JP5374997B2 - Active energy ray-curable resin composition for coating and film substrate - Google Patents
Active energy ray-curable resin composition for coating and film substrate Download PDFInfo
- Publication number
- JP5374997B2 JP5374997B2 JP2008247824A JP2008247824A JP5374997B2 JP 5374997 B2 JP5374997 B2 JP 5374997B2 JP 2008247824 A JP2008247824 A JP 2008247824A JP 2008247824 A JP2008247824 A JP 2008247824A JP 5374997 B2 JP5374997 B2 JP 5374997B2
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- JP
- Japan
- Prior art keywords
- meth
- acrylate
- active energy
- energy ray
- resin composition
- 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.)
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- 239000011248 coating agent Substances 0.000 title claims description 52
- 238000000576 coating method Methods 0.000 title claims description 52
- 239000011342 resin composition Substances 0.000 title claims description 32
- 239000000758 substrate Substances 0.000 title claims description 15
- 239000000178 monomer Substances 0.000 claims description 49
- 229920000642 polymer Polymers 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 27
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 23
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008119 colloidal silica Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 129
- 239000010408 film Substances 0.000 description 64
- -1 polyethylene terephthalate Polymers 0.000 description 59
- 239000000203 mixture Substances 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 10
- 229920000058 polyacrylate Polymers 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 9
- 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 8
- 239000004593 Epoxy Substances 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 5
- 229920002284 Cellulose triacetate Polymers 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 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 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 229940059574 pentaerithrityl Drugs 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 229920013730 reactive polymer Polymers 0.000 description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 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 4
- 239000000126 substance Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- 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 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 2
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- OYLCUJRJCUXQBQ-UHFFFAOYSA-N 1-hepten-3-one Chemical compound CCCCC(=O)C=C OYLCUJRJCUXQBQ-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-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
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- SVIQBUBNVYWIDV-UHFFFAOYSA-N 2-methoxy-2-(2-methoxyphenyl)-1-phenylethanone Chemical compound C=1C=CC=C(OC)C=1C(OC)C(=O)C1=CC=CC=C1 SVIQBUBNVYWIDV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-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
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- WXDKFJRADUJSAK-AATRIKPKSA-N 4-o-butyl 1-o-methyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OC WXDKFJRADUJSAK-AATRIKPKSA-N 0.000 description 2
- JDOZUYVDIAKODH-SNAWJCMRSA-N 4-o-ethyl 1-o-methyl (e)-but-2-enedioate Chemical compound CCOC(=O)\C=C\C(=O)OC JDOZUYVDIAKODH-SNAWJCMRSA-N 0.000 description 2
- QSSQDVQKBZEBNP-UHFFFAOYSA-N 4-o-ethyl 1-o-methyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OC QSSQDVQKBZEBNP-UHFFFAOYSA-N 0.000 description 2
- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
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- 239000004640 Melamine resin Substances 0.000 description 1
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- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
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- TUOBEAZXHLTYLF-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CC)COC(=O)C=C TUOBEAZXHLTYLF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LXSJHLYEDBJAGK-UHFFFAOYSA-N [4-(2-phenylpropan-2-yl)phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=CC=C1 LXSJHLYEDBJAGK-UHFFFAOYSA-N 0.000 description 1
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- CBERLDHYJQHMCR-UHFFFAOYSA-N [4-dodecoxy-2-[(2-nitrophenyl)methoxy]phenyl]-phenylmethanone Chemical compound C=1C=CC=C([N+]([O-])=O)C=1COC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 CBERLDHYJQHMCR-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
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- 239000000460 chlorine Substances 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000013078 crystal Substances 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
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- 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 1
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- JPZYWLWSLROXQG-UHFFFAOYSA-N ethyl 2-prop-2-enoylperoxycarbonylbenzoate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OOC(=O)C=C JPZYWLWSLROXQG-UHFFFAOYSA-N 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
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- 125000002541 furyl group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 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
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 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
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
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- 125000001421 myristyl 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])[H] 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
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- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 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
- 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
- 238000007645 offset printing Methods 0.000 description 1
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- LXTZRIBXKVRLOA-UHFFFAOYSA-N padimate a Chemical class CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 LXTZRIBXKVRLOA-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
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- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- FAIDIRVMPHBRLT-UHFFFAOYSA-N propane-1,2,3-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OCC(O)CO FAIDIRVMPHBRLT-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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- 229960002447 thiram Drugs 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、特に、フィルム基材等の薄膜のプラスチック基材への塗工した際にも硬度が得られ、硬化の際も低収縮でフィルムの反り(カール)が少なく、且つ、透明性に優れる硬化塗膜が得られるコーティング用活性エネルギー線硬化型樹脂組成物、及び該組成物を硬化させた硬化層を有するフィルム基材に関する。 In particular, the present invention provides hardness even when a thin film such as a film substrate is applied to a plastic substrate, has low shrinkage even during curing, has little film warping (curl), and is transparent. The present invention relates to an active energy ray-curable resin composition for coating that provides an excellent cured coating film, and a film substrate having a cured layer obtained by curing the composition.
ポリエチレンテレフタレート樹脂(PET)、アクリル樹脂、ポリカーボネート樹脂、アセチル化セルロース樹脂などを用いて製造されるプラスチックフィルムは、工業用途で多用されている。これらフィルムは、例えば、フラットパネルディスプレイの内部に組み込まれる偏光板保護フィルムとして利用されるが、これらのフィルムには、高い耐擦傷性が求められている。 Plastic films produced using polyethylene terephthalate resin (PET), acrylic resin, polycarbonate resin, acetylated cellulose resin and the like are widely used in industrial applications. These films are used as, for example, a polarizing plate protective film incorporated into a flat panel display, and these films are required to have high scratch resistance.
耐擦傷性を高める方法としては、種々の方法が検討されているが、有機溶剤を使用しない等の環境上の優位性の点から、近年、フィルム上に架橋密度の高い多官能アクリレートを主体とした活性エネルギー線硬化型樹脂組成物を塗布し、紫外線(UV)や電子線(EB)等の活性エネルギー線で硬化させハードコート層を形成する方法が実施されるようになってきている。 Various methods have been studied as a method for enhancing the scratch resistance, but in recent years, mainly from polyfunctional acrylates having a high crosslinking density on the film from the viewpoint of environmental superiority such as not using an organic solvent. A method of forming a hard coat layer by applying the active energy ray-curable resin composition and curing it with active energy rays such as ultraviolet rays (UV) or electron beams (EB) has been implemented.
このハードコート層に要求される耐擦傷性としては、例えば、偏光板保護フィルムとして80μm厚TACフィルムを基材とする場合、該フィルム上で鉛筆硬度4Hレベルの高硬度が要求される。 As the scratch resistance required for the hard coat layer, for example, when a TAC film having a thickness of 80 μm is used as a polarizing plate protective film, a high hardness of 4H pencil hardness is required on the film.
しかしながら、前記活性エネルギー線硬化型樹脂組成物は硬化反応の際に体積収縮が生じ、その結果、フィルムがカールする場合がある。フィルムが薄いほどカールが起こり易いが、近年、例えば、フラットパネルディスプレイの薄型化に伴い、偏光板保護フィルムもより薄いもの、例えば、40μm厚のTACフィルムを用いる動きがあるなど、カールし易い膜厚のフィルムを用いるようになってきている。従って、硬度が高く、且つ、よりカールしにくい硬化塗膜が得られる活性エネルギー線硬化型樹脂組成物が要求されてきている。 However, the active energy ray-curable resin composition undergoes volume shrinkage during the curing reaction, and as a result, the film may curl. The thinner the film, the more likely it is to curl. In recent years, for example, as the flat panel display is made thinner, the polarizing plate protective film is thinner, for example, there is a movement using a 40 μm thick TAC film. Thick films have been used. Therefore, there has been a demand for an active energy ray-curable resin composition that provides a cured film that has high hardness and is less likely to curl.
硬度が高く、カールしにくい活性エネルギー線硬化型樹脂組成物としては、例えば、エポキシ当量が120〜500g/eq、重量平均分子量が5,000〜100,000およびガラス転移温度が30℃以上のエポキシ基含有(メタ)アクリル重合体にα,β−不飽和モノカルボン酸を付加反応させてなる(メタ)アクリル当量が200〜600g/eqである反応性ポリマー(A)を含有する組成物が開示されている(例えば、特許文献1参照)。しかしながら、該反応性ポリマーはエポキシ基含有(メタ)アクリル重合体とα,β−不飽和モノカルボン酸との反応により生成した2級水酸基を有し、ウレタンアクリレート等の他の重合性単量体との相溶性が悪い場合が有る。その為、該反応性ポリマーと他の重合性単量体とを混合して組成物の硬化塗膜は濁りが生じやすい。 Examples of the active energy ray-curable resin composition having high hardness and hardly curling include, for example, an epoxy having an epoxy equivalent of 120 to 500 g / eq, a weight average molecular weight of 5,000 to 100,000, and a glass transition temperature of 30 ° C. or higher. Disclosed is a composition containing a reactive polymer (A) having a (meth) acrylic equivalent of 200 to 600 g / eq obtained by addition reaction of an α, β-unsaturated monocarboxylic acid to a group-containing (meth) acrylic polymer. (For example, refer to Patent Document 1). However, the reactive polymer has a secondary hydroxyl group formed by the reaction of an epoxy group-containing (meth) acrylic polymer and an α, β-unsaturated monocarboxylic acid, and other polymerizable monomer such as urethane acrylate. There are cases where the compatibility with is poor. Therefore, the cured coating film of the composition is likely to be turbid by mixing the reactive polymer with another polymerizable monomer.
本発明の課題は、フィルム基材等の薄膜のプラスチック基材への塗工した際にも高硬度が得られ、硬化の際も低収縮でフィルムの反り(カール)が少なく、且つ、透明性に優れる硬化塗膜が得られるコーティング用活性エネルギー線硬化型樹脂組成物及び硬度が高く、カールが少なく、且つ、透明性に優れる硬化塗膜を有するフィルム基材を提供することにある。 The object of the present invention is to obtain a high hardness even when a thin film such as a film substrate is applied to a plastic substrate, a low shrinkage even during curing, and less warping (curl) of the film, and transparency. It is an object to provide an active energy ray-curable resin composition for coating that can provide a cured coating film that is excellent in coating, a film substrate that has a cured coating film that has high hardness, low curl, and excellent transparency.
本発明者らは、上記の課題を解決するため、鋭意検討した結果、前記特許文献1に開示されている反応性二重結合とイソシアネート基を有する単量体を含有する重合性単量体を重合させて得られるイソシアネート基含有重合体に、水酸基と(メタ)アクリロイル基とを有する化合物を反応させて得られる重合体は、ウレタン結合を有し、その為、他の重合性単量体、特に他のウレタン(メタ)アクリレートとは、ウレタン結合同士の水素結合により相溶性が好ましく、得られる硬化塗膜も透明性に優れる事、該硬化塗膜は硬度も高く、また、カールしにくい事等を見出し、本発明を完成するに至った。 As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have found a polymerizable monomer containing a monomer having a reactive double bond and an isocyanate group disclosed in Patent Document 1. A polymer obtained by reacting a compound having a hydroxyl group and a (meth) acryloyl group with an isocyanate group-containing polymer obtained by polymerization has a urethane bond, and thus other polymerizable monomers, In particular, compatibility with other urethane (meth) acrylates is preferable due to hydrogen bonding between urethane bonds, and the resulting cured coating film is excellent in transparency, and the cured coating film has high hardness and is difficult to curl. As a result, the present invention has been completed.
即ち、本発明は、反応性二重結合とイソシアネート基を有する下記一般式(1)
で示される単量体を70〜100重量%となる割合で含有する重合性単量体を(共)重合させて得られるイソシアネート基含有重合体(a1)に、水酸基と(メタ)アクリロイル基とを有する化合物(a2)を反応させて得られる重合体(A)を含有することを特徴とする活性エネルギー線硬化型樹脂組成物を提供するものである。
That is, the present invention provides the following general formula (1) having a reactive double bond and an isocyanate group.
To an isocyanate group-containing polymer (a1) obtained by (co) polymerizing a polymerizable monomer containing the monomer represented by 70 to 100% by weight with a hydroxyl group and a (meth) acryloyl group The present invention provides an active energy ray-curable resin composition comprising a polymer (A) obtained by reacting a compound (a2) having a hydrogen atom.
また、本発明は、前記コーティング用活性エネルギー線硬化型樹脂組成物を硬化させて得られる硬化層を有することを特徴とするフィルム基材を提供するものである。 The present invention also provides a film substrate comprising a cured layer obtained by curing the active energy ray-curable resin composition for coating.
本発明のコーティング用活性エネルギー線硬化型樹脂組成物は硬度が高く、また、硬化収縮も少ないことからカールしにくい硬化物が得られる。従って、フィルム基材の保護層を形成させるための組成物として特に好適に用いることができる。 Since the active energy ray-curable resin composition for coating of the present invention has high hardness and less curing shrinkage, a cured product that hardly curls can be obtained. Therefore, it can be particularly suitably used as a composition for forming a protective layer of a film substrate.
本発明で用いる重合体(A)は、反応性二重結合とイソシアネート基を有する単量体を含有する重合性単量体を(共)重合させて得られるイソシアネート基含有重合体(a1)に、水酸基と(メタ)アクリロイル基とを有する化合物(a2)を反応させて得られる重合体である。 The polymer (A) used in the present invention is an isocyanate group-containing polymer (a1) obtained by (co) polymerizing a polymerizable monomer containing a monomer having a reactive double bond and an isocyanate group. , A polymer obtained by reacting a compound (a2) having a hydroxyl group and a (meth) acryloyl group.
本発明で用いるイソシアネート基含有重合体(a1)は、反応性二重結合とイソシアネート基を有する単量体を含有する重合性単量体を単独、または他の銃合成単量体と共重合させて得られる重合体である。ここで用いる反応性二重結合とイソシアネート基を有する単量体を含有する重合性単量体中の反応性二重結合とイソシアネート基を有する単量体の含有率としては、50〜100重量%が好ましく、70〜100重量%がより好ましい。 The isocyanate group-containing polymer (a1) used in the present invention is obtained by copolymerizing a polymerizable monomer containing a monomer having a reactive double bond and an isocyanate group alone or with another gun synthesis monomer. It is a polymer obtained. As a content rate of the monomer which has a reactive double bond and an isocyanate group in the polymerizable monomer containing the monomer which has a reactive double bond and an isocyanate group used here, 50 to 100 weight% Is preferable, and 70 to 100 weight% is more preferable.
前記反応性二重結合とイソシアネート基を有する単量体としては、具体的には、例えば、一般式(1): The monomer having a reactive double bond and an isocyanate group, specifically, for example, the general formula (1):
(式中R1は水素原子又はメチル基である。R2は炭素原子数2から4のアルキレン基である。nは1〜5の整数を表す。)で表される化合物を好ましく例示することができる。具体的には、例えば、カレンズAOI、カレンズMOI、カレンズBEI(商品名、昭和電工(株)製)の他、ジイソシアネート化合物とヒドロキシアクリレートとを1:1のモル比にて反応させた生成物等が例示できる。ここで、ジイソシアネート化合物としては、公知のものを特に限定されず使用することができ、例えば、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート等が挙げられる。ヒドロキシアクリレートとしては、水酸基および(メタ)アクリル基を有する化合物であれば特に限定されず、公知のものを使用することができるが、例えば、2−ヒドロキシエチルアクリレート、2−ヒドロキシプロピルアクリレート、4−ヒドロキシブチルアクリレート、グリセリンジアクリレート、トリメチロールプロパンジアクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート等が挙げられる。また、カレンズMOI−BM、カレンズMOI−BP(商品名、昭和電工(株)製)のごとくイソシアネート基がブロックされており、熱処理によりイソシアネート基が再生されるものも反応性二重結合とイソシアネート基を有する単量体として使用することが出来る。 (Wherein R 1 is a hydrogen atom or a methyl group, R 2 is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 5). Can do. Specifically, for example, in addition to Karenz AOI, Karenz MOI, Karenz BEI (trade name, manufactured by Showa Denko KK), a product obtained by reacting a diisocyanate compound and hydroxyacrylate at a molar ratio of 1: 1, etc. Can be illustrated. Here, as a diisocyanate compound, a well-known thing can be used without being specifically limited, For example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc. are mentioned. The hydroxy acrylate is not particularly limited as long as it is a compound having a hydroxyl group and a (meth) acryl group, and a known one can be used. For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4- Examples thereof include hydroxybutyl acrylate, glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the like. In addition, isocyanate groups are blocked as in Karenz MOI-BM and Karenz MOI-BP (trade name, manufactured by Showa Denko KK), and those in which isocyanate groups are regenerated by heat treatment are also reactive double bonds and isocyanate groups. It can be used as a monomer having
前記反応性二重結合とイソシアネート基を有する単量体を含有する重合性単量体は、本発明の効果を損なわない範囲で他の重合性単量体と併用しても良い。他の重合性単量体としては、例えば、(1)(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプシル、(メタ)アクリル酸オクチル、(メタ)アクリル酸ノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸テトラデシル、(メタ)アクリル酸ヘキサデシル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸オクタデシル、(メタ)アクリル酸ドコシル等の炭素数1〜22のアルキル基を持つ(メタ)アクリル酸エステル類; The polymerizable monomer containing a monomer having a reactive double bond and an isocyanate group may be used in combination with another polymerizable monomer as long as the effects of the present invention are not impaired. Examples of other polymerizable monomers include (1) methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (Meth) acrylic acid hepsyl, (meth) acrylic acid octyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic acid tetradecyl, (meth) acrylic acid hexadecyl, ( (Meth) acrylic acid esters having an alkyl group having 1 to 22 carbon atoms such as stearyl (meth) acrylate, octadecyl (meth) acrylate, docosyl (meth) acrylate;
(2)(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸イソボロニル、(メタ)アクリル酸ジシクロペンタニル、(メタ)アクリル酸ジシクロペンテニルオキシエチル等の脂環式のアルキル基を有する(メタ)アクリル酸エステル類; (2) (meth) having an alicyclic alkyl group such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate Acrylic esters;
(3)(メタ)アクリル酸ベンゾイルオキシエチル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸フェニルエチル、(メタ)アクリル酸フェノキシエチル、(メタ)アクリル酸フェノキシジエチレングリコール、(メタ)アクリル酸2−ヒドロキシ−3−フェノキシプロピル等の芳香環を有する(メタ)アクリル酸エステル類; (3) Benzoyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2- (meth) acrylic acid 2- (Meth) acrylic acid esters having an aromatic ring such as hydroxy-3-phenoxypropyl;
(5)フマル酸ジメチル、フマル酸ジエチル、フマル酸ジブチル、イタコン酸ジメチル、イタコン酸ジブチル、フマル酸メチルエチル、フマル酸メチルブチル、イタコン酸メチルエチルなどの不飽和ジカルボン酸エステル類; (5) Unsaturated dicarboxylic acid esters such as dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, methyl ethyl fumarate, methyl butyl fumarate, methyl ethyl itaconate;
(6)スチレン、α−メチルスチレン、クロロスチレンなどのスチレン誘導体類; (6) Styrene derivatives such as styrene, α-methylstyrene and chlorostyrene;
(7)ブタジエン、イソプレン、ピペリレン、ジメチルブタジエンなどのジエン系化合物類; (7) Diene compounds such as butadiene, isoprene, piperylene, dimethylbutadiene;
(8)塩化ビニル、臭化ビニルなどのハロゲン化ビニルやハロゲン化ビニリデン類; (8) Vinyl halides and vinylidene halides such as vinyl chloride and vinyl bromide;
(9)メチルビニルケトン、ブチルビニルケトンなどの不飽和ケトン類; (9) Unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone;
(10)酢酸ビニル、酪酸ビニルなどのビニルエステル類; (10) Vinyl esters such as vinyl acetate and vinyl butyrate;
(11)メチルビニルエーテル、ブチルビニルエーテルなどのビニルエーテル類; (11) Vinyl ethers such as methyl vinyl ether and butyl vinyl ether;
(12)アクリロニトリル、メタクリロニトリル、シアン化ビニリデンなどのシアン化ビニル類; (12) Vinyl cyanides such as acrylonitrile, methacrylonitrile, vinylidene cyanide;
(13)アクリルアミドやそのアルキド置換アミド類; (13) Acrylamide and its alkyd-substituted amides;
(14)N−フェニルマレイミド、N−シクロヘキシルマレイミドなどのN−置換マレイミド類; (14) N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
(15)フッ化ビニル、フッ化ビニリデン、トリフルオロエチレン、クロロトリフルオロエチレン、ブロモトリフルオロエチレン、ペンタフルオロプロピレンもしくはヘキサフルオロプロピレンの如きフッ素含有α−オレフィン類;またはトリフルオロメチルトリフルオロビニルエーテル、ペンタフルオロエチルトリフルオロビニルエーテルもしくはヘプタフルオロプロピルトリフルオロビニルエーテルの如き(パー)フルオロアルキル基の炭素数が1から18なる(パー)フルオロアルキル・パーフルオロビニルエーテル類;2,2,2−トリフルオロエチル(メタ)アクリレート、2,2,3,3−テトラフルオロプロピル(メタ)アクリレート、1H,1H,5H−オクタフルオロペンチル(メタ)アクリレート、1H,1H,2H,2H−ヘプタデカフルオロデシル(メタ)アクリレートもしくはパーフルオロエチルオキシエチル(メタ)アクリレートの如き(パー)フルオロアルキル基の炭素数が1から18なる(パー)フルオロアルキル(メタ)アクリレート類等のフッ素含有エチレン性不飽和単量体類; (15) Fluorine-containing α-olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene; or trifluoromethyltrifluorovinyl ether, penta (Per) fluoroalkyl perfluorovinyl ethers having a (per) fluoroalkyl group of 1 to 18 carbon atoms such as fluoroethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether; 2,2,2-trifluoroethyl (meta ) Acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, Fluorine-containing such as (per) fluoroalkyl (meth) acrylates having 1 to 18 carbon atoms in the (per) fluoroalkyl group such as H-heptadecafluorodecyl (meth) acrylate or perfluoroethyloxyethyl (meth) acrylate Ethylenically unsaturated monomers;
(16)γ−メタクリロキシプロピルトリメトキシシラン等のシリル基含有(メタ)アクリレート類; (16) Silyl group-containing (meth) acrylates such as γ-methacryloxypropyltrimethoxysilane;
(17)N,N−ジメチルアミノエチル(メタ)アクリレート、N,N−ジエチルアミノエチル(メタ)アクリレートもしくはN,N−ジエチルアミノプロピル(メタ)アクリレート等のN,N−ジアルキルアミノアルキル(メタ)アクリレート等が挙げられる。 (17) N, N-dialkylaminoalkyl (meth) acrylate such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate or N, N-diethylaminopropyl (meth) acrylate Is mentioned.
これらの(メタ)アクリル系重合体(a1)や(メタ)アクリル系重合体(a2)を調製する際に用いる他の重合性不飽和単量体は、単独で用いても良いし、2種以上を併用しても良い。 Other polymerizable unsaturated monomers used when preparing these (meth) acrylic polymers (a1) and (meth) acrylic polymers (a2) may be used alone or in combination of two kinds. You may use the above together.
また、他の重合性単量体として不飽和二重結合及びエポキシ基を有する重合性単量体や不飽和二重結合及びカルボキシル基を有する重合性単量体も本発明の効果を損なわない限り使用する事ができる。 In addition, a polymerizable monomer having an unsaturated double bond and an epoxy group or a polymerizable monomer having an unsaturated double bond and a carboxyl group as other polymerizable monomers may be used as long as the effects of the present invention are not impaired. Can be used.
前記不飽和二重結合及びエポキシ基を有する重合性単量体しては、例えば、(メタ)アクリル酸グリシジル、α−エチル(メタ)アクリル酸グリシジル、α−n−プロピル(メタ)アクリル酸グリシジル、α−n−ブチル(メタ)アクリル酸グリシジル、(メタ)アクリル酸−3,4−エポキシブチル、(メタ)アクリル酸−4,5−エポキシペンチル、(メタ)アクリル酸−6,7−エポキシペンチル、α−エチル(メタ)アクリル酸−6,7−エポキシペンチル、βーメチルグリシジル(メタ)アクリレート、(メタ)アクリル酸−3,4−エポキシシクロヘキシル、ラクトン変性(メタ)アクリル酸−3,4−エポキシシクロヘキシル、ビニルシクロヘキセンオキシド等が挙げられる。これらは単独で用いても良いし、2種以上を併用しても良い。 Examples of the polymerizable monomer having an unsaturated double bond and an epoxy group include glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, and glycidyl α-n-propyl (meth) acrylate. , Glycidyl α-n-butyl (meth) acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxy Pentyl, α-ethyl (meth) acrylic acid-6,7-epoxypentyl, β-methylglycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexyl, lactone-modified (meth) acrylic acid-3, 4-epoxycyclohexyl, vinylcyclohexene oxide and the like can be mentioned. These may be used alone or in combination of two or more.
前記不飽和二重結合及びカルボキシル基を有する重合性単量体としては、例えば、(メタ)アクリル酸;β−カルボキシエチル(メタ)アクリレート、2ーアクリロイルオキシエチルコハク酸、2ーアクリロイルオキシエチルフタル酸、2ーアクリロイルオキシエチルヘキサヒドロフタル酸及びこれらのラクトン変性物等エステル結合を有する不飽和モノカルボン酸;マレイン酸等が挙げられる。これらは単独で用いても良いし、2種以上を併用しても良い。 Examples of the polymerizable monomer having an unsaturated double bond and a carboxyl group include (meth) acrylic acid; β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalate. Examples include acids, 2-acryloyloxyethyl hexahydrophthalic acid, and unsaturated monocarboxylic acids having an ester bond such as lactone-modified products thereof; maleic acid and the like. These may be used alone or in combination of two or more.
本発明で用いるイソシアネート基含有重合体(a1)は、例えば、反応性二重結合とイソシアネート基を有する単量体を含有する重合性単量体を重合させて得られる。具体的には、例えば、触媒(重合開始剤)の存在下に、付加重合により製造することができ、ランダム共重合体、ブロック共重合体、グラフト共重合体等のいずれでもよい。また共重合方法も塊状重合法、溶液重合法、懸濁重合法、乳化重合法等の公知の重合方法が使用できる。反応温度としては、通常60〜150℃である。反応時間は通常6〜24時間である。 The isocyanate group-containing polymer (a1) used in the present invention is obtained, for example, by polymerizing a polymerizable monomer containing a monomer having a reactive double bond and an isocyanate group. Specifically, for example, it can be produced by addition polymerization in the presence of a catalyst (polymerization initiator), and any of a random copolymer, a block copolymer, a graft copolymer and the like may be used. As the copolymerization method, a known polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method can be used. As reaction temperature, it is 60-150 degreeC normally. The reaction time is usually 6 to 24 hours.
ここで、溶液重合等に用いることができる溶媒として代表的なものを挙げれば、例えば、アセトン、メチルエチルケトン、メチル−n−プロピルケトン、メチルイソプロピルケトン、メチル−n−ブチルケトン、メチルイソブチルケトン、メチル−n−アミルケトン、メチル−n−ヘキシルケトン、ジエチルケトン、エチル−n−ブチルケトン、ジ−n−プロピルケトン、ジイソブチルケトン、シクロヘキサノン、ホロン等のケトン系溶媒; Here, as typical solvents that can be used for solution polymerization, for example, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl- ketone solvents such as n-amyl ketone, methyl-n-hexyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, and holon;
エチルエーテル、イソプロピルエーテル、n−ブチルエーテル、ジイソアミルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコール、ジオキサン、テトラヒドロフラン等のエーテル系溶媒; Ether solvents such as ethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, tetrahydrofuran;
ギ酸エチル、ギ酸プロピル、ギ酸−n−ブチル、酢酸エチル、酢酸−n−プロピル、酢酸イソプロピル、酢酸−nーブチル、酢酸−n−アミル、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、エチル−3−エトキシプロピオネート等のエステル系溶媒; Ethyl formate, propyl formate, n-butyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl Ester solvents such as ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate;
トルエン、キシレン、ソルベッソ100、ソルベッソ150、スワゾール1800、スワゾール310、アイソパーE、アイソパーG、エクソンナフサ5号、エクソンナフサ6号等の炭化水素系溶媒等が挙げられる。 Examples include toluene, xylene, Solvesso 100, Solvesso 150, Swazol 1800, Swazol 310, Isopar E, Isopar G, Exxon naphtha No. 5, Exxon Naphtha No. 6 and other hydrocarbon solvents.
前記触媒としては、ラジカル重合開始剤として一般的に知られるものが使用でき、例えば2,2’−アゾビスイソブチロニトリル、2,2’−アゾビス−(2,4−ジメチルバレロニトリル)、2,2’−アゾビス−(4−メトキシ−2,4−ジメチルバレロニトリル)等のアゾ化合物;ベンゾイルペルオキシド、ラウロイルペルオキシド、t−ブチルペルオキシピバレート、1,1’−ビス−(t−ブチルペルオキシ)シクロヘキサン、t−アミルペルオキシ−2−エチルヘキサノエート、t−ヘキシルペルオキシ−2−エチルヘキサノエート等の有機過酸化物および過酸化水素等が挙げられる。 As the catalyst, those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), Azo compounds such as 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) ) Organic peroxides such as cyclohexane, t-amylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, and hydrogen peroxide.
触媒として過酸化物を用いる場合には、過酸化物を還元剤とともに用いてレドックス型開始剤としてもよい。 When using a peroxide as a catalyst, it is good also as a redox type initiator using a peroxide with a reducing agent.
本発明で用いる水酸基と(メタ)アクリロイル基とを有する化合物(a2)としては、例えば、2−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、前記各アクリレートのカプロラクトンまたは酸化アルキレン付加物、グリセリンモノ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、グリシジルメタクリレート−アクリル酸付加物、トリメチロールプロパンモノ(メタ)アクリレート、トリメチロールジ(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、ジトリメチロールプロパントリ(メタ)アクリルレート、トリメチロールプロパン−酸化アルキレン付加物−ジ(メタ)アクリレート等が挙げられる。 Examples of the compound (a2) having a hydroxyl group and a (meth) acryloyl group used in the present invention include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the above acrylates. Caprolactone or alkylene oxide adduct, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, glycidyl methacrylate-acrylic acid adduct, trimethylolpropane mono (meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, trimethylolpropane-alkylene oxide adduct-di ( Data) acrylate, and the like.
前記した水酸基と(メタ)アクリロイル基とを有する化合物(a2)の中でも、(メタ)アクリロイル基を2〜5個有する化合物を用いると重合体(A)として1分子当たりの官能基数(エチレン性不飽和二重結合の数)が多いウレタン(メタ)アクリレートが得られ、その結果、高硬度の硬化塗膜が得られる活性エネルギー線硬化型アクリル樹脂組成物となることから好ましい。 Among the compounds (a2) having a hydroxyl group and a (meth) acryloyl group described above, when a compound having 2 to 5 (meth) acryloyl groups is used, the number of functional groups per molecule (ethylenic group) is determined as the polymer (A). A urethane (meth) acrylate having a large number of saturated double bonds) is obtained, and as a result, an active energy ray-curable acrylic resin composition from which a cured film with high hardness can be obtained is preferable.
更に、(メタ)アクリロイル基を2〜5個有する化合物の中でもグリシジルメタクリレート−アクリル酸付加物、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)アクリレートを用いるより好ましく、ペンタエリスリトールトリ(メタ)アクリレートは比較的低粘度である為、得られる活性エネルギー線硬化型アクリル樹脂混合物の粘度を低く抑える事が出来るので更に好ましい。 Further, among the compounds having 2 to 5 (meth) acryloyl groups, it is more preferable to use glycidyl methacrylate-acrylic acid adduct, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and pentaerythritol tri (meth) ) Since acrylate has a relatively low viscosity, the viscosity of the resulting active energy ray-curable acrylic resin mixture can be kept low, which is more preferable.
前記イソシアネート基含有重合体(a1)に、水酸基と(メタ)アクリロイル基とを有する化合物(a2)とを反応させる方法は、特に限定されず、公知の方法を採用することができる。具体的には、例えば、イソシアネート基含有重合体(a1)に水酸基と(メタ)アクリロイル基とを有する化合物(a2)滴下しながら加え、あるいは水酸基と(メタ)アクリロイル基とを有する化合物(a2)にイソシアネート基含有重合体(a1)を滴下しながら加えて、50〜120℃、より好ましくは、60〜90℃に加熱し反応させれば良い。なお、重合体(a1)と重合体(a2)の使用量は特に限定されないが、通常、重合体(a1)のイソシアネート基(モル):重合体(a2)の水酸基(モル)=1:1〜1:2であり、好ましくは、1:1〜1:1.6である。使用量を当該範囲にすることで、製造時のゲル化を防止しながら安定的に製造することができる。 The method for reacting the isocyanate group-containing polymer (a1) with the compound (a2) having a hydroxyl group and a (meth) acryloyl group is not particularly limited, and a known method can be employed. Specifically, for example, a compound (a2) having a hydroxyl group and a (meth) acryloyl group is added dropwise to the isocyanate group-containing polymer (a1), or a compound (a2) having a hydroxyl group and a (meth) acryloyl group. The isocyanate group-containing polymer (a1) may be added dropwise to the mixture and heated to 50 to 120 ° C., more preferably 60 to 90 ° C. for reaction. In addition, although the usage-amount of a polymer (a1) and a polymer (a2) is not specifically limited, Usually, the isocyanate group (mol) of a polymer (a1): The hydroxyl group (mol) of a polymer (a2) = 1: 1. ˜1: 2, preferably 1: 1 to 1: 1.6. By making the amount used within the range, it can be stably produced while preventing gelation during production.
本発明で用いるアクリル系重合体(A)の(メタ)アクリロイル当量としては、130〜600が高架橋密度が達成でき、高硬度を達成しうることから好ましく、130〜400がより好ましい。 As the (meth) acryloyl equivalent of the acrylic polymer (A) used in the present invention, 130 to 600 is preferable because a high crosslinking density can be achieved and high hardness can be achieved, and 130 to 400 is more preferable.
本発明で重量平均分子量と数平均分子量の測定は、ゲルパーミエーションクロマトグラフ(GPC)を用い、下記の条件により求めた。
測定装置 ; 東ソー株式会社製 HLC−8220
カラム ; 東ソー株式会社製ガードカラムHXL−H
+東ソー株式会社製 TSKgel G5000HXL
+東ソー株式会社製 TSKgel G4000HXL
+東ソー株式会社製 TSKgel G3000HXL
+東ソー株式会社製 TSKgel G2000HXL
検出器 ; RI(示差屈折計)
データ処理:東ソー株式会社製 SC−8010
測定条件: カラム温度 40℃
溶媒 テトラヒドロフラン
流速 1.0ml/分
標準 ;ポリスチレン
試料 ;樹脂固形分換算で0.4重量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(100μl)
In the present invention, the weight average molecular weight and the number average molecular weight were measured using a gel permeation chromatograph (GPC) under the following conditions.
Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Guard column H XL- H manufactured by Tosoh Corporation
+ Tosoh Corporation TSKgel G5000H XL
+ Tosoh Corporation TSKgel G4000H XL
+ Tosoh Corporation TSKgel G3000H XL
+ Tosoh Corporation TSKgel G2000H XL
Detector: RI (differential refractometer)
Data processing: Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate 1.0 ml / min Standard; polystyrene sample; 0.4% by weight tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)
更に、本発明のコーティング用活性エネルギー線硬化型樹脂組成物にはコロイダルシリカ(B)を含有させるのが好ましい。コロイダルシリカ(B)は、硬化塗膜の硬度を向上させ、耐擦り傷性を著しく改善する。コロイダルシリカ(B)の平均粒径(一次粒子径)としては硬度に対する効果と塗膜の透明性の観点から1〜100nmが好ましく、10〜50nmがより好ましい Further, the active energy ray-curable resin composition for coating of the present invention preferably contains colloidal silica (B). Colloidal silica (B) improves the hardness of the cured coating film and significantly improves the scratch resistance. The average particle size (primary particle size) of the colloidal silica (B) is preferably 1 to 100 nm, more preferably 10 to 50 nm, from the viewpoint of the effect on hardness and the transparency of the coating film.
また、本発明のコーティング用活性エネルギー線硬化型樹脂組成物中のコロイダルシリカ(B)の含有率としては、硬度に対する効果と硬化性の観点から、該組成分中の塗膜形成成分の重量を基準として15〜60重量%が好ましく、20〜50重量%がより好ましい。 In addition, the content of colloidal silica (B) in the active energy ray-curable resin composition for coating of the present invention is the weight of the coating film-forming component in the composition from the viewpoint of the effect on hardness and curability. The reference is preferably 15 to 60% by weight, and more preferably 20 to 50% by weight.
また、本発明のコロイダルシリカ(B)としては、表面修飾によりその表面に二重結合等の機能性基を導入したものも用いることが出来る。 Further, as the colloidal silica (B) of the present invention, those obtained by introducing a functional group such as a double bond on the surface by surface modification can be used.
本発明のコーティングコーティング用活性エネルギー線硬化型樹脂組成物は、前記アクリル系重合体(A)を含有するものであるが、更に、本発明の効果を損なわない範囲で種々の化合物を添加することができる。これらの化合物としては、例えば、前記重合体(A)以外の重合性不飽和二重結合を有する単量体、紫外線吸収剤、酸化防止剤、シリコン系添加剤、フッ素系添加剤、レオロジーコントロール剤、脱泡剤、離型剤、シランカップリング剤、帯電防止剤、防曇剤、着色剤等が挙げられる。 The active energy ray-curable resin composition for coating coating according to the present invention contains the acrylic polymer (A), and further various compounds are added within a range not impairing the effects of the present invention. Can do. Examples of these compounds include monomers having a polymerizable unsaturated double bond other than the polymer (A), ultraviolet absorbers, antioxidants, silicon additives, fluorine additives, rheology control agents. , Defoaming agents, mold release agents, silane coupling agents, antistatic agents, antifogging agents, colorants and the like.
前記重合体(A)以外の重合性不飽和二重結合を有する単量体としては、例えば、芳香環を有する重合性単量体、環状脂肪族構造を有する重合性単量体、複素環構造を有する重合性単量体、スチレン系化合物、直鎖状脂肪族構造を有する重合性単量体等が挙げられる。 Examples of the monomer having a polymerizable unsaturated double bond other than the polymer (A) include a polymerizable monomer having an aromatic ring, a polymerizable monomer having a cyclic aliphatic structure, and a heterocyclic structure. And a polymerizable monomer having a linear aliphatic structure, and the like.
前記芳香環を有する重合性単量体としては、例えば、芳香環を有する(メタ)アクリル酸エステル類等が挙げられる。芳香環を有する(メタ)アクリル酸エステル類としては、例えば、ベンゾイルオキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェニルエチル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、フェノキシジエチレングリコール(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、2−フェニル−2−(4−アクリロイルオキシフェニル)プロパン、2−フェニル−2−(4−アクリロイルオキシアルコキシフェニル)プロパン、2,4,6−トリクロロフェニル(メタ)アクリレート、2,4,6−トリブロモフェニル(メタ)アクリレート、2,4,6−トリクロロベンジル(メタ)アクリレート、2,4,6−トリブロモベンジル(メタ)アクリレート、2,4,6−トリクロロフェノキシエチル(メタ)アクリレート、2,4,6−トリブロモフェノキシエチル(メタ)アクリレート、o−フェニルフェノール(ポリ)エトキシ(メタ)アクリレート、p−フェニルフェノール(ポリ)エトキシ(メタ)アクリレート; Examples of the polymerizable monomer having an aromatic ring include (meth) acrylic acid esters having an aromatic ring. Examples of (meth) acrylic acid esters having an aromatic ring include benzoyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate. 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-phenyl-2- (4-acryloyloxyphenyl) propane, 2-phenyl-2- (4-acryloyloxyalkoxyphenyl) propane, 2,4,6 -Trichlorophenyl (meth) acrylate, 2,4,6-tribromophenyl (meth) acrylate, 2,4,6-trichlorobenzyl (meth) acrylate, 2,4,6-tribromobenzyl (meth) acrylate, 2 , 4,6-tric Borophenoxyethyl (meth) acrylate, 2,4,6-tribromophenoxyethyl (meth) acrylate, o-phenylphenol (poly) ethoxy (meth) acrylate, p-phenylphenol (poly) ethoxy (meth) acrylate;
ビスフェノールAのアルキレンオキシド付加物構造を含む単量体、具体的には、例えば、下記一般式(1)で表される2官能(メタ)アクリレート A monomer containing an alkylene oxide adduct structure of bisphenol A, specifically, for example, a bifunctional (meth) acrylate represented by the following general formula (1)
ビスフェノールFのエチレンオキシド付加物、ビスフェノールFのプロピレンオキシド付加物、ハロゲン化ビスフェノールFのエチレンオキシド付加物、ハロゲン化ビスフェノールFのプロピレンオキシド付加物等のビスフェノールFのアルキレンオキサイド付加物に(メタ)アクリル酸がエステル結合したビスフェノールFのアルキレンオキサイド付加物構造を有する単量体; Ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, ethylene oxide adduct of halogenated bisphenol F, propylene oxide adduct of halogenated bisphenol F, etc. (meth) acrylic acid ester to alkylene oxide adduct of bisphenol F A monomer having a bonded bisphenol F alkylene oxide adduct structure;
ビスフェノールSのエチレンオキシド付加物、ビスフェノールSのプロピレンオキシド付加物、ハロゲン化ビスフェノールSのエチレンオキシド付加物、ハロゲン化ビスフェノールSのプロピレンオキシド付加物等のビスフェノールSのアルキレンオキサイド付加物に(メタ)アクリル酸がエステル結合したビスフェノールSのアルキレンオキサイド付加物構造を有する単量体; Ethylene oxide adduct of bisphenol S, propylene oxide adduct of bisphenol S, ethylene oxide adduct of halogenated bisphenol S, propylene oxide adduct of halogenated bisphenol S, etc. (meth) acrylic acid ester to alkylene oxide adduct of bisphenol S A monomer having an alkylene oxide adduct structure of bound bisphenol S;
2,2′−ジ(ヒドロキシプロポキシフェニル)プロパン及びそれらのハロゲン化物、2,2′−ジ(ヒドロキシエトキシフェニル)プロパン及びそれらのハロゲン化物に(メタ)アクリル酸がエステル結合した化合物; 2,2′-di (hydroxypropoxyphenyl) propane and their halides, 2,2′-di (hydroxyethoxyphenyl) propane and their halides with (meth) acrylic acid ester-bonded;
ビス[4−(メタ)アクリロイルオキシフェニル]−スルフィド、ビス[4−(メタ)アクリロイルオキシエトキシフェニル]−スルフィド、ビス[4−(メタ)アクリロイルオキシペンタエトキシフェニル]−スルフィド、ビス[4−(メタ)アクリロイルオキシエトキシ−3−フェニルフェニル]−スルフィド、ビス[4−(メタ)アクリロイルオキシエトキシ−3,5−ジメチルフェニル]−スルフィド、ビス(4−(メタ)アクリロイルオキシエトキシフェニル)スルフォン; Bis [4- (meth) acryloyloxyphenyl] -sulfide, bis [4- (meth) acryloyloxyethoxyphenyl] -sulfide, bis [4- (meth) acryloyloxypentaethoxyphenyl] -sulfide, bis [4- ( (Meth) acryloyloxyethoxy-3-phenylphenyl] -sulfide, bis [4- (meth) acryloyloxyethoxy-3,5-dimethylphenyl] -sulfide, bis (4- (meth) acryloyloxyethoxyphenyl) sulfone;
ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、一部ハロゲン置換されたビスフェノールA型エポキシ樹脂、一部ハロゲン置換されたビスフェノールF型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、及びそれらの混合物からなる群から選ばれる1種以上のエポキシ樹脂と(メタ)アクリル酸との反応で得られるビスフェノール型のエポキシ(メタ)アクリレートやフェノールノボラック型のエポキシ(メタ)アクリレート、クレゾールノボラック型のエポキシ(メタ)アクリレート、ナフタレン骨格のエポキシ(メタ)アクリレートまたはこれらの混合物; Bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, partially halogen-substituted bisphenol A-type epoxy resin, partially halogen-substituted bisphenol F-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, and mixtures thereof Bisphenol type epoxy (meth) acrylate, phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate obtained by reaction of one or more epoxy resins selected from the group with (meth) acrylic acid , Epoxy (meth) acrylate of naphthalene skeleton or a mixture thereof;
ポリオールと環状構造を有する有機ポリイソシアネートと水酸基含有(メタ)アクリレートの反応により得られるウレタン(メタ)アクリレート、環状構造を有するジオールと有機ポリイソシアネートと水酸基含有(メタ)アクリレートの反応により得られるウレタン(メタ)アクリレート、環状構造を有する有機ポリイソシアネートと水酸基含有(メタ)アクリレートの反応により得られるウレタン(メタ)アクリレート等が挙げられる。 Urethane (meth) acrylate obtained by reaction of polyol and organic polyisocyanate having a cyclic structure and hydroxyl group-containing (meth) acrylate, urethane obtained by reaction of diol having cyclic structure, organic polyisocyanate and hydroxyl group-containing (meth) acrylate ( Examples thereof include (meth) acrylate, urethane (meth) acrylate obtained by a reaction of an organic polyisocyanate having a cyclic structure and a hydroxyl group-containing (meth) acrylate.
前記環状脂肪族構造を有する重合性単量体としては、例えば、環状脂肪族を有する(メタ)アクリル酸エステル類等が挙げられる。環状脂肪族を有する(メタ)アクリル酸エステル類としては、例えば、シクロヘキシル(メタ)アクリレート、イソボロニル(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、ジシクロペンテニルオキシエチル(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、グリシジルシクロカーボネート(メタ)アクリレート、トリシクロデカンジメチロールジ(メタ)アクリレート等が挙げられる。 Examples of the polymerizable monomer having a cycloaliphatic structure include (meth) acrylic acid esters having a cycloaliphatic group. Examples of (meth) acrylic acid esters having a cycloaliphatic group include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and tetrahydroflurane. Examples include furyl (meth) acrylate, glycidyl cyclocarbonate (meth) acrylate, and tricyclodecane dimethylol di (meth) acrylate.
前記スチレン系化合物としては、例えば、スチレン、α−メチルスチレン、クロロスチレン等が挙げられる。 Examples of the styrene compound include styrene, α-methylstyrene, chlorostyrene, and the like.
前記複素環系化合物としては、例えば、N−ビニルピロリドン、N−ビニルカプロラクトン、アクリロイルホルモリン; Examples of the heterocyclic compound include N-vinylpyrrolidone, N-vinylcaprolactone, acryloylformoline;
トリス(2−ヒドロキシエチル)イソシアヌレート、トリス(ヒドロキシプロピル)イソシアヌレート、およびそれらに1〜20モルのアルキレンオキサイドあるいはεカプロラクトンを開環付加させた水酸基含有化合物などの水酸基を有する化合物に(メタ)アクリル酸がエステル結合したイソシアヌル酸構造を有する化合物等が挙げられる。 To compounds having a hydroxyl group such as tris (2-hydroxyethyl) isocyanurate, tris (hydroxypropyl) isocyanurate, and a hydroxyl group-containing compound obtained by ring-opening addition of 1 to 20 moles of alkylene oxide or ε-caprolactone to (meth) Examples include compounds having an isocyanuric acid structure in which acrylic acid is ester-bonded.
直鎖状脂肪族構造を有する重合性単量体としては、例えば、アルキル基を有する(メタ)アクリル酸エステル類等が挙げられる。アルキル基を有する(メタ)アクリル酸エステル類としては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプシル、(メタ)アクリル酸オクチル、(メタ)アクリル酸ノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸テトラデシル、(メタ)アクリル酸ヘキサデシル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸オクタデシル、(メタ)アクリル酸ドコシル等の炭素数1〜22のアルキル基を持つ(メタ)アクリル酸エステル類;(メタ)アクリル酸ヒドロキエチル、(メタ)アクリル酸ヒドロキシプロピル、(メタ)アクリル酸グリセロール、ラクトン変性(メタ)アクリル酸ヒドロキシエチル、(メタ)アクリル酸ポリエチレングリコール、(メタ)アクリル酸ポリプロピレングリコール等のヒドロキシアルキル基を有するアクリル酸エステル類等が挙げられる。 Examples of the polymerizable monomer having a linear aliphatic structure include (meth) acrylic acid esters having an alkyl group. Examples of (meth) acrylic acid esters having an alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and hexyl (meth) acrylate. , Heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, (Meth) acrylic acid esters having an alkyl group having 1 to 22 carbon atoms such as stearyl (meth) acrylate, octadecyl (meth) acrylate, docosyl (meth) acrylate; hydroxyethyl (meth) acrylate, (meta ) Hydroxypropyl acrylate, glycerol (meth) acrylate, lactone modification (Meth) acrylate, hydroxypropyl (meth) polyethylene glycol acrylate, acrylic acid esters having a (meth) hydroxyalkyl group, such as acrylic acid polypropylene glycol.
また、以下の重合性単量体も本発明で用いる重合性不飽和二重結合を有する単量体として例示する事ができる。例えば、(メタ)アクリル酸グリシジル、α−エチル(メタ)アクリル酸グリシジル、α−n−プロピル(メタ)アクリル酸グリシジル、α−n−ブチル(メタ)アクリル酸グリシジル、(メタ)アクリル酸−3,4−エポキシブチル、(メタ)アクリル酸−4,5−エポキシペンチル、(メタ)アクリル酸−6,7−エポキシペンチル、α−エチル(メタ)アクリル酸−6,7−エポキシペンチル、βーメチルグリシジル(メタ)アクリレート、(メタ)アクリル酸−3,4−エポキシシクロヘキシル、ラクトン変性(メタ)アクリル酸−3,4−エポキシシクロヘキシル、ビニルシクロヘキセンオキシド等の重合性不飽和二重結合及びエポキシ基を有する重合性単量体; The following polymerizable monomers can also be exemplified as monomers having a polymerizable unsaturated double bond used in the present invention. For example, glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, glycidyl α-n-butyl (meth) acrylate, (meth) acrylic acid-3 , 4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxypentyl, α-ethyl (meth) acrylic acid-6,7-epoxypentyl, β- Polymerizable unsaturated double bonds such as methyl glycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexyl, lactone-modified (meth) acrylic acid-3,4-epoxycyclohexyl, vinylcyclohexene oxide and epoxy groups A polymerizable monomer having:
(メタ)アクリル酸;β−カルボキシエチル(メタ)アクリレート、2ーアクリロイルオキシエチルコハク酸、2ーアクリロイルオキシエチルフタル酸、2ーアクリロイルオキシエチルヘキサヒドロフタル酸及びこれらのラクトン変性物等エステル結合を有する不飽和モノカルボン酸;マレイン酸等の重合性不飽和二重結合及びカルボキシル基を有する重合性単量体; (Meth) acrylic acid; β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid and ester bonds such as lactone modified products thereof An unsaturated monocarboxylic acid having a polymerizable monomer having a polymerizable unsaturated double bond and a carboxyl group such as maleic acid;
フマル酸ジメチル、フマル酸ジエチル、フマル酸ジブチル、イタコン酸ジメチル、イタコン酸ジブチル、フマル酸メチルエチル、フマル酸メチルブチル、イタコン酸メチルエチルなどの不飽和ジカルボン酸エステル類; Unsaturated dicarboxylic esters such as dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, methyl ethyl fumarate, methyl butyl fumarate, methyl ethyl itaconate;
スチレン、α−メチルスチレン、クロロスチレンなどのスチレン誘導体類;ブタジエン、イソプレン、ピペリレン、ジメチルブタジエンなどのジエン系化合物類;塩化ビニル、臭化ビニルなどのハロゲン化ビニルやハロゲン化ビニリデン類;メチルビニルケトン、ブチルビニルケトンなどの不飽和ケトン類;酢酸ビニル、酪酸ビニルなどのビニルエステル類;メチルビニルエーテル、ブチルビニルエーテルなどのビニルエーテル類;アクリロニトリル、メタクリロニトリル、シアン化ビニリデンなどのシアン化ビニル類;アクリルアミドやそのアルキド置換アミド類;N−フェニルマレイミド、N−シクロヘキシルマレイミドなどのN−置換マレイミド類; Styrene derivatives such as styrene, α-methylstyrene and chlorostyrene; diene compounds such as butadiene, isoprene, piperylene and dimethylbutadiene; vinyl halides and vinylidene halides such as vinyl chloride and vinyl bromide; methyl vinyl ketone Unsaturated vinyls such as butyl vinyl ketone; vinyl esters such as vinyl acetate and vinyl butyrate; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; vinyl cyanides such as acrylonitrile, methacrylonitrile and vinylidene cyanide; acrylamide and Its alkyd substituted amides; N-substituted maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide;
フッ化ビニル、フッ化ビニリデン、トリフルオロエチレン、クロロトリフルオロエチレン、ブロモトリフルオロエチレン、ペンタフルオロプロピレンもしくはヘキサフルオロプロピレンの如きフッ素含有α−オレフィン類;またはトリフルオロメチルトリフルオロビニルエーテル、ペンタフルオロエチルトリフルオロビニルエーテルもしくはヘプタフルオロプロピルトリフルオロビニルエーテルの如き(パー)フルオロアルキル基の炭素数が1から18なる(パー)フルオロアルキル・パーフルオロビニルエーテル類;2,2,2−トリフルオロエチル(メタ)アクリレート、2,2,3,3−テトラフルオロプロピル(メタ)アクリレート、1H,1H,5H−オクタフルオロペンチル(メタ)アクリレート、1H,1H,2H,2H−ヘプタデカフルオロデシル(メタ)アクリレートもしくはパーフルオロエチルオキシエチル(メタ)アクリレートの如き(パー)フルオロアルキル基の炭素数が1から18なる(パー)フルオロアルキル(メタ)アクリレート類等のフッ素含有エチレン性不飽和単量体類; Fluorine-containing α-olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene; or trifluoromethyl trifluorovinyl ether, pentafluoroethyltri (Per) fluoroalkyl perfluorovinyl ethers having a (per) fluoroalkyl group such as fluorovinyl ether or heptafluoropropyl trifluorovinyl ether having 1 to 18 carbon atoms; 2,2,2-trifluoroethyl (meth) acrylate; 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, 2H-he Fluorine-containing ethylenic compounds such as (per) fluoroalkyl (meth) acrylates having a (per) fluoroalkyl group of 1 to 18 carbon atoms such as tadecafluorodecyl (meth) acrylate or perfluoroethyloxyethyl (meth) acrylate Unsaturated monomers;
(16)γ−メタクリロキシプロピルトリメトキシシラン等のシリル基含有(メタ)アクリレート類;N,N−ジメチルアミノエチル(メタ)アクリレート、N,N−ジエチルアミノエチル(メタ)アクリレートもしくはN,N−ジエチルアミノプロピル(メタ)アクリレート等のN,N−ジアルキルアミノアルキル(メタ)アクリレート; (16) Silyl group-containing (meth) acrylates such as γ-methacryloxypropyltrimethoxysilane; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate or N, N-diethylamino N, N-dialkylaminoalkyl (meth) acrylates such as propyl (meth) acrylate;
(メタ)アクリル酸フォスフォエチル、N,N−ジメチルアミノエチル(メタ)アクリレート、N,N−ジエチルアミノエチル(メタ)アクリレートもしくはN,N−ジエチルアミノプロピル(メタ)アクリレート、ジ[(メタ)アクリロイルオキシエチル]フォスフェート、トリ[(メタ)アクリロイルオキシエチル]フォスフェート、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;ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエ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、 Phosphoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate or N, N-diethylaminopropyl (meth) acrylate, di [(meth) acryloyloxy Ethyl] phosphate, tri [(meth) acryloyloxyethyl] phosphate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetra Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
ジプロピレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、テトラプロピレングリコールジ(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、1,3−ブチレングリコールジ(メタ)アクリレート、1,4−ブチレングリコールジ(メタ)アクリレート、1,6−ヘキサメチレングリコールジ(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、ネオペンチルグリコールジ(メタ)アクリレート、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、ヒドロキシピバリン酸ネオペンチルグリコールにカプロラクトン付加した化合物のジ(メタ)アクリレート、ネオペンチルグリコールアジペートジ(メタ)アクリレート、 Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4 -Butylene glycol di (meth) acrylate, 1,6-hexamethylene glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (Meth) acrylate, di (meth) acrylate of a compound obtained by adding caprolactone to neopentyl glycol hydroxypivalate, neopentyl glycol adipate di (meth) acrylate,
トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、テトラメチロールメタン、およびそれらに1〜20モルのアルキレンオキサイドを付加させた水酸基含有化合物などの水酸基を3つ以上有する化合物に(メタ)アクリル酸が3分子以上エステル結合した化合物等が挙げられる。 (Meth) acrylic to compounds having 3 or more hydroxyl groups such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tetramethylolmethane, and a hydroxyl group-containing compound in which 1 to 20 mol of alkylene oxide is added thereto. Examples include compounds in which three or more molecules of acid are ester-bonded.
前記重合体(A)以外の重合性不飽和二重結合を有する単量体を使用する場合、その使用量としては、塗膜形成成分の重量を基準として0〜80重量%が好ましい。 When using the monomer which has polymerizable unsaturated double bonds other than the said polymer (A), as the usage-amount, 0 to 80 weight% is preferable on the basis of the weight of a coating-film formation component.
前記紫外線吸収剤としては、例えば、2−[4−{(2−ヒドロキシ−3−ドデシルオキシプロピル)オキシ}−2−ヒドロキシフェニル]−4,6−ビス(2,4−ジメチルフェニル)−1,3,5−トリアジン、2−[4−{(2−ヒドロキシ−3−トリデシルオキシプロピル)オキシ}−2−ヒドロキシフェニル]−4,6−ビス(2,4−ジメチルフェニル)−1,3,5−トリアジン等のトリアジン誘導体、2−(2′−キサンテンカルボキシ−5′−メチルフェニル)ベンゾトリアゾール、2−(2′−o−ニトロベンジロキシ−5′−メチルフェニル)ベンゾトリアゾール、2−キサンテンカルボキシ−4−ドデシロキシベンゾフェノン、2−o−ニトロベンジロキシ−4−ドデシロキシベンゾフェノン等が挙げられる。 Examples of the ultraviolet absorber include 2- [4-{(2-hydroxy-3-dodecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine, 2- [4-{(2-hydroxy-3-tridecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, Triazine derivatives such as 3,5-triazine, 2- (2′-xanthenecarboxy-5′-methylphenyl) benzotriazole, 2- (2′-o-nitrobenzyloxy-5′-methylphenyl) benzotriazole, 2 -Xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone and the like.
前記酸化防止剤としては、例えば、ヒンダードフェノール系酸化防止剤、ヒンダードアミン系酸化防止剤、有機硫黄系酸化防止剤、リン酸エステル系酸化防止剤等が挙げられる。 Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate ester-based antioxidants.
前記シリコン系添加剤としては、例えば、ジメチルポリシロキサン、メチルフェニルポリシロキサン、環状ジメチルポリシロキサン、メチルハイドロゲンポリシロキサン、ポリエーテル変性ジメチルポリシロキサン共重合体、ポリエステル変性ジメチルポリシロキサン共重合体、フッ素変性ジメチルポリシロキサン共重合体、アミノ変性ジメチルポリシロキサン共重合体など如きアルキル基やフェニル基を有するポリオルガノシロキサン類が挙げられる。 Examples of the silicon-based additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified. Examples thereof include polyorganosiloxanes having an alkyl group or a phenyl group, such as a dimethylpolysiloxane copolymer and an amino-modified dimethylpolysiloxane copolymer.
上記した如き種々の添加剤の使用量としては、その効果を十分発揮し、また紫外線硬化を阻害しない範囲であることから、該注型重合用活性エネルギー線硬化型樹脂組成物100重量部に対し、それぞれ0.01〜10重量部の範囲であることが好ましい。 The amount of the various additives as described above is sufficient to exert its effect and does not hinder ultraviolet curing, so that the active energy ray-curable resin composition for casting polymerization is 100 parts by weight. , Each preferably in the range of 0.01 to 10 parts by weight.
本発明のコーティング用活性エネルギー線硬化型樹脂組成物に加えることができる光重合開始剤(C)としては、例えば、ベンゾフェノン、3,3′−ジメチル−4−メトキシベンゾフェノン、4,4′−ビスジメチルアミノベンゾフェノン、4,4′−ビスジエチルアミノベンゾフェノン、4,4′−ジクロロベンゾフェノン、ミヒラーズケトン、3,3′,4,4′-テトラ(t-ブチルパーオキシカルボニル)ベンゾフェノンなどのベンゾフェノン類; Examples of the photopolymerization initiator (C) that can be added to the active energy ray-curable resin composition for coating of the present invention include benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, and 4,4′-bis. Benzophenones such as dimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, Michler's ketone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;
キサントン、チオキサントン、2−メチルチオキサントン、2−クロロチオキサントン、2,4−ジエチルチオキサントンなどのキサントン、チオキサントン類;ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテルなどのアシロインエーテル類; Xanthones such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone; thioxanthones; acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether;
ベンジル、ジアセチルなどのα-ジケトン類;テトラメチルチウラムジスルフィド、p−トリルジスルフィドなどのスルフィド類;4−ジメチルアミノ安息香酸、4−ジメチルアミノ安息香酸エチルなどの安息香酸類; Α-diketones such as benzyl and diacetyl; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; benzoic acids such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate;
3,3′-カルボニル-ビス(7-ジエチルアミノ)クマリン、1−ヒドロキシシクロへ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、2−メチル−1−〔4−(メチルチオ)フェニル〕−2−モルフオリノプロパン−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、2,4,6−トリメチルベンゾイルジフェニルホスフィンオキシド、ビス(2,4,6−トリメチルベンゾイル)フェニルホスフィンオキシド、1−〔4−(2−ヒドロキシエトキシ)フェニル〕−2−ヒドロキシ−2−メチル−1−プロパン−1−オン、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、1−(4−ドデシルフェニル)−2−ヒドロキシ−2−メチルプロパン−1−オン、4−ベンゾイル−4′−メチルジメチルスルフィド、2,2′−ジエトキシアセトフェノン、ベンジルジメチルケタ−ル、ベンジル−β−メトキシエチルアセタール、o−ベンゾイル安息香酸メチル、ビス(4−ジメチルアミノフェニル)ケトン、p−ジメチルアミノアセトフェノン、α,α−ジクロロ−4−フェノキシアセトフェノン、ペンチル−4−ジメチルアミノベンゾエート、2−(o−クロロフェニル)−4,5−ジフェニルイミダゾリルニ量体、2,4−ビス−トリクロロメチル−6−[ジ−(エトキシカルボニルメチル)アミノ]フェニル−S−トリアジン、2,4−ビス−トリクロロメチル−6−(4−エトキシ)フェニル−S−トリアジン、2,4−ビス−トリクロロメチル−6−(3−ブロモ−4−エトキシ)フェニル−S−トリアジンアントラキノン、2−t−ブチルアントラキノン、2−アミルアントラキノン、β−クロルアントラキノン等が挙げられる。 3,3′-carbonyl-bis (7-diethylamino) coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl -1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] 2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- -Methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone, Benzyldimethylketal, benzyl-β-methoxyethyl acetal, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α, α-dichloro-4-phenoxyacetophenone, pentyl- 4-dimethylaminobenzoate, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,4-bis-trichloromethyl-6- [di- (ethoxycarbonylmethyl) amino] phenyl-S-triazine 2,4-bis-trichloromethyl-6- (4-eth C) Phenyl-S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-ethoxy) phenyl-S-triazine anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloro Anthraquinone etc. are mentioned.
前記光重合開始剤は、単独あるいは2種以上を組み合わせて用いることもできる。その使用量は特に制限はないが、感度を良好に保ち、結晶の析出、塗膜物性の劣化等防止するため、本発明のコーティング用活性エネルギー線硬化型樹脂組成物100重量部に対して0.05〜20重量部用いることが好ましく、なかでも0.1〜10重量部が特に好ましい。 The photopolymerization initiators can be used alone or in combination of two or more. The amount used is not particularly limited, but is 0 with respect to 100 parts by weight of the active energy ray-curable resin composition for coating of the present invention in order to maintain good sensitivity and prevent precipitation of crystals and deterioration of physical properties of the coating film. It is preferable to use 0.05 to 20 parts by weight, and 0.1 to 10 parts by weight is particularly preferable.
前記光重合開始剤としては、1−ヒドロキシシクロヘキシルフェニルケトン、2−ヒドロキシ−2−メチル−1−フェニルプロパン−1−オン、1−〔4−(2−ヒドロキシエトキシ)フェニル〕−2−ヒドロキシ−2−メチル−1−プロパン−1−オン、チオキサントン及びチオキサントン誘導体、2,2′−ジメトキシ−1,2−ジフェニルエタン−1−オン、2,4,6−トリメチルベンゾイルジフェニルホスフィンオキシド、ビス(2,4,6−トリメチルベンゾイル)フェニルホスフィンオキシド、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)−ブタン−1−オンの群から選ばれる1種または2種類以上の混合系が、硬化性が高いコーティング用活性エネルギー線硬化型樹脂組成物が得られるため特に好ましい。 Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- 2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2 , 4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholino One or more mixed systems selected from the group of phenyl) -butan-1-one High curable coating for the active energy ray curable resin composition is particularly preferred because the resulting.
前記光重合開始剤の市販品としては、例えば、Irgacure−184、同149、同261、同369、同500、同651、同754、同784、同819、同907、同1116、同1664、同1700、同1800、同1850、同2959、同4043、Darocur−1173(チバスペシャルティーケミカルズ社製)、ルシリンTPO(BASFF社製)、KAYACURE−DETX、同MBP、同DMBI、同EPA、同OA〔日本化薬(株)製〕、VICURE−10、同55(STAUFFER Co.LTD製)、TRIGONALP1(AKZO Co.LTD製)、SANDORY 1000(SANDOZ Co.LTD製)、DEAP(APJOHN Co.LTD製)、QUANTACURE−PDO、同ITX、同EPD(WARD BLEKINSOP Co.LTD製)等が挙げられる。 Examples of commercially available photopolymerization initiators include Irgacure-184, 149, 261, 369, 500, 651, 754, 784, 819, 907, 1116, 1664, 1700, 1800, 1850, 2959, 4043, Darocur-1173 (manufactured by Ciba Specialty Chemicals), Lucirin TPO (manufactured by BASF), KAYACURE-DETX, MBP, DMBI, EPA, OA [Nippon Kayaku Co., Ltd.], VICURE-10, 55 (manufactured by STAUFER Co. LTD), TRIGONALP1 (manufactured by AKZO Co. LTD), SANDORY 1000 (manufactured by SANDOZ Co. LTD), DEAP (manufactured by APJOHN Co. LTD) ), QUANTACURE-PDO, the same ITX, EPD (manufactured by WARD BLEKINSOP Co. LTD), and the like.
さらに、本発明のコーティング用活性エネルギー線硬化型樹脂組成物では、前記光重合開始剤に種々の光増感剤を併用することができる。光増感剤としては、例えば、アミン類、尿素類、含硫黄化合物、含燐化合物、含塩素化合物またはニトリル類もしくはその他の含窒素化合物等が挙げられる。 Furthermore, in the active energy ray-curable resin composition for coating of the present invention, various photosensitizers can be used in combination with the photopolymerization initiator. Examples of the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.
更に本発明のコーティング用活性エネルギー線硬化型樹脂組成物は、粘度や基板への接着性改良等を目的として、前記重合体(A)以外のその他の樹脂を併用することができる。 Furthermore, the active energy ray-curable resin composition for coating of the present invention can be used in combination with other resins other than the polymer (A) for the purpose of improving viscosity and adhesion to a substrate.
前記その他の樹脂としては、例えば、メチルメタクリレート樹脂、メチルメタクリレート系共重合物等のアクリル樹脂;ポリスチレン、メチルメタクリレート−スチレン系共重合物;ポリエステル樹脂;ポリウレタン樹脂;ポリブタジエンやブタジエン−アクリロニトリル系共重合物などのポリブタジエン樹脂;ビスフェノール型エポキシ樹脂、フェノキシ樹脂やノボラック型エポキシ樹脂などのエポキシ樹脂等が挙げられる。 Examples of the other resins include acrylic resins such as methyl methacrylate resin and methyl methacrylate copolymer; polystyrene, methyl methacrylate-styrene copolymer; polyester resin; polyurethane resin; polybutadiene and butadiene-acrylonitrile copolymer. Polybutadiene resins such as bisphenol type epoxy resins, epoxy resins such as phenoxy resins and novolac type epoxy resins, and the like.
本発明のフィルム基材は、本発明のコーティング用活性エネルギー線硬化型樹脂組成物を硬化させて得られる硬化層を有することを特徴とする。具体的には、各種フィルム基材に公知の方法でコーティング用活性エネルギー線硬化型樹脂組成物を塗布、乾燥後、活性エネルギー線を照射することにより硬化させて得られるものである。 The film base material of the present invention has a cured layer obtained by curing the active energy ray-curable resin composition for coating of the present invention. Specifically, the active energy ray-curable resin composition for coating is applied to various film substrates by a known method, dried, and then cured by irradiation with active energy rays.
コーティング用活性エネルギー線硬化型樹脂組成物の塗布量としては、例えば、各種フィルム基材上に、乾燥後の重量が0.1〜30g/m2、好ましくは1〜20g/m2になるように塗布するのが好ましい。 The coating amount of the active energy ray-curable resin composition for coating is, for example, such that the weight after drying is 0.1 to 30 g / m 2 , preferably 1 to 20 g / m 2 on various film substrates. It is preferable to apply to.
本発明のコーティング用活性エネルギー線硬化型樹脂組成物を塗布するフィルム基材としては、各種公知の基材にもちいることができる。具体的には、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)等が挙げられる。 As a film substrate on which the active energy ray-curable resin composition for coating of the present invention is applied, various known substrates can be used. Specifically, for example, plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc.) and the like can be mentioned.
本発明のコーティング用活性エネルギー線硬化型樹脂組成物の塗布方法としては、特に限定されず公知の方法を採用することができ、例えばバーコーター塗工、メイヤーバー塗工、エアナイフ塗工、グラビア塗工、リバースグラビア塗工、オフセット印刷、フレキソ印刷、スクリーン印刷法等が挙げられる。 The application method of the active energy ray-curable resin composition for coating of the present invention is not particularly limited, and a known method can be adopted, for example, bar coater coating, Mayer bar coating, air knife coating, gravure coating. And the like, reverse gravure coating, offset printing, flexographic printing, screen printing method and the like.
照射する活性エネルギー線としては、例えば、紫外線や電子線が挙げられる。紫外線により硬化させる場合、光源としてキセノンランプ、高圧水銀灯、メタルハライドランプを有する紫外線照射装置が使用され、必要に応じて光量、光源の配置などが調整されるが、高圧水銀灯を使用する場合、通常80〜160W/cmの光量を有したランプ1灯に対して搬送速度5〜50m/分で硬化させるのが好ましい。一方、電子線により硬化させる場合、通常10〜300kVの加速電圧を有する電子線加速装置にて、搬送速度5〜50m/分で硬化させるのが好ましい。 Examples of the active energy rays to be irradiated include ultraviolet rays and electron beams. In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp is used as a light source, and the amount of light and the arrangement of the light source are adjusted as necessary. It is preferable to cure at a conveyance speed of 5 to 50 m / min with respect to one lamp having a light quantity of ˜160 W / cm. On the other hand, in the case of curing with an electron beam, it is preferably cured with an electron beam accelerator having an accelerating voltage of usually 10 to 300 kV at a conveyance speed of 5 to 50 m / min.
以下に実施例及び比較例を挙げて、本発明をより具体的に説明する。例中の部及び%は、特に記載のない限り、すべて重量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. All parts and percentages in the examples are by weight unless otherwise specified.
実施例1
攪拌装置、冷却管、滴下ロートおよび窒素導入管を備えた反応装置に、酢酸ブチルを42.2重量部仕込み、攪拌しながら系内温度が120℃になるまで昇温した。ついで、2−イソシアナトエチルアクリレート(昭和電工株式会社製「カレンズAOI」)60.0重量部、t−ブチルパーオキシ−2−エチルヘキサノエート(日油株式会社製「パーブチルO」)3.0重量部、酢酸ブチル12.0重量部からなる混合液を4時間かけて滴下した。滴下後、同温度で6時間保持し、イソシアナト基含有重合中間体を得た。
Example 1
A reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube was charged with 42.2 parts by weight of butyl acetate, and the temperature was raised until the system temperature reached 120 ° C. while stirring. 2. 60.0 parts by weight of 2-isocyanatoethyl acrylate (“Karenz AOI” manufactured by Showa Denko KK), t-butyl peroxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation) A mixed solution consisting of 0 parts by weight and 12.0 parts by weight of butyl acetate was added dropwise over 4 hours. After dropping, the mixture was held at the same temperature for 6 hours to obtain an isocyanato group-containing polymerization intermediate.
続いて、反応系が40℃以下まで冷却されたのを確認した後に窒素導入管を空気導入管に付け替え、メトキノン0.8重量部、ジブチル錫ジアセテート(日東化成株式会社製「ネオスタンU−200」0.54重量部、酢酸ブチル1295重量部を加えた。反応液中に空気をバブリングさせ、系内が均一となったところでペンタエリスリトールトリアクリレート(東亞合成株式会社製「アロニックスM−305」)2012重量部を滴下しながら加えた。滴下終了後は80℃まで昇温し、8時間保持して反応させて、側鎖に(メタ)アクリロイル基を有するアクリル系重合体(A1)を得た。得られた(A1)は不揮発分60.5%、粘度160.8mPa・sであった。また、アクリロイル基当量は142g/eq(固形分)、重量平均分子量は340,000であった。 Subsequently, after confirming that the reaction system was cooled to 40 ° C. or lower, the nitrogen introduction tube was replaced with an air introduction tube, 0.8 parts by weight of methoquinone, dibutyltin diacetate (“Neostan U-200 manufactured by Nitto Kasei Co., Ltd.) 0.54 parts by weight and 1295 parts by weight of butyl acetate were added. Air was bubbled into the reaction solution, and when the system became uniform, pentaerythritol triacrylate (“Aronix M-305” manufactured by Toagosei Co., Ltd.) 2012 part by weight was added dropwise, after completion of the dropwise addition, the temperature was raised to 80 ° C., and the reaction was continued for 8 hours to obtain an acrylic polymer (A1) having a (meth) acryloyl group in the side chain. The obtained (A1) had a nonvolatile content of 60.5% and a viscosity of 160.8 mPa · s, and an acryloyl group equivalent was 142 g / eq (solid content), a weight average content. The amount was 340,000.
得られたアクリロイル基を有するアクリル系重合体(A1)165部(固形分換算100部)、1−ヒドロキシ−シクロヘキシル−フェニル−ケトン(チバスペシャルティケミカルズ社製Irgacure184)4重量部、酢酸ブチル91重量部を攪拌混合してハードコート用活性エネルギー線硬化型組成物を調整した。得られた組成物を、トリアセチルセルロースフィルム(80μm厚)に膜厚10μmになるように塗布し、80℃で1分乾燥させ、窒素雰囲気下で高圧水銀灯を用いて250mJ/cm2照射して硬化させた。 165 parts of the obtained acrylic polymer (A1) having an acryloyl group (100 parts in terms of solid content), 1 part by weight of 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by Ciba Specialty Chemicals), 91 parts by weight of butyl acetate Were mixed with stirring to prepare an active energy ray-curable composition for hard coat. The obtained composition was applied to a triacetyl cellulose film (80 μm thickness) so as to have a film thickness of 10 μm, dried at 80 ° C. for 1 minute, and irradiated with 250 mJ / cm 2 using a high-pressure mercury lamp in a nitrogen atmosphere. Cured.
得られた塗膜の鉛筆硬度は4H、5cm角のフィルムの4頂点の浮き平均で表されるカール値は6mmであった。尚、カール値は小さい程フィルムのカールが小さいことを表す。また、硬化塗膜の外観を目視で評価し、以下の基準に従って評価し、その結果は○であった。
○:全く濁りがない。
△:やや濁り、曇りがある。
×:白濁している。
The pencil hardness of the obtained coating film was 4H, and the curl value represented by the average of the four vertices of a 5 cm square film was 6 mm. The smaller the curl value, the smaller the curl of the film. Moreover, the external appearance of the cured coating film was visually evaluated and evaluated according to the following criteria, and the result was good.
○: No turbidity at all.
Δ: Slightly cloudy and cloudy.
X: It is cloudy.
実施例2
得られたアクリロイル基を有するアクリル系重合体(A1)116重量部(固形分換算70重量部)、DIC株式会社製ウレタンアクリレートオリゴマー「ユニディック17−803」37.5重量部(固形分換算30重量部)、1−ヒドロキシ−シクロヘキシル−フェニル−ケトン(チバスペシャルティケミカルズ社製Irgacure184)4重量部、酢酸ブチル50.5重量部を攪拌混合してハードコート用活性エネルギー線硬化型組成物を調整した。得られた組成物を、トリアセチルセルロースフィルム(80μm厚)に膜厚10μmになるように塗布し、80℃で1分乾燥させ、窒素雰囲気下で高圧水銀灯を用いて250mJ/cm2照射して硬化させた。
Example 2
116 parts by weight of acrylic polymer (A1) having an acryloyl group (70 parts by weight in terms of solids), 37.5 parts by weight of urethane acrylate oligomer “Unidic 17-803” (30 parts in terms of solids) manufactured by DIC Corporation Part by weight), 4 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by Ciba Specialty Chemicals) and 50.5 parts by weight of butyl acetate were mixed with stirring to prepare an active energy ray-curable composition for hard coat. . The obtained composition was applied to a triacetyl cellulose film (80 μm thickness) so as to have a film thickness of 10 μm, dried at 80 ° C. for 1 minute, and irradiated with 250 mJ / cm 2 using a high-pressure mercury lamp in a nitrogen atmosphere. Cured.
得られた塗膜の鉛筆硬度は4H、5cm角のフィルムの4頂点の浮き平均で表されるカール値は8mmであった。尚、カール値は小さい程フィルムのカールが小さいことを表す。また、硬化塗膜の外観の評価結果は○であった。
実施例3
得られたアクリロイル基を有するアクリル系重合体(A1)116重量部(固形分換算60重量部)、nanoresins社製ナノシリカのアクリル分散体であるNanocryl XP21/1364(ジペンタエリスリトールヘキサアクリレート中へのナノシリカ40重量%分散体)40部、1−ヒドロキシ−シクロヘキシル−フェニル−ケトン(チバスペシャルティケミカルズ社製Irgacure184)4重量部、酢酸ブチル48重量部を攪拌混合してハードコート用活性エネルギー線硬化型組成物を調整した。得られた組成物を、トリアセチルセルロースフィルム(80μm厚)に膜厚10μmになるように塗布し、80℃で1分乾燥させ、窒素雰囲気下で高圧水銀灯を用いて250mJ/cm2照射して硬化させた。
得られた塗膜の鉛筆硬度は4H、5cm角のフィルムの4頂点の浮き平均で表されるカール値は4mmであった。尚、カール値は小さい程フィルムのカールが小さいことを表す。また、硬化塗膜の外観の評価結果は○であった。
The pencil hardness of the obtained coating film was 4H, and the curl value represented by the average of the four vertices of a 5 cm square film was 8 mm. The smaller the curl value, the smaller the curl of the film. Moreover, the evaluation result of the external appearance of the cured coating film was (circle).
Example 3
116 parts by weight of acrylic polymer (A1) having an acryloyl group obtained (60 parts by weight in terms of solid content), Nanocryl XP21 / 1364, nanosilica acrylic dispersion of nanoresins (Nanosilica in dipentaerythritol hexaacrylate) 40 wt% dispersion) 40 parts, 4 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by Ciba Specialty Chemicals) and 48 parts by weight of butyl acetate are stirred and mixed to obtain an active energy ray-curable composition for hard coat. Adjusted. The obtained composition was applied to a triacetyl cellulose film (80 μm thickness) so as to have a film thickness of 10 μm, dried at 80 ° C. for 1 minute, and irradiated with 250 mJ / cm 2 using a high-pressure mercury lamp in a nitrogen atmosphere. Cured.
The pencil hardness of the obtained coating film was 4H, and the curl value represented by the average of the four vertices of a 5 cm square film was 4 mm. The smaller the curl value, the smaller the curl of the film. Moreover, the evaluation result of the external appearance of the cured coating film was (circle).
比較例1
撹拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応装置に、グリシジルメタアクリレート250g、ラウリルメルカプタン1.3g、酢酸ブチル1000g及び2,2´−アゾビスイソブチロニトリル7.5gを仕込んだ後、窒素気流下に約1時間かけて系内温度が約90℃になるまで昇温し、1時間保温した。次いで、あらかじめグリシジルメタアクリレート750g、ラウリルメルカプタン3.7g及び2,2´−アゾビスイソブチロニトリル22.5gからなる混合液を仕込んだ滴下ロートより、窒素気流下に混合液を、約2時間を要して系内に滴下し、3時間同温度に保温後、2,2´−アゾビスイソブチロニトリル10gを仕込み、1時間保温した。その後、120℃に昇温し、2時間保温した。60℃まで冷却、共重合体a1の溶液を得た。a´1のエポキシ当量は、固形分換算で142g/eqで、重量平均分子量は、20,000で、ガラス転移温度は、46℃であった。
Comparative Example 1
A reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube was charged with 250 g of glycidyl methacrylate, 1.3 g of lauryl mercaptan, 1000 g of butyl acetate and 7.5 g of 2,2′-azobisisobutyronitrile. Thereafter, the system was heated to a temperature of about 90 ° C. over about 1 hour under a nitrogen stream, and kept warm for 1 hour. Next, the mixed solution was put in a nitrogen stream for about 2 hours from a dropping funnel previously charged with a mixed solution consisting of 750 g of glycidyl methacrylate, 3.7 g of lauryl mercaptan and 22.5 g of 2,2′-azobisisobutyronitrile. The mixture was added dropwise to the system and kept at the same temperature for 3 hours. Then, 10 g of 2,2′-azobisisobutyronitrile was charged and kept warm for 1 hour. Then, it heated up at 120 degreeC and heat-retained for 2 hours. It cooled to 60 degreeC and the solution of the copolymer a1 was obtained. The epoxy equivalent of a′1 was 142 g / eq in terms of solid content, the weight average molecular weight was 20,000, and the glass transition temperature was 46 ° C.
続いて、窒素導入管を空気導入管につけ替え、アクリル酸507g、メトキノン2.3g及びトリフェニルフォスフィン6.0gを仕込み混合した後、空気バブリング下にて、110℃まで昇温した。同温度にて8時間保温後、メトキノン1.6gを仕込み、冷却して、不揮発分が50%となるよう酢酸エチルを加え、反応性ポリマーA´1の溶液を得た。反応性ポリマー(のアクリル当量は、固形分換算で214g/eq、重量平均分子量 40,000(GPCによるポリスチレン換算による)であった。 Subsequently, the nitrogen introduction tube was replaced with an air introduction tube, 507 g of acrylic acid, 2.3 g of methoquinone and 6.0 g of triphenylphosphine were charged and mixed, and then the temperature was raised to 110 ° C. under air bubbling. After incubating at the same temperature for 8 hours, 1.6 g of methoquinone was charged and cooled, and ethyl acetate was added so that the non-volatile content was 50% to obtain a solution of reactive polymer A′1. The acrylic equivalent of the reactive polymer was 214 g / eq in terms of solid content, and the weight average molecular weight was 40,000 (in terms of polystyrene by GPC).
この共重合体a1 200部、Irgacure184 5部を攪拌混合してハードコート用活性エネルギー線硬化型組成物を調整した。実施例1と同様にして硬化塗膜を得た。得られた塗膜の鉛筆硬度は2H、5cm角のフィルムの4頂点の浮き平均で表されるカール値は0.2mmであった。また、塗膜の外観の評価は○であった。 200 parts of this copolymer a1 and 5 parts of Irgacure 184 were stirred and mixed to prepare an active energy ray-curable composition for hard coat. A cured coating film was obtained in the same manner as in Example 1. The pencil hardness of the obtained coating film was 2H, and the curl value represented by the average of the four vertices of the 5 cm square film was 0.2 mm. The evaluation of the appearance of the coating film was ○.
比較例2
共重合体A´1 120部重量部(固形分換算70部)、DIC株式会社製ウレタンアクリレートオリゴマー「ユニディック17−803」37.5重量部(固形分換算30重量部)、Irgacure184 4重量部、酢酸ブチル26.5重量部を攪拌混合してハードコート用活性エネルギー線硬化型組成物を調整した。得られた組成物を、トリアセチルセルロースフィルム(80μm厚)に膜厚10μmになるように塗布し、80℃で1分乾燥させ、窒素雰囲気下で高圧水銀灯を用いて250mJ/cm2照射して硬化させた。
Comparative Example 2
120 parts by weight of copolymer A′1 (70 parts in terms of solid content), 37.5 parts by weight of urethane acrylate oligomer “Unidic 17-803” (30 parts by weight in terms of solids) manufactured by DIC Corporation, 4 parts by weight of Irgacure 184 Then, 26.5 parts by weight of butyl acetate was stirred and mixed to prepare an active energy ray-curable composition for hard coat. The obtained composition was applied to a triacetyl cellulose film (80 μm thickness) so as to have a film thickness of 10 μm, dried at 80 ° C. for 1 minute, and irradiated with 250 mJ / cm 2 using a high-pressure mercury lamp in a nitrogen atmosphere. Cured.
得られた塗膜の鉛筆硬度は2H、5cm角のフィルムの4頂点の浮き平均で表されるカール値は3mmであった。尚、カール値は小さい程フィルムのカールが小さいことを表す。また、硬化塗膜の外観の評価結果は△〜×であった。 The resulting coating film had a pencil hardness of 2 mm, and a curl value represented by a floating average of 4 vertices of a 5 cm square film was 3 mm. The smaller the curl value, the smaller the curl of the film. The evaluation results of the appearance of the cured coating film were Δ to ×.
Claims (7)
で示される単量体を70〜100重量%となる割合で含有する重合性単量体を重合させて得られるイソシアネート基含有重合体(a1)に、水酸基と(メタ)アクリロイル基とを有する化合物(a2)を反応させて得られる重合体(A)を含有することを特徴とするコーティング用活性エネルギー線硬化型樹脂組成物。 The following general formula (1) having a reactive double bond and an isocyanate group
In in the polymerizable monomer is polymerized obtained isocyanate group-containing polymer of the monomer in a proportion to be 70 to 100 wt% as shown (a1), a compound having a hydroxyl group and a (meth) acryloyl groups An active energy ray-curable resin composition for coating, comprising a polymer (A) obtained by reacting (a2).
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