JP5476994B2 - Solvent-free curable composition for hard coat and cured film thereof - Google Patents
Solvent-free curable composition for hard coat and cured film thereof Download PDFInfo
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- JP5476994B2 JP5476994B2 JP2009537999A JP2009537999A JP5476994B2 JP 5476994 B2 JP5476994 B2 JP 5476994B2 JP 2009537999 A JP2009537999 A JP 2009537999A JP 2009537999 A JP2009537999 A JP 2009537999A JP 5476994 B2 JP5476994 B2 JP 5476994B2
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- meth
- acrylate
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- 239000000203 mixture Substances 0.000 title claims description 63
- 150000001875 compounds Chemical class 0.000 claims description 46
- -1 methacryloyl group Chemical group 0.000 claims description 39
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 33
- 229920001296 polysiloxane Polymers 0.000 claims description 24
- 239000003505 polymerization initiator Substances 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 150000003951 lactams Chemical class 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 112
- 239000010408 film Substances 0.000 description 36
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 21
- 230000005855 radiation Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000007870 radical polymerization initiator Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229940059574 pentaerithrityl Drugs 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 4
- 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 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 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 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XOSOQSHNDUDDKD-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.O=C1C=C(CC(C)(C)C1)C Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.O=C1C=C(CC(C)(C)C1)C XOSOQSHNDUDDKD-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C)(C1)CC(C)(C*C(OCC(CN=O)(CN=O)CN=O)=O)CC1*(C(OCC(CN=O)(CN=O)CN=O)=O)=C Chemical compound CC(C)(C1)CC(C)(C*C(OCC(CN=O)(CN=O)CN=O)=O)CC1*(C(OCC(CN=O)(CN=O)CN=O)=O)=C 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229940117969 neopentyl glycol Drugs 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002023 wood Substances 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
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- FWWWRCRHNMOYQY-UHFFFAOYSA-N 1,5-diisocyanato-2,4-dimethylbenzene Chemical compound CC1=CC(C)=C(N=C=O)C=C1N=C=O FWWWRCRHNMOYQY-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- UKDKWYQGLUUPBF-UHFFFAOYSA-N 1-ethenoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOC=C UKDKWYQGLUUPBF-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- SDXHBDVTZNMBEW-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol Chemical compound CCOC(O)COCCO SDXHBDVTZNMBEW-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
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- YHDVNSYMKOIPAK-UHFFFAOYSA-N 2,2,3-trimethyl-1,4-diazabicyclo[2.2.2]octane Chemical compound CC1C(N2CCN1CC2)(C)C YHDVNSYMKOIPAK-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
- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical compound C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 description 1
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- 101100389975 Mus musculus Ezhip gene Proteins 0.000 description 1
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- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- HIVQCJOGAHNXBO-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] propanoate Chemical compound CCC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C HIVQCJOGAHNXBO-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000002928 artificial marble Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- RFVHVYKVRGKLNK-UHFFFAOYSA-N bis(4-methoxyphenyl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1 RFVHVYKVRGKLNK-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- MZRQZJOUYWKDNH-UHFFFAOYSA-N diphenylphosphoryl-(2,3,4-trimethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MZRQZJOUYWKDNH-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- FSPSELPMWGWDRY-UHFFFAOYSA-N m-Methylacetophenone Chemical compound CC(=O)C1=CC=CC(C)=C1 FSPSELPMWGWDRY-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- PWGIEBRSWMQVCO-UHFFFAOYSA-N phosphono prop-2-enoate Chemical compound OP(O)(=O)OC(=O)C=C PWGIEBRSWMQVCO-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 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
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 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
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
Description
本発明は、ハードコート用硬化性組成物及びそれを硬化させてなる硬化膜に関する。さらに詳しくは、無溶剤であるにもかかわらず、優れた塗工性を有し、かつ各種基材の表面に、高硬度であるとともに耐擦傷性並びに基材との密着性に優れた塗膜（被膜）を形成し得るハードコート用硬化性組成物、及びカール性が小さく、耐薬品性に優れたハードコート用の硬化膜に関する。 The present invention relates to a curable composition for hard coat and a cured film obtained by curing the curable composition. More specifically, despite having no solvent, the coating film has excellent coatability and has high hardness on the surface of various base materials, as well as excellent scratch resistance and adhesion to the base material. The present invention relates to a curable composition for hard coat capable of forming a (coating film) and a cured film for hard coat having low curl properties and excellent chemical resistance.
近年、各種基材表面の傷付き（擦傷）防止や汚染防止のための保護コーティング材；各種基材の接着剤、シーリング材；印刷インクのバインダー材として、優れた塗工性を有し、かつ各種基材の表面に、硬度、屈曲性、耐擦傷性、耐摩耗性、低カール性（硬化膜の反りが小さいことをいう）、密着性、透明性、耐薬品性及び塗膜面の外観のいずれにも優れた硬化膜を形成し得る硬化性組成物が要請されている。 In recent years, it has excellent coating properties as a protective coating material for preventing scratches (scratching) on various substrate surfaces and preventing contamination; adhesives and sealing materials for various substrates; and a binder material for printing inks. Hardness, flexibility, scratch resistance, abrasion resistance, low curl (meaning that the cured film has low warpage), adhesion, transparency, chemical resistance, and coating surface appearance on the surface of various substrates There is a demand for a curable composition that can form an excellent cured film.
このような要請を満たすため、種々の組成物が提案されているが、硬化性組成物として優れた塗工性を有し、また硬化膜とした場合に、高硬度であるとともにカール性が小さいという特性を備えたものはまだ得られていないのが現状である。
例えば、塗工性を向上させるため、有機溶剤を用いて粘度を下げる方法が提案されている（特許文献１）。In order to satisfy such a demand, various compositions have been proposed, but they have excellent coating properties as a curable composition, and when used as a cured film, have high hardness and low curl properties. At present, no product with such characteristics has been obtained.
For example, in order to improve coatability, a method of reducing the viscosity using an organic solvent has been proposed (Patent Document 1).
特許文献２では、硬度を維持するために、イソシアヌレート環構造を有する化合物を含む組成物の硬化物を開示しているが、この発明では膜厚を大きくすることで、高硬度を発現させている。 In patent document 2, in order to maintain hardness, the hardened | cured material of the composition containing the compound which has an isocyanurate ring structure is disclosed, but in this invention, high hardness is expressed by enlarging a film thickness. Yes.
ハードコート用組成物として、良好な塗工性を有する溶剤を含むものが種々提案されているが、ハードコートを形成する際には、その溶剤を揮発させるための装置、及び加温静置するといったプロセスが必須となる。これらの装置やプロセスを割愛することは産業経済上好ましく、これを達成するために、無溶剤のハードコート用組成物が望まれている。
しかしながら、従来の組成物は、無溶剤で良好な塗工性を示し、かつ、硬化膜が良好な耐摩傷性、高い硬度、低いカール性を両立するという観点からは、上記のように満足しうるものではなかった。Various hard coat compositions containing a solvent having a good coating property have been proposed. When forming a hard coat, an apparatus for volatilizing the solvent and heating and standing are used. Such a process is essential. Omitting these devices and processes is preferable in terms of industrial economy, and in order to achieve this, a solvent-free hard coat composition is desired.
However, the conventional composition is satisfactory as described above from the viewpoint that it exhibits good coating properties without solvent and that the cured film has both good abrasion resistance, high hardness, and low curl properties. It wasn't good.
本発明は、上述の問題に鑑みてなされたものであり、無溶剤で優れた塗工性を有し、かつ各種基材の表面に、高硬度及び低カール性を備えた塗膜（被膜）を形成し得る硬化性組成物、及び耐薬品性に優れたハードコート用の硬化膜を提供することを目的とする。 The present invention has been made in view of the above-described problems, and has a coating property (coating film) that has excellent coating properties without a solvent, and has high hardness and low curl properties on the surface of various substrates. An object of the present invention is to provide a curable composition capable of forming a hard coat and a cured film for hard coat having excellent chemical resistance.
本発明によれば、以下の硬化性組成物、及びその硬化物を提供できる。
１．組成物全量を１００重量％としたときに、下記（Ａ）〜（Ｅ）成分を下記割合で含有することを特徴とする無溶剤型のハードコート用硬化性組成物。
（Ａ）分子中に環構造を有し、３個以上の（メタ）アクリロイル基を有し、（メタ）アクリロイル基１個当たりの分子量が４００以下であるウレタン（メタ）アクリレート ３０〜５０重量％
（Ｂ）１分子中に２個以上の（メタ）アクリロイル基を有する（Ａ）成分以外の重合性多官能化合物 １０〜５０重量％
（Ｃ）重合性単官能化合物 １５〜４０重量％
（Ｄ）シリコーン化合物 ０．０５〜５重量％
（Ｅ）光ラジカル重合開始剤 ０．１〜１０重量％
２．前記（Ａ）成分が、下記式（１）及び／又は（２）で示される化合物である上記１に記載のハードコート用硬化性組成物。
３．上記１又は２に記載のハードコート用硬化性組成物を硬化させてなる硬化膜。
According to the present invention, the following curable composition and its cured product can be provided.
1. A solvent-free curable composition for hard coat, comprising the following components (A) to (E) in the following proportions when the total amount of the composition is 100% by weight.
Has a ring structure in (A) molecules, have a three or more (meth) acryloyl group, (meth) urethane molecular weight per acryloyl group is 400 or less (meth) acrylate 30 to 50 wt%
(B) Polymerizable polyfunctional compound other than component (A) having two or more (meth) acryloyl groups in one molecule 10 to 50% by weight
(C) Polymerizable monofunctional compound 15-40% by weight
(D) Silicone compound 0.05 to 5% by weight
(E) Photoradical polymerization initiator 0.1 to 10% by weight
2. 2. The curable composition for hard coat according to 1 above, wherein the component (A) is a compound represented by the following formula (1) and / or (2).
3. A cured film obtained by curing the curable composition for hard coat according to 1 or 2 above.
本発明によれば、無溶剤であるにもかかわらず優れた塗工性を有し、かつ各種基材［例えば、プラスチック（ポリカーボネート、ポリメチルメタクリレート、ポリスチレン、ポリエステル、ポリオレフィン、エポキシ樹脂、メラミン樹脂、トリアセチルセルロース樹脂、ＡＢＳ樹脂、ＡＳ樹脂、ノルボルネン系樹脂等）、金属、木材、紙、ガラス、スレート等］の表面に、高硬度であるとともに耐擦傷性並びに基材との密着性に優れた塗膜（被膜）を形成し得る無溶剤型のハードコート用硬化性組成物、及びカール性が小さく、耐薬品性に優れたハードコート用の硬化膜を提供することができる。 According to the present invention, it has excellent coating properties in spite of being solvent-free, and various substrates [for example, plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, Triacetylcellulose resin, ABS resin, AS resin, norbornene resin, etc.), metal, wood, paper, glass, slate, etc.], and has high hardness and excellent scratch resistance and adhesion to the substrate. It is possible to provide a solvent-free curable composition for hard coat that can form a coating film (film), and a hard coat cured film that has low curl properties and excellent chemical resistance.
以下、本発明の硬化性組成物、その硬化物及び積層体の実施形態を具体的に説明する。
Ｉ．硬化性組成物
本発明の無溶剤型のハードコート用硬化性組成物（以下、「本発明の組成物」という）は、下記（Ａ）〜（Ｆ）成分を含有し得る。これらの成分のうち、（Ａ）〜（Ｅ）成分は必須成分であり、所定の配合量で配合される。（Ｆ）成分は必要に応じて添加される任意添加成分である。「無溶剤」とは溶剤が配合されることによる影響が発現する程度の溶剤量を含まないことを意味し、配合される原料に含まれる不純物等により、溶剤が組成物中に１重量％程度含まれていても構わない。
（Ａ）分子中に環構造を有し、３個以上の（メタ）アクリロイル基を有するウレタン（メタ）アクリレート重量
（Ｂ）１分子中に２個以上の（メタ）アクリロイル基を有する（Ａ）成分以外の重合性多官能化合物
（Ｃ）重合性単官能化合物
（Ｄ）シリコーン化合物
（Ｅ）ラジカル重合開始剤
（Ｆ）その他添加剤
以下、本発明の硬化性組成物の各構成成分について具体的に説明する。Hereinafter, embodiments of the curable composition, the cured product and the laminate of the present invention will be specifically described.
I. Curable composition The curable composition for a solvent-free hard coat of the present invention (hereinafter referred to as “the composition of the present invention”) may contain the following components (A) to (F). Among these components, the components (A) to (E) are essential components and are blended in a predetermined blending amount. Component (F) is an optional additive component added as necessary. “Solvent-free” means that the amount of solvent is not included so that the effect of mixing the solvent is expressed, and the solvent is contained in the composition by about 1% by weight due to impurities contained in the mixed material. It may be included.
(A) Urethane (meth) acrylate having a ring structure in the molecule and having three or more (meth) acryloyl groups Weight (B) Having two or more (meth) acryloyl groups in one molecule (A) Polymerizable polyfunctional compound other than components (C) Polymerizable monofunctional compound (D) Silicone compound (E) Radical polymerization initiator (F) Other additives Hereinafter, each component of the curable composition of the present invention is specifically described. Explained.
（Ａ）分子中に環構造を有し、３個以上の（メタ）アクリロイル基を有するウレタン（メタ）アクリレート
（Ａ）成分は、分子中に環構造を有し、かつ３個以上の（メタ）アクリロイル基を有するウレタン（メタ）アクリレートであり、（メタ）アクリロイル基の数は、６個以上が好ましく、８個以上がさらに好ましい。（Ａ）成分は、本発明の硬化性組成物を硬化させてなる硬化物の硬度を維持しつつカールを低減する機能を有する。
（Ａ）成分を含有することにより、架橋点間距離が大きくなり、カールが低減されるものと考えられ、また、特に芳香環を有するウレタン（メタ）アクリレートは結晶性を有するため、機械強度、靭性が向上し、架橋点間距離が大きくなっても硬度とのバランスが維持できるものと考えられる。(A) Urethane (meth) acrylate having a ring structure in the molecule and having 3 or more (meth) acryloyl groups (A) component has a ring structure in the molecule and 3 or more (meta ) Urethane (meth) acrylate having an acryloyl group, and the number of (meth) acryloyl groups is preferably 6 or more, more preferably 8 or more. The component (A) has a function of reducing curl while maintaining the hardness of a cured product obtained by curing the curable composition of the present invention.
By containing the component (A), it is considered that the distance between cross-linking points is increased and curling is reduced, and in particular, the urethane (meth) acrylate having an aromatic ring has crystallinity, so that the mechanical strength, It is considered that the balance with hardness can be maintained even when the toughness is improved and the distance between cross-linking points is increased.
（Ａ）成分の化合物中の環構造としては、特に限定されないが、脂肪族環、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、インデン環、ピレン環等の縮合ベンゼン環、チオフェン環、ピロール環、フラン環、ピリジン環等の複素芳香環等が好ましい。 (A) Although it does not specifically limit as a ring structure in the compound of a component, A condensed benzene ring, a thiophene ring, a pyrrole ring, such as an aliphatic ring, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an indene ring, a pyrene ring Heteroaromatic rings such as furan ring and pyridine ring are preferred.
（Ａ）成分は、（Ａ）成分が有する（メタ）アクリロイル基１個当たりの分子量が４００以下であることが好ましく、さらに好ましくは３００以下である。４００以下であることにより、耐擦傷性が向上する。 The component (A) preferably has a molecular weight of 400 or less, more preferably 300 or less per (meth) acryloyl group of the component (A). By being 400 or less, the scratch resistance is improved.
（Ａ）成分のウレタン（メタ）アクリレートは、環を有するジイソシアネートと水酸基を有する（メタ）アクリル化合物を、適当なウレタン化触媒の存在下で、６０℃、６時間の条件で攪拌して得ることができる。
ここで、環を有するジイソシアネートの具体例としては、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、１，３−キシリレンジイソシアネート、１，４−キシリレンジイソシアネート、１，５−ナフタレンジイソシアネート、ｍ−フェニレンジイソシアネート、ｐ−フェニレンジイソシアネート、３，３’−ジメチル−４，４’−ジフェニルメタンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、３，３’−ジメチルフェニレンジイソシアネート、４，４’−ビフェニレンジイソシアネート、６−イソプロピル−１，３−フェニルジイソシアネート、４−ジフェニルプロパンジイソシアネート、テトラメチルキシリレンジイソシアネート、イソホロンジアクリレート等が挙げられる。これらのうち、特に、２，４−トリレンジイソシアネート、イソホロンジアクリレート等が好ましい。The urethane (meth) acrylate of component (A) is obtained by stirring a diisocyanate having a ring and a (meth) acrylic compound having a hydroxyl group in the presence of a suitable urethanization catalyst at 60 ° C. for 6 hours. Can do.
Here, as specific examples of the diisocyanate having a ring, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene Diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethylphenylene diisocyanate, 4,4′-biphenylene Examples thereof include diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, tetramethylxylylene diisocyanate, and isophorone diacrylate. Of these, 2,4-tolylene diisocyanate, isophorone diacrylate, and the like are particularly preferable.
水酸基を有する（メタ）アクリル化合物の具体例としては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシ−３−フェニルオキシプロピル（メタ）アクリレート、１，４−ブタンジオールモノ（メタ）アクリレート、２−ヒドロキシアルキル（メタ）アクリロイルフォスフェート、４−ヒドロキシシクロヘキシル（メタ）アクリレート、１，６−ヘキサンジオールモノ（メタ）アクリレート、ネオペンチルグリコールモノ（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、トリメチロールエタンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、下記式（５）又は（６） Specific examples of the (meth) acrylic compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenyloxypropyl. (Meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neo Pentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta ( Data) acrylate, the following formula (5) or (6)
（式中、Ｒ１は水素原子又はメチル基を示し、ｎは１〜１５の数を示す）
で表される（メタ）アクリレート及びアルキルグリシジルエーテル、アリルグリシジルエーテル、グリシジル（メタ）アクリレートの如きグリシジル基含有化合物と、（メタ）アクリル酸との付加反応により得られる化合物等を挙げることができる。これら水酸基含有（メタ）アクリレートのうち、特に、ペンタエリスリトールトリ（メタ）アクリレート等が好ましい。(In the formula, R 1 represents a hydrogen atom or a methyl group, and n represents a number of 1 to 15)
And compounds obtained by addition reaction of (meth) acrylic acid with glycidyl group-containing compounds such as (meth) acrylate and alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate represented by formula (1). Of these hydroxyl group-containing (meth) acrylates, pentaerythritol tri (meth) acrylate and the like are particularly preferable.
ウレタン化触媒の具体例としては、通常ナフテン酸銅、ナフテン酸コバルト、ナフテン酸亜鉛、ジブチル錫ジラウレ−ト、トリエチルアミン、１，４−ジアザビシクロ〔２．２．２〕オクタン、２，６，７−トリメチル−１，４−ジアザビシクロ〔２．２．２〕オクタン等を挙げることができる。これらの中で、特に、ジブチル錫ジラウレ−ト等が好ましい。 Specific examples of the urethanization catalyst are usually copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7- And trimethyl-1,4-diazabicyclo [2.2.2] octane. Of these, dibutyltin dilaurate is particularly preferred.
（Ａ）成分として好ましい化合物としては、下記式（１）及び又は（２）で示される化合物が挙げられる。
上記式（１）及び（２）中、Ｚはそれぞれ独立してアクリロイル基又はメタクリロイル基を示し、好ましくは、いずれもＺがアクリロイル基である化合物である。式（１）において、Ｚがアクリロイル基である化合物を「ＰＴＰ」、式（２）においてＺがアクリロイル基である化合物を「ＰＩＰ」という。 In the above formulas (1) and (2), Z independently represents an acryloyl group or a methacryloyl group, and preferably both are compounds in which Z is an acryloyl group. A compound in which Z is an acryloyl group in formula (1) is referred to as “PTP”, and a compound in which Z is an acryloyl group in formula (2) is referred to as “PIP”.
（Ａ）成分の、（メタ）アクリロイル基１個当たりの分子量は４００以下であることが好ましく、３００以下であることがより好ましい。（メタ）アクリロイル基１個当たりの分子量が４００を超えると、十分な膜強度が得られないおそれがある。
上記ＰＴＰ及びＰＩＰの、アクリロイル基１個当たりの分子量は、それぞれ１２４．５及び１３４．５である。The molecular weight per (meth) acryloyl group of the component (A) is preferably 400 or less, and more preferably 300 or less. If the molecular weight per (meth) acryloyl group exceeds 400, sufficient film strength may not be obtained.
The molecular weights of the PTP and PIP per acryloyl group are 124.5 and 134.5, respectively.
本発明の組成物中における（Ａ）成分の含有量は、組成物全量を１００重量％としたときに、３０〜５０重量％の範囲内であることが必要であり、好ましくは３３〜４８重量％、より好ましくは３５〜４５重量％の範囲内である。（Ａ）成分の含有量が３０重量％未満であると、添加効果が得られない場合があり、５０重量％を超えると樹脂液の粘度が上がり塗工性に劣る場合がある。 The content of the component (A) in the composition of the present invention needs to be in the range of 30 to 50% by weight, preferably 33 to 48% by weight when the total amount of the composition is 100% by weight. %, More preferably in the range of 35 to 45% by weight. When the content of the component (A) is less than 30% by weight, the effect of addition may not be obtained, and when it exceeds 50% by weight, the viscosity of the resin liquid may increase and the coating property may be inferior.
（Ｂ）１分子中に２個以上の（メタ）アクリロイル基を有する（Ａ）成分以外の重合性多官能化合物
本発明の組成物における（Ｂ）成分は、分子内に２個以上の（メタ）アクリロイル基を有する（Ａ）成分以外の重合性多官能化合物である。「（Ａ）成分以外」であるから、（Ｂ）成分には、「分子中に環構造を有し、２個の（メタ）アクリロイル基を有するウレタン（メタ）アクリレート」、「分子中に環構造を有し、２個以上の（メタ）アクリロイル基を有し、ウレタン結合を有しない（メタ）アクリレート」、「環構造を有しない、２個以上の（メタ）アクリロイル基を有するウレタン（メタ）アクリレート」、「環構造を有しない、２個以上の（メタ）アクリロイル基を有し、ウレタン結合を有しない（メタ）アクリレート」等が含まれる。（Ｂ）成分は特に硬化膜の屈曲性を向上させるために好適に用いられる。(B) Polymerizable polyfunctional compound other than the component (A) having two or more (meth) acryloyl groups in one molecule The component (B) in the composition of the present invention contains two or more (meta ) A polymerizable polyfunctional compound other than the component (A) having an acryloyl group. Since it is “other than (A) component”, (B) component includes “urethane (meth) acrylate having a ring structure in the molecule and having two (meth) acryloyl groups”, “ring in the molecule” A (meth) acrylate having a structure, having two or more (meth) acryloyl groups and having no urethane bond "," a urethane having two or more (meth) acryloyl groups having no ring structure (meta ) Acrylate ”,“ (meth) acrylate having no ring structure and having two or more (meth) acryloyl groups and having no urethane bond ”and the like. The component (B) is particularly preferably used for improving the flexibility of the cured film.
（Ｂ）成分が有する重合性基は、（メタ）アクリロイル基のみであってもよいし、（メタ）アクリロイル基以外の重合性基をさらに有していてもよい。（Ｂ）成分としては、多官能（メタ）アクリレートが好ましい。多官能（メタ）アクリレート化合物は、硬化膜の硬化性、硬度を上げるために好適に用いられる。ここで多官能とは、１分子中に２個以上の（メタ）アクリロイル基を有することをいい、製膜性、硬度の観点から、３官能以上の（メタ）アクリレート化合物が好ましく、５官能以上の（メタ）アクリレート化合物がさらに好ましい。 The polymerizable group contained in the component (B) may be a (meth) acryloyl group alone or may further have a polymerizable group other than the (meth) acryloyl group. (B) As a component, polyfunctional (meth) acrylate is preferable. The polyfunctional (meth) acrylate compound is suitably used for increasing the curability and hardness of the cured film. Here, polyfunctional means having two or more (meth) acryloyl groups in one molecule, and a trifunctional or higher (meth) acrylate compound is preferable from the viewpoint of film-forming properties and hardness, and five or more functional groups. The (meth) acrylate compound is more preferable.
好ましい多官能（メタ）アクリレート化合物の具体例としては、（メタ）アクリルエステル類としては、トリメチロールプロパントリ（メタ）アクリレート、ジトリ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トリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（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、グリセリントリ（メタ）アクリレート、トリス（２−ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、エチレングルコールジ（メタ）アクリレート、１，３−ブタンジオールジ（メタ）アクリレート、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、ネオペンチルグリコールジ（メタ）アクリレート、ジエチレングルコールジ（メタ）アクリレート、トリエチレングルコールジ（メタ）アクリレート、ジプロピレングルコールジ（メタ）アクリレート、ビス（２−ヒドロキシエチル）イソシアヌレートジ（メタ）アクリレート、及びこれらの出発アルコール類へのエチレンオキシド又はプロピレンオキシド付加物のポリ（メタ）アクリレート類、分子内に２以上の（メタ）アクリロイル基を有するオリゴエステル（メタ）アクリレート類、オリゴエーテル（メタ）アクリレート類、及びオリゴエポキシ（メタ）アクリレート類等を挙げることができる。この中では、ジペンタエリスリトールヘキサ（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、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレートが好ましい。 Specific examples of preferred polyfunctional (meth) acrylate compounds include (meth) acrylic esters such as trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol Di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) a Relate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (Meth) acrylates, poly (meth) acrylates of adducts of ethylene oxide or propylene oxide to these starting alcohols, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoethers (Meth) acrylates, oligoepoxy (meth) acrylates and the like can be mentioned. Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate are preferable.
多官能（メタ）アクリレート化合物の市販品としては、（株）三和ケミカル製 商品名：ニカラック ＭＸ−３０２、東亞合成（株）製 商品名：アロニックス Ｍ−４００、Ｍ−４０２、Ｍ−４０３、Ｍ−４０４、Ｍ−４０８、Ｍ−４５０、Ｍ−３０５、Ｍ−３０９、Ｍ−３１０、Ｍ−３１３、Ｍ−３１５、Ｍ−３２０、Ｍ−３２５、Ｍ−３２６、Ｍ−３２７、Ｍ−３５０、Ｍ−３６０、Ｍ−２０８、Ｍ−２１０、Ｍ−２１５、Ｍ−２２０、Ｍ−２２５、Ｍ−２３３、Ｍ−２４０、Ｍ−２４５、Ｍ−２６０、Ｍ−２７０、Ｍ−１１００、Ｍ−１２００、Ｍ−１２１０、Ｍ−１３１０、Ｍ−１６００、Ｍ−２２１、Ｍ−２０３、ＴＯ−９２４、ＴＯ−１２７０、ＴＯ−１２３１、ＴＯ−５９５、ＴＯ−７５６、ＴＯ−１３４３、ＴＯ−１３８２、ＴＯ−９０２、ＴＯ−９０４、ＴＯ−９０５、ＴＯ−１３３０、日本化薬（株）製 商品名：ＫＡＹＡＲＡＤ Ｄ−３１０、Ｄ−３３０、ＤＰＨＡ、ＤＰＣＡ−２０、ＤＰＣＡ−３０、ＤＰＣＡ−６０、ＤＰＣＡ−１２０、ＤＰＨＡ、ＤＮ−００７５、ＤＮ−２４７５、ＳＲ−２９５、ＳＲ−３５５、ＳＲ−３９９Ｅ、ＳＲ−４９４、ＳＲ−９０４１、ＳＲ−３６８、ＳＲ−４１５、ＳＲ−４４４、ＳＲ−４５４、ＳＲ−４９２、ＳＲ−４９９、ＳＲ−５０２、ＳＲ−９０２０、ＳＲ−９０３５、ＳＲ−１１１、ＳＲ−２１２、ＳＲ−２１３、ＳＲ−２３０、ＳＲ−２５９、ＳＲ−２６８、ＳＲ−２７２、ＳＲ−３４４、ＳＲ−３４９、ＳＲ−３６８、ＳＲ−６０１、ＳＲ−６０２、ＳＲ−６１０、ＳＲ−９００３、ＰＥＴ−３０、Ｔ−１４２０、ＧＰＯ−３０３、ＴＣ−１２０Ｓ、ＨＤＤＡ、ＮＰＧＤＡ、ＴＰＧＤＡ、ＰＥＧ４００ＤＡ、ＭＡＮＤＡ、ＨＸ−２２０、ＨＸ−６２０、Ｒ−５５１、Ｒ−７１２、Ｒ−１６７、Ｒ−５２６、Ｒ−５５１、Ｒ−７１２、Ｒ−６０４、Ｒ−６８４、ＴＭＰＴＡ、ＴＨＥ−３３０、ＴＰＡ−３２０、ＴＰＡ−３３０、ＫＳ−ＨＤＤＡ、ＫＳ−ＴＰＧＤＡ、ＫＳ−ＴＭＰＴＡ、共栄社化学（株）製 商品名：ライトアクリレート ＰＥ−４Ａ、ＤＰＥ−６Ａ、ＤＴＭＰ−４Ａ等を挙げることができる。上記の化合物は、１種単独で、又は２種以上組み合わせて使用することができる。 As a commercial item of a polyfunctional (meth) acrylate compound, Sanwa Chemical Co., Ltd. product name: Nicarak MX-302, Toagosei Co., Ltd. product name: Aronix M-400, M-402, M-403, M-404, M-408, M-450, M-305, M-309, M-310, M-313, M-315, M-320, M-325, M-326, M-327, M- 350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO-1270, TO-1231, TO-595, TO-756, TO-1343, TO- 1382 TO-902, TO-904, TO-905, TO-1330, manufactured by Nippon Kayaku Co., Ltd. Trade names: KAYARAD D-310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA -120, DPHA, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR -492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344 SR-349, SR-368, SR-601, SR-602, SR-610, SR-9003, PET-30, T-14 0, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R- 712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, manufactured by Kyoeisha Chemical Co., Ltd. Trade name: Light acrylate PE-4A , DPE-6A, DTMP-4A and the like. Said compound can be used individually by 1 type or in combination of 2 or more types.
（Ｂ）成分としては、上記多官能（メタ）アクリレート以外に、（Ａ）成分以外の（メタ）アクリロイル基を２個以上有するウレタン（メタ）アクリレート、即ち、環構造を有しないウレタン多官能（メタ）アクリレートを用いることもできる。
このようなウレタン多官能（メタ）アクリレートは、特に限定されないが、基本的には、（ａ）ポリイソシアネート化合物及び（ｂ）ヒドロキシ基含有（メタ）アクリレートモノマーを反応させて得られる。ウレタン（メタ）アクリレートは、他のオリゴマーを主鎖として、それにウレタン結合したものであってもよい。
ウレタン多官能（メタ）アクリレートは、（メタ）アクリロイル基を２個以上有していなければならず、４個以上有することが好ましく、６個以上有することがさらに好ましい。このようなウレタン（メタ）アクリレートは、通常、それぞれイソシアネート基を２〜６個有する（ａ）ポリイソシアネート化合物の各イソシアネート基に（ｂ）ヒドロキシ基含有（メタ）アクリレートモノマーが結合した構造を有している。As the component (B), in addition to the polyfunctional (meth) acrylate, urethane (meth) acrylate having two or more (meth) acryloyl groups other than the component (A), that is, urethane polyfunctional having no ring structure ( A (meth) acrylate can also be used.
Such urethane polyfunctional (meth) acrylate is not particularly limited, but is basically obtained by reacting (a) a polyisocyanate compound and (b) a hydroxy group-containing (meth) acrylate monomer. Urethane (meth) acrylate may have other oligomer as a main chain and urethane bond thereto.
The urethane polyfunctional (meth) acrylate must have 2 or more (meth) acryloyl groups, preferably 4 or more, and more preferably 6 or more. Such urethane (meth) acrylate usually has a structure in which (b) a hydroxy group-containing (meth) acrylate monomer is bonded to each isocyanate group of (a) a polyisocyanate compound each having 2 to 6 isocyanate groups. ing.
本発明で用いるウレタン（メタ）アクリレートの市販品としては、例えば、荒川化学工業（株）製 商品名：ビームセット１０２、５０２Ｈ、５０５Ａ−６、５１０、５５０Ｂ、５５１Ｂ、５７５、５７５ＣＢ、ＥＭ−９０、ＥＭ９２、サンノプコ（株）製 商品名：フォトマー６００８、６２１０、新中村化学工業（株）製 商品名：ＮＫオリゴＵ−２ＰＰＡ、Ｕ−４ＨＡ、Ｕ−６ＨＡ、Ｈ−１５ＨＡ、ＵＡ−３２ＰＡ、Ｕ−３２４Ａ、Ｕ−４Ｈ、Ｕ−６Ｈ、東亜合成（株）製 商品名：アロニックスＭ−１１００、Ｍ−１２００、Ｍ−１２１０、Ｍ−１３１０、Ｍ−１６００、Ｍ−１９６０、共栄社化学（株）製 商品名：ＡＨ−６００、ＡＴ６０６、ＵＡ−３０６Ｈ、日本化薬（株）製 商品名：カヤラッドＵＸ−２２０１、ＵＸ−２３０１、ＵＸ−３２０４、ＵＸ−３３０１、ＵＸ−４１０１、ＵＸ−６１０１、ＵＸ−７１０１、日本合成化学工業（株）製 商品名：紫光ＵＶ−１７００Ｂ、ＵＶ−３０００Ｂ、ＵＶ−６１００Ｂ、ＵＶ−６３００Ｂ、ＵＶ−７０００、ＵＶ−２０１０Ｂ、根上工業（株）製 商品名：アートレジンＵＮ−１２５５、ＵＮ−５２００、ＨＤＰ−４Ｔ、ＨＭＰ−２、ＵＮ−９０１Ｔ、ＵＮ−３３２０ＨＡ、ＵＮ−３３２０ＨＢ、ＵＮ−３３２０ＨＣ、ＵＮ−３３２０ＨＳ、Ｈ−６１、ＨＤＰ−Ｍ２０、ダイセルユーシービー（株）製 商品名：Ｅｂｅｃｒｙｌ ６７００、２０４、２０５、２２０、２５４、１２５９、１２９０Ｋ、１７４８、２００２、２２２０、４８３３、４８４２、４８６６、５１２９、６６０２、８３０１等を挙げることができる。これらの中で、（メタ）アクリレート基を３個以上有するものとして、Ｕ−６ＨＡ等が好ましい。 As a commercial item of the urethane (meth) acrylate used by this invention, Arakawa Chemical Industries Co., Ltd. brand name: Beam set 102, 502H, 505A-6, 510, 550B, 551B, 575, 575CB, EM-90, for example. Product name: Photomer 6008, 6210, manufactured by Shin-Nakamura Chemical Co., Ltd. Product name: NK Oligo U-2PPA, U-4HA, U-6HA, H-15HA, UA-32PA, U -324A, U-4H, U-6H, manufactured by Toa Gosei Co., Ltd. Trade name: Aronix M-1100, M-1200, M-1210, M-1310, M-1600, M-1960, Kyoeisha Chemical Co., Ltd. Product names: AH-600, AT606, UA-306H, manufactured by Nippon Kayaku Co., Ltd. Product names: Kayarad UX-2201, UX-230 , UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Product names: Purple light UV-1700B, UV-3000B, UV-6100B, UV-6300B, UV -7000, UV-2010B, manufactured by Negami Kogyo Co., Ltd. Trade names: Art Resin UN-1255, UN-5200, HDP-4T, HMP-2, UN-901T, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, H-61, HDP-M20, manufactured by Daicel UC Corporation Product names: Ebecryl 6700, 204, 205, 220, 254, 1259, 1290K, 1748, 2002, 2220, 4833, 4842, 4866, 5129 , 6602, 8301 etc. Yes. Among these, U-6HA and the like are preferable as those having three or more (meth) acrylate groups.
本発明の組成物中における（Ｂ）成分の含有量は、組成物全量を１００重量％としたときに、１０〜５０重量％の範囲内であることが必要であり、好ましくは１５〜４５重量％、より好ましくは１５〜４０重量％の範囲内である。（Ｂ）成分の含有量が１０重量％未満であると、十分な耐擦傷性を得られないおそれがあり、５０重量％を超えると、硬化物の反りが大きくなるおそれがある。 The content of the component (B) in the composition of the present invention needs to be in the range of 10 to 50% by weight, preferably 15 to 45% by weight when the total amount of the composition is 100% by weight. %, More preferably in the range of 15-40% by weight. If the content of the component (B) is less than 10% by weight, sufficient scratch resistance may not be obtained, and if it exceeds 50% by weight, warpage of the cured product may be increased.
（Ｃ）重合性単官能化合物
本発明の組成物における（Ｃ）成分は、重合性単官能化合物、即ち、重合性基を１個有するモノマーである。重合性基としては、特に限定されないが、例えば、ビニル基、（メタ）アクリロイル基等が好ましい。重合性単官能化合物は、樹脂液の粘度の調整、及び、粘度の硬化物の反りを低減する目的で添加される。(C) Polymerizable monofunctional compound The component (C) in the composition of the present invention is a polymerizable monofunctional compound, that is, a monomer having one polymerizable group. Although it does not specifically limit as a polymeric group, For example, a vinyl group, a (meth) acryloyl group, etc. are preferable. The polymerizable monofunctional compound is added for the purpose of adjusting the viscosity of the resin liquid and reducing the warpage of the cured product having a viscosity.
（Ｃ）成分の重合性単官能化合物の例としては、例えば、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタムの如きビニル基含有ラクタム、イソボルニル（メタ）アクリレート、ボルニル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレートの如き脂環式構造含有（メタ）アクリレート、ベンジル（メタ）アクリレート、４−ブチルシクロヘキシル（メタ）アクリレート、アクリロイルモルホリン、ビニルイミダゾール、ビニルピリジン、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、メチル（メタ）アクリレート、エチル（メタ）アクリレート、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、ブチル（メタ）アクリレート、アミル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（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、イソステアリル（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、ブトキシエチル（メタ）アクリレート、エトキシジ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オキシド変成（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（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、メトキシポリプロピレングリコール（メタ）アクリレート、ジアセトン（メタ）アクリルアミド、イソブトキシメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、ｔ−オクチル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、７−アミノ−３，７−ジメチルオクチル（メタ）アクリレート、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、ヒドロキシブチルビニルエーテル、ラウリルビニルエーテル、セチルビニルエーテル、２−エチルヘキシルビニルエーテル及び下記式（３）〜（６）で表される化合物を挙げることができる。 Examples of the polymerizable monofunctional compound of component (C) include, for example, vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl ( (Meth) acrylate, alicyclic structure-containing (meth) acrylate such as dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, vinylpyridine, 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isop Pill (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, Heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, Dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Toxiethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (Meth) acrylamide, t-octyl (meth) acrylamide, dimethylamino ester Til (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, Examples thereof include hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether and compounds represented by the following formulas (3) to (6).
（式中、Ｒ2は水素原子又はメチル基を示し、Ｒ3は炭素数２〜６、好ましくは２〜４のアルキレン基を示し、Ｒ4は水素原子又は炭素数１〜１２、好ましくは１〜９のアルキル基を示し、ｍは０〜１２、好ましくは１〜８の数を示す。）(Wherein R 2 represents a hydrogen atom or a methyl group, R 3 represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R 4 represents a hydrogen atom or 1 to 12 carbon atoms, preferably 1 -9 represents an alkyl group, and m represents a number of 0 to 12, preferably 1 to 8.)
（式中、Ｒ5は水素原子又はメチル基を示し、Ｒ6は炭素数２〜８、好ましくは２〜５のアルキレン基を示し、Ｒ7はそれぞれ独立に水素原子又はメチル基を示し、ｐは好ましくは１〜４の数を示す。）(Wherein R 5 represents a hydrogen atom or a methyl group, R 6 represents an alkylene group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms, R 7 each independently represents a hydrogen atom or a methyl group, p Preferably represents a number from 1 to 4.)
（式中、Ｒ8、Ｒ9、Ｒ10及びＲ11は互いに独立に、水素原子又はメチル基であり、ｑは１〜５の整数を示す。）(In formula, R < 8 >, R <9> , R < 10 > and R < 11 > are a hydrogen atom or a methyl group mutually independently, and q shows the integer of 1-5.)
これら重合性単官能モノマーのうち、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタムの如きビニル基含有ラクタム、イソボルニル（メタ）アクリレートが好ましい。 Of these polymerizable monofunctional monomers, vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, and isobornyl (meth) acrylate are preferred.
これら重合性単官能化合物は、市販品ＩＢＸＡ（大阪有機化学工業（株）社製）、アロニックスＭ−１１１、Ｍ−１１３、Ｍ１１４、Ｍ−１１７、ＴＯ−１２１０（以上、東亞合成（株）社製）等として入手することができる。 These polymerizable monofunctional compounds are commercially available products IBXA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Aronix M-111, M-113, M114, M-117, TO-1210 (above, Toagosei Co., Ltd.) Etc.).
本発明の組成物中における（Ｃ）成分の含有量は、組成物全量を１００重量％としたときに、１５〜４０重量％、好ましくは、１５〜３５重量％の範囲内である。（Ｃ）成分の含有量が１５重量％未満であると、樹脂液の粘度が高く塗工性を悪化させるおそれがあり、４０重量％を超えると、硬化物の耐摩擦傷性が劣るおそれがある。 The content of the component (C) in the composition of the present invention is 15 to 40% by weight, preferably 15 to 35% by weight when the total amount of the composition is 100% by weight. When the content of the component (C) is less than 15% by weight, the viscosity of the resin liquid may be high and the coating property may be deteriorated, and when it exceeds 40% by weight, the scratch resistance of the cured product may be deteriorated. is there.
（Ｄ）シリコーン化合物
本発明の組成物における（Ｄ）成分はシリコーン化合物である。シリコーン化合物は、硬化物の耐擦傷性を改善することができるため好適に用いられる。(D) Silicone compound The component (D) in the composition of the present invention is a silicone compound. Silicone compounds are preferably used because they can improve the scratch resistance of the cured product.
本発明で用いる（Ｄ）シリコーン化合物としては、例えば、ポリエーテル変性シリコーン、アルキル変性シリコーン、ウレタンアクリレート変性シリコーン、ウレタン変性シリコーン、メチルスチリル変性シリコーン、エポキシポリエーテル変性シリコーン、アルキルアラルキルポリエーテル変性シリコーン等が挙げられ、このうちポリエーテル変性シリコーンが特に好ましい。ポリエーテル変性シリコーンとしては、少なくとも１個のケイ素原子に基Ｒ２２−（Ｒ２３Ｏ）ｖ−Ｒ２４−（ここで、Ｒ２２は水酸基又は炭素数１〜１０のアルコキシ基を示し、Ｒ２３は炭素数２〜４のアルキレン基を示し（ここでＲ２３は２種以上のアルキレン基が混在していてもよい）、Ｒ２４は炭素数２〜１２のアルキレン基を示し、ｖは１〜２０の数を示す）が結合しているポリジメチルシロキサン化合物が好ましい。このうちＲ２４としては、エチレン基、プロピレン基が好ましく、特にエチレン基が好ましい。当該シリコーン化合物の市販品としては、例えばＳＨ２８ＰＡ；ジメチルポリシロキサンポリオキシアルキレン共重合体、東レダウコーニング社、ＦＭ０４１１；サイラプレーン、チッソ、ＳＦ８４２８；ジメチルポリシロキサンポリオキシアルキレン共重合体（側鎖ＯＨ含有）、東レダウコーニング社、ＢＹＫ
ＵＶ３５１０（ビックケミー・ジャパン株式会社製、ジメチルポリシロキサン−ポリオキシアルキレン共重合体）、ＤＣ５７（東レ・ダウコーニング・シリコーン株式会社製、ジメチルポリシロキサン−ポリオキシアルキレン共重合体）等が挙げられ、これらのうち、ＤＣ５７等が好ましい。シリコーン化合物は市販品としても入手可能であり、例えば、ＳＨ８４００、ＤＣ５７（東レ・ダウコーニング・シリコーン株式会社製）等が挙げられる。シリコーン化合物は、１種単独で、あるいは、複数組み合わせて用いることができる。Examples of the silicone compound (D) used in the present invention include polyether-modified silicone, alkyl-modified silicone, urethane acrylate-modified silicone, urethane-modified silicone, methylstyryl-modified silicone, epoxy polyether-modified silicone, and alkylaralkyl polyether-modified silicone. Of these, polyether-modified silicone is particularly preferred. As the polyether-modified silicone, at least one silicon atom has a group R 22 — (R 23 O) v —R 24 — (wherein R 22 represents a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms, and R 23 Represents an alkylene group having 2 to 4 carbon atoms (wherein R 23 may be a mixture of two or more alkylene groups), R 24 represents an alkylene group having 2 to 12 carbon atoms, and v represents 1 to A polydimethylsiloxane compound having a bond number of 20 is preferred. Among these, R 24 is preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. Commercially available products of the silicone compound include, for example, SH28PA; dimethylpolysiloxane polyoxyalkylene copolymer, Toray Dow Corning, FM0411; Silaplane, Chisso, SF8428; dimethylpolysiloxane polyoxyalkylene copolymer (containing side chain OH) ), Toray Dow Corning, BYK
UV3510 (produced by Big Chemie Japan Co., Ltd., dimethylpolysiloxane-polyoxyalkylene copolymer), DC57 (produced by Toray Dow Corning Silicone Co., Ltd., dimethylpolysiloxane-polyoxyalkylene copolymer), and the like. Of these, DC57 and the like are preferable. Silicone compounds are also available as commercial products, and examples thereof include SH8400, DC57 (manufactured by Toray Dow Corning Silicone Co., Ltd.), and the like. A silicone compound can be used individually by 1 type or in combination of multiple.
本発明の組成物中における（Ｄ）成分の含有量は、組成物全量を１００重量％としたときに、０．０５〜５重量％、好ましくは、０．１〜４重量％の範囲内である。（Ｄ）成分の含有量が０．０５重量％未満では、耐擦傷性に劣る可能性があり、５重量％を超えると、経時で塗膜表面に析出して表面荒れの原因となるおそれがある。 The content of the component (D) in the composition of the present invention is 0.05 to 5% by weight, preferably 0.1 to 4% by weight when the total amount of the composition is 100% by weight. is there. If the content of the component (D) is less than 0.05% by weight, the scratch resistance may be inferior. If it exceeds 5% by weight, it may be deposited on the coating surface over time and cause surface roughness. is there.
（Ｅ）ラジカル重合開始剤
本発明の組成物における（Ｅ）成分はラジカル重合開始剤である。このようなラジカル重合開始剤（Ｅ）としては、例えば、熱的に活性ラジカル種を発生させる化合物等（熱重合開始剤）、及び放射線（光）照射により活性ラジカル種を発生させる化合物等（放射線（光）重合開始剤）を挙げることができ、放射線（光）ラジカル重合開始剤を用いることが好ましい。(E) Radical polymerization initiator The (E) component in the composition of the present invention is a radical polymerization initiator. Examples of such radical polymerization initiator (E) include a compound that thermally generates active radical species (thermal polymerization initiator) and a compound that generates active radical species by radiation (light) irradiation (radiation). (Photo) polymerization initiators), and radiation (photo) radical polymerization initiators are preferably used.
放射線（光）重合開始剤としては、光照射により分解してラジカルを発生して重合を開始せしめるものであれば特に制限はなく、例えば、アセトフェノン、アセトフェノンベンジルケタール、１−ヒドロキシシクロヘキシルフェニルケトン、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、キサントン、フルオレノン、ベンズアルデヒド、フルオレン、アントラキノン、トリフェニルアミン、カルバゾール、３−メチルアセトフェノン、４−クロロベンゾフェノン、４，４’−ジメトキシベンゾフェノン、４，４’−ジアミノベンゾフェノン、ベンゾインプロピルエーテル、ベンゾインエチルエーテル、ベンジルジメチルケタール、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、チオキサントン、ジエチルチオキサントン、２−イソプロピルチオキサントン、２−クロロチオキサントン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１，４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、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、ビス−（２，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルフォスフィンオキシド、オリゴ（２−ヒドロキシ−２−メチル−１−（４−（１−メチルビニル）フェニル）プロパノン）等を挙げることができる。 The radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2 , 2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy Roxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like.
放射線（光）重合開始剤の市販品としては、例えば、チバ・スペシャルティ・ケミカルズ（株）製 商品名：イルガキュア １８４、３６９、６５１、５００、８１９、９０７、７８４、２９５９、ＣＧＩ１７００、ＣＧＩ１７５０、ＣＧＩ１８５０、ＣＧ２４−６１、ダロキュア １１１６、１１７３、ＢＡＳＦ社製 商品名：ルシリン ＴＰＯ、ＴＰＯ−Ｘ、ＵＣＢ社製 商品名：ユベクリル Ｐ３６、ランベルティ社製 商品名：エザキュアー ＫＩＰ１５０、ＫＩＰ６５ＬＴ、ＫＩＰ１００Ｆ、ＫＴ３７、ＫＴ５５、ＫＴＯ４６、ＫＩＰ７５／Ｂ等を挙げることができる。 As a commercial item of a radiation (photo) polymerization initiator, for example, Ciba Specialty Chemicals Co., Ltd. trade name: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG24-61, Darocur 1116, 1173, manufactured by BASF, Inc. Product name: Lucillin TPO, TPO-X, manufactured by UCB, Inc. Product name: Uvekril P36, manufactured by Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46 , KIP75 / B and the like.
本発明の組成物中における（Ｅ）成分の含有量は、組成物全量を１００重量％としたときに、０．１〜１０重量％、好ましくは、０．５〜５重量％の範囲内である。（Ｅ）成分の含有量が０．１重量％未満であると、硬化物としたときの硬度が不十分となることがあり、１０重量％を超えると、硬化物としたときに内部（下層）まで硬化しないことがある。 The content of the component (E) in the composition of the present invention is 0.1 to 10% by weight, preferably 0.5 to 5% by weight when the total amount of the composition is 100% by weight. is there. When the content of the component (E) is less than 0.1% by weight, the hardness of the cured product may be insufficient. When it exceeds 10% by weight, ) May not cure.
本発明の組成物を硬化させる場合、必要に応じて光ラジカル重合開始剤の他に熱ラジカル重合開始剤を併用することができる。
好ましい熱ラジカル重合開始剤としては、例えば、過酸化物、アゾ化合物を挙げることができ、具体例としては、ベンゾイルパーオキサイド、ｔ−ブチル−パーオキシベンゾエート、アゾビスイソブチロニトリル等を挙げることができる。When the composition of the present invention is cured, a thermal radical polymerization initiator can be used in combination with the radical photopolymerization initiator as necessary.
Preferred examples of the thermal radical polymerization initiator include peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile, and the like. Can do.
（Ｆ）その他の添加剤
本発明の組成物には、本発明の効果を損なわない範囲内で、必要に応じて、光増感剤、重合禁止剤、重合開始助剤、レベリング剤、濡れ性改良剤、界面活性剤、可塑剤、紫外線吸収剤、酸化防止剤、帯電防止剤、無機充填剤、防汚剤、顔料、染料等を適宜配合できる。(F) Other additives In the composition of the present invention, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability may be added as necessary within the range not impairing the effects of the present invention. An improver, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, an inorganic filler, an antifouling agent, a pigment, a dye, and the like can be appropriately blended.
次に、本発明の組成物の製造方法について説明する。
環構造を有するウレタン（メタ）アクリレート（（Ａ）成分）、重合性多官能化合物（（Ｂ）成分）、重合性単官能化合物（（Ｃ）成分）、シリコーン化合物（（Ｄ）成分）、光ラジカル重合開始剤（（Ｅ）成分）を、それぞれ所定の配合量で、及び、必要に応じてその他の添加剤（（Ｆ）成分）を、攪拌機付きの反応容器に入れ、通常、５０〜６０℃で２〜４時間攪拌し本発明の組成物とする。Next, the manufacturing method of the composition of this invention is demonstrated.
Urethane (meth) acrylate having a ring structure (component (A)), polymerizable polyfunctional compound (component (B)), polymerizable monofunctional compound (component (C)), silicone compound (component (D)), light The radical polymerization initiator (component (E)) is added in a predetermined amount, and if necessary, other additives (component (F)) are placed in a reaction vessel equipped with a stirrer, usually 50-60. Stir at 4 ° C. for 2 to 4 hours to obtain the composition of the present invention.
このようにして得られた本発明の組成物の粘度は、２５℃において、４００〜１２００ｍＰａ・ｓ、好ましくは５００〜１０００ｍＰａ・ｓである。粘度がこれらの範囲を外れると、スピンコート等での薄膜を作る際に、膜厚の制御が困難になることがあり、また、粘度が４００ｍＰａ・ｓ未満であると、薄膜になりすぎて耐擦傷性が劣るおそれがあり、１２００ｍＰａ・ｓを超えると、膜厚が厚くなり得られる塗膜のカール性が悪化するおそれがある。 The viscosity of the composition of the present invention thus obtained is 400 to 1200 mPa · s, preferably 500 to 1000 mPa · s at 25 ° C. If the viscosity is out of these ranges, it may be difficult to control the film thickness when forming a thin film by spin coating or the like, and if the viscosity is less than 400 mPa · s, the film will be too thin and resistant. There is a possibility that the scratch resistance is inferior, and when it exceeds 1200 mPa · s, there is a possibility that the curl property of the resulting coating film is deteriorated because the film thickness is increased.
次に、本発明の組成物の硬化方法について説明する。
本発明の組成物は、放射線（光）のみ、又は放射線（光）及び熱によって硬化させることができる。熱による場合、その熱源としては、例えば、電気ヒーター、赤外線ランプ、熱風等を用いることができる。放射線（光）による場合、その線源としては、組成物をコーティング後短時間で硬化させることができるものである限り特に制限はないが、例えば、赤外線の線源として、ランプ、抵抗加熱板、レーザー等を、また可視光線の線源として、日光、ランプ、蛍光灯、レーザー等を、また紫外線の線源として、水銀ランプ、ハライドランプ、レーザー等を、また電子線の線源として、市販されているタングステンフィラメントから発生する熱電子を利用する方式、金属に高電圧パルスを通じて発生させる冷陰極方式及びイオン化したガス状分子と金属電極との衝突により発生する２次電子を利用する２次電子方式を挙げることができる。また、アルファ線、ベータ線及びガンマ線の線源として、例えば、６０Ｃｏ等の核分裂物質を挙げることができ、ガンマ線については加速電子を陽極へ衝突させる真空管等を利用することができる。これら放射線は１種単独で又は２種以上を同時に又は一定期間をおいて照射することができる。
本発明の組成物の硬化反応は、空気雰囲気下においても窒素等の嫌気的条件下においても行うことができ、嫌気的条件下で硬化せしめた場合においても、その硬化物は優れた耐擦傷性を有する。Next, a method for curing the composition of the present invention will be described.
The composition of the present invention can be cured by radiation (light) alone or by radiation (light) and heat. When using heat, as the heat source, for example, an electric heater, an infrared lamp, hot air, or the like can be used. In the case of radiation (light), the radiation source is not particularly limited as long as the composition can be cured in a short time after coating. For example, as an infrared radiation source, a lamp, a resistance heating plate, Commercially available lasers, etc., as visible ray sources, sunlight, lamps, fluorescent lamps, lasers, etc., ultraviolet ray sources, mercury lamps, halide lamps, lasers, etc., and electron beam sources Using thermionic electrons generated from tungsten filaments, cold cathode method for generating metal through high voltage pulse, and secondary electron method using secondary electrons generated by collision between ionized gaseous molecules and metal electrode Can be mentioned. Examples of the source of alpha rays, beta rays, and gamma rays include fission materials such as 60 Co. For gamma rays, a vacuum tube that collides accelerated electrons with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.
The curing reaction of the composition of the present invention can be performed under an anaerobic condition such as nitrogen in an air atmosphere, and even when cured under an anaerobic condition, the cured product has excellent scratch resistance. Have
ＩＩ．硬化膜
本発明の硬化膜は、前記本発明の組成物を種々の基材、例えば、プラスチック基材にコーティングして硬化させることにより得ることができる。具体的には、組成物をコーティングし、放射線、又は熱及び放射線で硬化処理を行うことにより被覆成形体として得ることができる。熱による場合の好ましい硬化条件は２０〜１５０℃であり、１０秒〜２４時間の範囲内で行われる。放射線による場合、紫外線又は電子線を用いることが好ましい。そのような場合、好ましい紫外線の照射光量は０．０１〜１０Ｊ／ｃｍ２であり、より好ましくは、０．１〜２Ｊ／ｃｍ２である。また、好ましい電子線の照射条件は、加圧電圧は１０〜３００ＫＶ、電子密度は０．０２〜０．３０ｍＡ／ｃｍ２であり、電子線照射量は１〜１０Ｍｒａｄである。II. Cured film The cured film of the present invention can be obtained by coating the composition of the present invention on various substrates, for example, plastic substrates, and curing them. Specifically, it can be obtained as a coated molded body by coating the composition and performing a curing treatment with radiation or heat and radiation. The preferable curing conditions in the case of heat are 20 to 150 ° C., and are performed within a range of 10 seconds to 24 hours. When using radiation, it is preferable to use ultraviolet rays or electron beams. In such a case, the preferable irradiation amount of ultraviolet rays is 0.01 to 10 J / cm 2 , more preferably 0.1 to 2 J / cm 2 . Moreover, as for the irradiation conditions of a preferable electron beam, a pressurization voltage is 10-300 KV, an electron density is 0.02-0.30 mA / cm < 2 >, and an electron beam irradiation amount is 1-10 Mrad.
本発明の硬化膜は、高硬度であるとともに、カールが小さく、耐擦傷性に優れ、並びに基材や低屈折率層等の隣接層との密着性に優れた塗膜（被膜）であるという特徴を有しているので、タッチパネル、プラスチック光学部品等の保護膜等に特に好適に用いられる。 The cured film of the present invention is a coating film (film) having high hardness, small curl, excellent scratch resistance, and excellent adhesion to adjacent layers such as a substrate and a low refractive index layer. Since it has the characteristic, it is used especially suitably for protective films etc., such as a touch panel and a plastic optical component.
上記本発明の組成物を基材上に塗布し、ＵＶ硬化させて得られた本発明の硬化膜は、カールが低減され、屈曲性、ヘイズに優れ、高硬度である。
本発明の硬化膜のカールが小さい理由は、（Ａ）分子中に環構造を有する多官能ウレタン（メタ）アクリレートを含有するため、架橋点間距離が大きくなり、カールが低減されるものと考えられ、また、芳香環を有する多官能ウレタン（メタ）アクリレートは結晶性を有するため、機械強度、靭性が向上しており、架橋点間距離が大きくなっても硬度のバランスを維持できるものと考えられる。
［実施例］The cured film of the present invention obtained by applying the composition of the present invention on a substrate and UV-curing has reduced curl, excellent flexibility and haze, and high hardness.
The reason why the curl of the cured film of the present invention is small is because (A) the polyfunctional urethane (meth) acrylate having a ring structure in the molecule is contained, the distance between the crosslinking points is increased, and the curl is reduced. In addition, since polyfunctional urethane (meth) acrylates having aromatic rings have crystallinity, mechanical strength and toughness are improved, and it is thought that the balance of hardness can be maintained even when the distance between cross-linking points is increased. It is done.
[Example]
以下、本発明の実施例を詳細に説明するが、本発明の範囲はこれら実施例の記載に限定されるものではない。また、実施例中、各成分の配合量は特に記載のない限り、「部」は重量部を、「％」は重量％を意味している。 Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to the description of these examples. In the examples, unless otherwise specified, the amount of each component means “parts” by weight and “%” means weight percent.
製造例１：ウレタン（メタ）アクリレート（（Ａ）成分）（ＰＴＰ）の製造
攪拌機付きの容器内の２，４−トリレンジイソシアネート１４．７部と、ジブチル錫ジラウレート０．２部とからなる溶液に対し、新中村化学製ＮＫエステルＡ−ＴＭＭ−３ＬＭ−Ｎ（反応に関与するのは、水酸基を有するペンタエリスリトールトリアクリレートのみである。）９３部を、１０℃、１時間の条件で滴下した後、６０℃、６時間の条件で攪拌し、反応液とした。
この生成物中の残存イソシアネート量をＦＴ−ＩＲで測定したところ、０．１重量％以下であり、反応がほぼ定量的に行われたことを確認した。また、生成物の赤外吸収スペクトルは原料中のメルカプト基に特徴的な２５５０ｃｍ−１の吸収ピーク及び原料イソシアネート化合物に特徴的な２２６０ｃｍ−１の吸収ピークが消失し、新たにウレタン結合及びＳ（Ｃ＝Ｏ）ＮＨ−基に特徴的な１６６０ｃｍ−１のピーク及びアクリロキシ基に特徴的な１７２０ｃｍ−１のピークが観察され、重合性不飽和基としてのアクリロキシ基と−Ｓ（Ｃ＝Ｏ）ＮＨ−、ウレタン結合を共に有するアクリロキシ基修飾アルコキシシランが生成していることを示した。
以上により、前記式（１）で示される化合物が７１部得られたほか、反応に関与しなかったペンタエリスリトールテトラアクリレート３７部が混在していた。Production Example 1: Production of urethane (meth) acrylate (component (A)) (PTP) A solution comprising 14.7 parts of 2,4-tolylene diisocyanate and 0.2 part of dibutyltin dilaurate in a container equipped with a stirrer. On the other hand, 93 parts of NK ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd. (only the pentaerythritol triacrylate having a hydroxyl group is involved in the reaction) was added dropwise at 10 ° C. for 1 hour. Then, it stirred on 60 degreeC and the conditions for 6 hours, and was set as the reaction liquid.
When the amount of residual isocyanate in this product was measured by FT-IR, it was 0.1 wt% or less, and it was confirmed that the reaction was carried out almost quantitatively. Further, the infrared absorption spectrum of the product absorption peak characteristic 2260 cm -1 to the absorption peak and the raw material isocyanate compounds characteristic 2550 cm -1 mercapto group in the raw material disappeared, a new urethane bond and S ( C = O) NH- peaks characteristic 1720 cm -1 to a peak and an acryloxy group of characteristic 1660 cm -1 was observed in group, acryloxy group and -S (C = O) NH as polymerizable unsaturated group It was shown that an acryloxy group-modified alkoxysilane having a urethane bond was formed.
As a result, 71 parts of the compound represented by the formula (1) was obtained, and 37 parts of pentaerythritol tetraacrylate which was not involved in the reaction were mixed.
製造例２：ウレタン（メタ）アクリレート（（Ａ）成分）（ＰＩＰ）の製造
攪拌機付きの容器内のイソホロンジイソシアネート１８．８部と、ジブチル錫ジラウレート０．２部とからなる溶液に対し、新中村化学株式会社製ＮＫエステルＡ−ＴＭＭ−３ＬＭ−Ｎ（反応に関与するのは、水酸基を有するペンタエリスリトールトリアクリレートのみである。）９３部を、１０℃、１時間の条件で滴下した後、６０℃、６時間の条件で攪拌し、反応液とした。
製造例１と同様にして、生成物中の残存イソシアネート量をＦＴ−ＩＲで測定したところ、０．１重量％以下であり、反応がほぼ定量的に行われたことを確認した。また、分子内に、ウレタン結合、及びアクリロイル基（重合性不飽和基）を含むことを確認した。
以上により、前記式（２）で示される化合物が７５部得られたほか、反応に関与しなかったペンタエリスリトールテトラアクリレート３７部が混在していた。Production Example 2: Production of urethane (meth) acrylate (component (A)) (PIP) Shin Nakamura for a solution consisting of 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a container equipped with a stirrer NK ester A-TMM-3LM-N manufactured by Kagaku Co., Ltd. (participating in the reaction is only pentaerythritol triacrylate having a hydroxyl group) 93 parts was added dropwise at 10 ° C. for 1 hour, and then 60 parts The mixture was stirred at 6 ° C. for 6 hours to prepare a reaction solution.
When the amount of residual isocyanate in the product was measured by FT-IR in the same manner as in Production Example 1, it was 0.1% by weight or less, and it was confirmed that the reaction was carried out almost quantitatively. Moreover, it confirmed that a urethane bond and an acryloyl group (polymerizable unsaturated group) were included in the molecule | numerator.
As a result, 75 parts of the compound represented by the formula (2) was obtained, and 37 parts of pentaerythritol tetraacrylate which was not involved in the reaction were mixed.
実施例１
上記製造例１で合成した（Ａ）成分ＰＴＰを３４．３部、（Ｂ）成分ＴＭＰＴＡ（大阪有機工業株式会社社製）１４．７部、同じく（Ｂ）成分ＶＲ−７７（昭和高分子社株式会社製）２４．５部、（Ｃ）成分Ｎ−ビニルピロリドン（ＩＰＳジャパン社製）２４．５部、（Ｄ）成分ＤＣ５７（東レ・ダウコーニング・シリコーン株式会社製）１部、（Ｅ）成分ＴＰＯ−Ｘ（ＢＡＳＦ社製）１部を攪拌機のついたフラスコに入れ、５５℃に保ち３時間攪拌し、透明液体を得た。Example 1
34.3 parts of component (A) PTP synthesized in Production Example 1 above, 14.7 parts of component (B) component TMPTA (manufactured by Osaka Organic Industry Co., Ltd.), component VR-77 (showa polymer company) 24.5 parts (made by Co., Ltd.), 24.5 parts (C) component N-vinylpyrrolidone (made by IPS Japan), 1 part (D) component DC57 (made by Toray Dow Corning Silicone Co., Ltd.), (E) 1 part of component TPO-X (manufactured by BASF) was put in a flask equipped with a stirrer and kept at 55 ° C. and stirred for 3 hours to obtain a transparent liquid.
実施例２〜４及び比較例１〜４
表１に示す組成とした以外は実施例１と同様の方法により、実施例２〜４及び比較例１〜４の各組成物を得た。Examples 2 to 4 and Comparative Examples 1 to 4
Except having set it as the composition shown in Table 1, according to the method similar to Example 1, each composition of Examples 2-4 and Comparative Examples 1-4 was obtained.
＜液特性＞
上記実施例及び比較例で得られた各組成物について、Ｂ型粘度計を用いて、２５℃での粘度（ｍＰａ・ｓ）を測定した。結果を表１に示す。<Liquid properties>
About each composition obtained by the said Example and comparative example, the viscosity (mPa * s) in 25 degreeC was measured using the B-type viscosity meter. The results are shown in Table 1.
＜硬化膜特性＞
上記実施例及び比較例で得られた各組成物を、ＰＥＴ上に１０μｍ厚になるようにスピンコートし、メタルハライドランプを用いて、大気中、１．０Ｊ／ｃｍ２の光照射条件で硬化膜を得た。そのガラス上の硬化膜を用いて、下記の特性を評価し、結果を表１に示した。<Curing film characteristics>
Each composition obtained in the above examples and comparative examples was spin-coated on PET so as to have a thickness of 10 μm, and a cured film was used under a light irradiation condition of 1.0 J / cm 2 in the air using a metal halide lamp. Got. The following properties were evaluated using the cured film on the glass, and the results are shown in Table 1.
（１）耐擦傷性
日本スチールウール株式会社製 Ｂｏｎ Ｓｔａｒ 型番００００を用いて、荷重５００ｇをかけて１０往復擦ったときの傷の有無を目視で判定した。(1) Scratch resistance Using a Bon Star model number 0000 manufactured by Nippon Steel Wool Co., Ltd., the presence or absence of scratches was determined visually by rubbing 10 reciprocations under a load of 500 g.
（２）カール
得られた硬化膜付きＰＥＴフィルムを８ｃｍ角の大きさに切り取り、水平に置き、四隅の水平面からの浮きの平均をカールの値とした。(2) Curl The obtained cured film-coated PET film was cut into a size of 8 cm square and placed horizontally, and the average of the floats from the horizontal surfaces at the four corners was taken as the curl value.
表１中の略号は下記のものを示す。
ＰＴＰ：式（１）で示されるウレタン（メタ）アクリレート（製造例１で合成）
ＰＩＰ：式（２）で示されるウレタン（メタ）アクリレート（製造例２で合成）
ＴＭＰＴＡ：大阪有機工業株式会社製テトラメチロールメタントリアクリレート
ＶＲ−７７：昭和高分子株式会社製エポキシジアクリレート
ＫＡＹＡＲＡＤ ＤＰＨＡ：日本化薬株式会社製ジペンタエリスリトールヘキサアクリレート
ＤＣ５７：東レ・ダウコーニング・シリコーン株式会社製ポリエーテル変性シリコーン
ＴＰＯ−Ｘ：ＢＡＳＦ社製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Abbreviations in Table 1 indicate the following.
PTP: urethane (meth) acrylate represented by the formula (1) (synthesized in Production Example 1)
PIP: Urethane (meth) acrylate represented by the formula (2) (synthesized in Production Example 2)
TMPTA: Tetramethylol Methane Triacrylate manufactured by Osaka Organic Industry Co., Ltd. VR-77: Epoxy diacrylate manufactured by Showa Polymer Co., Ltd. KAYARAD DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. DC57: Dow Corning Toray Silicone Co., Ltd. Polyether modified silicone TPO-X: Trimethylbenzoyldiphenylphosphine oxide manufactured by BASF
表１の結果から、（Ａ）成分の含有量が多い比較例１は、粘度が高く塗工性に劣ることがわかる。（Ａ）成分の含有量が少なく、（Ｂ）成分の含有量が多い比較例２は、カールが大きくなることがわかる。（Ａ）成分が少なく、（Ｃ）成分が多い比較例３は、粘度が低く塗工性に劣り、さらに耐擦傷性にも劣ることがわかる。（Ｄ）成分を含有しない比較例４は、耐擦傷性に劣ることがわかる。これに対し、実施例１〜４では、塗工性が良好であり、カールが小さく、かつ耐擦傷性にも優れることがわかる。 From the results of Table 1, it can be seen that Comparative Example 1 having a high content of the component (A) has a high viscosity and is inferior in coatability. It can be seen that the curl increases in Comparative Example 2 in which the content of the component (A) is small and the content of the component (B) is large. It can be seen that Comparative Example 3 having a small amount of component (A) and a large amount of component (C) has a low viscosity and poor coatability, and is also poor in scratch resistance. It can be seen that Comparative Example 4 containing no component (D) is inferior in scratch resistance. On the other hand, in Examples 1 to 4, it can be seen that the coatability is good, the curl is small, and the scratch resistance is excellent.
本発明のハードコート用硬化性組成物、その硬化膜（ハードコート）は、例えば、プラスチック光学部品、タッチパネル、フィルム型液晶素子、プラスチック製品や建築内装材としての床材、壁材、人工大理石等の傷付き（擦傷）防止や汚染防止のための保護コーティング材；各種基材の接着剤、シーリング材；印刷インクのバインダー材等として好適に用いることができる。
本発明のハードコート用硬化性組成物は、金属、プラスチック、木材等の保護膜用ハードコート、光ディスク用ハードコート形成用材料として有用である。The hard coating curable composition of the present invention and its cured film (hard coat) are, for example, plastic optical parts, touch panels, film-type liquid crystal elements, plastic products, floor materials as building interior materials, wall materials, artificial marble, etc. It can be suitably used as a protective coating material for preventing scratches (scratching) and preventing contamination; adhesives for various substrates, sealing materials; binder materials for printing inks, and the like.
The curable composition for hard coats of the present invention is useful as a material for forming hard coats for protective films of metals, plastics, wood, etc., and hard coats for optical discs.
Claims (3)
（Ａ）下記式（１）及び／又は（２）で示される化合物 ３０〜５０重量％
（Ｂ）１分子中に２個以上の（メタ）アクリロイル基を有する（Ａ）成分以外の重合性多官能化合物 １０〜５０重量％
（Ｃ）重合性単官能化合物 １５〜４０重量％
（Ｄ）シリコーン化合物 ０．０５〜５重量％
（Ｅ）光ラジカル重合開始剤 ０．１〜１０重量％ A solvent-free curable composition for hard coat, comprising the following components (A) to (E) in the following proportions when the total amount of the composition is 100% by weight.
(A) 30 to 50% by weight of a compound represented by the following formula (1) and / or (2)
(B) Polymerizable polyfunctional compound other than component (A) having two or more (meth) acryloyl groups in one molecule 10 to 50% by weight
(C) Polymerizable monofunctional compound 15-40% by weight
(D) Silicone compound 0.05 to 5% by weight
(E) Photoradical polymerization initiator 0.1 to 10% by weight
A cured film obtained by curing the curable composition for hard coat according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009537999A JP5476994B2 (en) | 2007-10-19 | 2008-09-08 | Solvent-free curable composition for hard coat and cured film thereof |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007272565 | 2007-10-19 | ||
| JP2007272565 | 2007-10-19 | ||
| JP2009537999A JP5476994B2 (en) | 2007-10-19 | 2008-09-08 | Solvent-free curable composition for hard coat and cured film thereof |
| PCT/JP2008/066147 WO2009050957A1 (en) | 2007-10-19 | 2008-09-08 | Solvent-free curable composition for hard coat and cured film thereof |
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| Publication Number | Publication Date |
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| JPWO2009050957A1 JPWO2009050957A1 (en) | 2011-02-24 |
| JP5476994B2 true JP5476994B2 (en) | 2014-04-23 |
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| JP2009537999A Active JP5476994B2 (en) | 2007-10-19 | 2008-09-08 | Solvent-free curable composition for hard coat and cured film thereof |
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| JP (1) | JP5476994B2 (en) |
| TW (1) | TW200927849A (en) |
| WO (1) | WO2009050957A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2011152404A1 (en) * | 2010-06-01 | 2013-08-01 | リケンテクノス株式会社 | Paint and adhesive composition, adhesion method and laminate |
| EP2612890A1 (en) * | 2010-09-02 | 2013-07-10 | Riken Technos Corp. | Coating for flooring materials and flooring material |
| WO2012032588A1 (en) * | 2010-09-06 | 2012-03-15 | リケンテクノス株式会社 | Coating and laminate |
| JP2012229412A (en) * | 2011-04-13 | 2012-11-22 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition and coating agent |
| KR101501686B1 (en) | 2012-05-31 | 2015-03-11 | 주식회사 엘지화학 | Hard coating film |
| KR101379491B1 (en) | 2012-05-31 | 2014-04-01 | 주식회사 엘지화학 | Hard coating film and method of preparing of hard coating film |
| KR101389967B1 (en) | 2012-05-31 | 2014-04-30 | 주식회사 엘지화학 | Method of preparing of hard coating film |
| KR101470465B1 (en) | 2012-08-23 | 2014-12-08 | 주식회사 엘지화학 | Hard coating film |
| JP2015196765A (en) * | 2014-04-01 | 2015-11-09 | 東洋インキＳｃホールディングス株式会社 | Active energy ray-curable varnish composition and laminate of the same |
| JP6455115B2 (en) * | 2014-12-10 | 2019-01-23 | 凸版印刷株式会社 | Photo-curable resin molding, polarizing plate, and transmissive liquid crystal display |
| JP2020002280A (en) * | 2018-06-29 | 2020-01-09 | 三菱ケミカル株式会社 | Active energy ray-curable composition and laminate |
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| JP2007046031A (en) * | 2004-12-17 | 2007-02-22 | Nitto Denko Corp | Hard coating film and method for producing the same |
| WO2007061027A1 (en) * | 2005-11-28 | 2007-05-31 | Nitto Denko Corporation | Polarizing plate with optical compensation layer and image display device using the same |
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2008
- 2008-09-08 JP JP2009537999A patent/JP5476994B2/en active Active
- 2008-09-08 WO PCT/JP2008/066147 patent/WO2009050957A1/en active Application Filing
- 2008-10-15 TW TW097139564A patent/TW200927849A/en unknown
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| JPH06136078A (en) * | 1992-10-21 | 1994-05-17 | Daiseru U C B Kk | Actinic energy ray-curing resin composition |
| JP2004001372A (en) * | 2002-04-10 | 2004-01-08 | Sumitomo Chem Co Ltd | Abrasion resistant resin board and its manufacturing process |
| JP2005330439A (en) * | 2004-05-21 | 2005-12-02 | Nof Corp | Coating agent composition, coating product prepared by curing the same, and antifogging sheet |
| WO2006038481A1 (en) * | 2004-10-06 | 2006-04-13 | Nitto Denko Corporation | Hard coating film, antireflective hard coating film, optical element and image display device |
| JP2007046031A (en) * | 2004-12-17 | 2007-02-22 | Nitto Denko Corp | Hard coating film and method for producing the same |
| JP2006220906A (en) * | 2005-02-10 | 2006-08-24 | Toray Ind Inc | Optical film |
| JP2006316249A (en) * | 2005-04-13 | 2006-11-24 | Daicel-Cytec Co Ltd | Hard coating agent composition and molded product |
| WO2007061027A1 (en) * | 2005-11-28 | 2007-05-31 | Nitto Denko Corporation | Polarizing plate with optical compensation layer and image display device using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200927849A (en) | 2009-07-01 |
| WO2009050957A1 (en) | 2009-04-23 |
| JPWO2009050957A1 (en) | 2011-02-24 |
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