)OCC(C)OC=C RQJCIXUNHZZFMB-UHFFFAOYSA-N 0.000 description 1
- FOWNZLLMQHBVQT-UHFFFAOYSA-N 1-ethenoxy-2-[2-(2-ethenoxypropoxy)propoxy]propane Chemical compound C=COCC(C)OCC(C)OCC(C)OC=C FOWNZLLMQHBVQT-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- ITLDHFORLZTRJI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-5-octoxyphenol Chemical compound OC1=CC(OCCCCCCCC)=CC=C1N1N=C2C=CC=CC2=N1 ITLDHFORLZTRJI-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- RQZUWSJHFBOFPI-UHFFFAOYSA-N 2-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COCC1CO1 RQZUWSJHFBOFPI-UHFFFAOYSA-N 0.000 description 1
- FVCHRIQAIOHAIC-UHFFFAOYSA-N 2-[1-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COC(C)COCC1CO1 FVCHRIQAIOHAIC-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-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
- 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
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-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
- 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 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
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- MOOIXEMFUKBQLJ-UHFFFAOYSA-N [1-(ethenoxymethyl)cyclohexyl]methanol Chemical compound C=COCC1(CO)CCCCC1 MOOIXEMFUKBQLJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006059 cover glass Substances 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
- JFHGLVIOIANSIN-UHFFFAOYSA-N dimethyl butanedioate;1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound COC(=O)CCC(=O)OC.CC1(C)CC(O)CC(C)(C)N1CCO JFHGLVIOIANSIN-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000006502 nitrobenzyl group Chemical group 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229960000834 vinyl ether Drugs 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- the present invention relates to a curable resin composition.
- the present invention also relates to coating layers and films formed using the curable resin composition.
- Optical semiconductor devices such as LEDs consume low power and have a long life, so they are widely used for backlights of liquid crystal display devices, lighting fixtures, and the like.
- An optical semiconductor element deteriorates when it comes into contact with moisture or gas in the atmosphere, and the light extraction efficiency decreases.
- a method for protecting and sealing optical semiconductor elements without using a cover glass or the like it has been studied to form a coating layer on the surface of the optical semiconductor element using a hard coating agent (for example, Patent Document 1 etc).
- An object of the present invention is to provide a curable resin composition that is excellent in colorability and hardness of the cured product. Another object of the present invention is to provide a coating layer and a film formed using the curable resin composition.
- the present disclosure 1 is a curable resin composition containing a curable resin, a photopolymerization initiator and a dye, wherein the curable resin is polysilsesquioxane having a cationically polymerizable group and the cationically polymerizable A curable resin composition containing a cationic polymerizable compound other than polysilsesquioxane having a group.
- the present disclosure 2 is the curable resin composition of the present disclosure 1, which has a viscosity of 500 mPa ⁇ s or more and 50,000 mPa ⁇ s or less.
- the present disclosure 3 is the curable resin composition of the present disclosure 1 or 2, wherein the photopolymerization initiator includes a photocationic polymerization initiator.
- This disclosure 4 is the curable resin composition of this disclosure 1, 2 or 3, further comprising an ultraviolet absorber.
- Disclosure 5 is the curable resin composition of Disclosure 1, 2, 3 or 4 further comprising a leveling agent.
- the present disclosure 6 is the curable resin composition of the present disclosure 1, 2, 3, 4 or 5 further comprising a thixotropic agent.
- the present disclosure 7 is a coating layer formed using the curable resin composition of the present disclosure 1, 2, 3, 4, 5 or 6.
- the present disclosure 8 is a film formed using the curable resin composition of the present disclosure 1, 2, 3, 4, 5 or 6. The present invention will be described in detail below.
- the present inventors added a dye instead of the pigment to the curable resin composition, and further improved the hardness of the cured product.
- the use of a polysilsesquioxane having a cationically polymerizable group in combination with another cationically polymerizable compound was investigated.
- the present inventors have found that it is possible to obtain a curable resin composition having excellent coloring properties and hardness of the cured product, and have completed the present invention.
- the curable resin composition of the present invention is also excellent in low outgassing properties by using polysilsesquioxane having a cationic polymerizable group.
- the curable resin composition of the present invention contains a curable resin.
- the curable resin is a polysilsesquioxane having a cationically polymerizable group (hereinafter also referred to as "cationically polymerizable polysilsesquioxane") and a polysilsesquioxane other than the polysilsesquioxane having the cationically polymerizable group.
- cationically polymerizable polysilsesquioxane a polysilsesquioxane other than the polysilsesquioxane having the cationically polymerizable group.
- polysilsesquioxane is a compound having a repeating structure of RSiO 1.5 (R is a hydrogen atom or an organic group) unit, and a silicon atom is added with an alkoxy group or the like. It is a compound having a network structure derived from a silane compound in which three decomposable groups are bonded.
- the cationically polymerizable polysilsesquioxane and the other cationically polymerizable compound have a cationically polymerizable group.
- Examples of the cationic polymerizable group include an epoxy group, an oxetanyl group, and a vinyl ether group. Among them, an epoxy group and an oxetanyl group are preferable.
- the cationically polymerizable group of the cationically polymerizable polysilsesquioxane and the cationically polymerizable group of the other cationically polymerizable compound may be the same or different.
- the cationically polymerizable polysilsesquioxane may have any one of a random structure, a ladder structure, and a cage structure, or may be a mixture of structures having these structures.
- a preferable lower limit of the content of the cationic polymerizable polysilsesquioxane in 100 parts by weight of the curable resin is 20 parts by weight, and a preferable upper limit is 80 parts by weight.
- the content of the cationically polymerizable polysilsesquioxane is 20 parts by weight or more, the obtained curable resin composition becomes excellent in hardness of the cured product.
- the content of the cationically polymerizable polysilsesquioxane is 80 parts by weight or less, the resulting curable resin composition has excellent coating properties.
- a more preferable lower limit to the content of the cationic polymerizable polysilsesquioxane is 40 parts by weight, and a more preferable upper limit is 70 parts by weight.
- Examples of the other cationic polymerizable compounds include 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexane carboxylate, 4,4′-bis(1,2-epoxycyclohexane), tetrahydroindene diepoxide, Bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexan-1-ylmethyl)adipate, 1,2-epoxy-4- of 2,2-bis(hydroxymethyl)-1-butanol (2-oxiranyl) cyclohexane adduct, [(3,4-epoxycyclohexane)-1-yl]methyl methacrylate, fluorene type epoxy compound, 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, ethylene glycol Diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidy
- alicyclic epoxy compounds are preferred, and 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxy 4,4′-bis(1,2-epoxycyclohexane), tetrahydroindene diepoxide, bis(3,4-epoxycyclohexylmethyl)ether are more preferred.
- a preferable lower limit of the content of the other cationic polymerizable compound in 100 parts by weight of the curable resin is 10 parts by weight, and a preferable upper limit thereof is 60 parts by weight.
- the content of the other cationically polymerizable compound is 10 parts by weight or more, the resulting curable resin composition has excellent curability.
- the content of the other cationically polymerizable compound is 60 parts by weight or less, the obtained curable resin composition becomes excellent in hardness of the cured product.
- a more preferable lower limit of the content of the other cationic polymerizable compound is 15 parts by weight, and a more preferable upper limit thereof is 50 parts by weight.
- the curable resin composition of the present invention contains a photopolymerization initiator.
- the photopolymerization initiator preferably contains a photocationic polymerization initiator.
- the photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid-generating type or a nonionic photoacid-generating type. may
- anion portion of the ionic photoacid-generating photocationic polymerization initiator examples include BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , (BX 4 ) ⁇ (wherein X is at least two or more fluorine or a phenyl group substituted with a trifluoromethyl group). Further, as the anion portion, PF m (C n F 2n+1 ) 6-m ⁇ (wherein m is an integer of 0 or more and 5 or less, and n is an integer of 1 or more and 6 or less), etc. mentioned.
- Examples of the ionic photoacid-generating photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, (2,4-cyclo pentadien-1-yl)((1-methylethyl)benzene)-Fe salts and the like.
- aromatic sulfonium salts include bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluoroantimonate, bis(4-( diphenylsulfonio)phenyl)sulfide bistetrafluoroborate, bis(4-(diphenylsulfonio)phenyl)sulfidetetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, diphenyl-4-( phenylthio)phenylsulfonium hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium tetrafluoroborate, diphenyl
- triarylsulfonium tetrakis(pentafluorophenyl)borate such as triphenylsulfonium tetrakis(pentafluorophenyl)borate is preferable.
- aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis (dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexa fluorophosphate, 4-methylphenyl-4-(1-methylethyl)
- aromatic diazonium salts examples include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis(pentafluorophenyl)borate.
- aromatic ammonium salts examples include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl -2-cyanopyridinium tetrakis(pentafluorophenyl)borate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1-(naphthylmethyl)-2-cyanopyridinium tetrakis(pentafluorophenyl)borate and the like.
- Examples of the (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt include (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene )-Fe(II) hexafluorophosphate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) hexafluoroantimonate, (2,4-cyclopentadiene-1 -yl)((1-methylethyl)benzene)-Fe(II) tetrafluoroborate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) tetrakis(penta fluorophenyl)borate and the like.
- nonionic photoacid-generating photocationic polymerization initiator examples include nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, diazonaphthoquinone, and N-hydroxyimide sulfonates.
- Examples of commercially available photocationic polymerization initiators include, for example, a photocationic polymerization initiator manufactured by Midori Chemical Co., Ltd., a photocationic polymerization initiator manufactured by Union Carbide, a photocationic polymerization initiator manufactured by ADEKA, Photocationic polymerization initiators manufactured by 3M, photocationic polymerization initiators manufactured by BASF, photocationic polymerization initiators manufactured by Solvay, and photocationic polymerization initiators manufactured by San-Apro. Examples of the photocationic polymerization initiator manufactured by Midori Kagaku Co., Ltd. include DTS-200 and the like. Examples of photo cationic polymerization initiators manufactured by Union Carbide include UVI6990 and UVI6974.
- Examples of photo cationic polymerization initiators manufactured by ADEKA include SP-150 and SP-170. Examples of photo cationic polymerization initiators manufactured by 3M include FC-508 and FC-512. Examples of photo cationic polymerization initiators manufactured by BASF include IRGACURE261 and IRGACURE290. Examples of photo cationic polymerization initiators manufactured by Solvay include PI2074. Examples of photo cationic polymerization initiators manufactured by San-Apro include CPI-100P, CPI-200K, CPI-210S and the like.
- a preferred lower limit to the content of the photopolymerization initiator is 1 part by weight, and a preferred upper limit is 20 parts by weight with respect to 100 parts by weight of the curable resin.
- a preferred lower limit for the content of the photopolymerization initiator is 3 parts by weight, and a more preferable upper limit is 16 parts by weight.
- the curable resin composition of the invention contains a dye. By containing the dye, the curable resin composition of the present invention becomes excellent in colorability.
- Cationic dyes and anionic dyes can be used as the above dyes, and examples thereof include azine dyes, oxazine dyes, allylmethane dyes, and azo dyes.
- the azine-based dyes are preferable, and the nigrosine-based dyes are more preferable because of their high blackness, high heat resistance, high solubility, and high molecular weight.
- the preferred lower limit is 0.1 parts by weight and the preferred upper limit is 5 parts by weight with respect to 100 parts by weight of the curable resin.
- the content of the dye is 0.1 parts by weight or more, the resulting curable resin composition is more excellent in colorability.
- the content of the dye is 5 parts by weight or less, the obtained curable resin composition has excellent deep-part curability.
- a more preferable lower limit of the dye content is 0.5 parts by weight, and a more preferable upper limit is 2 parts by weight.
- the curable resin composition of the present invention preferably further contains an ultraviolet absorber.
- Examples of the ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, bisanilide 2-ethoxy-2'-ethyloxalate, and dimethyl-1-(2-hydroxyethyl) succinate.
- -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-4'-n- octoxyphenyl)benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, phenyl salicylate, pt-butylphenyl salicylate, 2-ethylhexyl 2-cyano-3,3- diphenyl acrylate, 2-ethoxy-2'-ethyl oxalic acid bisanilide, dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpipe
- the content of the ultraviolet absorber has a preferable lower limit of 0.001 parts by weight and a preferable upper limit of 5 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the ultraviolet absorber is within this range, the resulting curable resin composition is more excellent in light resistance.
- a more preferable lower limit to the content of the ultraviolet absorber is 0.1 part by weight, and a more preferable upper limit is 1 part by weight.
- the curable resin composition of the present invention preferably further contains a leveling agent.
- leveling agent examples include silicone leveling agents, fluorine leveling agents, and acrylic leveling agents.
- the content of the leveling agent has a preferable lower limit of 0.01 parts by weight and a preferable upper limit of 10 parts by weight with respect to 100 parts by weight of the curable resin.
- the content of the leveling agent is within this range, the resulting curable resin composition is more excellent in coatability and flatness of the coating film.
- a more preferable lower limit to the content of the leveling agent is 0.03 parts by weight, and a more preferable upper limit is 1 part by weight.
- the curable resin composition of the present invention preferably further contains a thixotropic agent.
- thixotropic agent examples include polysiloxane, polyacryl, polyamide, polyvinyl alcohol, polyetherester, alkyl-modified cellulose, peptide, polypeptide, silica and the like.
- the preferable lower limit of the content of the thixotropic agent is 0.1 parts by weight, and the preferable upper limit thereof is 5 parts by weight with respect to 100 parts by weight of the curable resin.
- the content of the thixotropy-imparting agent is within this range, the resulting curable resin composition is more excellent in coatability.
- a more preferable lower limit to the content of the thixotropic agent is 1 part by weight, and a more preferable upper limit is 3 parts by weight.
- the curable resin composition of the present invention preferably contains no solvent. By not containing the solvent, the resulting curable resin composition is excellent in low outgassing properties and does not require a solvent removal step.
- the curable resin composition of the present invention may contain various known additives such as curing retarders, reinforcing agents, viscosity modifiers and antioxidants, if necessary.
- the curable resin composition of the present invention preferably has a lower limit of 500 mPa ⁇ s and a preferred upper limit of viscosity measured at 25° C. using an E-type viscometer of 50,000 mPa ⁇ s. When the viscosity is within this range, the resulting curable resin composition will have excellent coatability.
- a more preferable lower limit of the viscosity is 1000 mPa ⁇ s, and a more preferable upper limit is 10,000 mPa ⁇ s.
- the above viscosity can be measured, for example, by using VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) as an E-type viscometer.
- 1 rotor can be measured at a rotational speed of 1 rpm or 10 rpm.
- the viscosity can be easily set within the above range by adjusting the contents of the cationically polymerizable polysilsesquioxane and the other cationically polymerizable compound.
- the curable resin composition of the present invention can be used for hard coating agents, sealing agents for displays, microlenses and the like. Among others, it is preferably used to protect and seal the optical semiconductor element or the like by forming a coating layer on the optical semiconductor element or the like, or by covering the optical semiconductor element or the like in a film form.
- a coating layer formed using the curable resin composition of the present invention is also one aspect of the present invention.
- a film formed using the curable resin composition of the present invention is also one aspect of the present invention.
- the coating layer of the present invention can be formed by applying the curable resin composition of the present invention onto an object to be coated such as an optical semiconductor element and then curing the composition.
- the film of the present invention can be formed by applying the curable resin composition of the present invention to a release film or the like and then curing the composition.
- Examples of methods for applying the curable resin composition of the present invention include a spin coating method, a bar coating method, an inkjet method, and the like.
- the curable resin composition of the present invention can be easily cured by light irradiation.
- Examples of the method of curing the curable resin composition of the present invention by light irradiation include a method of irradiating light with a wavelength of 300 nm or more and 400 nm or less and an integrated light amount of 300 mJ/cm 2 or more and 3000 mJ/cm 2 or less. .
- Examples of light sources for irradiating the curable resin composition of the present invention with light include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, excimer lasers, chemical lamps, black light lamps, microwave-excited mercury lamps, Examples include metal halide lamps, sodium lamps, halogen lamps, xenon lamps, LED lamps, fluorescent lamps, sunlight, and electron beam irradiation devices. These light sources may be used alone, or two or more of them may be used in combination. These light sources are appropriately selected according to the absorption wavelength of the photopolymerization initiator.
- Examples of means for irradiating the curable resin composition of the present invention with light include simultaneous irradiation with various light sources, sequential irradiation with a time lag, and combined irradiation of simultaneous and sequential irradiation. means may be used.
- the curable resin composition of the present invention may be cured by heating after the light irradiation.
- the curable resin composition which is excellent in the hardness of coloring property and hardened
- Examples 1 to 9 and Comparative Examples 1 and 2 The curable resin compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were prepared by stirring and mixing each material using a stirring mixer according to the compounding ratio shown in Table 1.
- a stirring mixer Awatori Mixer ARE-310 (manufactured by Thinky Corporation) was used.
- the resulting curable resin composition was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., "VISCOMETER TV-22"). No. 1 rotor was used, and the viscosity was measured under the conditions of 25° C. and a rotation speed of 1 rpm or 10 rpm. Table 1 shows the results.
- Each curable resin composition obtained in Examples and Comparative Examples was coated on a glass substrate provided with a gap using a Kapton tape using a bar coater No. 1. 5 (manufactured by AS ONE) to a thickness of 30 ⁇ m, and then irradiated with ultraviolet rays (wavelength: 365 nm) of 100 mW/cm 2 for 30 seconds using a metal halide lamp to photocure the curable resin composition. and obtained a test piece.
- the optical density (OD value) of the obtained test piece was measured using an optical densitometer (manufactured by X-rite, "Spectrometer").
- the curable resin composition which is excellent in the hardness of coloring property and hardened
Abstract
One purpose of the present invention is to provide a curable resin composition having excellent coloration and giving cured objects having excellent hardness. Another is to provide a coating layer and a film which are formed using the curable resin composition. This curable resin composition comprises a curable resin, a photopolymerization initiator, and a dye, wherein the curable resin comprises a polysilsesquioxane having a cationically polymerizable group and a cationically polymerizable compound which is not the polysilsesquioxane having a cationically polymerizable group.
Description
本発明は、硬化性樹脂組成物に関する。また、本発明は、該硬化性樹脂組成物を用いて形成されるコーティング層及びフィルムに関する。
The present invention relates to a curable resin composition. The present invention also relates to coating layers and films formed using the curable resin composition.
ＬＥＤ等の光半導体素子は、消費電力が低く、長寿命であることから、液晶表示装置のバックライトや照明器具等に広く用いられている。光半導体素子は、大気中の水分やガスと接触することにより劣化し、光取り出し効率が低下するため、通常、封止剤で封止するとともにカバーガラス等で保護して用いられる。近年、カバーガラス等を用いずに光半導体素子を保護封止する方法として、ハードコート剤を用いて光半導体素子の表面上にコーティング層を形成することが検討されている（例えば、特許文献１等）。
2. Description of the Related Art Optical semiconductor devices such as LEDs consume low power and have a long life, so they are widely used for backlights of liquid crystal display devices, lighting fixtures, and the like. An optical semiconductor element deteriorates when it comes into contact with moisture or gas in the atmosphere, and the light extraction efficiency decreases. In recent years, as a method for protecting and sealing optical semiconductor elements without using a cover glass or the like, it has been studied to form a coating layer on the surface of the optical semiconductor element using a hard coating agent (for example, Patent Document 1 etc).
コントラスト向上等の観点からハードコート剤として用いる硬化性樹脂組成物を着色するために黒色顔料を分散させた場合、表面にむらが生じたり、硬化物の硬度が低下したりするという問題があった。
When a black pigment is dispersed in order to color a curable resin composition used as a hard coating agent from the viewpoint of improving contrast, etc., there are problems such as unevenness on the surface and a decrease in hardness of the cured product. .
本発明は、着色性及び硬化物の硬度に優れる硬化性樹脂組成物を提供することを目的とする。また、本発明は、該硬化性樹脂組成物を用いて形成されるコーティング層及びフィルムを提供することを目的とする。
An object of the present invention is to provide a curable resin composition that is excellent in colorability and hardness of the cured product. Another object of the present invention is to provide a coating layer and a film formed using the curable resin composition.
本開示１は、硬化性樹脂と光重合開始剤と染料とを含有する硬化性樹脂組成物であって、上記硬化性樹脂は、カチオン重合性基を有するポリシルセスキオキサン及び該カチオン重合性基を有するポリシルセスキオキサン以外の他のカチオン重合性化合物を含む硬化性樹脂組成物である。
本開示２は、粘度が５００ｍＰａ・ｓ以上５万ｍＰａ・ｓ以下である本開示１の硬化性樹脂組成物である。
本開示３は、上記光重合開始剤は、光カチオン重合開始剤を含む本開示１又は２の硬化性樹脂組成物である。
本開示４は、更に、紫外線吸収剤を含む本開示１、２又は３の硬化性樹脂組成物である。
本開示５は、更に、レベリング剤を含む本開示１、２、３又は４の硬化性樹脂組成物である。
本開示６は、更に、チキソ性付与剤を含む本開示１、２、３、４又は５の硬化性樹脂組成物である。
本開示７は、本開示１、２、３、４、５又は６の硬化性樹脂組成物を用いて形成されるコーティング層である。
本開示８は、本開示１、２、３、４、５又は６の硬化性樹脂組成物を用いて形成されるフィルムである。
以下に本発明を詳述する。 The present disclosure 1 is a curable resin composition containing a curable resin, a photopolymerization initiator and a dye, wherein the curable resin is polysilsesquioxane having a cationically polymerizable group and the cationically polymerizable A curable resin composition containing a cationic polymerizable compound other than polysilsesquioxane having a group.
The present disclosure 2 is the curable resin composition of the present disclosure 1, which has a viscosity of 500 mPa·s or more and 50,000 mPa·s or less.
The present disclosure 3 is the curable resin composition of the present disclosure 1 or 2, wherein the photopolymerization initiator includes a photocationic polymerization initiator.
This disclosure 4 is the curable resin composition of this disclosure 1, 2 or 3, further comprising an ultraviolet absorber.
Disclosure 5 is the curable resin composition of Disclosure 1, 2, 3 or 4 further comprising a leveling agent.
The present disclosure 6 is the curable resin composition of the present disclosure 1, 2, 3, 4 or 5 further comprising a thixotropic agent.
The present disclosure 7 is a coating layer formed using the curable resin composition of the present disclosure 1, 2, 3, 4, 5 or 6.
The present disclosure 8 is a film formed using the curable resin composition of the present disclosure 1, 2, 3, 4, 5 or 6.
The present invention will be described in detail below.
本開示２は、粘度が５００ｍＰａ・ｓ以上５万ｍＰａ・ｓ以下である本開示１の硬化性樹脂組成物である。
本開示３は、上記光重合開始剤は、光カチオン重合開始剤を含む本開示１又は２の硬化性樹脂組成物である。
本開示４は、更に、紫外線吸収剤を含む本開示１、２又は３の硬化性樹脂組成物である。
本開示５は、更に、レベリング剤を含む本開示１、２、３又は４の硬化性樹脂組成物である。
本開示６は、更に、チキソ性付与剤を含む本開示１、２、３、４又は５の硬化性樹脂組成物である。
本開示７は、本開示１、２、３、４、５又は６の硬化性樹脂組成物を用いて形成されるコーティング層である。
本開示８は、本開示１、２、３、４、５又は６の硬化性樹脂組成物を用いて形成されるフィルムである。
以下に本発明を詳述する。 The present disclosure 1 is a curable resin composition containing a curable resin, a photopolymerization initiator and a dye, wherein the curable resin is polysilsesquioxane having a cationically polymerizable group and the cationically polymerizable A curable resin composition containing a cationic polymerizable compound other than polysilsesquioxane having a group.
The present disclosure 2 is the curable resin composition of the present disclosure 1, which has a viscosity of 500 mPa·s or more and 50,000 mPa·s or less.
The present disclosure 3 is the curable resin composition of the present disclosure 1 or 2, wherein the photopolymerization initiator includes a photocationic polymerization initiator.
This disclosure 4 is the curable resin composition of this disclosure 1, 2 or 3, further comprising an ultraviolet absorber.
Disclosure 5 is the curable resin composition of Disclosure 1, 2, 3 or 4 further comprising a leveling agent.
The present disclosure 6 is the curable resin composition of the present disclosure 1, 2, 3, 4 or 5 further comprising a thixotropic agent.
The present disclosure 7 is a coating layer formed using the curable resin composition of the present disclosure 1, 2, 3, 4, 5 or 6.
The present disclosure 8 is a film formed using the curable resin composition of the present disclosure 1, 2, 3, 4, 5 or 6.
The present invention will be described in detail below.
本発明者は、表面のむらの発生や硬化物の硬度の低下を抑制するため、硬化性樹脂組成物に顔料に代えて染料を配合し、硬化物の硬度を更に向上させるため、硬化性樹脂として、カチオン重合性基を有するポリシルセスキオキサンと、他のカチオン重合性化合物とを組み合わせて用いることを検討した。その結果、着色性及び硬化物の硬度に優れる硬化性樹脂組成物を得ることができることを見出し、本発明を完成させるに至った。
本発明の硬化性樹脂組成物は、カチオン重合性基を有するポリシルセスキオキサンを用いることで低アウトガス性にも優れるものとなる。 In order to suppress the occurrence of surface unevenness and the decrease in the hardness of the cured product, the present inventors added a dye instead of the pigment to the curable resin composition, and further improved the hardness of the cured product. , the use of a polysilsesquioxane having a cationically polymerizable group in combination with another cationically polymerizable compound was investigated. As a result, the present inventors have found that it is possible to obtain a curable resin composition having excellent coloring properties and hardness of the cured product, and have completed the present invention.
The curable resin composition of the present invention is also excellent in low outgassing properties by using polysilsesquioxane having a cationic polymerizable group.
本発明の硬化性樹脂組成物は、カチオン重合性基を有するポリシルセスキオキサンを用いることで低アウトガス性にも優れるものとなる。 In order to suppress the occurrence of surface unevenness and the decrease in the hardness of the cured product, the present inventors added a dye instead of the pigment to the curable resin composition, and further improved the hardness of the cured product. , the use of a polysilsesquioxane having a cationically polymerizable group in combination with another cationically polymerizable compound was investigated. As a result, the present inventors have found that it is possible to obtain a curable resin composition having excellent coloring properties and hardness of the cured product, and have completed the present invention.
The curable resin composition of the present invention is also excellent in low outgassing properties by using polysilsesquioxane having a cationic polymerizable group.
本発明の硬化性樹脂組成物は、硬化性樹脂を含有する。
上記硬化性樹脂は、カチオン重合性基を有するポリシルセスキオキサン（以下、「カチオン重合性ポリシルセスキオキサン」ともいう）及び該カチオン重合性基を有するポリシルセスキオキサン以外の他のカチオン重合性化合物を含む。
上記カチオン重合性ポリシルセスキオキサン及び上記他のカチオン重合性化合物を組み合わせて含有することにより、本発明の硬化性樹脂組成物は、塗布性、硬化物の硬度、及び、低アウトガス性に優れるものとなる。
なお、本明細書において上記「ポリシルセスキオキサン」は、ＲＳｉＯ１．５（Ｒは、水素原子又は有機基である）単位の繰り返し構造を有する化合物であり、ケイ素原子にアルコキシ基等の加水分解性基が３つ結合したシラン化合物に由来するネットワーク構造を有する化合物である。 The curable resin composition of the present invention contains a curable resin.
The curable resin is a polysilsesquioxane having a cationically polymerizable group (hereinafter also referred to as "cationically polymerizable polysilsesquioxane") and a polysilsesquioxane other than the polysilsesquioxane having the cationically polymerizable group. Contains cationic polymerizable compounds.
By containing the cationically polymerizable polysilsesquioxane and the other cationically polymerizable compound in combination, the curable resin composition of the present invention is excellent in coatability, hardness of the cured product, and low outgassing. become a thing.
In this specification, the above-mentioned "polysilsesquioxane" is a compound having a repeating structure of RSiO 1.5 (R is a hydrogen atom or an organic group) unit, and a silicon atom is added with an alkoxy group or the like. It is a compound having a network structure derived from a silane compound in which three decomposable groups are bonded.
上記硬化性樹脂は、カチオン重合性基を有するポリシルセスキオキサン（以下、「カチオン重合性ポリシルセスキオキサン」ともいう）及び該カチオン重合性基を有するポリシルセスキオキサン以外の他のカチオン重合性化合物を含む。
上記カチオン重合性ポリシルセスキオキサン及び上記他のカチオン重合性化合物を組み合わせて含有することにより、本発明の硬化性樹脂組成物は、塗布性、硬化物の硬度、及び、低アウトガス性に優れるものとなる。
なお、本明細書において上記「ポリシルセスキオキサン」は、ＲＳｉＯ１．５（Ｒは、水素原子又は有機基である）単位の繰り返し構造を有する化合物であり、ケイ素原子にアルコキシ基等の加水分解性基が３つ結合したシラン化合物に由来するネットワーク構造を有する化合物である。 The curable resin composition of the present invention contains a curable resin.
The curable resin is a polysilsesquioxane having a cationically polymerizable group (hereinafter also referred to as "cationically polymerizable polysilsesquioxane") and a polysilsesquioxane other than the polysilsesquioxane having the cationically polymerizable group. Contains cationic polymerizable compounds.
By containing the cationically polymerizable polysilsesquioxane and the other cationically polymerizable compound in combination, the curable resin composition of the present invention is excellent in coatability, hardness of the cured product, and low outgassing. become a thing.
In this specification, the above-mentioned "polysilsesquioxane" is a compound having a repeating structure of RSiO 1.5 (R is a hydrogen atom or an organic group) unit, and a silicon atom is added with an alkoxy group or the like. It is a compound having a network structure derived from a silane compound in which three decomposable groups are bonded.
上記カチオン重合性ポリシルセスキオキサン及び上記他のカチオン重合性化合物は、カチオン重合性基を有する。
The cationically polymerizable polysilsesquioxane and the other cationically polymerizable compound have a cationically polymerizable group.
上記カチオン重合性基としては、例えば、エポキシ基、オキセタニル基、ビニルエーテル基等が挙げられる。なかでも、エポキシ基、オキセタニル基が好ましい。
上記カチオン重合性ポリシルセスキオキサンの有するカチオン重合性基と、上記他のカチオン重合性化合物の有するカチオン重合性基とは、同一であってもよいし異なっていてもよい。 Examples of the cationic polymerizable group include an epoxy group, an oxetanyl group, and a vinyl ether group. Among them, an epoxy group and an oxetanyl group are preferable.
The cationically polymerizable group of the cationically polymerizable polysilsesquioxane and the cationically polymerizable group of the other cationically polymerizable compound may be the same or different.
上記カチオン重合性ポリシルセスキオキサンの有するカチオン重合性基と、上記他のカチオン重合性化合物の有するカチオン重合性基とは、同一であってもよいし異なっていてもよい。 Examples of the cationic polymerizable group include an epoxy group, an oxetanyl group, and a vinyl ether group. Among them, an epoxy group and an oxetanyl group are preferable.
The cationically polymerizable group of the cationically polymerizable polysilsesquioxane and the cationically polymerizable group of the other cationically polymerizable compound may be the same or different.
上記カチオン重合性ポリシルセスキオキサンは、ランダム構造、ラダー構造、及び、ケージ構造のいずれの構造を有していてもよく、これらの構造を有する構造体の混合物であってもよい。
The cationically polymerizable polysilsesquioxane may have any one of a random structure, a ladder structure, and a cage structure, or may be a mixture of structures having these structures.
上記硬化性樹脂１００重量部中における上記カチオン重合性ポリシルセスキオキサンの含有量の好ましい下限は２０重量部、好ましい上限は８０重量部である。上記カチオン重合性ポリシルセスキオキサンの含有量が２０重量部以上であることにより、得られる硬化性樹脂組成物が硬化物の硬度により優れるものとなる。上記カチオン重合性ポリシルセスキオキサンの含有量が８０重量部以下であることにより、得られる硬化性樹脂組成物が塗布性により優れるものとなる。上記カチオン重合性ポリシルセスキオキサンの含有量のより好ましい下限は４０重量部、より好ましい上限は７０重量部である。
A preferable lower limit of the content of the cationic polymerizable polysilsesquioxane in 100 parts by weight of the curable resin is 20 parts by weight, and a preferable upper limit is 80 parts by weight. When the content of the cationically polymerizable polysilsesquioxane is 20 parts by weight or more, the obtained curable resin composition becomes excellent in hardness of the cured product. When the content of the cationically polymerizable polysilsesquioxane is 80 parts by weight or less, the resulting curable resin composition has excellent coating properties. A more preferable lower limit to the content of the cationic polymerizable polysilsesquioxane is 40 parts by weight, and a more preferable upper limit is 70 parts by weight.
上記他のカチオン重合性化合物としては、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、４，４’－ビス（１，２－エポキシシクロヘキサン）、テトラヒドロインデンジエポキシド、ビス（３，４－エポキシシクロヘキシルメチル）エーテル、アジピン酸ビス（３，４－エポキシシクロヘキサン－１－イルメチル）、２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物、メタクリル酸［（３，４－エポキシシクロヘキサン）－１－イル］メチル、フルオレン型エポキシ化合物、１，７－オクタジエンジエポキシド、ネオペンチルグリコールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ジプロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコ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、グリセリンジグリシジルエーテル、トリメチロ－ルプロパントリグリシジルエーテル、フェニルグリシジルエーテル、フェニレンジグリシジルエーテル、３－エチル－３－（（（３－エチルオキセタン－３－イル）メトキシ）メチル）オキセタン、３－エチル－３－（（２－エチルヘキシルオキシ）メチル）オキセタン、フェノールノボラックオキセタン、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、ベンジルビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、ジシクロペンタジエンビニルエーテル、１，４－ブタンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテル、トリプロピレングリコールジビニルエーテル等が挙げられる。なかでも、得られる硬化性樹脂組成物が硬化性及び硬化物の硬度により優れるものとなることから、脂環式エポキシ化合物が好ましく、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、４，４’－ビス（１，２－エポキシシクロヘキサン）、テトラヒドロインデンジエポキシド、ビス（３，４－エポキシシクロヘキシルメチル）エーテルがより好ましい。
Examples of the other cationic polymerizable compounds include 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexane carboxylate, 4,4′-bis(1,2-epoxycyclohexane), tetrahydroindene diepoxide, Bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexan-1-ylmethyl)adipate, 1,2-epoxy-4- of 2,2-bis(hydroxymethyl)-1-butanol (2-oxiranyl) cyclohexane adduct, [(3,4-epoxycyclohexane)-1-yl]methyl methacrylate, fluorene type epoxy compound, 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, ethylene glycol Diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether , glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, phenylglycidyl ether, phenylenediglycidyl ether, 3-ethyl-3-(((3-ethyloxetan-3-yl)methoxy)methyl)oxetane, 3-ethyl -3-((2-ethylhexyloxy)methyl)oxetane, phenol novolac oxetane, 1,4-bis(((3-ethyl-3-oxetanyl)methoxy)methyl)benzene, benzyl vinyl ether, cyclohexanedimethanol monovinyl ether, di cyclopentadiene vinyl ether, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether and the like. Among these, alicyclic epoxy compounds are preferred, and 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxy 4,4′-bis(1,2-epoxycyclohexane), tetrahydroindene diepoxide, bis(3,4-epoxycyclohexylmethyl)ether are more preferred.
上記硬化性樹脂１００重量部中における上記他のカチオン重合性化合物の含有量の好ましい下限は１０重量部、好ましい上限は６０重量部である。上記他のカチオン重合性化合物の含有量が１０重量部以上であることにより、得られる硬化性樹脂組成物が硬化性により優れるものとなる。上記他のカチオン重合性化合物の含有量が６０重量部以下であることにより、得られる硬化性樹脂組成物が硬化物の硬度により優れるものとなる。上記他のカチオン重合性化合物の含有量のより好ましい下限は１５重量部、より好ましい上限は５０重量部である。
A preferable lower limit of the content of the other cationic polymerizable compound in 100 parts by weight of the curable resin is 10 parts by weight, and a preferable upper limit thereof is 60 parts by weight. When the content of the other cationically polymerizable compound is 10 parts by weight or more, the resulting curable resin composition has excellent curability. When the content of the other cationically polymerizable compound is 60 parts by weight or less, the obtained curable resin composition becomes excellent in hardness of the cured product. A more preferable lower limit of the content of the other cationic polymerizable compound is 15 parts by weight, and a more preferable upper limit thereof is 50 parts by weight.
本発明の硬化性樹脂組成物は、光重合開始剤を含有する。
上記光重合開始剤は、光カチオン重合開始剤を含むことが好ましい。
上記光カチオン重合開始剤は、光照射によりプロトン酸又はルイス酸を発生するものであれば特に限定されず、イオン性光酸発生型であってもよいし、非イオン性光酸発生型であってもよい。 The curable resin composition of the present invention contains a photopolymerization initiator.
The photopolymerization initiator preferably contains a photocationic polymerization initiator.
The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid-generating type or a nonionic photoacid-generating type. may
上記光重合開始剤は、光カチオン重合開始剤を含むことが好ましい。
上記光カチオン重合開始剤は、光照射によりプロトン酸又はルイス酸を発生するものであれば特に限定されず、イオン性光酸発生型であってもよいし、非イオン性光酸発生型であってもよい。 The curable resin composition of the present invention contains a photopolymerization initiator.
The photopolymerization initiator preferably contains a photocationic polymerization initiator.
The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid-generating type or a nonionic photoacid-generating type. may
上記イオン性光酸発生型の光カチオン重合開始剤のアニオン部分としては、例えば、ＢＦ４
－、ＰＦ６
－、ＳｂＦ６
－、（ＢＸ４）－（但し、Ｘは、少なくとも２つ以上のフッ素又はトリフルオロメチル基で置換されたフェニル基を表す）等が挙げられる。また、上記アニオン部分としては、ＰＦｍ（ＣｎＦ２ｎ＋１）６－ｍ
－（但し、式中、ｍは０以上５以下の整数であり、ｎは１以上６以下の整数である）等も挙げられる。
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、例えば、上記アニオン部分を有する、芳香族スルホニウム塩、芳香族ヨードニウム塩、芳香族ジアゾニウム塩、芳香族アンモニウム塩、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ塩等が挙げられる。 Examples of the anion portion of the ionic photoacid-generating photocationic polymerization initiator include BF 4 − , PF 6 − , SbF 6 − , (BX 4 ) − (wherein X is at least two or more fluorine or a phenyl group substituted with a trifluoromethyl group). Further, as the anion portion, PF m (C n F 2n+1 ) 6-m − (wherein m is an integer of 0 or more and 5 or less, and n is an integer of 1 or more and 6 or less), etc. mentioned.
Examples of the ionic photoacid-generating photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, (2,4-cyclo pentadien-1-yl)((1-methylethyl)benzene)-Fe salts and the like.
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、例えば、上記アニオン部分を有する、芳香族スルホニウム塩、芳香族ヨードニウム塩、芳香族ジアゾニウム塩、芳香族アンモニウム塩、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ塩等が挙げられる。 Examples of the anion portion of the ionic photoacid-generating photocationic polymerization initiator include BF 4 − , PF 6 − , SbF 6 − , (BX 4 ) − (wherein X is at least two or more fluorine or a phenyl group substituted with a trifluoromethyl group). Further, as the anion portion, PF m (C n F 2n+1 ) 6-m − (wherein m is an integer of 0 or more and 5 or less, and n is an integer of 1 or more and 6 or less), etc. mentioned.
Examples of the ionic photoacid-generating photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, (2,4-cyclo pentadien-1-yl)((1-methylethyl)benzene)-Fe salts and the like.
上記芳香族スルホニウム塩としては、例えば、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロホスフェート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロアンチモネート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビステトラフルオロボレート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドテトラキス（ペンタフルオロフェニル）ボレート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムヘキサフルオロホスフェート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムヘキサフルオロアンチモネート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムテトラフルオロボレート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、トリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムテトラフルオロボレート、トリフェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロホスフェート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロアンチモネート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビステトラフルオロボレート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドテトラキス（ペンタフルオロフェニル）ボレート、トリス（４－（４－アセチルフェニル）チオフェニル）スルホニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。なかでも、トリフェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート等のトリアリールスルホニウムテトラキス（ペンタフルオロフェニル）ボレートが好ましい。
Examples of the aromatic sulfonium salts include bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluoroantimonate, bis(4-( diphenylsulfonio)phenyl)sulfide bistetrafluoroborate, bis(4-(diphenylsulfonio)phenyl)sulfidetetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, diphenyl-4-( phenylthio)phenylsulfonium hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium tetrafluoroborate, diphenyl-4-(phenylthio)phenylsulfonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexa fluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfide bishexafluorophosphate, Bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfide bishexafluoroantimonate, bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl ) sulfide bistetrafluoroborate, bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfide tetrakis(pentafluorophenyl)borate, tris(4-(4-acetylphenyl)thiophenyl) sulfonium tetrakis(pentafluorophenyl)borate and the like. Among them, triarylsulfonium tetrakis(pentafluorophenyl)borate such as triphenylsulfonium tetrakis(pentafluorophenyl)borate is preferable.
上記芳香族ヨードニウム塩としては、例えば、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムテトラフルオロボレート、ジフェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、ビス（ドデシルフェニル）ヨードニウムヘキサフルオロホスフェート、ビス（ドデシルフェニル）ヨードニウムヘキサフルオロアンチモネート、ビス（ドデシルフェニル）ヨードニウムテトラフルオロボレート、ビス（ドデシルフェニル）ヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムヘキサフルオロホスフェート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムヘキサフルオロアンチモネート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムテトラフルオロボレート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。
Examples of the aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis (dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexa fluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrafluoroborate, 4-methylphenyl-4-( 1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate and the like.
上記芳香族ジアゾニウム塩としては、例えば、フェニルジアゾニウムヘキサフルオロホスフェート、フェニルジアゾニウムヘキサフルオロアンチモネート、フェニルジアゾニウムテトラフルオロボレート、フェニルジアゾニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。
Examples of the aromatic diazonium salts include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis(pentafluorophenyl)borate.
上記芳香族アンモニウム塩としては、例えば、１－ベンジル－２－シアノピリジニウムヘキサフルオロホスフェート、１－ベンジル－２－シアノピリジニウムヘキサフルオロアンチモネート、１－ベンジル－２－シアノピリジニウムテトラフルオロボレート、１－ベンジル－２－シアノピリジニウムテトラキス（ペンタフルオロフェニル）ボレート、１－（ナフチルメチル）－２－シアノピリジニウムヘキサフルオロホスフェート、１－（ナフチルメチル）－２－シアノピリジニウムヘキサフルオロアンチモネート、１－（ナフチルメチル）－２－シアノピリジニウムテトラフルオロボレート、１－（ナフチルメチル）－２－シアノピリジニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。
Examples of the aromatic ammonium salts include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl -2-cyanopyridinium tetrakis(pentafluorophenyl)borate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1-(naphthylmethyl)-2-cyanopyridinium tetrakis(pentafluorophenyl)borate and the like.
上記（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ塩としては、例えば、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）ヘキサフルオロホスフェート、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）ヘキサフルオロアンチモネート、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）テトラフルオロボレート、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）テトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。
Examples of the (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt include (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene )-Fe(II) hexafluorophosphate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) hexafluoroantimonate, (2,4-cyclopentadiene-1 -yl)((1-methylethyl)benzene)-Fe(II) tetrafluoroborate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) tetrakis(penta fluorophenyl)borate and the like.
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、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－ヒドロキシイミドスルホネート等が挙げられる。
Examples of the nonionic photoacid-generating photocationic polymerization initiator include nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, diazonaphthoquinone, and N-hydroxyimide sulfonates.
上記光カチオン重合開始剤のうち市販されているものとしては、例えば、みどり化学社製の光カチオン重合開始剤、ユニオンカーバイド社製の光カチオン重合開始剤、ＡＤＥＫＡ社製の光カチオン重合開始剤、３Ｍ社製の光カチオン重合開始剤、ＢＡＳＦ社製の光カチオン重合開始剤、ソルベイ社製の光カチオン重合開始剤、サンアプロ社製の光カチオン重合開始剤等が挙げられる。
上記みどり化学社製の光カチオン重合開始剤としては、例えば、ＤＴＳ－２００等が挙げられる。
上記ユニオンカーバイド社製の光カチオン重合開始剤としては、例えば、ＵＶＩ６９９０、ＵＶＩ６９７４等が挙げられる。
上記ＡＤＥＫＡ社製の光カチオン重合開始剤としては、例えば、ＳＰ－１５０、ＳＰ－１７０等が挙げられる。
上記３Ｍ社製の光カチオン重合開始剤としては、例えば、ＦＣ－５０８、ＦＣ－５１２等が挙げられる。
上記ＢＡＳＦ社製の光カチオン重合開始剤としては、例えば、ＩＲＧＡＣＵＲＥ２６１、ＩＲＧＡＣＵＲＥ２９０等が挙げられる。
上記ソルベイ社製の光カチオン重合開始剤としては、例えば、ＰＩ２０７４等が挙げられる。
上記サンアプロ社製の光カチオン重合開始剤としては、例えば、ＣＰＩ－１００Ｐ、ＣＰＩ－２００Ｋ、ＣＰＩ－２１０Ｓ等が挙げられる。 Examples of commercially available photocationic polymerization initiators include, for example, a photocationic polymerization initiator manufactured by Midori Chemical Co., Ltd., a photocationic polymerization initiator manufactured by Union Carbide, a photocationic polymerization initiator manufactured by ADEKA, Photocationic polymerization initiators manufactured by 3M, photocationic polymerization initiators manufactured by BASF, photocationic polymerization initiators manufactured by Solvay, and photocationic polymerization initiators manufactured by San-Apro.
Examples of the photocationic polymerization initiator manufactured by Midori Kagaku Co., Ltd. include DTS-200 and the like.
Examples of photo cationic polymerization initiators manufactured by Union Carbide include UVI6990 and UVI6974.
Examples of photo cationic polymerization initiators manufactured by ADEKA include SP-150 and SP-170.
Examples of photo cationic polymerization initiators manufactured by 3M include FC-508 and FC-512.
Examples of photo cationic polymerization initiators manufactured by BASF include IRGACURE261 and IRGACURE290.
Examples of photo cationic polymerization initiators manufactured by Solvay include PI2074.
Examples of photo cationic polymerization initiators manufactured by San-Apro include CPI-100P, CPI-200K, CPI-210S and the like.
上記みどり化学社製の光カチオン重合開始剤としては、例えば、ＤＴＳ－２００等が挙げられる。
上記ユニオンカーバイド社製の光カチオン重合開始剤としては、例えば、ＵＶＩ６９９０、ＵＶＩ６９７４等が挙げられる。
上記ＡＤＥＫＡ社製の光カチオン重合開始剤としては、例えば、ＳＰ－１５０、ＳＰ－１７０等が挙げられる。
上記３Ｍ社製の光カチオン重合開始剤としては、例えば、ＦＣ－５０８、ＦＣ－５１２等が挙げられる。
上記ＢＡＳＦ社製の光カチオン重合開始剤としては、例えば、ＩＲＧＡＣＵＲＥ２６１、ＩＲＧＡＣＵＲＥ２９０等が挙げられる。
上記ソルベイ社製の光カチオン重合開始剤としては、例えば、ＰＩ２０７４等が挙げられる。
上記サンアプロ社製の光カチオン重合開始剤としては、例えば、ＣＰＩ－１００Ｐ、ＣＰＩ－２００Ｋ、ＣＰＩ－２１０Ｓ等が挙げられる。 Examples of commercially available photocationic polymerization initiators include, for example, a photocationic polymerization initiator manufactured by Midori Chemical Co., Ltd., a photocationic polymerization initiator manufactured by Union Carbide, a photocationic polymerization initiator manufactured by ADEKA, Photocationic polymerization initiators manufactured by 3M, photocationic polymerization initiators manufactured by BASF, photocationic polymerization initiators manufactured by Solvay, and photocationic polymerization initiators manufactured by San-Apro.
Examples of the photocationic polymerization initiator manufactured by Midori Kagaku Co., Ltd. include DTS-200 and the like.
Examples of photo cationic polymerization initiators manufactured by Union Carbide include UVI6990 and UVI6974.
Examples of photo cationic polymerization initiators manufactured by ADEKA include SP-150 and SP-170.
Examples of photo cationic polymerization initiators manufactured by 3M include FC-508 and FC-512.
Examples of photo cationic polymerization initiators manufactured by BASF include IRGACURE261 and IRGACURE290.
Examples of photo cationic polymerization initiators manufactured by Solvay include PI2074.
Examples of photo cationic polymerization initiators manufactured by San-Apro include CPI-100P, CPI-200K, CPI-210S and the like.
上記光重合開始剤の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が１重量部、好ましい上限が２０重量部である。上記光重合開始剤の含有量がこの範囲であることにより、得られる硬化性樹脂組成物が硬化性及び保存安定性により優れるものとなる。上記光重合開始剤の含有量のより好ましい下限は３重量部、より好ましい上限は１６重量部である。
A preferred lower limit to the content of the photopolymerization initiator is 1 part by weight, and a preferred upper limit is 20 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the photopolymerization initiator is within this range, the resulting curable resin composition is more excellent in curability and storage stability. A more preferable lower limit for the content of the photopolymerization initiator is 3 parts by weight, and a more preferable upper limit is 16 parts by weight.
本発明の硬化性樹脂組成物は、染料を含有する。
上記染料を含有することにより、本発明の硬化性樹脂組成物は、着色性に優れるものとなる。 The curable resin composition of the invention contains a dye.
By containing the dye, the curable resin composition of the present invention becomes excellent in colorability.
上記染料を含有することにより、本発明の硬化性樹脂組成物は、着色性に優れるものとなる。 The curable resin composition of the invention contains a dye.
By containing the dye, the curable resin composition of the present invention becomes excellent in colorability.
上記染料としては、カチオン染料及びアニオン染料を用いることができ、例えば、アジン系染料、オキサジン系染料、アリルメタン系染料、アゾ系染料等が挙げられる。
なかでも、上記アジン系染料が好ましく、黒色度が高く、高耐熱性、高分子量でありながら高溶解性であることから、ニグロシン系染料がより好ましい。 Cationic dyes and anionic dyes can be used as the above dyes, and examples thereof include azine dyes, oxazine dyes, allylmethane dyes, and azo dyes.
Among them, the azine-based dyes are preferable, and the nigrosine-based dyes are more preferable because of their high blackness, high heat resistance, high solubility, and high molecular weight.
なかでも、上記アジン系染料が好ましく、黒色度が高く、高耐熱性、高分子量でありながら高溶解性であることから、ニグロシン系染料がより好ましい。 Cationic dyes and anionic dyes can be used as the above dyes, and examples thereof include azine dyes, oxazine dyes, allylmethane dyes, and azo dyes.
Among them, the azine-based dyes are preferable, and the nigrosine-based dyes are more preferable because of their high blackness, high heat resistance, high solubility, and high molecular weight.
上記染料の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が５重量部である。上記染料の含有量が０．１重量部以上であることにより、得られる硬化性樹脂組成物が着色性により優れるものとなる。上記染料の含有量が５重量部以下であることにより、得られる硬化性樹脂組成物が深部硬化性により優れるものとなる。上記染料の含有量のより好ましい下限は０．５重量部、より好ましい上限は２重量部である。
As for the content of the dye, the preferred lower limit is 0.1 parts by weight and the preferred upper limit is 5 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the dye is 0.1 parts by weight or more, the resulting curable resin composition is more excellent in colorability. When the content of the dye is 5 parts by weight or less, the obtained curable resin composition has excellent deep-part curability. A more preferable lower limit of the dye content is 0.5 parts by weight, and a more preferable upper limit is 2 parts by weight.
本発明の硬化性樹脂組成物は、耐光性の観点から、更に、紫外線吸収剤を含有することが好ましい。
From the viewpoint of light resistance, the curable resin composition of the present invention preferably further contains an ultraviolet absorber.
上記紫外線吸収剤としては、例えば、２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール、２－エトキシ－２’－エチルシュウ酸ビスアニリド、コハク酸ジメチル－１－（２－ヒドロキシエチル）－４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン重縮合物、２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－４’－ｎ－オクトキシフェニル）ベンゾトリアゾール、２－ヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－ｎ－オクトキシベンゾフェノン、サリチル酸フェニル、サリチル酸ｐ－ｔ－ブチルフェニル、２－エチルヘキシル２－シアノ－３，３－ジフェニルアクリレート、２－エトキシ－２’－エチルシュウ酸ビスアニリド、コハク酸ジメチル－１－（２－ヒドロキシエチル）－４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン重縮合物等が挙げられる。
Examples of the ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, bisanilide 2-ethoxy-2'-ethyloxalate, and dimethyl-1-(2-hydroxyethyl) succinate. -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-4'-n- octoxyphenyl)benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, phenyl salicylate, pt-butylphenyl salicylate, 2-ethylhexyl 2-cyano-3,3- diphenyl acrylate, 2-ethoxy-2'-ethyl oxalic acid bisanilide, dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate and the like. .
上記紫外線吸収剤の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が０．００１重量部、好ましい上限が５重量部である。上記紫外線吸収剤の含有量がこの範囲であることにより、得られる硬化性樹脂組成物が耐光性により優れるものとなる。上記紫外線吸収剤の含有量のより好ましい下限は０．１重量部、より好ましい上限は１重量部である。
The content of the ultraviolet absorber has a preferable lower limit of 0.001 parts by weight and a preferable upper limit of 5 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the ultraviolet absorber is within this range, the resulting curable resin composition is more excellent in light resistance. A more preferable lower limit to the content of the ultraviolet absorber is 0.1 part by weight, and a more preferable upper limit is 1 part by weight.
本発明の硬化性樹脂組成物は、塗膜の平坦性の観点から、更に、レベリング剤を含有することが好ましい。
From the viewpoint of flatness of the coating film, the curable resin composition of the present invention preferably further contains a leveling agent.
上記レベリング剤としては、例えば、シリコーン系レベリング剤、フッ素系レベリング剤、アクリル系レベリング剤等が挙げられる。
Examples of the leveling agent include silicone leveling agents, fluorine leveling agents, and acrylic leveling agents.
上記レベリング剤の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が０．０１重量部、好ましい上限が１０重量部である。上記レベリング剤の含有量がこの範囲であることにより、得られる硬化性樹脂組成物が塗布性及び塗膜の平坦性により優れるものとなる。上記レベリング剤の含有量のより好ましい下限は０．０３重量部、より好ましい上限は１重量部である。
The content of the leveling agent has a preferable lower limit of 0.01 parts by weight and a preferable upper limit of 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the leveling agent is within this range, the resulting curable resin composition is more excellent in coatability and flatness of the coating film. A more preferable lower limit to the content of the leveling agent is 0.03 parts by weight, and a more preferable upper limit is 1 part by weight.
本発明の硬化性樹脂組成物は、塗布性の観点から、更に、チキソ性付与剤を含有することが好ましい。
From the viewpoint of coatability, the curable resin composition of the present invention preferably further contains a thixotropic agent.
上記チキソ性付与剤としては、例えば、ポリシロキサン、ポリアクリル、ポリアミド、ポリビニルアルコール、ポリエーテルエステル、アルキル変性セルロース、ペプチド、ポリペプチド、シリカ等が挙げられる。
Examples of the thixotropic agent include polysiloxane, polyacryl, polyamide, polyvinyl alcohol, polyetherester, alkyl-modified cellulose, peptide, polypeptide, silica and the like.
上記チキソ性付与剤の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が５重量部である。上記チキソ性付与剤の含有量がこの範囲であることにより、得られる硬化性樹脂組成物が塗布性により優れるものとなる。上記チキソ性付与剤の含有量のより好ましい下限は１重量部、より好ましい上限は３重量部である。
The preferable lower limit of the content of the thixotropic agent is 0.1 parts by weight, and the preferable upper limit thereof is 5 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the thixotropy-imparting agent is within this range, the resulting curable resin composition is more excellent in coatability. A more preferable lower limit to the content of the thixotropic agent is 1 part by weight, and a more preferable upper limit is 3 parts by weight.
本発明の硬化性樹脂組成物は、溶剤を含有しないことが好ましい。
上記溶剤を含有しないことにより、得られる硬化性樹脂組成物が、低アウトガス性により優れ、かつ、脱溶剤工程を要しないものとなる。 The curable resin composition of the present invention preferably contains no solvent.
By not containing the solvent, the resulting curable resin composition is excellent in low outgassing properties and does not require a solvent removal step.
上記溶剤を含有しないことにより、得られる硬化性樹脂組成物が、低アウトガス性により優れ、かつ、脱溶剤工程を要しないものとなる。 The curable resin composition of the present invention preferably contains no solvent.
By not containing the solvent, the resulting curable resin composition is excellent in low outgassing properties and does not require a solvent removal step.
また、本発明の硬化性樹脂組成物は、必要に応じて、硬化遅延剤、補強剤、粘度調整剤、酸化防止剤等の公知の各種添加剤を含有してもよい。
In addition, the curable resin composition of the present invention may contain various known additives such as curing retarders, reinforcing agents, viscosity modifiers and antioxidants, if necessary.
本発明の硬化性樹脂組成物は、Ｅ型粘度計を用いて、２５℃にて測定した粘度の好ましい下限が５００ｍＰａ・ｓ、好ましい上限が５万ｍＰａ・ｓである。上記粘度がこの範囲であることにより、得られる硬化性樹脂組成物が塗布性に優れるものとなる。上記粘度のより好ましい下限は１０００ｍＰａ・ｓ、より好ましい上限は１万ｍＰａ・ｓである。
上記粘度は、例えば、Ｅ型粘度計としてＶＩＳＣＯＭＥＴＥＲ ＴＶ－２２（東機産業社製）、Ｎｏ．１のローターを用いて１ｒｐｍ若しくは１０ｒｐｍの回転速度にて測定することができる。
なお、上記粘度は、上記カチオン重合性ポリシルセスキオキサン及び上記他のカチオン重合性化合物の含有量を調整すること等によって容易に上記範囲とすることができる。 The curable resin composition of the present invention preferably has a lower limit of 500 mPa·s and a preferred upper limit of viscosity measured at 25° C. using an E-type viscometer of 50,000 mPa·s. When the viscosity is within this range, the resulting curable resin composition will have excellent coatability. A more preferable lower limit of the viscosity is 1000 mPa·s, and a more preferable upper limit is 10,000 mPa·s.
The above viscosity can be measured, for example, by using VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) as an E-type viscometer. 1 rotor can be measured at a rotational speed of 1 rpm or 10 rpm.
The viscosity can be easily set within the above range by adjusting the contents of the cationically polymerizable polysilsesquioxane and the other cationically polymerizable compound.
上記粘度は、例えば、Ｅ型粘度計としてＶＩＳＣＯＭＥＴＥＲ ＴＶ－２２（東機産業社製）、Ｎｏ．１のローターを用いて１ｒｐｍ若しくは１０ｒｐｍの回転速度にて測定することができる。
なお、上記粘度は、上記カチオン重合性ポリシルセスキオキサン及び上記他のカチオン重合性化合物の含有量を調整すること等によって容易に上記範囲とすることができる。 The curable resin composition of the present invention preferably has a lower limit of 500 mPa·s and a preferred upper limit of viscosity measured at 25° C. using an E-type viscometer of 50,000 mPa·s. When the viscosity is within this range, the resulting curable resin composition will have excellent coatability. A more preferable lower limit of the viscosity is 1000 mPa·s, and a more preferable upper limit is 10,000 mPa·s.
The above viscosity can be measured, for example, by using VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) as an E-type viscometer. 1 rotor can be measured at a rotational speed of 1 rpm or 10 rpm.
The viscosity can be easily set within the above range by adjusting the contents of the cationically polymerizable polysilsesquioxane and the other cationically polymerizable compound.
本発明の硬化性樹脂組成物は、ハードコート剤、ディスプレイ用封止剤、マイクロレンズ等に用いることができる。なかでも、光半導体素子等の上にコーティング層を形成する、又は、フィルム状として光半導体素子等を被覆することにより、該光半導体素子等を保護封止するために好適に用いられる。
本発明の硬化性樹脂組成物を用いて形成されるコーティング層もまた、本発明の１つである。本発明の硬化性樹脂組成物を用いて形成されるフィルムもまた、本発明の１つである。 The curable resin composition of the present invention can be used for hard coating agents, sealing agents for displays, microlenses and the like. Among others, it is preferably used to protect and seal the optical semiconductor element or the like by forming a coating layer on the optical semiconductor element or the like, or by covering the optical semiconductor element or the like in a film form.
A coating layer formed using the curable resin composition of the present invention is also one aspect of the present invention. A film formed using the curable resin composition of the present invention is also one aspect of the present invention.
本発明の硬化性樹脂組成物を用いて形成されるコーティング層もまた、本発明の１つである。本発明の硬化性樹脂組成物を用いて形成されるフィルムもまた、本発明の１つである。 The curable resin composition of the present invention can be used for hard coating agents, sealing agents for displays, microlenses and the like. Among others, it is preferably used to protect and seal the optical semiconductor element or the like by forming a coating layer on the optical semiconductor element or the like, or by covering the optical semiconductor element or the like in a film form.
A coating layer formed using the curable resin composition of the present invention is also one aspect of the present invention. A film formed using the curable resin composition of the present invention is also one aspect of the present invention.
本発明のコーティング層は、本発明の硬化性樹脂組成物を光半導体素子等の被塗布物上に塗布した後、硬化させることにより形成することができる。また、本発明のフィルムは、本発明の硬化性樹脂組成物を離型フィルム等に塗布した後、硬化させることにより形成することができる。
The coating layer of the present invention can be formed by applying the curable resin composition of the present invention onto an object to be coated such as an optical semiconductor element and then curing the composition. Moreover, the film of the present invention can be formed by applying the curable resin composition of the present invention to a release film or the like and then curing the composition.
本発明の硬化性樹脂組成物を塗布する方法としては、例えば、スピンコート法、バーコート法、インクジェット法等が挙げられる。
Examples of methods for applying the curable resin composition of the present invention include a spin coating method, a bar coating method, an inkjet method, and the like.
本発明の硬化性樹脂組成物は、光照射によって容易に硬化させることができる。
本発明の硬化性樹脂組成物を光照射によって硬化させる方法としては、例えば、３００ｎｍ以上４００ｎｍ以下の波長及び３００ｍＪ／ｃｍ２以上３０００ｍＪ／ｃｍ２以下の積算光量の光を照射する方法等が挙げられる。 The curable resin composition of the present invention can be easily cured by light irradiation.
Examples of the method of curing the curable resin composition of the present invention by light irradiation include a method of irradiating light with a wavelength of 300 nm or more and 400 nm or less and an integrated light amount of 300 mJ/cm 2 or more and 3000 mJ/cm 2 or less. .
本発明の硬化性樹脂組成物を光照射によって硬化させる方法としては、例えば、３００ｎｍ以上４００ｎｍ以下の波長及び３００ｍＪ／ｃｍ２以上３０００ｍＪ／ｃｍ２以下の積算光量の光を照射する方法等が挙げられる。 The curable resin composition of the present invention can be easily cured by light irradiation.
Examples of the method of curing the curable resin composition of the present invention by light irradiation include a method of irradiating light with a wavelength of 300 nm or more and 400 nm or less and an integrated light amount of 300 mJ/cm 2 or more and 3000 mJ/cm 2 or less. .
本発明の硬化性樹脂組成物に光を照射するための光源としては、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、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、ＬＥＤランプ、蛍光灯、太陽光、電子線照射装置等が挙げられる。これらの光源は単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。
これらの光源は、上記光重合開始剤の吸収波長に合わせて適宜選択される。 Examples of light sources for irradiating the curable resin composition of the present invention with light include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, excimer lasers, chemical lamps, black light lamps, microwave-excited mercury lamps, Examples include metal halide lamps, sodium lamps, halogen lamps, xenon lamps, LED lamps, fluorescent lamps, sunlight, and electron beam irradiation devices. These light sources may be used alone, or two or more of them may be used in combination.
These light sources are appropriately selected according to the absorption wavelength of the photopolymerization initiator.
これらの光源は、上記光重合開始剤の吸収波長に合わせて適宜選択される。 Examples of light sources for irradiating the curable resin composition of the present invention with light include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, excimer lasers, chemical lamps, black light lamps, microwave-excited mercury lamps, Examples include metal halide lamps, sodium lamps, halogen lamps, xenon lamps, LED lamps, fluorescent lamps, sunlight, and electron beam irradiation devices. These light sources may be used alone, or two or more of them may be used in combination.
These light sources are appropriately selected according to the absorption wavelength of the photopolymerization initiator.
本発明の硬化性樹脂組成物への光の照射手段としては、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、いずれの照射手段を用いてもよい。
Examples of means for irradiating the curable resin composition of the present invention with light include simultaneous irradiation with various light sources, sequential irradiation with a time lag, and combined irradiation of simultaneous and sequential irradiation. means may be used.
本発明の硬化性樹脂組成物は、上記光照射を行った後、加熱することにより硬化させてもよい。
The curable resin composition of the present invention may be cured by heating after the light irradiation.
本発明によれば、着色性及び硬化物の硬度に優れる硬化性樹脂組成物を提供することができる。また、本発明によれば、該硬化性樹脂組成物を用いて形成されるコーティング層及びフィルムを提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which is excellent in the hardness of coloring property and hardened|cured material can be provided. Moreover, according to the present invention, it is possible to provide a coating layer and a film formed using the curable resin composition.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。
EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples.
（実施例１～９及び比較例１、２）
表１に記載された配合比に従い、各材料を、撹拌混合機を用いて撹拌混合することにより、実施例１～９及び比較例１、２の各硬化性樹脂組成物を作製した。撹拌混合機としては、あわとり練太郎ＡＲＥ－３１０（シンキー社製）を用いた。
得られた硬化性樹脂組成物について、Ｅ型粘度計（東機産業社製、「ＶＩＳＣＯＭＥＴＥＲ ＴＶ－２２」）を用い、Ｎｏ．１のローターにて、２５℃、回転速度１ｒｐｍ又は１０ｒｐｍの条件で粘度を測定した。結果を表１に示した。 (Examples 1 to 9 and Comparative Examples 1 and 2)
The curable resin compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were prepared by stirring and mixing each material using a stirring mixer according to the compounding ratio shown in Table 1. As a stirring mixer, Awatori Mixer ARE-310 (manufactured by Thinky Corporation) was used.
The resulting curable resin composition was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., "VISCOMETER TV-22"). No. 1 rotor was used, and the viscosity was measured under the conditions of 25° C. and a rotation speed of 1 rpm or 10 rpm. Table 1 shows the results.
表１に記載された配合比に従い、各材料を、撹拌混合機を用いて撹拌混合することにより、実施例１～９及び比較例１、２の各硬化性樹脂組成物を作製した。撹拌混合機としては、あわとり練太郎ＡＲＥ－３１０（シンキー社製）を用いた。
得られた硬化性樹脂組成物について、Ｅ型粘度計（東機産業社製、「ＶＩＳＣＯＭＥＴＥＲ ＴＶ－２２」）を用い、Ｎｏ．１のローターにて、２５℃、回転速度１ｒｐｍ又は１０ｒｐｍの条件で粘度を測定した。結果を表１に示した。 (Examples 1 to 9 and Comparative Examples 1 and 2)
The curable resin compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were prepared by stirring and mixing each material using a stirring mixer according to the compounding ratio shown in Table 1. As a stirring mixer, Awatori Mixer ARE-310 (manufactured by Thinky Corporation) was used.
The resulting curable resin composition was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., "VISCOMETER TV-22"). No. 1 rotor was used, and the viscosity was measured under the conditions of 25° C. and a rotation speed of 1 rpm or 10 rpm. Table 1 shows the results.
＜評価＞
実施例及び比較例で得られた各硬化性樹脂組成物について以下の評価を行った。結果を表１に示した。 <Evaluation>
Each curable resin composition obtained in Examples and Comparative Examples was evaluated as follows. Table 1 shows the results.
実施例及び比較例で得られた各硬化性樹脂組成物について以下の評価を行った。結果を表１に示した。 <Evaluation>
Each curable resin composition obtained in Examples and Comparative Examples was evaluated as follows. Table 1 shows the results.
（着色性（ＯＤ値））
実施例及び比較例で得られた各硬化性樹脂組成物を、カプトンテープを用いてギャップを設けたガラス基板上に、バーコーターＮｏ．５（アズワン社製）を用いて厚さ３０μｍとなるようにして塗布した後、メタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線（波長３６５ｎｍ）を３０秒照射して硬化性樹脂組成物を光硬化させ、試験片を得た。得られた試験片について、光学濃度計（Ｘ－ｒｉｔｅ社製、「スペクトロメーター」）を用いて光学濃度（ＯＤ値）を測定した。 (Colorability (OD value))
Each curable resin composition obtained in Examples and Comparative Examples was coated on a glass substrate provided with a gap using a Kapton tape using a bar coater No. 1. 5 (manufactured by AS ONE) to a thickness of 30 μm, and then irradiated with ultraviolet rays (wavelength: 365 nm) of 100 mW/cm 2 for 30 seconds using a metal halide lamp to photocure the curable resin composition. and obtained a test piece. The optical density (OD value) of the obtained test piece was measured using an optical densitometer (manufactured by X-rite, "Spectrometer").
実施例及び比較例で得られた各硬化性樹脂組成物を、カプトンテープを用いてギャップを設けたガラス基板上に、バーコーターＮｏ．５（アズワン社製）を用いて厚さ３０μｍとなるようにして塗布した後、メタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線（波長３６５ｎｍ）を３０秒照射して硬化性樹脂組成物を光硬化させ、試験片を得た。得られた試験片について、光学濃度計（Ｘ－ｒｉｔｅ社製、「スペクトロメーター」）を用いて光学濃度（ＯＤ値）を測定した。 (Colorability (OD value))
Each curable resin composition obtained in Examples and Comparative Examples was coated on a glass substrate provided with a gap using a Kapton tape using a bar coater No. 1. 5 (manufactured by AS ONE) to a thickness of 30 μm, and then irradiated with ultraviolet rays (wavelength: 365 nm) of 100 mW/cm 2 for 30 seconds using a metal halide lamp to photocure the curable resin composition. and obtained a test piece. The optical density (OD value) of the obtained test piece was measured using an optical densitometer (manufactured by X-rite, "Spectrometer").
（鉛筆硬度）
実施例及び比較例で得られた各硬化性樹脂組成物を、厚さ３０μｍのカプトンテープを用いてギャップを設けたガラス基板上に、バーコーターＮｏ．５（アズワン社製）を用いて厚さ３０μｍとなるようにして塗布した。次いで、メタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線（波長３６５ｎｍ）を３０秒照射して硬化性樹脂組成物を光硬化させ、試験片を得た。
得られた試験片について、ＪＩＳ Ｋ ５６００－５－４に準拠して鉛筆硬度を測定した。 (Pencil hardness)
Each curable resin composition obtained in Examples and Comparative Examples was coated on a glass substrate provided with a gap using a Kapton tape having a thickness of 30 μm using a bar coater No. 1. 5 (manufactured by AS ONE) was applied to a thickness of 30 μm. Next, a metal halide lamp was used to irradiate ultraviolet rays (wavelength: 365 nm) of 100 mW/cm 2 for 30 seconds to photo-cure the curable resin composition, thereby obtaining a test piece.
The obtained test piece was measured for pencil hardness according to JIS K 5600-5-4.
実施例及び比較例で得られた各硬化性樹脂組成物を、厚さ３０μｍのカプトンテープを用いてギャップを設けたガラス基板上に、バーコーターＮｏ．５（アズワン社製）を用いて厚さ３０μｍとなるようにして塗布した。次いで、メタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線（波長３６５ｎｍ）を３０秒照射して硬化性樹脂組成物を光硬化させ、試験片を得た。
得られた試験片について、ＪＩＳ Ｋ ５６００－５－４に準拠して鉛筆硬度を測定した。 (Pencil hardness)
Each curable resin composition obtained in Examples and Comparative Examples was coated on a glass substrate provided with a gap using a Kapton tape having a thickness of 30 μm using a bar coater No. 1. 5 (manufactured by AS ONE) was applied to a thickness of 30 μm. Next, a metal halide lamp was used to irradiate ultraviolet rays (wavelength: 365 nm) of 100 mW/cm 2 for 30 seconds to photo-cure the curable resin composition, thereby obtaining a test piece.
The obtained test piece was measured for pencil hardness according to JIS K 5600-5-4.
本発明によれば、着色性及び硬化物の硬度に優れる硬化性樹脂組成物を提供することができる。また、本発明によれば、該硬化性樹脂組成物を用いて形成されるコーティング層及びフィルムを提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which is excellent in the hardness of coloring property and hardened|cured material can be provided. Moreover, according to the present invention, it is possible to provide a coating layer and a film formed using the curable resin composition.
Claims (8)
- 硬化性樹脂と光重合開始剤と染料とを含有する硬化性樹脂組成物であって、
前記硬化性樹脂は、カチオン重合性基を有するポリシルセスキオキサン及び該カチオン重合性基を有するポリシルセスキオキサン以外の他のカチオン重合性化合物を含む
ことを特徴とする硬化性樹脂組成物。 A curable resin composition containing a curable resin, a photoinitiator and a dye,
A curable resin composition, wherein the curable resin comprises a polysilsesquioxane having a cationically polymerizable group and a cationically polymerizable compound other than the polysilsesquioxane having the cationically polymerizable group. . - 粘度が５００ｍＰａ・ｓ以上５万ｍＰａ・ｓ以下である請求項１記載の硬化性樹脂組成物。 2. The curable resin composition according to claim 1, which has a viscosity of 500 mPa.s or more and 50,000 mPa.s or less.
- 前記光重合開始剤は、光カチオン重合開始剤を含む請求項１又は２記載の硬化性樹脂組成物。 The curable resin composition according to claim 1 or 2, wherein the photopolymerization initiator contains a photocationic polymerization initiator.
- 更に、紫外線吸収剤を含む請求項１、２又は３記載の硬化性樹脂組成物。 4. The curable resin composition according to claim 1, 2 or 3, further comprising an ultraviolet absorber.
- 更に、レベリング剤を含む請求項１、２、３又は４記載の硬化性樹脂組成物。 5. The curable resin composition according to claim 1, further comprising a leveling agent.
- 更に、チキソ性付与剤を含む請求項１、２、３、４又は５記載の硬化性樹脂組成物。 6. The curable resin composition according to claim 1, further comprising a thixotropic agent.
- 請求項１、２、３、４、５又は６記載の硬化性樹脂組成物を用いて形成されるコーティング層。 A coating layer formed using the curable resin composition according to claim 1, 2, 3, 4, 5 or 6.
- 請求項１、２、３、４、５又は６記載の硬化性樹脂組成物を用いて形成されるフィルム。 A film formed using the curable resin composition according to claim 1, 2, 3, 4, 5 or 6.
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Citations (6)
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|---|---|---|---|---|
| US20110124764A1 (en) * | 2008-06-10 | 2011-05-26 | Christoph Thalacker | Initiator system with biphenylene derivates, method of production and use thereof |
| WO2016203957A1 (en) * | 2015-06-17 | 2016-12-22 | 株式会社ダイセル | Curable composition, and moulded body |
| WO2016204115A1 (en) * | 2015-06-17 | 2016-12-22 | 株式会社ダイセル | Process for producing cured object, cured object, and layered product including said cured object |
| WO2018037565A1 (en) * | 2016-08-26 | 2018-03-01 | Jnc株式会社 | Epoxy resin composition and cured resin film with low curing shrinkage and excellent adhesion |
| WO2018189945A1 (en) * | 2017-04-12 | 2018-10-18 | 株式会社ダイセル | Curable composition, cured product, and hardcoat film |
| JP2018177952A (en) * | 2017-04-12 | 2018-11-15 | 株式会社ダイセル | Curable composition, cured article, and hard coat film |
-
2022
- 2022-09-29 WO PCT/JP2022/036375 patent/WO2023054561A1/en active Application Filing
- 2022-09-30 TW TW111137235A patent/TW202323461A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110124764A1 (en) * | 2008-06-10 | 2011-05-26 | Christoph Thalacker | Initiator system with biphenylene derivates, method of production and use thereof |
| WO2016203957A1 (en) * | 2015-06-17 | 2016-12-22 | 株式会社ダイセル | Curable composition, and moulded body |
| WO2016204115A1 (en) * | 2015-06-17 | 2016-12-22 | 株式会社ダイセル | Process for producing cured object, cured object, and layered product including said cured object |
| WO2018037565A1 (en) * | 2016-08-26 | 2018-03-01 | Jnc株式会社 | Epoxy resin composition and cured resin film with low curing shrinkage and excellent adhesion |
| WO2018189945A1 (en) * | 2017-04-12 | 2018-10-18 | 株式会社ダイセル | Curable composition, cured product, and hardcoat film |
| JP2018177952A (en) * | 2017-04-12 | 2018-11-15 | 株式会社ダイセル | Curable composition, cured article, and hard coat film |
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