JPWO2020095627A1 - Photocurable composition - Google Patents
Photocurable composition Download PDFInfo
- Publication number
- JPWO2020095627A1 JPWO2020095627A1 JP2020556713A JP2020556713A JPWO2020095627A1 JP WO2020095627 A1 JPWO2020095627 A1 JP WO2020095627A1 JP 2020556713 A JP2020556713 A JP 2020556713A JP 2020556713 A JP2020556713 A JP 2020556713A JP WO2020095627 A1 JPWO2020095627 A1 JP WO2020095627A1
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate monomer
- acrylate
- photocurable composition
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 93
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 154
- 239000000178 monomer Substances 0.000 claims abstract description 106
- 239000002904 solvent Substances 0.000 claims abstract description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 11
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 28
- 239000010419 fine particle Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 12
- 230000001588 bifunctional effect Effects 0.000 claims description 11
- 229920000058 polyacrylate Polymers 0.000 claims description 10
- 238000001723 curing Methods 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 8
- 150000003138 primary alcohols Chemical class 0.000 claims description 8
- 150000003333 secondary alcohols Chemical class 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000000016 photochemical curing Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 30
- 238000003860 storage Methods 0.000 abstract description 10
- 238000001879 gelation Methods 0.000 abstract description 8
- 230000001678 irradiating effect Effects 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 40
- 239000011248 coating agent Substances 0.000 description 36
- 239000000047 product Substances 0.000 description 32
- 238000000034 method Methods 0.000 description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 23
- -1 unsaturated silane compound Chemical class 0.000 description 17
- 239000011347 resin Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 11
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000007529 inorganic bases Chemical class 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007646 gravure printing Methods 0.000 description 3
- 238000007645 offset printing Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- GZZRDBYXGPSMCR-UHFFFAOYSA-N 1-(2-chlorophenyl)-3,5-bis(trichloromethyl)-1,3,5-triazinane Chemical compound ClC1=CC=CC=C1N1CN(C(Cl)(Cl)Cl)CN(C(Cl)(Cl)Cl)C1 GZZRDBYXGPSMCR-UHFFFAOYSA-N 0.000 description 1
- NQUXRXBRYDZZDL-UHFFFAOYSA-N 1-(2-prop-2-enoyloxyethyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCOC(=O)C=C)C(O)=O NQUXRXBRYDZZDL-UHFFFAOYSA-N 0.000 description 1
- IZBKLNBONDCDHZ-UHFFFAOYSA-N 1-(4-methoxyphenyl)-3,5-bis(trichloromethyl)-1,3,5-triazinane Chemical compound C1=CC(OC)=CC=C1N1CN(C(Cl)(Cl)Cl)CN(C(Cl)(Cl)Cl)C1 IZBKLNBONDCDHZ-UHFFFAOYSA-N 0.000 description 1
- YQBKVGJYMFZJRZ-UHFFFAOYSA-N 1-(9h-carbazol-3-yl)-2-(dimethylamino)-2-methylpropan-1-one Chemical compound C1=CC=C2C3=CC(C(=O)C(C)(C)N(C)C)=CC=C3NC2=C1 YQBKVGJYMFZJRZ-UHFFFAOYSA-N 0.000 description 1
- RWEAGLZFYKQPLZ-UHFFFAOYSA-N 1-[4,5-diphenyl-2-(2,4,6-trichlorophenyl)imidazol-2-yl]-4,5-diphenyl-2-(2,4,6-trichlorophenyl)imidazole Chemical compound ClC1=CC(Cl)=CC(Cl)=C1C(N1C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC(Cl)=CC=2Cl)Cl)=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 RWEAGLZFYKQPLZ-UHFFFAOYSA-N 0.000 description 1
- WQHNZXURJISVCT-UHFFFAOYSA-N 1-butoxyethane-1,2-diol Chemical compound CCCCOC(O)CO WQHNZXURJISVCT-UHFFFAOYSA-N 0.000 description 1
- XKPKIGSYCLTAJO-UHFFFAOYSA-N 1-butoxypropane-1,2-diol Chemical compound CCCCOC(O)C(C)O XKPKIGSYCLTAJO-UHFFFAOYSA-N 0.000 description 1
- WWVBRUMYFUDEJQ-UHFFFAOYSA-N 1-ethoxyethane-1,2-diol Chemical compound CCOC(O)CO WWVBRUMYFUDEJQ-UHFFFAOYSA-N 0.000 description 1
- DMLNYLURSAKWRC-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O.CCOCC(C)O DMLNYLURSAKWRC-UHFFFAOYSA-N 0.000 description 1
- NVNRCMRKQVEOMZ-UHFFFAOYSA-N 1-ethoxypropane-1,2-diol Chemical compound CCOC(O)C(C)O NVNRCMRKQVEOMZ-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- CSCSROFYRUZJJH-UHFFFAOYSA-N 1-methoxyethane-1,2-diol Chemical compound COC(O)CO CSCSROFYRUZJJH-UHFFFAOYSA-N 0.000 description 1
- UYVDGHOUPDJWAZ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O.COCC(C)O UYVDGHOUPDJWAZ-UHFFFAOYSA-N 0.000 description 1
- OEYNWAWWSZUGDU-UHFFFAOYSA-N 1-methoxypropane-1,2-diol Chemical compound COC(O)C(C)O OEYNWAWWSZUGDU-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- NKVCQMYWYHDOOF-UHFFFAOYSA-N 1-phenoxyethane-1,2-diol Chemical compound OCC(O)OC1=CC=CC=C1 NKVCQMYWYHDOOF-UHFFFAOYSA-N 0.000 description 1
- BOXFZQOSJPDVOZ-UHFFFAOYSA-N 1-propan-2-ylxanthen-9-one Chemical compound O1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C BOXFZQOSJPDVOZ-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- VSLIZFRORGVSOU-UHFFFAOYSA-N 2,4-dichloro-n-[3-cyano-6-[(4-hydroxyphenyl)methyl]-5,7-dihydro-4h-thieno[2,3-c]pyridin-2-yl]-5-morpholin-4-ylsulfonylbenzamide Chemical compound C1=CC(O)=CC=C1CN1CC(SC(NC(=O)C=2C(=CC(Cl)=C(C=2)S(=O)(=O)N2CCOCC2)Cl)=C2C#N)=C2CC1 VSLIZFRORGVSOU-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- IETCLBGYEVVQQL-UHFFFAOYSA-N 2-(2,4-dibromophenyl)-1-[2-(2,4-dibromophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound BrC1=CC(Br)=CC=C1C(N1C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC(Br)=CC=2)Br)=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 IETCLBGYEVVQQL-UHFFFAOYSA-N 0.000 description 1
- JKQRNTIBBOTABS-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)-1-[2-(2,4-dichlorophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound ClC1=CC(Cl)=CC=C1C(N1C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC(Cl)=CC=2)Cl)=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 JKQRNTIBBOTABS-UHFFFAOYSA-N 0.000 description 1
- IAMASUILMZETHW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOCC(O)OC1=CC=CC=C1 IAMASUILMZETHW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 1
- QTUVQQKHBMGYEH-UHFFFAOYSA-N 2-(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC=NC=N1 QTUVQQKHBMGYEH-UHFFFAOYSA-N 0.000 description 1
- ANZONXRNCWFEIL-UHFFFAOYSA-N 2-[2-(2,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound COC1=CC(OC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 ANZONXRNCWFEIL-UHFFFAOYSA-N 0.000 description 1
- WPTIDPUGZXGDEV-UHFFFAOYSA-N 2-[2-(2-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound COC1=CC=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 WPTIDPUGZXGDEV-UHFFFAOYSA-N 0.000 description 1
- ZJRNXDIVAGHETA-UHFFFAOYSA-N 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=C(OC)C(OC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 ZJRNXDIVAGHETA-UHFFFAOYSA-N 0.000 description 1
- MCNPOZMLKGDJGP-UHFFFAOYSA-N 2-[2-(4-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 MCNPOZMLKGDJGP-UHFFFAOYSA-N 0.000 description 1
- OPCSNSADWKDQDU-UHFFFAOYSA-N 2-[2-(4-pentoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OCCCCC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 OPCSNSADWKDQDU-UHFFFAOYSA-N 0.000 description 1
- YCPMSWJCWKUXRH-UHFFFAOYSA-N 2-[4-[9-[4-(2-prop-2-enoyloxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethyl prop-2-enoate Chemical compound C1=CC(OCCOC(=O)C=C)=CC=C1C1(C=2C=CC(OCCOC(=O)C=C)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YCPMSWJCWKUXRH-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- WVRHNZGZWMKMNE-UHFFFAOYSA-N 2-hydroxy-1-[2-(2-methylpropyl)phenyl]-2-phenylethanone Chemical compound CC(C)CC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 WVRHNZGZWMKMNE-UHFFFAOYSA-N 0.000 description 1
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- 239000000057 synthetic resin Substances 0.000 description 1
- DPPBKURCPGWRJU-UHFFFAOYSA-N tert-butyl 4-(4-tert-butylperoxycarbonylbenzoyl)benzenecarboperoxoate Chemical compound C1=CC(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C=C1 DPPBKURCPGWRJU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WPZJSWWEEJJSIZ-UHFFFAOYSA-N tetrabromobisphenol-F Natural products C1=C(Br)C(O)=C(Br)C=C1CC1=CC(Br)=C(O)C(Br)=C1 WPZJSWWEEJJSIZ-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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- C08F290/06—Polymers provided for in subclass C08G
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
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Abstract
【課題】 保存安定性に優れ、且つ無機基材に対する密着性が良好な硬化膜を形成できる光硬化性組成物を提供すること。【解決手段】 光硬化性組成物は、シランカップリング剤(A)、リン酸(メタ)アクリレートモノマー(B)、前記(A)および前記(B)以外の(メタ)アクリレートモノマー(C)、光重合開始剤(D)、ならびに溶剤(E)を含んでおり、前記溶剤(E)がアルコールを含むから、光を照射することにより、無機基材に対する密着性が良く硬度が高い硬化膜を形成することができるとともに、時間経過に伴うゲル化が抑制された保存安定性が良好なものになる。【選択図】 なしPROBLEM TO BE SOLVED: To provide a photocurable composition capable of forming a cured film having excellent storage stability and good adhesion to an inorganic substrate. A photocurable composition comprises a silane coupling agent (A), a phosphoric acid (meth) acrylate monomer (B), the above (A) and a (meth) acrylate monomer (C) other than the above (B). Since the photopolymerization initiator (D) and the solvent (E) are contained and the solvent (E) contains alcohol, a cured film having good adhesion to an inorganic substrate and high hardness can be obtained by irradiating with light. It can be formed, and gelation with the passage of time is suppressed, resulting in good storage stability. [Selection diagram] None
Description
本発明は、金属やガラスなどの無機基材に対する密着性が良好であり、高い硬度を備えた硬化物を形成することができる、保存安定性に優れた光硬化性組成物に関する。 The present invention relates to a photocurable composition having good adhesion to an inorganic substrate such as metal or glass, capable of forming a cured product having high hardness, and excellent storage stability.
従来、建築資材や電気・電子分野などで用いられる各種樹脂板、ガラス板、金属板などの基材表面に皮膜を形成し、基材を傷付きや汚染などから守ることを目的としたコーティング剤の研究が種々行われている。コーティング剤としては熱硬化性樹脂や光硬化性樹脂が用いられるが、光硬化性樹脂を用いた場合には、表面硬度の高い硬化膜が得られることが多く、また光照射により瞬時に硬化し生産性が高いことから、有機基材の表面保護用として光硬化性樹脂がしばしば使用されている。しかし、光硬化性樹脂を用いた硬化膜は、一般に無機基材に対する密着性が十分ではないことが多い。このため、密着性を向上させるためのプライマー層が基材上に設けられ、その上に光硬化性樹脂を用いた硬化膜が形成されることがある。また、プライマー層を設けずに無機基材との密着性を付与するための方法として、例えば、金属に対する密着性に優れたものとするため、不飽和シラン化合物および不飽和リン酸エステルを感光性樹脂組成物に加えることが特許文献1に記載されている。 A coating agent that forms a film on the surface of base materials such as various resin plates, glass plates, and metal plates used in the fields of building materials and electrical and electronic fields, and protects the base material from scratches and contamination. Various studies have been conducted. A thermosetting resin or a photocurable resin is used as the coating agent, but when a photocurable resin is used, a cured film having a high surface hardness is often obtained, and it is instantly cured by light irradiation. Due to its high productivity, photocurable resins are often used to protect the surface of organic substrates. However, a cured film using a photocurable resin generally does not have sufficient adhesion to an inorganic substrate. Therefore, a primer layer for improving adhesion may be provided on the base material, and a cured film using a photocurable resin may be formed on the primer layer. Further, as a method for imparting adhesion to an inorganic base material without providing a primer layer, for example, an unsaturated silane compound and an unsaturated phosphoric acid ester are photosensitive in order to have excellent adhesion to a metal. Patent Document 1 describes that it is added to a resin composition.
また、特許文献2には、無機基材に対する密着性が良好な硬化膜の形成に用いられる光硬化性樹脂として、アクリル系樹脂(A)、エチレン性不飽和基を2個以上含有する不飽和化合物(B)、リン酸基含有エチレン性不飽和化合物(C)、およびシランカップリング剤(D)を含有してなる活性エネルギー線硬化性樹脂組成物が記載されているが、当該組成物から得られる硬化物は表面硬度が十分ではないという問題がある。 Further, Patent Document 2 describes an unsaturated resin (A) containing two or more ethylenically unsaturated groups as a photocurable resin used for forming a cured film having good adhesion to an inorganic substrate. An active energy ray-curable resin composition containing a compound (B), a phosphate group-containing ethylenically unsaturated compound (C), and a silane coupling agent (D) has been described. The obtained cured product has a problem that the surface hardness is not sufficient.
無機基材に対する密着性が良好な硬化膜を形成するためにシランカップリング剤とリン酸基を有するモノマーを添加すると、時間経過に伴って光硬化性樹脂組成物のゲル化が生じ、保存安定性が低下する場合がある。特許文献1〜2には、光硬化性樹脂組成物のゲル化の問題について記載されていない。
本発明の課題は、無機基材に対する密着性が良く、表面硬度の高い硬化膜を形成することができる、保存安定性の良好な光硬化性組成物を提供することにある。When a silane coupling agent and a monomer having a phosphoric acid group are added to form a cured film having good adhesion to an inorganic substrate, the photocurable resin composition gels over time and is stable in storage. Sex may be reduced. Patent Documents 1 and 2 do not describe the problem of gelation of the photocurable resin composition.
An object of the present invention is to provide a photocurable composition having good adhesion to an inorganic substrate, capable of forming a cured film having high surface hardness, and having good storage stability.
本発明者らは、前記問題点を解決すべく鋭意検討を行った結果、特定の成分の組み合わせにより無機基材に対する密着性が良好な高い硬度を備えた硬化膜を形成することができ、光硬化性組成物の成分を溶解する溶剤にアルコールを含有させることにより、時間経過に伴うゲル化を抑制できることを見出した。本発明は、当該知見に基づいたものであり、以下の構成を備えている。 As a result of diligent studies to solve the above problems, the present inventors have been able to form a cured film having high hardness with good adhesion to an inorganic substrate by combining specific components, and light It has been found that gelation over time can be suppressed by containing alcohol in a solvent that dissolves the components of the curable composition. The present invention is based on this finding and has the following configurations.
〔1〕 シランカップリング剤(A)、リン酸(メタ)アクリレートモノマー(B)、前記シランカップリング剤(A)および前記リン酸(メタ)アクリレートモノマー(B)以外の(メタ)アクリレートモノマー(C)、光重合開始剤(D)、ならびに溶剤(E)を含み、前記溶剤(E)はアルコールを含むことを特徴とする光硬化性組成物。 [1] A (meth) acrylate monomer other than the silane coupling agent (A), the phosphoric acid (meth) acrylate monomer (B), the silane coupling agent (A) and the phosphoric acid (meth) acrylate monomer (B). A photocurable composition containing C), a photopolymerization initiator (D), and a solvent (E), wherein the solvent (E) contains an alcohol.
〔2〕 前記アルコールが炭素数3〜6の第1級アルコールおよび/または炭素数3〜6の第2級アルコールである〔1〕に記載の光硬化性組成物。
〔3〕 前記溶剤(E)100重量部に対する前記アルコールの含有量が20重量部以上である〔1〕または〔2〕に記載の光硬化性組成物。[2] The photocurable composition according to [1], wherein the alcohol is a primary alcohol having 3 to 6 carbon atoms and / or a secondary alcohol having 3 to 6 carbon atoms.
[3] The photocurable composition according to [1] or [2], wherein the content of the alcohol with respect to 100 parts by weight of the solvent (E) is 20 parts by weight or more.
〔4〕 光硬化性組成物100重量部中の前記溶剤(E)の含有量が30重量部以上である〔1〕〜〔3〕のいずれか一項に記載の光硬化性組成物。
〔5〕 前記シランカップリング剤(A)が光重合性官能基を有する〔1〕〜〔4〕のいずれか一項に記載の光硬化性組成物。[4] The photocurable composition according to any one of [1] to [3], wherein the content of the solvent (E) in 100 parts by weight of the photocurable composition is 30 parts by weight or more.
[5] The photocurable composition according to any one of [1] to [4], wherein the silane coupling agent (A) has a photopolymerizable functional group.
〔6〕 前記(メタ)アクリレートモノマー(C)が単官能(メタ)アクリレートモノマー(C−1)および1種類以上の多官能(メタ)アクリレートモノマー(C−2)からなり、前記多官能(メタ)アクリレートモノマーが2〜10官能である〔1〕〜〔5〕のいずれか一項に記載の光硬化性組成物。
〔7〕 前記多官能(メタ)アクリレートモノマー(C−2)が少なくとも1種類のウレタンアクリレートモノマーを含む〔6〕に記載の光硬化性組成物。
〔8〕 前記多官能(メタ)アクリレートモノマー(C−2)に含まれる前記ウレタンアクリレートが、ウレタン結合および飽和環状脂肪族構造を有する2官能のウレタンアクリレートモノマーである〔7〕に記載の光硬化性組成物。[6] The (meth) acrylate monomer (C) is composed of a monofunctional (meth) acrylate monomer (C-1) and one or more kinds of polyfunctional (meth) acrylate monomers (C-2), and the polyfunctional (meth) acrylate monomer (C-2) is formed. ) The photocurable composition according to any one of [1] to [5], wherein the acrylate monomer is 2 to 10 functional.
[7] The photocurable composition according to [6], wherein the polyfunctional (meth) acrylate monomer (C-2) contains at least one type of urethane acrylate monomer.
[8] The photocuring according to [7], wherein the urethane acrylate contained in the polyfunctional (meth) acrylate monomer (C-2) is a bifunctional urethane acrylate monomer having a urethane bond and a saturated cyclic aliphatic structure. Sex composition.
〔9〕 前記多官能(メタ)アクリレートモノマー(C−2)が、ウレタン結合および飽和環状脂肪族構造を有する2官能のウレタンアクリレートモノマーと、ジペンタエリスリトールポリアクリレートモノマーとからなる〔8〕に記載の光硬化性組成物。
〔10〕 前記ジペンタエリスリトールポリアクリレートモノマーの含有量と前記ウレタンアクリレートモノマーの含有量との比率(ジペンタエリスリトールポリアクリレートモノマー/ウレタンアクリレートモノマー)が10/2〜10/10である〔9〕に記載の光硬化性組成物。[9] The polyfunctional (meth) acrylate monomer (C-2) is composed of a bifunctional urethane acrylate monomer having a urethane bond and a saturated cyclic aliphatic structure and a dipentaerythritol polyacrylate monomer [8]. Photocurable composition.
[10] The ratio of the content of the dipentaerythritol polyacrylate monomer to the content of the urethane acrylate monomer (dipentaerythritol polyacrylate monomer / urethane acrylate monomer) is 10/2 to 10/10 [9]. The photocurable composition according to the above.
〔11〕 さらに、無機微粒子(F)を含有する、〔1〕〜〔10〕のいずれか1項に記載の光硬化性組成物。
〔12〕 前記無機微粒子(F)が表面改質されたシリカ微粒子である〔11〕に記載の光硬化性組成物。[11] The photocurable composition according to any one of [1] to [10], which further contains inorganic fine particles (F).
[12] The photocurable composition according to [11], wherein the inorganic fine particles (F) are surface-modified silica fine particles.
〔13〕 〔1〕〜〔12〕のいずれか1項に記載の光硬化性組成物を硬化してなる硬化膜。
〔14〕 〔13〕に記載の硬化膜を含む積層体。[13] A cured film obtained by curing the photocurable composition according to any one of [1] to [12].
[14] A laminate containing the cured film according to [13].
本発明の光硬化性組成物は、シランカップリング剤(A)、リン酸(メタ)アクリレートモノマー(B)、前記(A)および前記(B)以外の(メタ)アクリレートモノマー(C)、光重合開始剤(D)ならびに溶剤(E)を含んでおり、アルコールを含む溶剤(E)を用いることで、光照射により、高い硬度を備えた無機基材に対する密着性が良好な硬化膜を形成できるとともに、ゲル化が抑制された保存安定性の良好なものとなる。 The photocurable composition of the present invention includes a silane coupling agent (A), a phosphoric acid (meth) acrylate monomer (B), a (meth) acrylate monomer (C) other than the above (A) and the above (B), and light. By using the polymerization initiator (D) and the solvent (E) and the alcohol-containing solvent (E), a cured film having high adhesion to an inorganic substrate having high hardness is formed by light irradiation. At the same time, gelation is suppressed and storage stability is good.
シランカップリング剤(A)、リン酸(メタ)アクリレートモノマー(B)、前記(A)および前記(B)以外の(メタ)アクリレートモノマー(C)、光重合開始剤(D)ならびに溶剤(E)を含み、前記溶剤(E)がアルコールを含んでいる本発明の光硬化性組成物(以下「組成物」ともいう。)について以下に説明する。 Silane coupling agent (A), phosphoric acid (meth) acrylate monomer (B), (meth) acrylate monomer (C) other than (A) and (B), photopolymerization initiator (D) and solvent (E). ), And the solvent (E) contains alcohol, the photocurable composition of the present invention (hereinafter, also referred to as “composition”) will be described below.
[シランカップリング剤(A)]
シランカップリング剤としては、公知のものを用いることができる。無機基材に対する密着性を良好にする観点から、光重合性官能基を有するシランカップリング剤が好ましい。本発明の組成物中の固形分100重量部に対するシランカップリング剤の配合量は、2〜10重量部が好ましく、2.3〜9重量部がより好ましく、2.5〜8重量部がさらに好ましい。シランカップリング剤(A)は1種のみを用いてもよく、2種以上を混合して用いてもよい。なお、1種のみを用いても2種以上を混合して用いてもよいことは、本発明の組成物中の他の成分についても同様である。組成物中の固形分とは、組成物を硬化させた硬化物を構成する成分をいう。[Silane Coupling Agent (A)]
As the silane coupling agent, known ones can be used. From the viewpoint of improving the adhesion to the inorganic substrate, a silane coupling agent having a photopolymerizable functional group is preferable. The blending amount of the silane coupling agent with respect to 100 parts by weight of the solid content in the composition of the present invention is preferably 2 to 10 parts by weight, more preferably 2.3 to 9 parts by weight, and further preferably 2.5 to 8 parts by weight. preferable. Only one type of silane coupling agent (A) may be used, or two or more types may be mixed and used. The same applies to the other components in the composition of the present invention that only one type may be used or two or more types may be mixed and used. The solid content in the composition refers to a component constituting a cured product obtained by curing the composition.
シランカップリング剤が備えることが好ましい光重合性官能基としては、(メタ)アクリル基、(メタ)アクリルアミド基、ビニルエーテル基、ビニルエステル基、アリルエーテル基、アリルエステル基などが挙げられる。 Examples of the photopolymerizable functional group preferably contained in the silane coupling agent include a (meth) acrylic group, a (meth) acrylamide group, a vinyl ether group, a vinyl ester group, an allyl ether group, and an allyl ester group.
光重合性官能基を備えるシランカップリング剤には、シランカップリング剤および(メタ)アクリレートモノマーにも該当し得る化合物が存在する。このような化合物は、本発明ではシランカップリング剤にのみ該当し、(メタ)アクリレートモノマーに該当しないものとする。例えば、シランカップリング剤が(メタ)アクリル基を備えた(メタ)アクリレートモノマーでもある場合、本発明において当該化合物はシランカップリング剤であり、(メタ)アクリレートモノマーではないものとする。 As the silane coupling agent having a photopolymerizable functional group, there are compounds that can also correspond to the silane coupling agent and the (meth) acrylate monomer. In the present invention, such a compound corresponds only to a silane coupling agent and does not correspond to a (meth) acrylate monomer. For example, when the silane coupling agent is also a (meth) acrylate monomer having a (meth) acrylic group, the compound in the present invention is a silane coupling agent, not a (meth) acrylate monomer.
光重合性官能基を有するシランカップリング剤としては、3−メタクリロキシプロピルトリメトキシシラン、3−メタクリロキシプロピルメチルジメトキシシラン、3−メタクリロキシプロピルトリエトキシシラン、3−メタクリロキシプロピルメチルジエトキシシラン、3−アクリロキシプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシランなどが挙げられる。 Examples of the silane coupling agent having a photopolymerizable functional group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. , 3-Acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and the like.
[リン酸(メタ)アクリレートモノマー(B)]
リン酸(メタ)アクリレートモノマーは、リン酸基を有するアクリレートおよび/またはメタクリレートである。上述したシランカップリング剤同様、リン酸(メタ)アクリレートモノマーにあたる化合物は、本発明において(メタ)アクリレートモノマーにはあたらないものとする。組成物中の固形分100重量部に対するリン酸(メタ)アクリレートモノマーの含有量は、0.1〜5重量部が好ましく0.3〜3重量部がより好ましく、0.5〜2重量部がさらに好ましい。[Phosphoric acid (meth) acrylate monomer (B)]
The phosphoric acid (meth) acrylate monomer is an acrylate and / or methacrylate having a phosphoric acid group. Similar to the above-mentioned silane coupling agent, the compound corresponding to the phosphoric acid (meth) acrylate monomer does not correspond to the (meth) acrylate monomer in the present invention. The content of the phosphoric acid (meth) acrylate monomer with respect to 100 parts by weight of the solid content in the composition is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 3 parts by weight, and 0.5 to 2 parts by weight. More preferred.
[(メタ)アクリレートモノマー(C)]
(メタ)アクリレートモノマー(C)は、モノマーからなるものであり、通常、重量平均分子量が70〜10,000であり、好ましくは100〜9,000であり、さらに好ましくは200〜7000である。組成物中の固形分100重量部に対する(メタ)アクリレートモノマー(C)の含有量は、20〜90重量部が好ましく、30〜80重量部がより好ましく、40〜75重量部がさらに好ましい。[(Meta) Acrylate Monomer (C)]
The (meth) acrylate monomer (C) is composed of a monomer, and usually has a weight average molecular weight of 70 to 10,000, preferably 100 to 9,000, and more preferably 200 to 7,000. The content of the (meth) acrylate monomer (C) with respect to 100 parts by weight of the solid content in the composition is preferably 20 to 90 parts by weight, more preferably 30 to 80 parts by weight, still more preferably 40 to 75 parts by weight.
上述したように、本発明では(メタ)アクリレートモノマー(C)は、シランカップリング剤(A)およびリン酸(メタ)アクリレートモノマー(B)に該当するものを含まない。(メタ)アクリレートモノマー(C)は、1種からなるものでもよいが、無機基材への接着性の良好な表面硬度が高い硬化膜を得る観点から、単官能(メタ)アクリレートモノマー(C−1)および多官能(メタ)アクリレートモノマー(C−2)を含有するものが好ましい。組成物中の単官能(メタ)アクリレートモノマーが硬化物の無機基材に対する密着性の向上に寄与するとともに、多官能(メタ)アクリレートモノマーが硬化物の硬度の向上に寄与すると考えられる。 As described above, in the present invention, the (meth) acrylate monomer (C) does not include those corresponding to the silane coupling agent (A) and the phosphoric acid (meth) acrylate monomer (B). The (meth) acrylate monomer (C) may consist of one type, but from the viewpoint of obtaining a cured film having good adhesion to an inorganic substrate and high surface hardness, a monofunctional (meth) acrylate monomer (C-) Those containing 1) and a polyfunctional (meth) acrylate monomer (C-2) are preferable. It is considered that the monofunctional (meth) acrylate monomer in the composition contributes to the improvement of the adhesion of the cured product to the inorganic substrate, and the polyfunctional (meth) acrylate monomer contributes to the improvement of the hardness of the cured product.
[単官能(メタ)アクリレートモノマー(C−1)]
単官能(メタ)アクリレートモノマーとしては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ノルマルプロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、ノルマルブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、sec−ブチル(メタ)アクリレート、tert−ブチル(メタ)アクリレート、ノルマルペンチル(メタ)アクリレート、イソペンチル(メタ)アクリレート、ネオペンチル(メタ)アクリレート、ノルマルヘキシル(メタ)アクリレート、ノルマルヘプチル(メタ)アクリレート、ノルマルオクチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、ノルマルデシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、フェニルフェノール(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、ベンジル(メタ)アクリレート、イソボルニル(メタ)アクリレート、アダマンチル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンタニルオキシエチル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、ヒドロキシブチル(メタ)アクリレート、2−ヒドロキシ−3−フェノキシプロピル(メタ)アクリレート、グリシジル(メタ)アクリレート、メトキシエチレングリコール(メタ)アクリレート、エトキシエチレングリコール(メタ)アクリレート、ブトキシエチレングリコール(メタ)アクリレート、フェノキシエチレングリコール(メタ)アクリレート、ノニルフェノールエチレングリコール(メタ)アクリレート、2−エチルヘキシルエチレングリコール(メタ)アクリレート、メトキシプロピレングリコール(メタ)アクリレート、エトキシプロピレングリコール(メタ)アクリレート、ブトキシプロピレングリコール(メタ)アクリレート、メトキシポリエチレングリコール(メタ)アクリレート、エトキシポリエチレングリコール(メタ)アクリレート、ブトキシポリエチレングリコール(メタ)アクリレート、フェノキシポリエチレングリコール(メタ)アクリレート、ノニルフェノールポリエチレングリコール(メタ)アクリレート、2−エチルヘキシルポリエチレングリコール(メタ)アクリレート、メトキシポリプロピレングリコール(メタ)アクリレート、エトキシポリプロピレングリコール(メタ)アクリレート、ブトキシポリプロピレングリコール(メタ)アクリレート、(メタ)アクリル酸、(メタ)アクリロイルオキシエチルコハク酸、(メタ)アクリロイルオキシエチルフタル酸、2−(メタ)アクリロイルオキシエチル−2−ヒドロキシエチルフタル酸、(メタ)アクリロイルオキシエチルヘキサヒドロフタル酸、(メタ)アクリロイルモルホリン、N,N−ジメチル(メタ)アクリルアミド、N,N−ジエチル(メタ)アクリルアミド、N−イソプロピル(メタ)アクリルアミド、ヒドロキシエチル(メタ)アクリルアミドなどが挙げられる。[Monofunctional (meth) acrylate monomer (C-1)]
Examples of the monofunctional (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, normal propyl (meth) acrylate, isopropyl (meth) acrylate, normal butyl (meth) acrylate, isobutyl (meth) acrylate, and sec-. Butyl (meth) acrylate, tert-butyl (meth) acrylate, normal pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, normal hexyl (meth) acrylate, normal heptyl (meth) acrylate, normal octyl (meth) Meta) acrylate, 2-ethylhexyl (meth) acrylate, normal decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, phenylphenol (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclo Penthenyloxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethylene Glycol (meth) acrylate, ethoxyethylene glycol (meth) acrylate, butoxyethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, nonylphenolethylene glycol (meth) acrylate, 2-ethylhexylethylene glycol (meth) acrylate, methoxypropylene Glycol (meth) acrylate, ethoxypropylene glycol (meth) acrylate, butoxypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol ( Meta) Acrylate, Nonylphenol Polyethylene Glycol (Meta) Ac Relate, 2-ethylhexyl polyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, butoxypolypropylene glycol (meth) acrylate, (meth) acrylic acid, (meth) acryloyloxyethyl succinic acid , (Meta) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, (meth) acryloyloxyethyl hexahydrophthalic acid, (meth) acryloylmorpholin, N, N-dimethyl (meth) ) Acryloyl, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, hydroxyethyl (meth) acrylamide and the like.
組成物中の固形分100重量部に対する単官能(メタ)アクリレートモノマーの含有量は、2〜30重量部が好ましく、3〜20重量部がより好ましく、4〜15重量部がさらに好ましい。 The content of the monofunctional (meth) acrylate monomer in the composition with respect to 100 parts by weight is preferably 2 to 30 parts by weight, more preferably 3 to 20 parts by weight, still more preferably 4 to 15 parts by weight.
[多官能(メタ)アクリレートモノマー(C−2)]
無機基材に対する接着性の良好で表面硬度が高い硬化物を得る観点から、多官能(メタ)アクリレートモノマーの備える(メタ)アクリル基の数が2〜10個の2〜10官能(メタ)アクリレートモノマーが好ましい。[Polyfunctional (meth) acrylate monomer (C-2)]
From the viewpoint of obtaining a cured product having good adhesiveness to an inorganic substrate and high surface hardness, the polyfunctional (meth) acrylate monomer contains 2 to 10 functional (meth) acrylates having 2 to 10 (meth) acrylic groups. Monomers are preferred.
組成物中の固形分100重量部に対する多官能(メタ)アクリレートモノマーの含有量は、15〜80重量部が好ましく、20〜70重量部がより好ましく、25〜65重量部がさらに好ましい。 The content of the polyfunctional (meth) acrylate monomer in the composition with respect to 100 parts by weight is preferably 15 to 80 parts by weight, more preferably 20 to 70 parts by weight, still more preferably 25 to 65 parts by weight.
2官能(メタ)アクリレートモノマーとしては、1,4−ブタンジオールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、1,9−ノナンジオールジ(メタ)アクリレート、1,10−デカンジオールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、3−メチルペンタンジオールジ(メタ)アクリレート、ポリテトラメチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、エトキシ化ポリプロピレングリコールジ(メタ)アクリレート、ビス[(メタ)アクリロイルオキシエトキシ]ビスフェノールA、ビス[(メタ)アクリロイルオキシエトキシ]水添ビスフェノールA、ビス[(メタ)アクリロイルオキシエトキシ]テトラブロモビスフェノールA、ビス[(メタ)アクリロイルオキシプロポキシ]ビスフェノールA、プロポキシ化エトキシ化ビスフェノールAジ(メタ)アクリレート、ビス[(メタ)アクリロイルオキシエトキシ]ビスフェノールF、ビス[(メタ)アクリロイルオキシエトキシ]水添ビスフェノールF、ビス[(メタ)アクリロイルオキシエトキシ]テトラブロモビスフェノールF、ビス[(メタ)アクリロイルオキシプロポキシ]ビスフェノールF、グリセリンジ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、トリシクロデカンジメタノールジ(メタ)アクリレート、9,9−ビス[4−(2−アクリロイルオキシエトキシ)フェニル]フルオレン、ヒドロキシピバリン酸ネオペンチルグリコールジ(メタ)アクリレートなどが挙げられる。 Examples of the bifunctional (meth) acrylate monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-. Decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, polytetramethylene glycol di ( Meta) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, bis [(meth) acryloyloxyethoxy] bisphenol A, bis [(meth) acryloyloxyethoxy) ] Hydrogenated bisphenol A, bis [(meth) acryloyloxyethoxy] tetrabromobisphenol A, bis [(meth) acryloyloxypropoxy] bisphenol A, propoxylated ethoxylated bisphenol A di (meth) acrylate, bis [(meth) acryloyl Oxyethoxy] bisphenol F, bis [(meth) acryloyl oxyethoxy] hydrogenated bisphenol F, bis [(meth) acryloyl oxyethoxy] tetrabromo bisphenol F, bis [(meth) acryloyl oxypropoxy] bisphenol F, glycerinji (meth) ) Acrylate, trimethylolpropandi (meth) acrylate, pentaerythritol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, Examples thereof include neopentyl glycol di (meth) acrylate of hydroxypivalate.
3〜8官能(メタ)アクリルモノマーとしては、グリセリントリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、エトキシ化グリセリントリ(メタ)アクリレート、エトキシ化トリメチロールプロパントリ(メタ)アクリレート、エトキシ化ペンタエリスリトールトリ(メタ)アクリレート、プロポキシ化グリセリントリ(メタ)アクリレート、プロポキシ化トリメチロールプロパントリ(メタ)アクリレート、プロポキシ化ペンタエリスリトールトリ(メタ)アクリレート、ジグリセリンテトラ(メタ)アクリレート、ジメチロールプロパンテトラ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、エトキシ化ジグリセリンテトラ(メタ)アクリレート、エトキシ化ジメチロールプロパンテトラ(メタ)アクリレート、エトキシ化ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリペンタエリスリトールオクタ(メタ)アクリレートなどが挙げられる。 Examples of the 3 to 8-functional (meth) acrylic monomer include glycerintri (meth) acrylate, trimethylolpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated glycerintri (meth) acrylate, and ethoxylated trimethylolpropane. Tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, propoxylated glycerin tri (meth) acrylate, propoxylated trimethylol propantri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, diglycerin tetra ( Meta) acrylate, dimethylol propanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated diglycerin tetra (meth) acrylate, ethoxylated dimethylol propanetetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) Examples thereof include acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tripentaerythritol octa (meth) acrylate.
上記多官能(メタ)アクリレートモノマーは、無機基材に対する接着性の良好な硬化物を得る観点から、少なくとも1種類のウレタンアクリレートモノマーを含むことが好ましい。ウレタンアクリレートモノマーとしては、ウレタン結合および飽和環状脂肪族構造を有する2官能のウレタンアクリレートモノマーが好ましく用いられる。当該2官能のウレタンアクリレートモノマーの製造方法として、例えば、特開2017−78840に製造例1として記載されている製造方法を用いることができる。 The polyfunctional (meth) acrylate monomer preferably contains at least one type of urethane acrylate monomer from the viewpoint of obtaining a cured product having good adhesiveness to an inorganic substrate. As the urethane acrylate monomer, a bifunctional urethane acrylate monomer having a urethane bond and a saturated cyclic aliphatic structure is preferably used. As a method for producing the bifunctional urethane acrylate monomer, for example, the production method described as Production Example 1 in Japanese Patent Application Laid-Open No. 2017-78840 can be used.
無機基材に対する接着性の良好な硬化物を得る観点から、(メタ)アクリル基の数が異なる複数種の多官能(メタ)アクリレートモノマーを併用することがさらに好ましい。複数種の多官能(メタ)アクリレートモノマーを用いる場合、官能基数が2のものと、官能基数が5〜6のものとを併用することが好ましい。好ましい組み合わせとして、2官能のウレタンアクリレートモノマーと5および/または6官能のジペンタエリスリトールポリアクリレートモノマーとの組合せを挙げることができる。 From the viewpoint of obtaining a cured product having good adhesiveness to an inorganic substrate, it is more preferable to use a plurality of types of polyfunctional (meth) acrylate monomers having different numbers of (meth) acrylic groups in combination. When a plurality of types of polyfunctional (meth) acrylate monomers are used, it is preferable to use those having 2 functional groups and those having 5 to 6 functional groups in combination. Preferred combinations include a combination of a bifunctional urethane acrylate monomer and a 5-and / or hexafunctional dipentaerythritol polyacrylate monomer.
組成物中の固形分100重量部に対する2官能のウレタンアクリレートモノマーの含有量は、3〜40重量部が好ましく、4〜30重量部がより好ましく、5〜20重量部がさらに好ましい。
組成物中の固形分100重量部に対する5および/または6官能のジペンタエリスリトールポリアクリレートモノマーの含有量は、10〜60重量部が好ましく、12〜50重量部がより好ましく、15〜45重量部がさらに好ましい。The content of the bifunctional urethane acrylate monomer with respect to 100 parts by weight of the solid content in the composition is preferably 3 to 40 parts by weight, more preferably 4 to 30 parts by weight, still more preferably 5 to 20 parts by weight.
The content of the 5- and / or hexafunctional dipentaerythritol polyacrylate monomer in the composition is preferably 10 to 60 parts by weight, more preferably 12 to 50 parts by weight, and 15 to 45 parts by weight with respect to 100 parts by weight of the solid content. Is even more preferable.
組成物がジペンタエリスリトールポリアクリレートモノマーとウレタンアクリレートモノマーとを含有する場合、両者の含有量(重量部)の比率(ジペンタエリスリトールポリアクリレート/ウレタンアクリレート)は、10/2〜10/10が好ましく、10/3〜10/6がより好ましい。 When the composition contains a dipentaerythritol polyacrylate monomer and a urethane acrylate monomer, the ratio of the contents (parts by weight) of both (dipentaerythritol polyacrylate / urethane acrylate) is preferably 10/2 to 10/10. More preferably, 10/3 to 10/6.
上記ウレタンアクリレートモノマーは、市販品として、例えば、新中村化学工業(株)製、製品名:UA−200PA、UA−160TM、UA−290TM、UA4200、UA4400、UA−122P;日本合成化学工業(株)製、製品名:紫光シリーズUV−6630B、UV−6640B、UV−3000B、UV−3200B、UV−3300B、UV−3700B;亜細亜工業(株)製、製品名:EXCELATEシリーズRUA−012、SUA−008、SUA−023、SUA−074;ダイセル・オルネクス(株)製、製品名:EBECRYL230、EBECRYL270、EBECRYL4858、EBECRYL8402、EBECRYL8804、EBECRYL8807、EBECRYL9270、KRM8191などが挙げられる。また、アクリル酸(2−ヒドロキシエチル)とイソシアン酸(3−イソシアナトメチル−3,5,5−トリメチルシクロヘキシル)とトリシクロ[5.2.1.02,6]デカン−4,8−ジメタノールとヘキサノ−6−ラクトンとの反応生成物を用いてもよい。The urethane acrylate monomer is a commercially available product, for example, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product names: UA-200PA, UA-160TM, UA-290TM, UA4200, UA4400, UA-122P; Nippon Synthetic Chemical Industry Co., Ltd. ), Product name: Shikou series UV-6630B, UV-6640B, UV-3000B, UV-3200B, UV-3300B, UV-3700B; 008, SUA-023, SUA-074; manufactured by Daicel Ornex Co., Ltd., product names: EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8807, EBECRYL9270, KR81, etc. In addition, acrylic acid (2-hydroxyethyl), isocyanic acid (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl) and tricyclo [5.2.1.0 2,6 ] decane-4,8-di. The reaction product of methanol and hexano-6-lactone may be used.
[光重合開始剤(D)]
本発明の感光性組成物に含有される光重合開始剤は、本発明の組成物が含有するモノマー成分の重合を開始し得る、紫外線、可視光線、電磁波等の照射によってラジカルを発生する化合物であればよく、一般に用いられるものを使用できる。光重合開始剤の具体例としては、ベンゾフェノン、ミヒラーズケトン、4,4′−ビス(ジエチルアミノ)ベンゾフェノン、キサントン、チオキサントン、イソプロピルキサントン、2,4−ジエチルチオキサントン、2−エチルアントラキノン、アセトフェノン、2−ヒドロキシ−2−メチルプロピオフェノン、2−ヒドロキシ−2−メチル−4′−イソプロピルプロピオフェノン、1−ヒドロキシシクロヘキシルフェニルケトン、イソプロピルベンゾインエーテル、イソブチルベンゾインエーテル、2,2−ジエトキシアセトフェノン、2,2−ジメトキシ−2−フェニルアセトフェノン、1,1′−(メチレン−ジ−4,1−フェニレン)ビス(2−ヒドロキシ−2−メチル−1−プロパノン)、カンファーキノン、ベンズアントロン、2−メチル−1−[4−(メチルチオ)フェニル]−2−モルホリノ−1−プロパノン、2−ベンジル−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン−1,4−ジメチルアミノ安息香酸エチル、4−ジメチルアミノ安息香酸イソアミル、4,4′−ジ(tert−ブチルペルオキシカルボニル)ベンゾフェノン、3,4,4′−トリ(tert−ブチルペルオキシカルボニル)ベンゾフェノン、2,4,6−トリメチルベンゾイルジフェニルフォスフィンオキサイド、2−(4′−メトキシスチリル)−4,6−ビス(トリクロロメチル)−s−トリアジン、2−(3′,4′−ジメトキシスチリル)−4,6−ビス(トリクロロメチル)−s−トリアジン、2−(2′,4′−ジメトキシスチリル)−4,6−ビス(トリクロロメチル)−s−トリアジン、2−(2′−メトキシスチリル)−4,6−ビス(トリクロロメチル)−s−トリアジン、2−(4′−ペンチルオキシスチリル)−4,6−ビス(トリクロロメチル)−s−トリアジン、4−[p−N,N−ジ(エトキシカルボニルメチル)]−2,6−ジ(トリクロロメチル)−s−トリアジン、1,3−ビス(トリクロロメチル)−5−(2′−クロロフェニル)−s−トリアジン、1,3−ビス(トリクロロメチル)−5−(4′−メトキシフェニル)−s−トリアジン、2−(p−ジメチルアミノスチリル)ベンズオキサゾール、2−(p−ジメチルアミノスチリル)ベンズチアゾール、2−メルカプトベンゾチアゾール、3,3′−カルボニルビス(7−ジエチルアミノクマリン)、2−(o−クロロフェニル)−4,4′,5,5′−テトラフェニル−1,2′−ビイミダゾール、2,2′−ビス(2−クロロフェニル)−4,4′,5,5′−テトラキス(4−エトキシカルボニルフェニル)−1,2′−ビイミダゾール、2,2′−ビス(2,4−ジクロロフェニル)−4,4′,5,5′−テトラフェニル−1,2′−ビイミダゾール、2,2′−ビス(2,4−ジブロモフェニル)−4,4′,5,5′−テトラフェニル−1,2′−ビイミダゾール、2,2′−ビス(2,4,6−トリクロロフェニル)−4,4′,5,5′−テトラフェニル−1,2′−ビイミダゾール、3−(2−メチル−2−ジメチルアミノプロピオニル)カルバゾール、3,6−ビス(2−メチル−2−モルホリノプロピオニル)−9−n−ドデシルカルバゾール、ビス(η5−2,4−シクロペンタジエン−1−イル)−ビス(2,6−ジフルオロ−3−(1H−ピロール−1−イル)−フェニル)チタニウム、3,3′,4,4′−テトラ(tert−ブチルペルオキシカルボニル)ベンゾフェノン、3,3′,4,4′−テトラ(tert−ヘキシルペルオキシカルボニル)ベンゾフェノン、3,3′−ジ(メトキシカルボニル)−4,4′−ジ(tert−ブチルペルオキシカルボニル)ベンゾフェノン、3,4′−ジ(メトキシカルボニル)−4,3′−ジ(tert−ブチルペルオキシカルボニル)ベンゾフェノン、4,4′−ジ(メトキシカルボニル)−3,3′−ジ(tert−ブチルペルオキシカルボニル)ベンゾフェノンなどである。市販品として、例えば、BASF製、製品名:Irgacure127、Irgacure184、IGM Resins B.V.製、製品名:Omnirad127、Omnirad184などが挙げられる。[Photopolymerization Initiator (D)]
The photopolymerization initiator contained in the photosensitive composition of the present invention is a compound that can initiate polymerization of the monomer component contained in the composition of the present invention and generates radicals by irradiation with ultraviolet rays, visible light, electromagnetic waves, or the like. Anything that is generally used can be used. Specific examples of the photopolymerization initiator include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-. 2-Methylpropiophenone, 2-Hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2- Dimethoxy-2-phenylacetophenone, 1,1'-(methylene-di-4,1-phenylene) bis (2-hydroxy-2-methyl-1-propanone), camphorquinone, benzanthron, 2-methyl-1- [4- (Methylthio) Phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4-dimethylaminoethyl benzoate, 4-dimethyl Isoamyl aminobenzoate, 4,4'-di (tert-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine , 2- (2', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pn, N-di (ethoxycarbonylmethyl)] -2,6-di ( Trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -S-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2 − (O-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole , 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6- Trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-) 2-morpholinopropionyl) -9-n-dodecylcarbazole, bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl ) Titanium, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3'-di ( Methoxycarbonyl) -4,4'-di (tert-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di (tert-butylperoxycarbonyl) benzophenone, 4,4'- Di (methoxycarbonyl) -3,3'-di (tert-butylperoxycarbonyl) benzophenone and the like. As commercially available products, for example, manufactured by BASF, product names: Irgacure 127, Irgacure 184, IGM Resins B.I. V. Manufacture, product name: Omnirad 127, Omnirad 184 and the like.
組成物中の固形分100重量部に対する光重合開始剤の含有量は、1〜15重量部が好ましく、1.5〜10重量部がより好ましく、2〜7.5重量部がさらに好ましい。 The content of the photopolymerization initiator in the composition with respect to 100 parts by weight of the solid content is preferably 1 to 15 parts by weight, more preferably 1.5 to 10 parts by weight, still more preferably 2 to 7.5 parts by weight.
[溶剤(E)]
本発明の組成物は、上述した(A)から(D)の成分を溶解する溶剤を含有している。溶剤が含有するアルコールとして、例えば、1−プロパノール、1−ブタノールなどの第1級アルコール類、2−プロパノール、2−ブタノールなどの第2級アルコール類、等が挙げられ、一価のアルコールが好ましい。溶剤100重量部におけるアルコールの含有量の下限は、20重量部以上が好ましく、25重量部以上がより好ましく、30重量部以上がさらに好ましい。また、溶剤100重量部におけるアルコールの含有量の上限は、90重量部以下が好ましく、80重量部以下がより好ましく、70重量部以下がさらに好ましい。[Solvent (E)]
The composition of the present invention contains a solvent that dissolves the above-mentioned components (A) to (D). Examples of the alcohol contained in the solvent include primary alcohols such as 1-propanol and 1-butanol, secondary alcohols such as 2-propanol and 2-butanol, and the like, and monohydric alcohols are preferable. .. The lower limit of the alcohol content in 100 parts by weight of the solvent is preferably 20 parts by weight or more, more preferably 25 parts by weight or more, and further preferably 30 parts by weight or more. The upper limit of the alcohol content in 100 parts by weight of the solvent is preferably 90 parts by weight or less, more preferably 80 parts by weight or less, and further preferably 70 parts by weight or less.
溶剤は、アルコール以外に他の溶媒を含有していても良い。他の溶媒として、例えば、プロピレングリコールモノメチルエーテル(1−メトキシ−2−プロパノール)、プロピレングリコールモノエチルエーテル(1−エトキシ−2−プロパノール)などのグリコールエーテル類、シクロペンチルメチルエーテルなどのエーテル類2−ヒドロキシイソ酪酸メチルなどのエステル類、ケトン類、炭化水素類、ハロゲン化炭化水素類、ニトリル類、カーボネート類などが挙げられる。本発明において、グリコールエーテル類はアルコールに含まれないものとする。 The solvent may contain other solvents other than alcohol. As other solvents, for example, glycol ethers such as propylene glycol monomethyl ether (1-methoxy-2-propanol) and propylene glycol monoethyl ether (1-ethoxy-2-propanol), ethers such as cyclopentyl methyl ether 2- Examples thereof include esters such as methyl hydroxyisobutyrate, ketones, hydrocarbons, halogenated hydrocarbons, nitriles, carbonates and the like. In the present invention, glycol ethers are not included in alcohol.
組成物100重量部に対する溶剤の含有量は、30〜95重量部が好ましく、35〜90重量部がより好ましく、40〜85重量部がさらに好ましい。 The content of the solvent with respect to 100 parts by weight of the composition is preferably 30 to 95 parts by weight, more preferably 35 to 90 parts by weight, still more preferably 40 to 85 parts by weight.
組成物の保存安定性の観点から、溶剤が第1級アルコールおよび/または第2級アルコールを含んでいること、すなわち、第1級アルコールおよび第2級アルコールからなる群から選ばれた1種または2種以上を含んでいることが好ましい。溶剤が第1級アルコールおよび/または第2級アルコールを含有することにより、組成物のゲル化を抑制または防止することができる。第1級アルコールおよび/または第2級アルコールの含有量は、組成物が含有する他の成分の種類や量に応じて適宜調整すればよい。 From the viewpoint of storage stability of the composition, the solvent contains a primary alcohol and / or a secondary alcohol, that is, one selected from the group consisting of primary alcohols and secondary alcohols or It is preferable that two or more kinds are contained. When the solvent contains a primary alcohol and / or a secondary alcohol, gelation of the composition can be suppressed or prevented. The content of the primary alcohol and / or the secondary alcohol may be appropriately adjusted according to the type and amount of other components contained in the composition.
外観の良好な硬化物を効率良く製造する観点から、第1級アルコールおよび/または第2級アルコールは、炭素数3〜6のものが好ましい。炭素数が2以下のものは沸点が低く揮発速度が高いことから、組成物から硬化膜を形成する際、蒸発潜熱によって結露が生じ、塗膜の白濁など外観不良の原因となるおそれがある。また,炭素数が7以上のものは沸点が高いことから、組成物から硬化膜を形成する際における溶剤の十分な乾燥が困難であり、製造効率の低下を招くおそれがある。 From the viewpoint of efficiently producing a cured product having a good appearance, the primary alcohol and / or the secondary alcohol preferably has 3 to 6 carbon atoms. Since a material having 2 or less carbon atoms has a low boiling point and a high volatilization rate, dew condensation may occur due to latent heat of vaporization when forming a cured film from the composition, which may cause poor appearance such as white turbidity of the coating film. Further, since a solvent having 7 or more carbon atoms has a high boiling point, it is difficult to sufficiently dry the solvent when forming a cured film from the composition, which may lead to a decrease in production efficiency.
[無機微粒子(F)]
本発明の組成物は、高い硬度を備えた硬化膜を形成するために、上述した(A)〜(E)の各成分に加えてさらに、無機微粒子を含有することが好ましい。無機微粒子としては、シリカ微粒子、アルミナ微粒子、ジルコニア微粒子、酸化チタン微粒子などが挙げられる。透明性と高い硬度を備えた硬化膜を形成する観点から、無機微粒子は表面改質されたシリカ微粒子が好ましい。ここで、「表面改質」とは、シリカ表面の全体又は一部をシリカ以外の素材で覆うことにより、シリカを変質させることをいう。シリカ表面を覆う素材として、シランカップリング剤などが挙げられる。[Inorganic fine particles (F)]
The composition of the present invention preferably further contains inorganic fine particles in addition to the above-mentioned components (A) to (E) in order to form a cured film having high hardness. Examples of the inorganic fine particles include silica fine particles, alumina fine particles, zirconia fine particles, and titanium oxide fine particles. From the viewpoint of forming a cured film having transparency and high hardness, the inorganic fine particles are preferably surface-modified silica fine particles. Here, "surface modification" means that silica is altered by covering the entire or part of the silica surface with a material other than silica. Examples of the material covering the silica surface include a silane coupling agent.
無機微粒子の平均粒径は、レーザー光を用いた光散乱法による球相当径(メジアン径、D50)をいい、1〜100nmが好ましく、透明性の観点から、1〜40nmであることがより好ましく、さらに好ましくは1〜20nmである。また、粒度分布は狭いほうが好ましい。
無機微粒子の形状は特に限定されないが、球状、不定形、りん片状等のいずれの形態であってもよい。密着性向上、透明性の観点から、球状が好ましい。
本発明の組成物において、組成物中の固形分100重量部に対する無機微粒子の含有量は、5〜50重量部であることが好ましく、10〜45重量部であることがより好ましい。The average particle size of the inorganic fine particles refers to the equivalent sphere diameter (median diameter, D50) by a light scattering method using laser light, preferably 1 to 100 nm, and more preferably 1 to 40 nm from the viewpoint of transparency. , More preferably 1 to 20 nm. Further, it is preferable that the particle size distribution is narrow.
The shape of the inorganic fine particles is not particularly limited, but may be any shape such as spherical, amorphous, and flaky. From the viewpoint of improving adhesion and transparency, a spherical shape is preferable.
In the composition of the present invention, the content of the inorganic fine particles with respect to 100 parts by weight of the solid content in the composition is preferably 5 to 50 parts by weight, more preferably 10 to 45 parts by weight.
本発明の組成物は、目的とする特性に応じて、上述した成分以外の添加剤を含有してもよい。添加剤としては、例えば、反応促進剤、界面活性剤、エポキシ化合物、エポキシ硬化剤、ポリイミド樹脂、(メタ)アクリレートモノマー(C)以外の重合性モノマー、帯電防止剤、pH調整剤、防錆剤、防腐剤、防黴剤、酸化防止剤、還元防止剤、蒸発促進剤、キレート化剤、水溶性ポリマー、紫外線吸収剤、ヒンダードアミン系光安定剤(HALS)、重合禁止剤、活性エネルギー線増感剤などが挙げられる。また、基材との密着性を補う成分として、光硬化性接着剤を追加してもよい。市販の光硬化性接着剤としては、例えば(株)スリーボンド製:製品名ThreeBondシリーズ3013Q、3027G、3042、3052、3055、3067B、ヘンケルジャパン(株)製:製品名ロックタイトシリーズ3103、3105、3106、3108、デンカ(株)製:製品名ハードロックシリーズOP−1020Z、OP−1030Z、OP−1050Z、OP−1805、OP−1540、OP−1903R、UVX−7000、UVX−3037P、UVX−8204、東亜合成(株)製:製品名アロニックスシリーズLCR0628A、LCR0632、LCR0305E、BU−810、BU−510U、BU−730UF、UV−3300、UV−3600、UV−3610などが挙げられる。また、所望の用途に応じて顔料または染料を含有してもよい。 The composition of the present invention may contain additives other than the above-mentioned components, depending on the desired properties. Examples of the additive include a reaction accelerator, a surfactant, an epoxy compound, an epoxy curing agent, a polyimide resin, a polymerizable monomer other than the (meth) acrylate monomer (C), an antioxidant, a pH adjuster, and a rust preventive. , Preservatives, fungicides, antioxidants, antioxidants, evaporation promoters, chelating agents, water-soluble polymers, UV absorbers, hindered amine-based light stabilizers (HALS), polymerization inhibitors, active energy ray sensitization Examples include agents. Further, a photocurable adhesive may be added as a component for supplementing the adhesion to the base material. Examples of commercially available photocurable adhesives include: ThreeBond Co., Ltd .: Product name ThreeBond series 3013Q, 3027G, 3042, 3052, 3055, 3067B, Henkel Japan Ltd .: Product name Loctite series 3103, 3105, 3106, 3108, manufactured by Denka Co., Ltd .: Product name Hard Lock Series OP-1020Z, OP-1030Z, OP-1050Z, OP-1805, OP-1540, OP-1903R, UVX-7000, UVX-3037P, UVX-8204, Toa Manufactured by Synthetic Co., Ltd .: Product names Aronix series LCR0628A, LCR0632, LCR0305E, BU-810, BU-510U, BU-730UF, UV-3300, UV-3600, UV-3610 and the like can be mentioned. It may also contain pigments or dyes depending on the desired application.
(硬化膜)
本発明の硬化膜は、前記本発明の組成物を硬化させることによって得られる膜であれば特に制限されない。本発明の硬化膜は、例えば、本発明の組成物を、基板上に塗布し、乾燥後に光照射をすることにより得られる。なお、光照射の後にアニール処理を目的として加熱を行ってもよい。(Hardened film)
The cured film of the present invention is not particularly limited as long as it is a film obtained by curing the composition of the present invention. The cured film of the present invention can be obtained, for example, by applying the composition of the present invention on a substrate, drying it, and then irradiating it with light. After the light irradiation, heating may be performed for the purpose of annealing treatment.
以下、本発明の組成物を用いた硬化膜の形成方法における、塗布方法および硬化方法について説明する。
基板上への本発明の組成物の塗布は、スプレーコート法、スピンコート法、ロールコート法、ディッピング法、スリットコート法、バーコート法、グラビア印刷法、フレキソ印刷法、オフセット印刷法、ディスペンサー法、スクリーン印刷法、インクジェット印刷法、ダイコート法、エアナイフコート法、カーテンコート法など従来から公知の方法により行うことができる。Hereinafter, the coating method and the curing method in the method for forming a cured film using the composition of the present invention will be described.
The composition of the present invention can be applied onto a substrate by a spray coating method, a spin coating method, a roll coating method, a dipping method, a slit coating method, a bar coating method, a gravure printing method, a flexographic printing method, an offset printing method, or a dispenser method. , Screen printing method, inkjet printing method, die coating method, air knife coating method, curtain coating method and the like.
例えば、本発明の組成物から透明絶縁膜を形成する場合、パターン形成が容易であるという点で、グラビア印刷法、フレキソ印刷法、オフセット印刷法、ディスペンサー法、スクリーン印刷法およびインクジェット印刷法などの印刷法が好ましい。 For example, when a transparent insulating film is formed from the composition of the present invention, a gravure printing method, a flexographic printing method, an offset printing method, a dispenser method, a screen printing method, an inkjet printing method, etc. The printing method is preferred.
また、例えば、本発明の組成物からオーバーコートを形成する場合、全面印刷が容易であるという点で、スピンコート法、スリットコート法、ダイコート法、グラビア印刷法、フレキソ印刷法、オフセット印刷法、ディスペンサー法、スクリーン印刷法などの塗布法が好ましい。 Further, for example, when an overcoat is formed from the composition of the present invention, the spin coating method, the slit coating method, the die coating method, the gravure printing method, the flexographic printing method, the offset printing method, etc. A coating method such as a dispenser method or a screen printing method is preferable.
本発明の組成物を塗布した後に、基板上に塗布された組成物を乾燥した後、紫外線などの活性エネルギー線を照射して硬化膜を得ることができる。活性エネルギー線照射工程で用いられる光源としては、用いる活性エネルギー線硬化剤(光重合開始剤)の性質に応じて、例えばUV−LED(紫外線LED)、低圧水銀灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアーク、キセノンアーク、気体レーザー、固体レーザー、電子線照射装置などが挙げられる。 After applying the composition of the present invention, the composition applied on the substrate is dried, and then irradiated with active energy rays such as ultraviolet rays to obtain a cured film. The light source used in the active energy ray irradiation step is, for example, UV-LED (ultraviolet LED), low pressure mercury lamp, high pressure mercury lamp, ultrahigh pressure mercury lamp, metal halide, depending on the properties of the active energy ray curing agent (photopolymerization initiator) used. Examples include lamps, carbon arcs, xenon arcs, gas lasers, solid-state lasers, and electron beam irradiators.
組成物を硬化して硬化物とする際、上述した紫外線照射工程および加熱工程の他の工程を実施しても良い。例えば、上述したように、紫外線照射工程の前に、組成物中の溶媒をある程度を乾燥させる乾燥工程を行っても良い。 When the composition is cured to obtain a cured product, other steps of the above-mentioned ultraviolet irradiation step and heating step may be carried out. For example, as described above, a drying step of drying the solvent in the composition to some extent may be performed before the ultraviolet irradiation step.
(積層体)
本発明は、上述した硬化膜を含む積層体として実施することができる。当該積層板としては、例えば、硬化膜付き基板、電子部品、光学部品、ディスプレイ、透明導電フィルム、バリアフィルム、レンズなどが挙げられる。硬化膜付き基板は、本発明の硬化膜を有すれば特に制限されない。本発明の組成物は、無機基材に対する密着性が良好であるから、表面が無機物からなる基板表面に硬化膜を形成するのに適している。無機基材としては、金属酸化物(例えば、石英、ガラス、シリカ、アルミナ、サファイア、インジウムドープ酸化スズ)、金属(例えば、鉄、クロム、ニッケル、銅、銀、金、白金、チタン、アルミニウム、亜鉛、シリコン)、合金(前記金属の組み合わせ)、窒化物(例えば、チッ化ケイ素)などが挙げられる。また有機基材としては、ポリカーボネート、ポリエステル、アクリル樹脂、塩化ビニール樹脂、ポリアミド樹脂、ポリアミドイミド、ポリイミド、トリアセテート、ジアセテートなどの合成樹脂製シート、フィルム;ノルボルネン系樹脂を含むシクロオレフィン系樹脂(商品名;ゼオノア、ゼオネックス、日本ゼオン(株)、商品名;アートン、JSR(株)、メタクリルスチレン、ポリサルフォン、脂環式アクリル樹脂、ポリアリレートなどの光学用途に用いる透明樹脂基板、ウレタンゴム、スチレンゴムなどが挙げられる。(Laminated body)
The present invention can be carried out as a laminate containing the above-mentioned cured film. Examples of the laminated board include a substrate with a cured film, an electronic component, an optical component, a display, a transparent conductive film, a barrier film, a lens and the like. The substrate with a cured film is not particularly limited as long as it has the cured film of the present invention. Since the composition of the present invention has good adhesion to an inorganic base material, it is suitable for forming a cured film on the surface of a substrate whose surface is made of an inorganic material. Inorganic substrates include metal oxides (eg quartz, glass, silica, alumina, sapphire, indium-doped tin oxide), metals (eg iron, chromium, nickel, copper, silver, gold, platinum, titanium, aluminum, etc. Examples include zinc, silicon), alloys (combination of the metals), nitrides (eg, silicon nitride) and the like. Examples of the organic base material include sheets and films made of synthetic resins such as polycarbonate, polyester, acrylic resin, vinyl chloride resin, polyamide resin, polyamideimide, polyimide, triacetate, and diacetate; cycloolefin resins containing norbornene resins (commodities). Name: Zeonoa, Zeonex, Nippon Zeon Co., Ltd., Product name: Arton, JSR Co., Ltd., methacrylic styrene, polysulfone, alicyclic acrylic resin, transparent resin substrate used for optical applications such as polyarylate, urethane rubber, styrene rubber And so on.
このような硬化膜付き基板は、例えば、無機基材の表面からなる基板上に、本発明の組成物を前記塗布法などによって全面または所定のパターン状(ライン状など)に塗布し、その後、前記で説明したような乾燥処理および硬化処理を経ることで、形成することができる。 In such a substrate with a cured film, for example, the composition of the present invention is applied to the entire surface or a predetermined pattern (line shape or the like) by the coating method or the like on a substrate made of the surface of an inorganic base material, and then It can be formed by undergoing a drying treatment and a curing treatment as described above.
以下、本発明を実施例により説明するが、本発明はこれらの実施例に限定されるものではない。実施例で用いた成分の名称ならびにその略号を示す。以下の記述にはこれらの略号を使用する。実施例および比較例の組成物では、溶剤(E)を除いた(A)〜(D)、(F)および他の成分が固形分である。 Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples. The names of the components used in the examples and their abbreviations are shown. These abbreviations are used in the following descriptions. In the compositions of Examples and Comparative Examples, the components (A) to (D), (F) and other components excluding the solvent (E) are solids.
<シランカップリング剤(A)>
S710:メタクリル酸3−(トリメトキシシリル)プロピル、サイラエースS710(製品名、JNC(株)製)<Silane coupling agent (A)>
S710: 3- (trimethoxysilyl) propyl methacrylate, Sila Ace S710 (product name, manufactured by JNC Co., Ltd.)
<リン酸(メタ)アクリレートモノマー(B)>
P−2M:2−メタクリロキシエチルアシッドホスフェート、ライトエステルP−2M(製品名、共栄社化学(株)製)<Phosphoric acid (meth) acrylate monomer (B)>
P-2M: 2-methacryloxyethyl acid phosphate, light ester P-2M (product name, manufactured by Kyoeisha Chemical Co., Ltd.)
<(メタ)アクリレートモノマー(C)>
<単官能(メタ)アクリレートモノマー(C−1)>
AMP−20GY:フェノキシジエチレングリコールアクリレート、NKエステルAMP−20GY(製品名、新中村化学工業(株)製)
<多官能(メタ)アクリレートモノマー(C−2)>
ウレタンアクリレート(2官能、ウレタン結合および飽和環状脂肪族構造を有する、特開2017−78840の製造例1に記載のウレタンアクリレートモノマー)
A−DPH:ジペンタエリスリトールヘキサアクリレート(6官能)、NKエステルA−DPH(製品名、新中村化学工業(株)製)<(Meta) Acrylate Monomer (C)>
<Monofunctional (meth) acrylate monomer (C-1)>
AMP-20GY: Phenoxydiethylene glycol acrylate, NK ester AMP-20GY (Product name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
<Polyfunctional (meth) acrylate monomer (C-2)>
Urethane acrylate (Urethane acrylate monomer according to Production Example 1 of JP-A-2017-78840, which has a bifunctional, urethane bond and saturated cyclic aliphatic structure)
A-DPH: Dipentaerythritol hexaacrylate (hexafunctional), NK ester A-DPH (product name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
<光重合開始剤(D)>
Omnirad127(製品名、IGM Resins B.V.製):1,1′−(メチレン−ジ−4,1−フェニレン)ビス[2−ヒドロキシ−2−メチルプロパン−1−オン])<Photopolymerization initiator (D)>
Omnirad 127 (Product name, manufactured by IGM Resins VV): 1,1'-(methylene-di-4,1-phenylene) bis [2-hydroxy-2-methylpropane-1-one])
<溶剤(E)>
NPA:ノルマルプロピルアルコール
PGME:プロピレングリコールモノメチルエーテル<Solvent (E)>
NPA: Normal Propyl Alcohol PGME: Propylene Glycol Monomethyl Ether
<無機微粒子(F)>
PGM−AC−2140Y:(製品名、日産化学(株)製、プロピレングリコールモノメチルエーテル分散シリカゾルの表面改質グレード、表1にはフィラー分の配合量を記載し、分散媒は溶剤(E)に含めて記載した。)
<他の成分>
TB3052:紫外線硬化性樹脂3000シリーズ(製品名、(株)スリーボンド製)
UP−1000:オールアクリル構造の無溶剤型アクリル樹脂、ARUFON UP−1000(製品名、東亜合成(株)製)<Inorganic fine particles (F)>
PGM-AC-2140Y: (Product name, Nissan Chemical Industries, Ltd., surface modification grade of propylene glycol monomethyl ether dispersed silica sol, Table 1 shows the amount of filler compounded, and the dispersion medium is solvent (E). Including.)
<Other ingredients>
TB3052: UV curable resin 3000 series (product name, manufactured by ThreeBond Co., Ltd.)
UP-1000: Solvent-free acrylic resin with an all-acrylic structure, ARUFON UP-1000 (product name, manufactured by Toagosei Corporation)
[実施例1〜4]
(塗剤調製)
シランカップリング剤(A)としてS710、リン酸(メタ)アクリレートモノマー(B)としてP−2M、単官能(メタ)アクリレートモノマー(C−1)としてAMP−20GY、多官能(メタ)アクリレートモノマー(C−2)として特開2017−78840の製造例1に記載のウレタンアクリレート、およびA−DPH、光重合開始剤(D)としてOmnirad127、無機微粒子(F)としてPGM−AC−2140Yを表1に記載の割合となるように混合し、最終的に固形分濃度が30重量%、溶剤組成がNPA/PGME=50/50となるようにNPAとPGMEを加え、室温下で攪拌して均一な溶液を得た。[Examples 1 to 4]
(Preparation of coating material)
S710 as the silane coupling agent (A), P-2M as the phosphoric acid (meth) acrylate monomer (B), AMP-20GY as the monofunctional (meth) acrylate monomer (C-1), and the polyfunctional (meth) acrylate monomer (meth). Table 1 shows the urethane acrylate described in Production Example 1 of JP-A-2017-78840 as C-2), A-DPH, Monomer 127 as the photopolymerization initiator (D), and PGM-AC-2140Y as the inorganic fine particles (F). Mix to the stated ratio, add NPA and PGME so that the solid content concentration is 30% by weight and the solvent composition is NPA / PGME = 50/50, and stir at room temperature to make a uniform solution. Got
(硬化膜調製)
1)硬化膜付きフィルムの作製
得られた溶液(組成物)を、R.D.スペシャリティーズ社製コーティングロッド(#12)を用いてSiO2を蒸着したポリエチレンテレフタレートフィルム(厚さ:50μm)のSiO2を蒸着した面上に塗布した。
得られた塗膜付きフィルムを、80℃のオーブンで2分間乾燥させ、岩崎電気(株)製高圧水銀ランプ(H08−L41、定格 160W/cm)が付属したコンベア式UV照射装置を用いて、照度200mW/cm2、露光量500mJ/cm2で紫外線を照射し、膜厚4μmの透明な硬化膜を有するフィルムを得た。露光量は、岩崎電気(株)製照度計(UVPF−A1/PD−365)で測定した。(Preparation of cured film)
1) Preparation of a film with a cured film The obtained solution (composition) was subjected to R. D. A polyethylene terephthalate film (thickness: 50 μm) in which SiO 2 was vapor-deposited was applied onto the surface on which SiO 2 was vapor-deposited using a coating rod (# 12) manufactured by Specialties.
The obtained film with a coating film was dried in an oven at 80 ° C. for 2 minutes, and a conveyor-type UV irradiation device equipped with a high-pressure mercury lamp (H08-L41, rated 160 W / cm) manufactured by Iwasaki Electric Co., Ltd. was used. Ultraviolet rays were irradiated at an illuminance of 200 mW / cm2 and an exposure amount of 500 mJ / cm2 to obtain a film having a transparent cured film having a film thickness of 4 μm. The exposure amount was measured with an illuminance meter (UVPF-A1 / PD-365) manufactured by Iwasaki Electric Co., Ltd.
2)硬化膜付きガラス基板の作製
得られた溶液(組成物)を、コーニング社製無アルカリガラス(Eagle XG)上にスピンコート(400rpm/10秒)し、塗膜を得た。
得られた塗膜付きガラスを120℃のオーブンで2分間乾燥させ、硬化膜付きフィルムを作製したときと同様に紫外線照射を行い、膜厚4μmの透明な硬化膜を有するガラス基板を得た。2) Preparation of Glass Substrate with Hardened Film The obtained solution (composition) was spin-coated (400 rpm / 10 seconds) on non-alkali glass (Eagle XG) manufactured by Corning Inc. to obtain a coating film.
The obtained glass with a coating film was dried in an oven at 120 ° C. for 2 minutes and irradiated with ultraviolet rays in the same manner as when the film with a cured film was prepared to obtain a glass substrate having a transparent cured film having a film thickness of 4 μm.
[実施例5]
その他成分として、TB3052を表1の組成となるように配合した以外は実施例1と同様にして塗剤調製を行い、塗膜を作製して硬化し、得られた塗剤(組成物)と硬化膜を評価した。[Example 5]
As other components, a coating film was prepared in the same manner as in Example 1 except that TB3052 was blended so as to have the composition shown in Table 1, a coating film was prepared and cured, and the coating film (composition) obtained was obtained. The cured film was evaluated.
[比較例1]
(A)成分として、S710を配合しなかった以外は実施例1と同様にして塗剤調製を行い、塗膜を作製して硬化し、得られた塗剤と硬化膜を評価した。[Comparative Example 1]
A coating film was prepared in the same manner as in Example 1 except that S710 was not blended as the component (A), a coating film was prepared and cured, and the obtained coating film and cured film were evaluated.
[比較例2]
(B)成分として、P−2Mを配合しなかった以外は実施例1と同様にして塗剤調製を行い、塗膜を作製して硬化し、得られた塗剤と硬化膜を評価した。[Comparative Example 2]
A coating film was prepared in the same manner as in Example 1 except that P-2M was not blended as the component (B), a coating film was prepared and cured, and the obtained coating film and cured film were evaluated.
[比較例3]
(C−1)成分として、AMP−20GYを配合しなかった以外は実施例1と同様にして塗剤調製を行い、塗膜を作製して硬化し、得られた塗剤と硬化膜を評価した。[Comparative Example 3]
A coating film was prepared in the same manner as in Example 1 except that AMP-20GY was not blended as the component (C-1), a coating film was prepared and cured, and the obtained coating film and cured film were evaluated. bottom.
[比較例4]
(C−2)成分として、ウレタンアクリレートモノマーを配合しなかった以外は実施例1と同様にして塗剤調製を行い、塗膜を作製して硬化し、得られた塗剤と硬化膜を評価した。[Comparative Example 4]
A coating film was prepared in the same manner as in Example 1 except that a urethane acrylate monomer was not blended as a component (C-2), a coating film was prepared and cured, and the obtained coating film and cured film were evaluated. bottom.
[比較例5]
(C−2)成分として、ウレタンアクリレートモノマーを、無官能アクリル樹脂UP−1000に変更した以外は実施例1と同様にして塗剤調製を行い、塗膜を作製して硬化し、得られた塗剤と硬化膜を評価した。[Comparative Example 5]
A coating film was prepared in the same manner as in Example 1 except that the urethane acrylate monomer was changed to the non-functional acrylic resin UP-1000 as the component (C-2), and a coating film was prepared and cured to obtain the obtained film. The coating and cured film were evaluated.
[比較例6]
(C−2)成分として、A−DPHを配合しなかった以外は実施例1と同様にして塗剤調製を行い、塗膜を作製して硬化し、得られた塗剤と硬化膜を評価した。[Comparative Example 6]
A coating film was prepared in the same manner as in Example 1 except that A-DPH was not blended as the component (C-2), a coating film was prepared and cured, and the obtained coating film and cured film were evaluated. bottom.
[比較例7]
(F)成分として、PGM−AC−2140Yを配合しなかった以外は実施例1と同様にして塗剤調製を行い、塗膜を作製して硬化し、得られた塗剤と硬化膜を評価した。[Comparative Example 7]
A coating film was prepared in the same manner as in Example 1 except that PGM-AC-2140Y was not blended as the component (F), a coating film was prepared and cured, and the obtained coating film and cured film were evaluated. bottom.
[比較例8]
(E)成分として、溶剤組成をNPA/PGME=0/100に変更した以外は実施例1と同様にして塗剤調製を行い、塗膜を作製して硬化し、得られた塗剤と硬化膜を評価した。[Comparative Example 8]
As the component (E), a coating film was prepared in the same manner as in Example 1 except that the solvent composition was changed to NPA / PGME = 0/100, a coating film was prepared and cured, and the obtained coating film and curing were performed. The membrane was evaluated.
[評価方法]
(保存安定性)
実施例および比較例の組成物を45℃の恒温槽で90日間保管し、目視によりゲル化の発生を確認した結果を表1に示す。表1には、ゲル化した組成物は45℃での保管開始からゲル化発生までに要した日数を示し、保管開始から90日経過時点においてゲル化しなかった組成物は「>90」とした。[Evaluation method]
(Storage stability)
Table 1 shows the results of visually confirming the occurrence of gelation after storing the compositions of Examples and Comparative Examples in a constant temperature bath at 45 ° C. for 90 days. Table 1 shows the number of days required from the start of storage at 45 ° C. to the occurrence of gelation for the gelled composition, and “> 90” for the composition that did not gel after 90 days from the start of storage. ..
(密着性:碁盤目剥離試験)
得られた硬化膜を1mm×1mmの正方形(碁盤目)状にクロスカットして、切り目に囲まれた100個の領域を作製した。その領域の上から粘着性のある剥離用のテープを貼り付けて、剥がした時の剥がれた領域の数により評価を行った。その結果を下記評価基準にのっとり評価した。剥離用のテープは、Scotch#610、スリーエム社製:402N/100mm(縦方向)を使用した。
評価基準
5B:100個の領域のうち1個も剥がれない。
4B:欠損エリア(剥がれた領域)が5%以下
3B:欠損エリア5%を超えて15%以下
2B:欠損エリアが15%を超えて35%以下
1B:欠損エリアが35%を超えて65%以下
0B:上記4つの分類に属さないもの(欠損エリアが65%を超える)(Adhesion: checkerboard peeling test)
The obtained cured film was cross-cut into a 1 mm × 1 mm square (grid) shape to prepare 100 regions surrounded by the cuts. A sticky peeling tape was attached from above the region, and the evaluation was performed based on the number of peeled regions when the tape was peeled off. The results were evaluated according to the following evaluation criteria. As the peeling tape, Scotch # 610, manufactured by 3M Ltd .: 402N / 100 mm (longitudinal direction) was used.
Evaluation Criteria 5B: Not even one of the 100 areas is peeled off.
4B: Defect area (peeled area) is 5% or less 3B: Defect area is more than 5% and 15% or less 2B: Defect area is more than 15% and 35% or less 1B: Defect area is more than 35% and 65% 0B below: Those that do not belong to the above four categories (defective area exceeds 65%)
(表面硬度:鉛筆硬度)
上述のようにしてガラス基板上に調製した硬化膜を用い、JIS−K−5600−5−4に順じ、鉛筆硬度計で硬化膜表面の鉛筆硬度を測定した。(Surface hardness: Pencil hardness)
Using the cured film prepared on the glass substrate as described above, the pencil hardness on the surface of the cured film was measured with a pencil hardness tester in accordance with JIS-K-5600-5-4.
表1に示す実施例および比較例の評価結果から、以下のことが分かった。
アクリレートモノマーを含む組成物に溶剤(E)を、PGMEとNPA(ノルマルプロピルアルコール)とから構成することにより、組成物のゲル化を防ぐことができる。
組成物がシランカップリング剤(A)、リン酸(メタ)アクリレートモノマー(B)、ウレタンアクリレートモノマー(2官能、(C−2))およびAMP−20GY(PEG鎖を有するアクリレートモノマー、単官能、(C−1))を含むことにより、ガラス基板に対する硬化膜の密着性が向上する。
組成物がジペンタエリスリトールヘキサアクリレート(6官能、(C−2))およびシリカ(PGM−AC−2140Y)を含むことにより、硬化物のハードコート性(塗膜表面硬度)が向上する。
ウレタンアクリレートモノマーを含有する組成物により、無溶剤型の架橋しないアクリル樹脂を含有する組成物よりも、表面硬度が高い硬化物が得られる。From the evaluation results of the examples and comparative examples shown in Table 1, the following was found.
By forming the solvent (E) in the composition containing the acrylate monomer with PGME and NPA (normal propyl alcohol), gelation of the composition can be prevented.
The composition is a silane coupling agent (A), a phosphoric acid (meth) acrylate monomer (B), a urethane acrylate monomer (bifunctional, (C-2)) and AMP-20GY (acrylate monomer having a PEG chain, monofunctional, By including (C-1)), the adhesion of the cured film to the glass substrate is improved.
When the composition contains dipentaerythritol hexaacrylate (hexafunctional, (C-2)) and silica (PGM-AC-2140Y), the hard coat property (coating film surface hardness) of the cured product is improved.
A composition containing a urethane acrylate monomer provides a cured product having a higher surface hardness than a composition containing a solvent-free non-crosslinking acrylic resin.
本発明の光硬化性組成物から得られる硬化膜は、無機基材を保護する表面保護膜、プライマー層として利用することができる。 The cured film obtained from the photocurable composition of the present invention can be used as a surface protective film and a primer layer for protecting an inorganic base material.
Claims (14)
リン酸(メタ)アクリレートモノマー(B)、
前記シランカップリング剤(A)および前記リン酸(メタ)アクリレートモノマー(B)以外の(メタ)アクリレートモノマー(C)、
光重合開始剤(D)、ならびに
溶剤(E)を含み、前記溶剤(E)はアルコールを含むことを特徴とする光硬化性組成物。Silane coupling agent (A),
Phosphoric acid (meth) acrylate monomer (B),
A (meth) acrylate monomer (C) other than the silane coupling agent (A) and the phosphoric acid (meth) acrylate monomer (B),
A photocurable composition containing a photopolymerization initiator (D) and a solvent (E), wherein the solvent (E) contains an alcohol.
前記多官能(メタ)アクリレートモノマー(C−2)が2〜10官能である請求項1〜5のいずれか一項に記載の光硬化性組成物。The (meth) acrylate monomer (C) is composed of a monofunctional (meth) acrylate monomer (C-1) and one or more kinds of polyfunctional (meth) acrylate monomers (C-2).
The photocurable composition according to any one of claims 1 to 5, wherein the polyfunctional (meth) acrylate monomer (C-2) is 2 to 10 functional.
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