WO2023054563A1 - Curable resin composition, coating layer, and film - Google Patents
Curable resin composition, coating layer, and film Download PDFInfo
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- WO2023054563A1 WO2023054563A1 PCT/JP2022/036380 JP2022036380W WO2023054563A1 WO 2023054563 A1 WO2023054563 A1 WO 2023054563A1 JP 2022036380 W JP2022036380 W JP 2022036380W WO 2023054563 A1 WO2023054563 A1 WO 2023054563A1
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- WIPO (PCT)
- Prior art keywords
- curable resin
- resin composition
- hydrogen
- functional group
- bonding functional
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- 239000011342 resin composition Substances 0.000 title claims abstract description 63
- 239000011247 coating layer Substances 0.000 title claims abstract description 12
- 239000010408 film Substances 0.000 title 1
- 125000000524 functional group Chemical group 0.000 claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- 239000003505 polymerization initiator Substances 0.000 claims description 22
- 125000002091 cationic group Chemical group 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 abstract description 4
- -1 silane compound Chemical class 0.000 description 58
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 238000010538 cationic polymerization reaction Methods 0.000 description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical class CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000013008 thixotropic agent Substances 0.000 description 4
- 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
- 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
- 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
- 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
- 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 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-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
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 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
- 238000010943 off-gassing Methods 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
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical class CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-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
- 239000004952 Polyamide 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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-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
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 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
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 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
- 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
- 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
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920001184 polypeptide 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
- 239000000600 sorbitol Substances 0.000 description 1
- 238000004528 spin coating 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
- 125000003396 thiol group Chemical group [H]S* 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
- 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).
- the organic-inorganic hybrid hard coating agent disclosed in Cited Document 1 has difficulty in achieving both adhesion (especially adhesion to glass) and hardness (surface hardness) of the cured product.
- An object of the present invention is to provide a curable resin composition having excellent adhesiveness 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 and a photopolymerization initiator, wherein the curable resin includes polysilsesquioxane having a cationic polymerizable group, an alicyclic epoxy compound, and a curable resin composition containing a compound having a hydrogen-bonding functional group and a cationically polymerizable group and having a hydrogen-bonding functional group value of 1.0 ⁇ 10 ⁇ 3 mol/g or more.
- the present disclosure 2 is the curable resin composition of the present disclosure 1, wherein the photopolymerization initiator includes a photocationic polymerization initiator.
- the present disclosure 3 is a coating layer formed using the curable resin composition of the present disclosure 1 or 2.
- the present disclosure 4 is a film formed using the curable resin composition of the present disclosure 1 or 2. The present invention will be described in detail below.
- the present inventor has, as a curable resin, a polysilsesquioxane having a cationic polymerizable group, an alicyclic epoxy compound, a hydrogen-bonding functional group and a cationic polymerizable group, and a hydrogen-bonding functional group
- a curable resin composition having excellent adhesiveness and hardness of the cured product can be obtained, 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 has a polysilsesquioxane having a cationic polymerizable group, an alicyclic epoxy compound, a hydrogen-bonding functional group and a cationic polymerizable group, and has a hydrogen-bonding functional group value of 1.5. Including compounds that are 0 ⁇ 10 ⁇ 3 mol/g or more.
- the polysilsesquioxane having the cationically polymerizable group is also referred to as “cationically polymerizable polysilsesquioxane”, and has the hydrogen-bonding functional group and the cationically-polymerizable group, and has a hydrogen-bonding functional group value.
- the curable resin composition of the present invention has adhesiveness. (especially adhesion to glass) and hardness of the cured product.
- 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.
- a compound having a hydrogen-bonding functional group and an alicyclic epoxy skeleton and having a hydrogen-bonding functional group value of 1.0 ⁇ 10 ⁇ 3 mol/g or more is not the above alicyclic epoxy compound. It is treated as the above-mentioned hydrogen-bonding functional group-containing cationically polymerizable compound.
- the cationically polymerizable polysilsesquioxane and the cationically polymerizable compound containing a hydrogen-bonding functional group 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 possessed by the cationically polymerizable polysilsesquioxane and the cationically polymerizable group possessed by the cationically polymerizable compound containing a hydrogen-bonding functional group 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 coatability and adhesiveness (especially adhesiveness to glass).
- 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.
- alicyclic epoxy compounds examples include 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane carboxylate, 4,4′-bis(1,2-epoxycyclohexane), tetrahydroindene diepoxide, Cyclic epoxy-modified silicone compound, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexan-1-ylmethyl)adipate, 1 of 2,2-bis(hydroxymethyl)-1-butanol , 2-epoxy-4-(2-oxiranyl)cyclohexane adduct, [(3,4-epoxycyclohexane)-1-yl]methyl methacrylate, and the like.
- 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane carboxylate, 4,4'-bis (1,2-epoxycyclohexane), tetrahydroindene diepoxide, alicyclic epoxy-modified silicone compounds, and bis(3,4-epoxycyclohexylmethyl) ether are more preferred.
- a preferable lower limit of the content of the alicyclic epoxy compound in 100 parts by weight of the curable resin is 5 parts by weight, and a preferable upper limit thereof is 50 parts by weight.
- the content of the alicyclic epoxy compound is 5 parts by weight or more and 50 parts by weight or less, the resulting curable resin composition is excellent in curability and hardness of the cured product.
- a more preferable lower limit for the content of the alicyclic epoxy compound is 10 parts by weight, and a more preferable upper limit is 30 parts by weight.
- Examples of the hydrogen-bonding functional group possessed by the cationically polymerizable compound containing a hydrogen-bonding functional group include a hydroxyl group, an amino group, an amide group, a carboxyl group, and a thiol group. Among them, a hydroxyl group is preferred. Further, when the cationically polymerizable compound containing a hydrogen-bonding functional group has a hydroxyl group generated by a ring-opening reaction of an epoxy group, the cationically polymerizable compound containing a hydrogen-bonding functional group is further subjected to a ring-opening reaction of the epoxy group. It is preferable to have a hydrogen-bonding functional group other than the resulting hydroxyl group.
- the practical upper limit is six.
- the cationically polymerizable compound containing a hydrogen-bonding functional group has a hydroxyl group generated by the ring-opening reaction of the epoxy group
- one hydrogen-bonding functional group other than the hydroxyl group generated by the ring-opening reaction of the epoxy group is contained in one molecule. It is preferable to have one or more.
- the hydrogen-bonding functional group-containing cationically polymerizable compound has a hydrogen-bonding functional group value with a lower limit of 1.0 ⁇ 10 ⁇ 3 mol/g. Since the hydrogen-bonding functional group-containing cationically polymerizable compound has a hydrogen-bonding functional group value of 1.0 ⁇ 10 ⁇ 3 mol/g or more, the curable resin composition of the present invention exhibits adhesiveness (especially glass (adhesiveness to) will be excellent.
- a preferable lower limit of the hydrogen-bonding functional group value of the cationically polymerizable compound containing a hydrogen-bonding functional group is 2.0 ⁇ 10 ⁇ 3 mol/g, and a more preferable lower limit is 3.0 ⁇ 10 ⁇ 3 mol/g.
- hydrogen-bonding functional group value of the cationically polymerizable compound containing a hydrogen-bonding functional group
- practical upper limit is 3.0 ⁇ 10 ⁇ 2 mol/g.
- hydrogen-bonding functional group value is a value obtained by dividing the number of hydrogen-bonding functional groups in one molecule of a compound by the molecular weight of the compound.
- the hydrogen-bonding functional group-containing cationically polymerizable compound preferably has 4 or more of the above-described cationically polymerizable groups in one molecule from the viewpoint of further improving the hardness of the cured product of the curable resin composition obtained. .
- the substantial upper limit is six.
- the hydrogen-bonding functional group-containing cationically polymerizable compound has a hydrogen-bonding functional group and a cationically polymerizable group in its molecular structure, and has a hydrogen-bonding functional group value of 1.0 ⁇ 10 ⁇ 3 mol/g. It is not particularly limited as long as it is the above. Among these, polyglycerol polyglycidyl ether and sorbitol polyglycidyl ether are preferable from the viewpoint of the curability of the resulting curable resin composition and the hardness of the cured product.
- a preferable lower limit of the content of the cationically polymerizable compound containing a hydrogen-bonding functional group in 100 parts by weight of the curable resin is 2 parts by weight, and a preferable upper limit thereof is 30 parts by weight.
- the content of the cationically polymerizable compound containing a hydrogen-bonding functional group is 2 parts by weight or more, the obtained curable resin composition has excellent adhesiveness (especially adhesiveness to glass).
- the content of the cationically polymerizable compound containing a hydrogen-bonding functional group is 30 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 cationically polymerizable compound containing a hydrogen-bonding functional group is 4 parts by weight, and a more preferable upper limit thereof is 20 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 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.
- the resulting curable resin composition is more excellent in curability and storage stability.
- a more preferable lower limit to the content of the photopolymerization initiator is 3 parts by weight, and a more preferable upper limit is 15 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 dyes, 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 used and measured at a rotational speed of 1 rpm or 10 rpm.
- 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 adhesiveness and the hardness of hardened
- Examples 1 to 7 and Comparative Examples 1 to 4 The curable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4 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.
- 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 ⁇ m using a bar coater No. 1. 5 (manufactured by AS ONE) was applied to a thickness of 30 ⁇ m. 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 cut in a grid pattern at intervals of 1 cm using a cutter to provide four test points. After affixing a tape ("Cellotape (registered trademark) No.
- the tape was peeled off, and the number of test points remaining on the substrate without being peeled off was counted. If the number of test points remaining on the substrate was 4, " ⁇ ", if there were 1 or more and 3 or less, " ⁇ ", and if there were 0, " ⁇ ", the adhesiveness was evaluated. evaluated.
- the curable resin composition which is excellent in adhesiveness and the hardness of hardened
Abstract
The purpose of the present invention is to provide a curable resin composition which has excellent adhesiveness and is capable of forming a cured product having excellent hardness. In addition, the purpose of the present invention is to provide a coating layer and a film formed using said curable resin composition. The present invention provides a curable composition containing a curable resin and a photoinitiator, wherein the curable resin includes a polysilsesquioxane having a cationically polymerizable group, an alicyclic epoxy compound, and a compound having a hydrogen-bonding functional group and a cationically polymerizable group and having a hydrogen-bonding functional group value of at least 1.0×10-3 mol/g.
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).
引用文献１に開示されているような有機無機ハイブリット系のハードコート剤は、接着性（特にガラスに対する接着性）と硬化物の硬度（表面硬度）とを両立させることが困難であった。
本発明は、接着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。 The organic-inorganic hybrid hard coating agent disclosed in Cited Document 1 has difficulty in achieving both adhesion (especially adhesion to glass) and hardness (surface hardness) of the cured product.
An object of the present invention is to provide a curable resin composition having excellent adhesiveness 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.
本発明は、接着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。 The organic-inorganic hybrid hard coating agent disclosed in Cited Document 1 has difficulty in achieving both adhesion (especially adhesion to glass) and hardness (surface hardness) of the cured product.
An object of the present invention is to provide a curable resin composition having excellent adhesiveness 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、脂環式エポキシ化合物、及び、水素結合性官能基とカチオン重合性基とを有し、水素結合性官能基価が１．０×１０－３ｍｏｌ／ｇ以上である化合物を含む硬化性樹脂組成物である。
本開示２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の硬化性樹脂組成物である。
本開示３は、本開示１又は２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４は、本開示１又は２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 and a photopolymerization initiator, wherein the curable resin includes polysilsesquioxane having a cationic polymerizable group, an alicyclic epoxy compound, and a curable resin composition containing a compound having a hydrogen-bonding functional group and a cationically polymerizable group and having a hydrogen-bonding functional group value of 1.0×10 −3 mol/g or more.
The present disclosure 2 is the curable resin composition of the present disclosure 1, wherein the photopolymerization initiator includes a photocationic polymerization initiator.
The present disclosure 3 is a coating layer formed using the curable resin composition of the present disclosure 1 or 2.
The present disclosure 4 is a film formed using the curable resin composition of the present disclosure 1 or 2.
The present invention will be described in detail below.
本開示２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の硬化性樹脂組成物である。
本開示３は、本開示１又は２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４は、本開示１又は２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 and a photopolymerization initiator, wherein the curable resin includes polysilsesquioxane having a cationic polymerizable group, an alicyclic epoxy compound, and a curable resin composition containing a compound having a hydrogen-bonding functional group and a cationically polymerizable group and having a hydrogen-bonding functional group value of 1.0×10 −3 mol/g or more.
The present disclosure 2 is the curable resin composition of the present disclosure 1, wherein the photopolymerization initiator includes a photocationic polymerization initiator.
The present disclosure 3 is a coating layer formed using the curable resin composition of the present disclosure 1 or 2.
The present disclosure 4 is a film formed using the curable resin composition of the present disclosure 1 or 2.
The present invention will be described in detail below.
本発明者は、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、脂環式エポキシ化合物と、水素結合性官能基とカチオン重合性基とを有し、水素結合性官能基価が１．０×１０－３ｍｏｌ／ｇ以上である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、接着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。 The present inventor has, as a curable resin, a polysilsesquioxane having a cationic polymerizable group, an alicyclic epoxy compound, a hydrogen-bonding functional group and a cationic polymerizable group, and a hydrogen-bonding functional group The use of a compound having a molecular weight of 1.0×10 −3 mol/g or more was investigated. As a result, the inventors have found that a curable resin composition having excellent adhesiveness and hardness of the cured product can be obtained, 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。 The present inventor has, as a curable resin, a polysilsesquioxane having a cationic polymerizable group, an alicyclic epoxy compound, a hydrogen-bonding functional group and a cationic polymerizable group, and a hydrogen-bonding functional group The use of a compound having a molecular weight of 1.0×10 −3 mol/g or more was investigated. As a result, the inventors have found that a curable resin composition having excellent adhesiveness and hardness of the cured product can be obtained, 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、脂環式エポキシ化合物、及び、水素結合性官能基とカチオン重合性基とを有し、水素結合性官能基価が１．０×１０－３ｍｏｌ／ｇ以上である化合物を含む。以下、上記カチオン重合性基を有するポリシルセスキオキサンを「カチオン重合性ポリシルセスキオキサン」ともいい、上記水素結合性官能基とカチオン重合性基とを有し、水素結合性官能基価が１．０×１０－３ｍｏｌ／ｇ以上である化合物を「水素結合性官能基含有カチオン重合性化合物」ともいう。
上記カチオン重合性ポリシルセスキオキサン、上記脂環式エポキシ化合物、及び、上記水素結合性官能基含有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、接着性（特にガラスに対する接着性）及び硬化物の硬度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。
また、水素結合性官能基と脂環式エポキシ骨格とを有し、水素結合性官能基価が１．０×１０－３ｍｏｌ／ｇ以上である化合物については、上記脂環式エポキシ化合物ではなく上記水素結合性官能基含有カチオン重合性化合物として扱う。 The curable resin composition of the present invention contains a curable resin.
The curable resin has a polysilsesquioxane having a cationic polymerizable group, an alicyclic epoxy compound, a hydrogen-bonding functional group and a cationic polymerizable group, and has a hydrogen-bonding functional group value of 1.5. Including compounds that are 0×10 −3 mol/g or more. Hereinafter, the polysilsesquioxane having the cationically polymerizable group is also referred to as “cationically polymerizable polysilsesquioxane”, and has the hydrogen-bonding functional group and the cationically-polymerizable group, and has a hydrogen-bonding functional group value. is 1.0×10 −3 mol/g or more is also referred to as “hydrogen-bonding functional group-containing cationically polymerizable compound”.
By containing the cationically polymerizable polysilsesquioxane, the alicyclic epoxy compound, and the cationically polymerizable compound containing a hydrogen-bonding functional group in combination, the curable resin composition of the present invention has adhesiveness. (especially adhesion to glass) and hardness of the cured product.
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.
In addition, a compound having a hydrogen-bonding functional group and an alicyclic epoxy skeleton and having a hydrogen-bonding functional group value of 1.0×10 −3 mol/g or more is not the above alicyclic epoxy compound. It is treated as the above-mentioned hydrogen-bonding functional group-containing cationically polymerizable compound.
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、脂環式エポキシ化合物、及び、水素結合性官能基とカチオン重合性基とを有し、水素結合性官能基価が１．０×１０－３ｍｏｌ／ｇ以上である化合物を含む。以下、上記カチオン重合性基を有するポリシルセスキオキサンを「カチオン重合性ポリシルセスキオキサン」ともいい、上記水素結合性官能基とカチオン重合性基とを有し、水素結合性官能基価が１．０×１０－３ｍｏｌ／ｇ以上である化合物を「水素結合性官能基含有カチオン重合性化合物」ともいう。
上記カチオン重合性ポリシルセスキオキサン、上記脂環式エポキシ化合物、及び、上記水素結合性官能基含有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、接着性（特にガラスに対する接着性）及び硬化物の硬度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。
また、水素結合性官能基と脂環式エポキシ骨格とを有し、水素結合性官能基価が１．０×１０－３ｍｏｌ／ｇ以上である化合物については、上記脂環式エポキシ化合物ではなく上記水素結合性官能基含有カチオン重合性化合物として扱う。 The curable resin composition of the present invention contains a curable resin.
The curable resin has a polysilsesquioxane having a cationic polymerizable group, an alicyclic epoxy compound, a hydrogen-bonding functional group and a cationic polymerizable group, and has a hydrogen-bonding functional group value of 1.5. Including compounds that are 0×10 −3 mol/g or more. Hereinafter, the polysilsesquioxane having the cationically polymerizable group is also referred to as “cationically polymerizable polysilsesquioxane”, and has the hydrogen-bonding functional group and the cationically-polymerizable group, and has a hydrogen-bonding functional group value. is 1.0×10 −3 mol/g or more is also referred to as “hydrogen-bonding functional group-containing cationically polymerizable compound”.
By containing the cationically polymerizable polysilsesquioxane, the alicyclic epoxy compound, and the cationically polymerizable compound containing a hydrogen-bonding functional group in combination, the curable resin composition of the present invention has adhesiveness. (especially adhesion to glass) and hardness of the cured product.
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.
In addition, a compound having a hydrogen-bonding functional group and an alicyclic epoxy skeleton and having a hydrogen-bonding functional group value of 1.0×10 −3 mol/g or more is not the above alicyclic epoxy compound. It is treated as the above-mentioned hydrogen-bonding functional group-containing cationically polymerizable compound.
上記カチオン重合性ポリシルセスキオキサン及び上記水素結合性官能基含有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 cationically polymerizable compound containing a hydrogen-bonding functional group 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、上記水素結合性官能基含有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 possessed by the cationically polymerizable polysilsesquioxane and the cationically polymerizable group possessed by the cationically polymerizable compound containing a hydrogen-bonding functional group 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、上記水素結合性官能基含有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 possessed by the cationically polymerizable polysilsesquioxane and the cationically polymerizable group possessed by the cationically polymerizable compound containing a hydrogen-bonding functional group 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及び接着性（特にガラスに対する接着性）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 coatability and adhesiveness (especially adhesiveness to glass). 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.
上記脂環式エポキシ化合物としては、例えば、３，４－エポキシシクロヘキシルメチル（３，４－エポキシ）シクロヘキサンカルボキシレート、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、脂環式エポキシ変性シリコーン化合物、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、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、脂環式エポキシ変性シリコーン化合物、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 alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane carboxylate, 4,4′-bis(1,2-epoxycyclohexane), tetrahydroindene diepoxide, Cyclic epoxy-modified silicone compound, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexan-1-ylmethyl)adipate, 1 of 2,2-bis(hydroxymethyl)-1-butanol , 2-epoxy-4-(2-oxiranyl)cyclohexane adduct, [(3,4-epoxycyclohexane)-1-yl]methyl methacrylate, and the like. Among them, 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane carboxylate, 4,4'-bis (1,2-epoxycyclohexane), tetrahydroindene diepoxide, alicyclic epoxy-modified silicone compounds, and 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脂環式エポキシ化合物の含有量の好ましい下限は５重量部、好ましい上限は５０重量部である。上記脂環式エポキシ化合物の含有量が５重量部以上、５０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性及び硬化物の硬度により優れるものとなる。上記脂環式エポキシ化合物の含有量のより好ましい下限は１０重量部、より好ましい上限は３０重量部である。
A preferable lower limit of the content of the alicyclic epoxy compound in 100 parts by weight of the curable resin is 5 parts by weight, and a preferable upper limit thereof is 50 parts by weight. When the content of the alicyclic epoxy compound is 5 parts by weight or more and 50 parts by weight or less, the resulting curable resin composition is excellent in curability and hardness of the cured product. A more preferable lower limit for the content of the alicyclic epoxy compound is 10 parts by weight, and a more preferable upper limit is 30 parts by weight.
上記水素結合性官能基含有カチオン重合性化合物の有する水素結合性官能基としては、例えば、水酸基、アミノ基、アミド基、カルボキシ基、チオール基等が挙げられる。なかでも、水酸基が好ましい。
また、上記水素結合性官能基含有カチオン重合性化合物がエポキシ基の開環反応によって生じる水酸基を有する場合、該水素結合性官能基含有カチオン重合性化合物は、更に、該エポキシ基の開環反応によって生じる水酸基以外の水素結合性官能基を有することが好ましい。 Examples of the hydrogen-bonding functional group possessed by the cationically polymerizable compound containing a hydrogen-bonding functional group include a hydroxyl group, an amino group, an amide group, a carboxyl group, and a thiol group. Among them, a hydroxyl group is preferred.
Further, when the cationically polymerizable compound containing a hydrogen-bonding functional group has a hydroxyl group generated by a ring-opening reaction of an epoxy group, the cationically polymerizable compound containing a hydrogen-bonding functional group is further subjected to a ring-opening reaction of the epoxy group. It is preferable to have a hydrogen-bonding functional group other than the resulting hydroxyl group.
また、上記水素結合性官能基含有カチオン重合性化合物がエポキシ基の開環反応によって生じる水酸基を有する場合、該水素結合性官能基含有カチオン重合性化合物は、更に、該エポキシ基の開環反応によって生じる水酸基以外の水素結合性官能基を有することが好ましい。 Examples of the hydrogen-bonding functional group possessed by the cationically polymerizable compound containing a hydrogen-bonding functional group include a hydroxyl group, an amino group, an amide group, a carboxyl group, and a thiol group. Among them, a hydroxyl group is preferred.
Further, when the cationically polymerizable compound containing a hydrogen-bonding functional group has a hydroxyl group generated by a ring-opening reaction of an epoxy group, the cationically polymerizable compound containing a hydrogen-bonding functional group is further subjected to a ring-opening reaction of the epoxy group. It is preferable to have a hydrogen-bonding functional group other than the resulting hydroxyl group.
上記水素結合性官能基含有カチオン重合性化合物１分子中の上記水素結合性官能基の数の好ましい上限は特にないが、実質的な上限は６個である。
また、上記水素結合性官能基含有カチオン重合性化合物がエポキシ基の開環反応によって生じる水酸基を有する場合、該エポキシ基の開環反応によって生じる水酸基以外の水素結合性官能基を１分子中に１個以上有することが好ましい。 Although there is no particular upper limit for the number of hydrogen-bonding functional groups in one molecule of the cationically polymerizable compound containing a hydrogen-bonding functional group, the practical upper limit is six.
Further, when the cationically polymerizable compound containing a hydrogen-bonding functional group has a hydroxyl group generated by the ring-opening reaction of the epoxy group, one hydrogen-bonding functional group other than the hydroxyl group generated by the ring-opening reaction of the epoxy group is contained in one molecule. It is preferable to have one or more.
また、上記水素結合性官能基含有カチオン重合性化合物がエポキシ基の開環反応によって生じる水酸基を有する場合、該エポキシ基の開環反応によって生じる水酸基以外の水素結合性官能基を１分子中に１個以上有することが好ましい。 Although there is no particular upper limit for the number of hydrogen-bonding functional groups in one molecule of the cationically polymerizable compound containing a hydrogen-bonding functional group, the practical upper limit is six.
Further, when the cationically polymerizable compound containing a hydrogen-bonding functional group has a hydroxyl group generated by the ring-opening reaction of the epoxy group, one hydrogen-bonding functional group other than the hydroxyl group generated by the ring-opening reaction of the epoxy group is contained in one molecule. It is preferable to have one or more.
上記水素結合性官能基含有カチオン重合性化合物は、水素結合性官能基価の下限が１．０×１０－３ｍｏｌ／ｇである。上記水素結合性官能基含有カチオン重合性化合物の水素結合性官能基価が１．０×１０－３ｍｏｌ／ｇ以上であることにより、本発明の硬化性樹脂組成物は、接着性（特にガラスに対する接着性）に優れるものとなる。上記水素結合性官能基含有カチオン重合性化合物の水素結合性官能基価の好ましい下限は２．０×１０－３ｍｏｌ／ｇ、より好ましい下限は３．０×１０－３ｍｏｌ／ｇである。
上記水素結合性官能基含有カチオン重合性化合物の水素結合性官能基価の好ましい上限は特にないが、実質的な上限は３．０×１０－２ｍｏｌ／ｇである。
なお、本明細書において上記「水素結合性官能基価」は、化合物１分子中の水素結合性官能基数を当該化合物の分子量で除することにより求められる値である。 The hydrogen-bonding functional group-containing cationically polymerizable compound has a hydrogen-bonding functional group value with a lower limit of 1.0×10 −3 mol/g. Since the hydrogen-bonding functional group-containing cationically polymerizable compound has a hydrogen-bonding functional group value of 1.0×10 −3 mol/g or more, the curable resin composition of the present invention exhibits adhesiveness (especially glass (adhesiveness to) will be excellent. A preferable lower limit of the hydrogen-bonding functional group value of the cationically polymerizable compound containing a hydrogen-bonding functional group is 2.0×10 −3 mol/g, and a more preferable lower limit is 3.0×10 −3 mol/g.
Although there is no particular upper limit for the hydrogen-bonding functional group value of the cationically polymerizable compound containing a hydrogen-bonding functional group, the practical upper limit is 3.0×10 −2 mol/g.
The term "hydrogen-bonding functional group value" as used herein is a value obtained by dividing the number of hydrogen-bonding functional groups in one molecule of a compound by the molecular weight of the compound.
上記水素結合性官能基含有カチオン重合性化合物の水素結合性官能基価の好ましい上限は特にないが、実質的な上限は３．０×１０－２ｍｏｌ／ｇである。
なお、本明細書において上記「水素結合性官能基価」は、化合物１分子中の水素結合性官能基数を当該化合物の分子量で除することにより求められる値である。 The hydrogen-bonding functional group-containing cationically polymerizable compound has a hydrogen-bonding functional group value with a lower limit of 1.0×10 −3 mol/g. Since the hydrogen-bonding functional group-containing cationically polymerizable compound has a hydrogen-bonding functional group value of 1.0×10 −3 mol/g or more, the curable resin composition of the present invention exhibits adhesiveness (especially glass (adhesiveness to) will be excellent. A preferable lower limit of the hydrogen-bonding functional group value of the cationically polymerizable compound containing a hydrogen-bonding functional group is 2.0×10 −3 mol/g, and a more preferable lower limit is 3.0×10 −3 mol/g.
Although there is no particular upper limit for the hydrogen-bonding functional group value of the cationically polymerizable compound containing a hydrogen-bonding functional group, the practical upper limit is 3.0×10 −2 mol/g.
The term "hydrogen-bonding functional group value" as used herein is a value obtained by dividing the number of hydrogen-bonding functional groups in one molecule of a compound by the molecular weight of the compound.
上記水素結合性官能基含有カチオン重合性化合物は、得られる硬化性樹脂組成物の硬化物の硬度をより向上させる観点から、上述したカチオン重合性基を１分子中に４個以上有することが好ましい。
上記水素結合性官能基含有カチオン重合性化合物１分子中の上記カチオン重合性基の数の好ましい上限は特にないが、実質的な上限は６個である。 The hydrogen-bonding functional group-containing cationically polymerizable compound preferably has 4 or more of the above-described cationically polymerizable groups in one molecule from the viewpoint of further improving the hardness of the cured product of the curable resin composition obtained. .
Although there is no particular upper limit for the number of cationically polymerizable groups in one molecule of the cationically polymerizable compound containing a hydrogen-bonding functional group, the substantial upper limit is six.
上記水素結合性官能基含有カチオン重合性化合物１分子中の上記カチオン重合性基の数の好ましい上限は特にないが、実質的な上限は６個である。 The hydrogen-bonding functional group-containing cationically polymerizable compound preferably has 4 or more of the above-described cationically polymerizable groups in one molecule from the viewpoint of further improving the hardness of the cured product of the curable resin composition obtained. .
Although there is no particular upper limit for the number of cationically polymerizable groups in one molecule of the cationically polymerizable compound containing a hydrogen-bonding functional group, the substantial upper limit is six.
上記水素結合性官能基含有カチオン重合性化合物としては、分子構造中に水素結合性官能基とカチオン重合性基とを有し、水素結合性官能基価が１．０×１０－３ｍｏｌ／ｇ以上であるものであれば特に限定されない。なかでも、得られる硬化性樹脂組成物の硬化性及び硬化物の硬度の観点から、ポリグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテルが好ましい。
The hydrogen-bonding functional group-containing cationically polymerizable compound has a hydrogen-bonding functional group and a cationically polymerizable group in its molecular structure, and has a hydrogen-bonding functional group value of 1.0×10 −3 mol/g. It is not particularly limited as long as it is the above. Among these, polyglycerol polyglycidyl ether and sorbitol polyglycidyl ether are preferable from the viewpoint of the curability of the resulting curable resin composition and the hardness of the cured product.
上記硬化性樹脂１００重量部中における上記水素結合性官能基含有カチオン重合性化合物の含有量の好ましい下限は２重量部、好ましい上限は３０重量部である。上記水素結合性官能基含有カチオン重合性化合物の含有量が２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接着性（特にガラスに対する接着性）により優れるものとなる。上記水素結合性官能基含有カチオン重合性化合物の含有量が３０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。上記水素結合性官能基含有カチオン重合性化合物の含有量のより好ましい下限は４重量部、より好ましい上限は２０重量部である。
A preferable lower limit of the content of the cationically polymerizable compound containing a hydrogen-bonding functional group in 100 parts by weight of the curable resin is 2 parts by weight, and a preferable upper limit thereof is 30 parts by weight. When the content of the cationically polymerizable compound containing a hydrogen-bonding functional group is 2 parts by weight or more, the obtained curable resin composition has excellent adhesiveness (especially adhesiveness to glass). When the content of the cationically polymerizable compound containing a hydrogen-bonding functional group is 30 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 cationically polymerizable compound containing a hydrogen-bonding functional group is 4 parts by weight, and a more preferable upper limit thereof is 20 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１５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 to the content of the photopolymerization initiator is 3 parts by weight, and a more preferable upper limit is 15 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、染料、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。
Moreover, the curable resin composition of the present invention may contain various known additives such as dyes, 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又は１０ｒｐｍの回転速度にて測定することができる。 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 used and measured at a rotational speed of 1 rpm or 10 rpm.
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又は１０ｒｐｍの回転速度にて測定することができる。 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 used and measured at a rotational speed of 1 rpm or 10 rpm.
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、接着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 adhesiveness and the hardness of 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１～７及び比較例１～４）
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１～７及び比較例１～４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。 (Examples 1 to 7 and Comparative Examples 1 to 4)
The curable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4 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.
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１～７及び比較例１～４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。 (Examples 1 to 7 and Comparative Examples 1 to 4)
The curable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4 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.
＜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.
（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.
（接着性）
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、カッターを用いて１ｃｍ間隔で碁盤目に切り込みを入れ、４個の試験箇所を設けた。試験箇所に対してテープ（ニチバン社製、「セロテープ（登録商標）Ｎｏ．４０５」）を貼り付けた後、テープを剥離し、剥離せずに基板上に残存した試験箇所の数を数えた。
基板上に残存した試験箇所数が４箇所であった場合を「○」、１箇所以上３箇所以下であった場合を「△」、０箇所であった場合を「×」として、接着性を評価した。 (Adhesiveness)
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 cut in a grid pattern at intervals of 1 cm using a cutter to provide four test points. After affixing a tape ("Cellotape (registered trademark) No. 405" manufactured by Nichiban Co., Ltd.) to the test points, the tape was peeled off, and the number of test points remaining on the substrate without being peeled off was counted.
If the number of test points remaining on the substrate was 4, "○", if there were 1 or more and 3 or less, "△", and if there were 0, "×", the adhesiveness was evaluated. evaluated.
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、カッターを用いて１ｃｍ間隔で碁盤目に切り込みを入れ、４個の試験箇所を設けた。試験箇所に対してテープ（ニチバン社製、「セロテープ（登録商標）Ｎｏ．４０５」）を貼り付けた後、テープを剥離し、剥離せずに基板上に残存した試験箇所の数を数えた。
基板上に残存した試験箇所数が４箇所であった場合を「○」、１箇所以上３箇所以下であった場合を「△」、０箇所であった場合を「×」として、接着性を評価した。 (Adhesiveness)
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 cut in a grid pattern at intervals of 1 cm using a cutter to provide four test points. After affixing a tape ("Cellotape (registered trademark) No. 405" manufactured by Nichiban Co., Ltd.) to the test points, the tape was peeled off, and the number of test points remaining on the substrate without being peeled off was counted.
If the number of test points remaining on the substrate was 4, "○", if there were 1 or more and 3 or less, "△", and if there were 0, "×", the adhesiveness was evaluated. evaluated.
本発明によれば、接着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 adhesiveness and the hardness of 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 (4)
- 硬化性樹脂と光重合開始剤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、脂環式エポキシ化合物、及び、水素結合性官能基とカチオン重合性基とを有し、水素結合性官能基価が１．０×１０－３ｍｏｌ／ｇ以上である化合物を含む
ことを特徴とする硬化性樹脂組成物。 A curable resin composition containing a curable resin and a photopolymerization initiator,
The curable resin has a polysilsesquioxane having a cationic polymerizable group, an alicyclic epoxy compound, a hydrogen-bonding functional group and a cationic polymerizable group, and has a hydrogen-bonding functional group value of 1.5. A curable resin composition comprising a compound having a concentration of 0×10 −3 mol/g or more. - 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記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, wherein the photopolymerization initiator contains a photocationic polymerization initiator.
- 請求項１又は２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 or 2.
- 請求項１又は２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 or 2.
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| JP2021-161676 | 2021-09-30 | ||
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| 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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2022
- 2022-09-29 WO PCT/JP2022/036380 patent/WO2023054563A1/en active Application Filing
- 2022-09-30 TW TW111137236A patent/TW202323462A/en unknown
Patent Citations (7)
| 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 |
| JP2018111786A (en) * | 2017-01-13 | 2018-07-19 | 三菱製紙株式会社 | Laminate |
| 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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| TW202323462A (en) | 2023-06-16 |
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