JPWO2018021351A1 - Method for forming easily releasable protective resin film and easily releasable protective resin film forming composition - Google Patents
Method for forming easily releasable protective resin film and easily releasable protective resin film forming composition Download PDFInfo
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- JPWO2018021351A1 JPWO2018021351A1 JP2018530312A JP2018530312A JPWO2018021351A1 JP WO2018021351 A1 JPWO2018021351 A1 JP WO2018021351A1 JP 2018530312 A JP2018530312 A JP 2018530312A JP 2018530312 A JP2018530312 A JP 2018530312A JP WO2018021351 A1 JPWO2018021351 A1 JP WO2018021351A1
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- Prior art keywords
- meth
- acrylate
- resin film
- radical polymerization
- protective resin
- Prior art date
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- 239000011347 resin Substances 0.000 title claims abstract description 99
- 229920005989 resin Polymers 0.000 title claims abstract description 99
- 239000000203 mixture Substances 0.000 title claims abstract description 93
- 230000001681 protective effect Effects 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 135
- -1 acrylate compound Chemical class 0.000 claims abstract description 99
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 66
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 58
- 239000010409 thin film Substances 0.000 claims abstract description 42
- 239000010408 film Substances 0.000 claims abstract description 35
- 239000011521 glass Substances 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 34
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000004224 protection Effects 0.000 claims abstract description 26
- 229920001610 polycaprolactone Polymers 0.000 claims description 14
- 239000004632 polycaprolactone Substances 0.000 claims description 14
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 125000003827 glycol group Chemical group 0.000 claims description 9
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 claims description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 235000000346 sugar Nutrition 0.000 claims description 6
- 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 claims description 4
- 244000028419 Styrax benzoin Species 0.000 claims description 4
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 4
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 4
- 229960002130 benzoin Drugs 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 235000019382 gum benzoic Nutrition 0.000 claims description 4
- 150000008163 sugars Chemical class 0.000 claims description 4
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 claims description 3
- HUDYANRNMZDQGA-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]ethanone Chemical compound CN(C)C1=CC=C(C(C)=O)C=C1 HUDYANRNMZDQGA-UHFFFAOYSA-N 0.000 claims description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 3
- DXUMYHZTYVPBEZ-UHFFFAOYSA-N 2,4,6-tris(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 DXUMYHZTYVPBEZ-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims description 3
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 claims description 3
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 claims description 3
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 claims description 3
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 claims description 3
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 3
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 claims description 3
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 claims description 3
- VSJBBIJIXZVVLQ-UHFFFAOYSA-N tert-butyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(C)(C)C VSJBBIJIXZVVLQ-UHFFFAOYSA-N 0.000 claims description 3
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 claims description 3
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 claims description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 3
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 claims description 3
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- CAAIULQYGCAMCD-UHFFFAOYSA-L zinc;hydroxymethanesulfinate Chemical compound [Zn+2].OCS([O-])=O.OCS([O-])=O CAAIULQYGCAMCD-UHFFFAOYSA-L 0.000 claims description 2
- LDQYWNUWKVADJV-UHFFFAOYSA-N 2-[(1-amino-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanamide;dihydrate Chemical compound O.O.NC(=O)C(C)(C)N=NC(C)(C)C(N)=O LDQYWNUWKVADJV-UHFFFAOYSA-N 0.000 claims 1
- 229940064734 aminobenzoate Drugs 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 claims 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 description 29
- 230000001588 bifunctional effect Effects 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 10
- 239000003973 paint Substances 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 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 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 238000012719 thermal polymerization Methods 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
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=C(C)C=C1 PUBNJSZGANKUGX-UHFFFAOYSA-N 0.000 description 2
- PYKCEDJHRUUDRK-UHFFFAOYSA-N 2-(tert-butyldiazenyl)-2-methylpropanenitrile Chemical compound CC(C)(C)N=NC(C)(C)C#N PYKCEDJHRUUDRK-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
- 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 2
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- HHEFNVCDPLQQTP-UHFFFAOYSA-N ammonium perchlorate Chemical class [NH4+].[O-]Cl(=O)(=O)=O HHEFNVCDPLQQTP-UHFFFAOYSA-N 0.000 description 2
- 150000003519 bicyclobutyls Chemical group 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 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 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 229960002446 octanoic acid Drugs 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
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- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
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- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
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- 239000012966 redox initiator Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
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- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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Abstract
ウレタン（メタ）アクリレート化合物と、単官能（メタ）アクリレートを少なくとも含む（メタ）アクリレートと、分子末端に水酸基を有しないラジカル重合開始剤又は分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤とを含む易剥離性保護用樹脂薄膜形成組成物を調製する工程と、易剥離性保護用樹脂薄膜形成組成物をガラス基板上に塗布して易剥離性保護用樹脂薄膜を形成する工程とを経て、易剥離性保護用樹脂薄膜を形成する。Urethane (meth) acrylate compound, (meth) acrylate containing at least monofunctional (meth) acrylate, and radical polymerization initiator having no hydroxyl group at the molecular end or radical polymerization initiator having hydroxyl group at the molecular end and a hindered structure And a step of preparing a resin film-forming composition for easy peelability protection and a resin film-forming composition for easy peelability protection on a glass substrate to form a resin film for easy peelability protection. Then, an easily peelable protective resin thin film is formed.
Description
本発明は、易剥離性保護用樹脂薄膜の形成方法及び易剥離性保護用樹脂薄膜形成組成物に関する。 The present invention relates to a method for forming a peelable protective resin thin film and a peelable protective resin thin film-forming composition.
物品（以下、「被塗布体」ともいう）の表面を磨耗や腐食から一時的に保護するために、その表面に塗布して膜を形成し、必要期間が過ぎたときに被塗布体を損傷させずに剥ぎ取ることができる塗料は、一般的に、ストリッパブルペイントと呼ばれる。 In order to temporarily protect the surface of an article (hereinafter also referred to as "application") from abrasion and corrosion, it is applied to the surface to form a film, and the object is damaged when the required period is over. Paints that can be stripped without being commonly referred to as strippable paints.
このストリッパブルペイントとしては、被塗布体の表面に一時的な保護塗膜を形成するための組成物として、（メタ）アクリル酸と（メタ）アクリル酸エステルとの共重合体と、重合可能な二重結合を有する不飽和化合物、例えばフェニルグリシジルエーテルのアクリル酸付加物と、ラジカル硬化系の光重合開始剤（以下、「ラジカル重合開始剤」ともいう）とを含む光硬化型樹脂組成物が提案されている（例えば特許文献１〜３参照）。 As this strippable paint, a copolymer of (meth) acrylic acid and (meth) acrylic acid ester is polymerizable as a composition for forming a temporary protective coating on the surface of a coated body. A photocurable resin composition comprising an unsaturated compound having a double bond, for example, an acrylic acid adduct of phenyl glycidyl ether, and a radical curing type photopolymerization initiator (hereinafter also referred to as "radical polymerization initiator") It is proposed (for example, refer patent documents 1-3).
このような光硬化型樹脂組成物は、塗工後に短時間（１〜５分間程度）の光照射及び／又は加熱をすることで硬化し、強靭な被膜を形成することから、作業性の向上が期待できる上に、有機溶剤を用いずに調製が可能であるため、被塗布体表面の侵食の抑制効果も期待されている。 Such a photocurable resin composition is cured by light irradiation and / or heating for a short time (about 1 to 5 minutes) after coating to form a tough coating, thereby improving workability. In addition, since the preparation is possible without using an organic solvent, the effect of suppressing the erosion of the surface of the coated body is also expected.
ところで、被塗布体がソーダガラス等のガラス基板である場合には、塗工時に被塗布体から剥離することなく、且つ、必要期間経過後に手で容易に被塗布体から剥離できる程度の密着力を有するストリッパブルペイントが要望されている。 By the way, when a to-be-coated body is glass substrates, such as soda glass, the adhesion which is a grade which can be easily peeled from a to-be-coated body by hand after required time progress, without peeling from a to-be-coated body There is a need for a strippable paint having the
しかしながら、ガラス基板である被塗布体に対し、樹脂成分とラジカル重合開始剤とを含む光硬化型樹脂組成物を接着剤として用いることについては多数提案されているものの（例えば特許文献４〜９参照）、剥離性に優れたストリッパブルペイントとしては提案されていない。 However, although many proposals have been made for using a photocurable resin composition containing a resin component and a radical polymerization initiator as an adhesive for an object to be coated which is a glass substrate (see, for example, Patent Documents 4 to 9). 2.) It is not proposed as a strippable paint excellent in peelability.
本発明は、上記実情に鑑みて提案されるものであり、ストリッパブルペイントとして好適な剥離性に優れた易剥離性保護用樹脂薄膜の形成方法及び易剥離性保護用樹脂薄膜形成組成物を提供することを目的とする。 The present invention is proposed in view of the above situation, and provides a method of forming a resin film for easy releasability protection having excellent releasability, which is suitable as a strippable paint, and a resin film forming composition for easily releasable protection. The purpose is to
そこで、本発明者は、上記目的を達成するために光硬化型樹脂組成物のラジカル重合開始剤に着目し、剥離性に優れたストリッパブルペイントを開発するべく鋭意検討を重ねたところ、下記（１）及び（２）の知見を得るに至った。 Therefore, in order to achieve the above object, the present inventor focused attention on the radical polymerization initiator of the photocurable resin composition and conducted intensive studies to develop a strippable paint having excellent releasability. The findings of 1) and (2) were obtained.
（１）分子末端に水酸基を有しないラジカル重合開始剤（例えばＩＲＧＡＣＵＲＥ（登録商標）９０７やＩＲＧＡＣＵＲＥ（登録商標）３７９ＥＧ）を用いるとガラスへの密着力が低下する。
（２）分子末端に水酸基を有するラジカル重合開始剤であっても、ヒンダード構造（立体障害構造）等を有するもの（例えばＩＲＧＡＣＵＲＥ（登録商標）１８４）を用いた場合にも、ガラスへの密着力が低下する。(1) When a radical polymerization initiator (for example, IRGACURE (registered trademark) 907 or IRGACURE (registered trademark) 379 EG) having no hydroxyl group at the molecular terminal is used, the adhesion to glass is reduced.
(2) Adhesion force to glass even when a radical polymerization initiator having a hydroxyl group at the molecular terminal, or one having a hindered structure (steric hindrance structure) or the like (for example, IRGACURE (registered trademark) 184) is used Decreases.
そして、本発明者は、ウレタン（メタ）アクリレート化合物を、所定の割合の単官能（メタ）アクリレートを少なくとも含む（メタ）アクリレート又は所定の割合の単官能（メタ）アクリレート及び２官能以上の（メタ）アクリレート、並びに分子末端に水酸基を有しないラジカル重合開始剤又は分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤と共に混合して易剥離性保護用樹脂薄膜形成組成物とすることで、当該組成物を均一且つ容易に調製できることを見出した。更に、本発明者は、易剥離性保護用樹脂薄膜形成組成物から硬化物が得られ、この硬化物が、塗工時に被塗布体であるガラス基板から剥離することなく、且つ、必要期間経過後に手で容易に当該基板から剥離できる程度の密着力を有することを見出し、本発明を完成させた。 Then, the present inventors have found that a urethane (meth) acrylate compound is a (meth) acrylate containing at least a predetermined proportion of monofunctional (meth) acrylate or a predetermined proportion of monofunctional (meth) acrylate and ) Acrylate and a radical polymerization initiator having no hydroxyl group at the molecular end or a radical polymerization initiator having a hydroxyl group at the molecular end and a hindered structure to form a resin thin film-forming composition for easy releasability, It has been found that the composition can be prepared uniformly and easily. Furthermore, the present inventor obtains a cured product from the easily releasable protective resin film-forming composition, and the cured product does not separate from the glass substrate which is the coated object at the time of coating, and the necessary period has elapsed. The inventors have found that the adhesive strength is such that it can be easily peeled off from the substrate later by hand, and the present invention is completed.
即ち、本発明は、
１．ウレタン（メタ）アクリレート化合物と、単官能（メタ）アクリレートを少なくとも含む（メタ）アクリレートと、分子末端に水酸基を有しないラジカル重合開始剤又は分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤とを含む易剥離性保護用樹脂薄膜形成組成物を調製する工程と、前記易剥離性保護用樹脂薄膜形成組成物をガラス基板上に塗布して易剥離性保護用樹脂薄膜を形成する工程とを有することを特徴とする易剥離性保護用樹脂薄膜の形成方法、
２．前記分子末端に水酸基を有しないラジカル重合開始剤は、ジアセチル、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、チオキサントン、２，４−ジエチルチオキサントン、チオキサントン−４−スルホン酸、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、アセトフェノン、ｐ−ジメチルアミノアセトフェノン、α，α−ジメトキシ−α−アセトキシアセトフェノン、α，α−ジメトキシ−α−フェニルアセトフェノン、ｐ−メトキシアセトフェノン、２−メチル−１−（４−メチルチオフェニル）−２−モルホリノプロパン−１−オン、１−（２−メチル−４−メチルチオフェニル）−２−モルホリノ−１−プロパノン、α，α−ジメトキシ−α−（４−モルホリノメチルチオフェニル）アセトフェノン、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、２−ジメチルアミノ−１−（４−モルホリノフェニル）−２−（ｐ−トリルメチル）ブタン−１−オン、アントラキノン、１，４−ナフトキノン、フェナシルクロリド、トリブロモメチルフェニルスルホン、トリス（トリクロロメチル）−ｓ−トリアジン、［１，２’−ビスイミダゾール］−３，３’，４，４’−テトラフェニル、［１，２’−ビスイミダゾール］−１，２’−ジクロロフェニル−３，３’，４，４’−テトラフェニル、ジ−ｔｅｒｔ−ブチルパ−オキシド、ジフェニル（２，４，６−トリメチルベンゾイル）ホスフィンオキシド、ｐ−ジメチルアミノ安息香酸エチル、ｔｅｒｔ−ブチル（３，５，５−トリメチルヘキサノイル）ペルオキシド、ペルオキシ酢酸ｔｅｒｔ−ブチル、ペルオキシ安息香酸ｔｅｒｔ−ブチル、ペルオキシオクタン酸ｔｅｒｔ−ブチル、ペルオキシネオデカン酸ｔｅｒｔ−ブチル、ペルオキシイソ酪酸ｔｅｒｔ−ブチル、過酸化ラウロイル、ペルオキシピバル酸ｔｅｒｔ−アミル、ペルオキシピバル酸ｔｅｒｔ−ブチル、過酸化ジクミル、過酸化ベンゾイル、過硫酸カリウム、過硫酸アンモニウム、２，２’−アゾビス（２−メチルプロピオン酸）ジメチル、２，２’−アゾビス（イソブチロニトリル）、２，２’−アゾビス（２−ブタンニトリル）、１，１’−アゾビス（シクロヘキサンカルボニトリル）、２−（ｔｅｒｔ−ブチルアゾ）−２−シアノプロパン、２，２’−アゾビス（Ｎ，Ｎ’−ジメチレンイソブチルアミジン）ジクロリド、２，２’−アゾビス（２−アミジノプロパン）ジクロリド、２，２’−アゾビス（Ｎ，Ｎ−ジメチレンイソブチルアミド）、２，２’−アゾビス（イソブチルアミド）二水和物；過酸化水素、過酸化アルキル、過酸化エステル又は過炭酸塩と、鉄塩、第１チタン塩、亜鉛ホルムアルデヒドスルホキシレート、ナトリウムホルムアルデヒドスルホキシレート又は還元糖との混合物；過硫酸、過ホウ酸若しくは過塩素酸のアルカリ金属塩又は過塩素酸のアンモニウム塩と、重亜硫酸アルカリ金属塩又は還元糖との混合物；過硫酸アルカリ金属塩と、ベンゼンホスホン酸又は還元糖との混合物からなる群より選択される何れか１種単独又は２種以上を組み合わせた混合物であることを特徴とする１の易剥離性保護用樹脂薄膜の形成方法、
３．前記分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤は、１−ヒドロキシシクロヘキシル＝フェニル＝ケトンであることを特徴とする１の易剥離性保護用樹脂薄膜の形成方法、
４．前記ウレタン（メタ）アクリレート化合物は、ポリカプロラクトン骨格又はポリテトラメチレングリコール骨格を主骨格とするウレタン（メタ）アクリレート化合物であることを特徴とする１〜３の何れかの易剥離性保護用樹脂薄膜の形成方法、
５．前記単官能（メタ）アクリレートの含有量が、前記（メタ）アクリレートの全量に対して５０質量％以上であることを特徴とする１〜４の何れかの易剥離性保護用樹脂薄膜の形成方法、
６．前記（メタ）アクリレートは、前記単官能（メタ）アクリレートと、２官能以上の（メタ）アクリレートとを含むことを特徴とする１〜５の何れかの易剥離性保護用樹脂薄膜の形成方法、
７．前記単官能（メタ）アクリレートが、環状構造を有する単官能（メタ）アクリレートを含むことを特徴とする１〜６の何れかの易剥離性保護用樹脂薄膜の形成方法、
８．前記易剥離性保護用樹脂薄膜形成組成物中の前記ウレタン（メタ）アクリレート化合物の含有量が、８０質量％未満であることを特徴とする１〜７の何れかの易剥離性保護用樹脂薄膜の形成方法、
９．前記易剥離性保護用樹脂薄膜形成組成物中の前記ウレタン（メタ）アクリレート化合物の含有量が、１０質量％以上であることを特徴とする１〜８の何れかの易剥離性保護用樹脂薄膜の形成方法、
１０．前記易剥離性保護用樹脂薄膜は、前記易剥離性保護用樹脂薄膜形成組成物の硬化物であることを特徴とする１〜９の何れかの易剥離性保護用樹脂薄膜の形成方法、
１１．ポリカプロラクトン骨格又はポリテトラメチレングリコール骨格を主骨格とするウレタン（メタ）アクリレート化合物と、単官能（メタ）アクリレートを少なくとも含む（メタ）アクリレートと、分子末端に水酸基を有しないラジカル重合開始剤又は分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤とを含むことを特徴とする易剥離性保護用樹脂薄膜形成組成物を提供する。That is, the present invention
1. Urethane (meth) acrylate compound, (meth) acrylate containing at least monofunctional (meth) acrylate, and radical polymerization initiator having no hydroxyl group at the molecular end or radical polymerization initiator having hydroxyl group at the molecular end and a hindered structure Preparing the resin thin film-forming composition for easy peelability protection comprising the step of forming the resin thin film-forming composition for easy peelability protection on a glass substrate to form the resin thin film for easy peelability protection; A method of forming a peelable protective resin thin film, characterized in that
2. The radical polymerization initiator having no hydroxyl group at the molecular terminal is diacetyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4, 4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, acetophenone, p-dimethylaminoacetophenone, α, α-dimethoxy-α-acetoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone P-Methoxyacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1- (2-methyl-4-methylthiophenyl) -2-morpholino-1-p Panone, α, α-dimethoxy-α- (4-morpholinomethylthiophenyl) acetophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-1- ( 4-morpholinophenyl) -2- (p-tolylmethyl) butan-1-one, anthraquinone, 1,4-naphthoquinone, phenacyl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) -s-triazine, [1,1 2'-Bisimidazole] -3,3 ', 4,4'-tetraphenyl, [1,2'-bisimidazole] -1,2'-dichlorophenyl-3,3', 4,4'-tetraphenyl, Di-tert-butyl peroxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, p-dimethylamide Ethyl benzoate, tert-butyl (3,5,5-trimethylhexanoyl) peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyoctanoate, tert-butyl peroxyneodecanoate, peroxyisobutyric acid tert-Butyl, lauroyl peroxide, tert-amyl peroxypivalate, tert-butyl peroxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, 2,2'-azobis (2-methylpropion) Acid) dimethyl, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-butanenitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2- (tert-butylazo)- 2-cyanopropane, 2, '-Azobis (N, N'-dimethylene isobutyl amidine) dichloride, 2,2'-azobis (2-amidinopropane) dichloride, 2,2'-azobis (N, N-dimethylene isobutylamide), 2,2 Hydrogen peroxide, alkyl peroxide, peroxide ester or percarbonate, iron salt, first titanium salt, zinc formaldehyde sulfoxylate, sodium formaldehyde sulfoxylate or reduction Mixtures with sugars; persulphates, perborates or alkali metal salts of perchlorates or ammonium perchlorates with alkali metal bisulfites or reducing sugars; alkali metal persulfates, benzene phosphonic acid Or any one selected from the group consisting of a mixture with reducing sugars alone or a mixture of two or more The method forming one of the easily peelable protective resin thin film characterized,
3. The radical polymerization initiator having a hydroxyl group at the molecular terminal and having a hindered structure is 1-hydroxycyclohexyl = phenyl = ketone, The method for forming a resin film for easy peeling protection according to 1 above,
4. The urethane (meth) acrylate compound is a urethane (meth) acrylate compound having a polycaprolactone skeleton or a polytetramethylene glycol skeleton as a main skeleton, and the easily releasable protective resin film according to any one of 1 to 3 How to form the
5. Content of the said monofunctional (meth) acrylate is 50 mass% or more with respect to whole quantity of said (meth) acrylate, The formation method of the resin thin film for easily peelable protections in any one of 1-4 characterized by the above-mentioned ,
6. The (meth) acrylate comprises the monofunctional (meth) acrylate and a bifunctional or higher functional (meth) acrylate, and the method for forming the easily releasable protective resin film according to any one of 1 to 5,
7. The method for forming the easily releasable protective resin thin film according to any one of 1 to 6, wherein the monofunctional (meth) acrylate comprises a monofunctional (meth) acrylate having a cyclic structure,
8. The content of the urethane (meth) acrylate compound in the easily releasable protective resin film-forming composition is less than 80% by mass, the easily releasable protective resin film according to any one of 1 to 7 How to form the
9. The content of the urethane (meth) acrylate compound in the easily releasable protective resin film-forming composition is 10% by mass or more, and the easily releasable protective resin film according to any one of 1 to 8 How to form the
10. The method for forming the easily releasable protective resin film according to any one of 1 to 9, wherein the easily releasable protective resin film is a cured product of the easily releasable protective resin film-forming composition.
11. A urethane (meth) acrylate compound having a polycaprolactone skeleton or a polytetramethylene glycol skeleton as a main skeleton, a (meth) acrylate containing at least monofunctional (meth) acrylate, and a radical polymerization initiator or molecule having no hydroxyl group at the molecular terminal There is provided a resin thin film-forming composition for easy releasability protection comprising a radical polymerization initiator having a hydroxyl group at the end and having a hindered structure.
本発明の易剥離性保護用樹脂薄膜の形成方法を用いることで、均一な易剥離性保護用樹脂薄膜形成組成物を容易に調製できると共に、調整した組成物を用いてガラス基板に対する剥離性に優れた易剥離性保護用樹脂薄膜を形成できる。即ち、当該樹脂薄膜は、例えば温水に浸漬してもガラス基板から剥離しないが、手で容易にガラス基板から剥離できる程度の密着力を有している。当該樹脂薄膜は、このような特徴を備えることから、ガラス基板を研磨・切断する場合やガラス基板を保管する場合等に、当該基板の表面を腐食、磨耗、汚れ等から一時的に保護するためのストリッパブルペイントとして使用できる。 By using the method for forming a resin film for easy peeling protection of the present invention, it is possible to easily prepare a uniform resin thin film-forming composition for easy peeling protection, and using the prepared composition for peeling to a glass substrate. It is possible to form an excellent easily peelable protective resin thin film. That is, although the said resin thin film does not peel from a glass substrate, for example, even if it immerses it in warm water, it has adhesiveness of the extent which can be easily peeled from a glass substrate by hand. Since the resin thin film has such a feature, it temporarily protects the surface of the substrate from corrosion, abrasion, dirt, etc. when polishing or cutting the glass substrate, storing the glass substrate, etc. It can be used as a strippable paint.
本発明の実施形態にかかる易剥離性保護用樹脂薄膜の形成方法は、ウレタン（メタ）アクリレート化合物と、単官能（メタ）アクリレートを少なくとも含む（メタ）アクリレートと、分子末端に水酸基を有しないラジカル重合開始剤又は分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤とを含む易剥離性保護用樹脂薄膜形成組成物を調製する工程と、易剥離性保護用樹脂薄膜形成組成物をガラス基板上に塗布して易剥離性保護用樹脂薄膜を形成する工程とを有する。 A method of forming a resin film for easy peeling protection according to an embodiment of the present invention comprises a urethane (meth) acrylate compound, (meth) acrylate containing at least monofunctional (meth) acrylate, and a radical having no hydroxyl group at the molecular terminal A process for preparing a resin film-forming composition for easy peelability protection comprising a polymerization initiator or a radical polymerization initiator having a hydroxyl group at the molecular end and having a hindered structure, and a resin film formation composition for resin film for easy peelability And (d) applying on a substrate to form a peelable protective resin thin film.
まず、易剥離性保護用樹脂薄膜形成組成物（以下、「組成物」ともいう）を調製する工程について説明する。本実施形態の組成物は、ウレタン（メタ）アクリレート化合物、単官能（メタ）アクリレート、必要に応じて２官能以上の（メタ）アクリレート、分子末端に水酸基を有しないラジカル重合開始剤又は分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤等の各成分を混合することで調製できる。 First, the process of preparing the easily releasable protective resin thin film-forming composition (hereinafter, also referred to as “composition”) will be described. The composition of this embodiment is a urethane (meth) acrylate compound, a monofunctional (meth) acrylate, optionally a bifunctional or higher (meth) acrylate, a radical polymerization initiator having no hydroxyl group at the molecular end, or a molecular end It can be prepared by mixing each component such as a radical polymerization initiator having a hydroxyl group and a hindered structure.
例えば、撹拌羽根を有するＳＵＳ製調製タンクに各成分を所定量投入し、室温（およそ２５℃）又は加温下で、均一になるまで撹拌する。また、必要に応じて、各成分を混合することで得られる組成物を、メッシュ、メンブレンフィルター等でろ過してもよい。このようにして得られた組成物は、液状であり樹脂液ともいう。なお、本実施形態の組成物を構成するある成分が、他の成分の機能を兼ね備える場合には、その点を考慮して、各成分の量を決める必要がある。 For example, a predetermined amount of each component is charged into a preparation tank made of SUS having a stirring blade, and stirring is performed at room temperature (approximately 25 ° C.) or under heating until uniform. Moreover, you may filter the composition obtained by mixing each component with a mesh, a membrane filter, etc. as needed. The composition obtained in this way is liquid and is also called resin liquid. In addition, when a certain component which comprises the composition of this embodiment combines the function of another component, it is necessary to consider the point and to decide the quantity of each component.
次に、本実施形態の組成物の各成分の原料について説明する。この組成物は、ウレタン（メタ）アクリレート化合物を含むものであり、好ましくは、ポリカプロラクトン骨格又はポリテトラメチレングリコール骨格を主骨格とするウレタン（メタ）アクリレート化合物を含むものである。 Next, the raw material of each component of the composition of this embodiment is demonstrated. This composition contains a urethane (meth) acrylate compound, and preferably contains a urethane (meth) acrylate compound having a polycaprolactone skeleton or a polytetramethylene glycol skeleton as a main skeleton.
ポリカプロラクトン骨格を主骨格とするウレタン（メタ）アクリレート化合物は、カプロラクトンの開環重合体であるポリカプロラクトン骨格を主骨格として有するものであれば特に限定されるものではなく、市販品を用いてもよいし、公知の方法によって製造したものを用いてもよい。このようなポリカプロラクトン骨格を有するウレタン（メタ）アクリレート化合物としては、例えば、ポリカプロラクトンポリオール（（株）ダイセル製プラクセルシリーズ等）と、ポリイソシアネート化合物と、水酸基を有する（メタ）アクリレート化合物との反応物を用いることができる。また、市販品としては、アートレジンＵＮ−３５２（根上工業（株）製）等が挙げられるが、これらに限定されない。 The urethane (meth) acrylate compound having a polycaprolactone skeleton as a main skeleton is not particularly limited as long as it has a polycaprolactone skeleton, which is a ring-opened polymer of caprolactone, as a main skeleton, and a commercially available product may be used. It is good and you may use what was manufactured by the well-known method. As the urethane (meth) acrylate compound having such a polycaprolactone skeleton, for example, polycaprolactone polyol (Placcel series manufactured by Daicel Co., Ltd., etc.), polyisocyanate compound, and (meth) acrylate compound having a hydroxyl group Reactants can be used. Moreover, although a commercially available product includes Art Resin UN-352 (manufactured by Negami Chemical Industry Co., Ltd.) and the like, it is not limited thereto.
ポリテトラメチレングリコール骨格を主骨格とするウレタン（メタ）アクリレート化合物は、特に限定されるものではなく、市販品を用いてもよいし、公知の方法によって製造したものを用いてもよい。このようなポリテトラメチレングリコール骨格を有するウレタン（メタ）アクリレート化合物としては、例えば、二官能性ポリテトラメチレングリコールと、ポリイソシアネート化合物と、水酸基を有する（メタ）アクリレート化合物との反応物等を用いることができる。また、市販品としては、紫光（登録商標）ＵＶ−２７５０Ｂ、同ＵＶ−７０００Ｂ(以上、日本合成化学工業（株）製）等が挙げられるが、これらに限定されない。 The urethane (meth) acrylate compound having a polytetramethylene glycol skeleton as a main skeleton is not particularly limited, and a commercially available product may be used, or one produced by a known method may be used. As the urethane (meth) acrylate compound having such a polytetramethylene glycol skeleton, for example, a reaction product of a difunctional polytetramethylene glycol, a polyisocyanate compound, and a (meth) acrylate compound having a hydroxyl group is used. be able to. Moreover, as a commercial item, although a violet light (registered trademark) UV-2750B, the same UV-7000B (above, Nippon Synthetic Chemical Industry Co., Ltd. product) etc. are mentioned, it is not limited to these.
ウレタン（メタ）アクリレート化合物の重量平均分子量は、通常、５００〜１００，０００程度であるが、得られる易剥離性保護用樹脂薄膜（以下、「樹脂薄膜」ともいう）の強靭性等の観点から、好ましくは１，０００以上、より一層好ましくは２，０００以上である。また、本実施形態の組成物の過度の粘度の増加を抑制して塗工性を確保する観点から、好ましくは５０，０００以下、より好ましくは１０，０００以下、より一層好ましくは８，０００以下、更に好ましくは５，０００以下である。なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算測定値である（以下、同様）。 The weight average molecular weight of the urethane (meth) acrylate compound is usually about 500 to 100,000, but from the viewpoint of the toughness and the like of the easily releasable protective resin thin film (hereinafter also referred to as "resin thin film") obtained. Preferably, it is 1,000 or more, more preferably 2,000 or more. Further, from the viewpoint of suppressing the increase in the viscosity of the composition of the present embodiment to secure the coatability, it is preferably 50,000 or less, more preferably 10,000 or less, still more preferably 8,000 or less More preferably, it is 5,000 or less. In addition, a weight average molecular weight is a polystyrene conversion measurement value by gel permeation chromatography (GPC) (following, the same).
本実施形態の組成物（樹脂液）全体に対するウレタン（メタ）アクリレート化合物の含有量は、好ましくは１０質量％以上８０質量％未満、又は１０質量％以上７０質量％未満、又は２０質量％以上７０質量％未満、又は３０質量％以上６０質量％未満である。当該化合物の含有量を８０質量％未満とすることで、組成物の粘度が過度に上昇することを抑制し、当該組成物の塗工性を維持し易くなるだけでなく、相対的にエチレン性不飽和単量体の量が多くなり、ガラス基板への密着力等の調整が容易になる。一方、当該化合物の含有量を１０質量％以上とすることで、本実施形態の樹脂薄膜の剥離性を確保し易くなる。 The content of the urethane (meth) acrylate compound to the whole composition (resin liquid) of the present embodiment is preferably 10% by mass to less than 80% by mass, or 10% by mass to 70% by mass, or 20% by mass to 70%. It is less than mass%, or 30 mass% or more and less than 60 mass%. By setting the content of the compound to less than 80% by mass, it is possible to suppress an excessive increase in the viscosity of the composition, and to make it easy to maintain the coatability of the composition, and to be relatively ethylenic. The amount of unsaturated monomer increases, and adjustment of adhesion to a glass substrate and the like becomes easy. On the other hand, when the content of the compound is 10% by mass or more, the peelability of the resin thin film of the present embodiment can be easily secured.
本実施形態の組成物は、得られる樹脂薄膜の密着性の改善、組成物の低粘度化等を目的に、エチレン性不飽和単量体として、少なくとも単官能（メタ）アクリレートを含む（メタ）アクリレートを含有する。（メタ）アクリレートは、単官能（メタ）アクリレートと２官能以上の（メタ）アクリレートとを含んでもよい。なお、エチレン性不飽和単量体とは、少なくとも１個のエチレン性不飽和二重結合を有する化合物である。 The composition of the present embodiment contains (meth) at least a monofunctional (meth) acrylate as an ethylenically unsaturated monomer for the purpose of improving the adhesion of the obtained resin thin film, reducing the viscosity of the composition, etc. Contains an acrylate. The (meth) acrylate may include a monofunctional (meth) acrylate and a bifunctional or more (meth) acrylate. The ethylenically unsaturated monomer is a compound having at least one ethylenically unsaturated double bond.
単官能（メタ）アクリレートとしては、アルキル単官能（メタ）アクリレートが好適であり、そのアルキル基の炭素数が６以上のアルキル単官能（メタ）アクリレートがより好適である。 As the monofunctional (meth) acrylate, an alkyl monofunctional (meth) acrylate is preferable, and an alkyl monofunctional (meth) acrylate having 6 or more carbon atoms in the alkyl group is more preferable.
アルキル基としては、直鎖状、分岐状、環状の何れでもよく、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基等の炭素数１〜２０の直鎖状又は分岐状アルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、ビシクロブチル基、ビシクロペンチル基、ビシクロヘキシル基、ビシクロヘプチル基、ビシクロオクチル基、ビシクロノニル基、ビシクロデシル基等の炭素数３〜２０の環状アルキル基等が挙げられる。 The alkyl group may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. A linear or branched alkyl group having 1 to 20 carbon atoms such as n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl; cyclopropyl Group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclobutyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, bicyclo group A C3-C20 cyclic alkyl group, such as a decyl group, etc. are mentioned.
また、単官能（メタ）アクリレートとしては、本実施形態の樹脂薄膜の靱性向上の観点から、分子内に環構造（「環状構造」ともいう）を有しているものが好ましい。環構造を有する（メタ）アクリレートの重合物は、直鎖状の置換基を有するものよりガラス転移温度（Ｔｇ）が高く、硬い膜が得られやすい。一方で環構造の置換基は、直鎖状の置換基より自由体積が小さく、樹脂薄膜の靭性に必要な（メタ）アクリレート主鎖同士の絡み合いを阻害しづらい。そのため環構造を有している単官能（メタ）アクリレートを配合した樹脂薄膜は、硬いながらも靭性がある膜になると考えられる。 Moreover, as a monofunctional (meth) acrylate, what has ring structure (it is also called "cyclic structure") in a molecule | numerator from a viewpoint of the toughness improvement of the resin thin film of this embodiment is preferable. The polymer of (meth) acrylate having a ring structure has a glass transition temperature (Tg) higher than that of a polymer having a linear substituent, and a hard film is easily obtained. On the other hand, the substituent of the ring structure has a free volume smaller than that of the linear substituent, and it is difficult to inhibit the entanglement of (meth) acrylate main chains necessary for the toughness of the resin thin film. Therefore, it is considered that a resin thin film containing a monofunctional (meth) acrylate having a ring structure will be a hard but tough film.
アルキル基の炭素数が６以上の単官能アルキル（メタ）アクリレートの具体例としては、ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、６−メチルヘプチル（メタ）アクリレート、ノニル（メタ）アクリレート、７−メチルオクチル（メタ）アクリレート、デシル（メタ）アクリレート、８−メチルノニル（メタ）アクリレート、ラウリル（メタ）アクリレート、１０−メチルウンデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、１６−メチルヘプタデシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等が挙げられる。 Specific examples of the monofunctional alkyl (meth) acrylate having 6 or more carbon atoms in the alkyl group include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 6- Methyl heptyl (meth) acrylate, nonyl (meth) acrylate, 7-methyl octyl (meth) acrylate, decyl (meth) acrylate, 8-methyl nonyl (meth) acrylate, lauryl (meth) acrylate, 10-methyl undecyl (meth) Acrylate, stearyl (meth) acrylate, 16-methylheptadecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl ( Data) acrylate, and the like.
また、このようなアルキル基の炭素数が６以上の単官能アルキル（メタ）アクリレート以外の（メタ）アクリレートの具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、グリシジル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ベンジル（メタ）アクリレート、エチレンオキシド変性（ｎ＝２）フェノール（メタ）アクリレート、プロピレンオキシド変性（ｎ＝２．５）ノニルフェノール（メタ）アクリレート、２−（メタ）アクリロイルオキシエチルアシッドホスフェート、フルフリル（メタ）アクリレート、カルビトール（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、アリル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、２−フェノキシ−２−ヒドロキシプロピル（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、３−クロロ−２−ヒドロキシプロピル（メタ）アクリレート等が挙げられ、中でも、水酸基を含有しないものが好ましく、また、分子量は１００〜３００程度が好ましい。 Moreover, as a specific example of (meth) acrylate other than monofunctional alkyl (meth) acrylate whose carbon number of such an alkyl group is 6 or more, methyl (meth) acrylate, ethyl (meth) acrylate, phenoxyethyl (meth) Acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, n-butyl (meth) acrylate, benzyl (meth) acrylate, ethylene oxide modified (n = 2) phenol (meth) acrylate, propylene oxide modified (n = 2. 5) Nonylphenol (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, furfuryl (meth) acrylate, carbitol (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate , 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl ( Examples thereof include meta) acrylate and 3-chloro-2-hydroxypropyl (meth) acrylate. Among them, those containing no hydroxyl group are preferable, and the molecular weight is preferably about 100 to 300.
中でも、８−メチルノニル（メタ）アクリレート、ラウリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、１６−メチルヘプタデシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレートが好ましい。 Among them, 8-methylnonyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, 16-methylheptadecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and isobornyl (meth) acrylate are preferable.
単官能（メタ）アクリレートは、１種単独又は２種以上を組み合わせて使用できる。 Monofunctional (meth) acrylate can be used individually by 1 type or in combination of 2 or more types.
２官能以上の（メタ）アクリレートとしては、２官能（メタ）アクリレート、３官能以上の（メタ）アクリレート等が挙げられる。 Examples of the bifunctional or higher (meth) acrylate include bifunctional (meth) acrylates and trifunctional or higher (meth) acrylates.
２官能（メタ）アクリレートとしては、例えば、エチレングリコールジ（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、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、プロピレングリコールジ（メタ）アクリレート、ジ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、ブチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エチレンオキシド変性ビスフェノールＡジ（メタ）アクリレート、プロピレンオキシド変性ビスフェノールＡジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、エチレングリコールジグリシジルエーテル（メタ）アクリル酸付加物、ジエチレングリコールジグリシジルエーテル（メタ）アクリル酸付加物、フタル酸ジグリシジルエステル（メタ）アクリル酸付加物、ヒドロキシピバリン酸変性ネオペンチルグリコールジ（メタ）アクリレート等が挙げられる。 Examples of difunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate , Dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerys Tall di (meth) acrylate, ethylene glycol diglycidyl ether (meth) acrylic acid adduct, diethylene glycol diglycidyl ether (meth) acrylic acid adduct, phthalic acid diglycidyl ester (meth) acrylic acid adduct, hydroxypivalic acid modified neopentyl Examples include glycol di (meth) acrylate and the like.
３官能以上の（メタ）アクリレートとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、エチレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、グリセリンポリグリシジルエーテル（メタ）アクリル酸付加物等が挙げられる。 Examples of trifunctional or higher (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol Examples thereof include hexa (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, glycerin polyglycidyl ether (meth) acrylic acid adduct and the like.
中でも、２官能（メタ）アクリレート又は３官能以上の（メタ）アクリレートが好ましく、２官能（メタ）アクリレートがより好ましい。 Among them, bifunctional (meth) acrylates or trifunctional or higher (meth) acrylates are preferable, and bifunctional (meth) acrylates are more preferable.
２官能以上の（メタ）アクリレートは、１種単独又は２種以上を組み合わせて使用できる。 The bifunctional or higher (meth) acrylate can be used singly or in combination of two or more.
本実施形態の組成物全体に対する（メタ）アクリレート、即ち単官能（メタ）アクリレートと２官能以上の（メタ）アクリレートの含有量は、組成物を低粘度化し、作業性を高める観点から、通常、１０質量％以上であるが、好ましくは２０質量％以上、より一層好ましくは３０質量％以上であり、後述する組成物の樹脂薄膜（硬化物）の靭性及び密着力を制御する観点から、好ましくは３５質量％以上、より好ましくは４０質量％以上である。 The content of (meth) acrylate, that is, monofunctional (meth) acrylate and bifunctional or higher (meth) acrylate with respect to the entire composition of the present embodiment is generally from the viewpoint of lowering the viscosity of the composition and improving workability. The content is 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and preferably from the viewpoint of controlling the toughness and adhesion of the resin thin film (cured product) of the composition described later. It is 35% by mass or more, more preferably 40% by mass or more.
単官能（メタ）アクリレートに２官能以上の（メタ）アクリレートを併用する場合、ストリッパブルペイントして使用できる程度の樹脂薄膜の靭性を確保する観点から、単官能（メタ）アクリレートの含有量を、２官能以上の（メタ）アクリレートの含有量より多くする。２官能以上の（メタ）アクリレートの含有量が単官能（メタ）アクリレートの含有量よりも多くなると、樹脂薄膜は硬くなる一方、脆くなり、靭性が低下する。 When using a monofunctional (meth) acrylate in combination with a bifunctional or higher functional (meth) acrylate, the content of the monofunctional (meth) acrylate is, from the viewpoint of securing the toughness of the resin thin film that can be used as a strippable paint. It is more than the content of the (meth) acrylate having two or more functional groups. When the content of the bifunctional or higher (meth) acrylate is larger than the content of the monofunctional (meth) acrylate, the resin thin film becomes hard but becomes brittle and the toughness decreases.
単官能（メタ）アクリレートの含有量（Ｗｓ）と２官能以上の（メタ）アクリレートの含有量（Ｗｍ）との含有割合は、［Ｗｍ／（Ｗｓ＋Ｗｍ）］×１００＜５０質量％（言い換えると、［Ｗｓ／（Ｗｓ＋Ｗｍ）］×１００≧５０質量％）を満たす。樹脂薄膜の靭性の観点から、これらの含有割合は、好ましくは４０質量％以下、より好ましくは３０質量％以下であり、得られる樹脂薄膜の耐水性を向上させる観点から、好ましくは１質量％以上、より好ましくは５質量％以上、より一層好ましくは、１０質量％以上、更に好ましくは１５質量％以上である。The content ratio of the monofunctional (meth) acrylate content (W s ) to the bifunctional or higher (meth) acrylate content (W m ) is [W m / (W s + W m )] × 100 <50 Mass% (in other words, [W s / (W s + W m )] × 100 × 50 mass%) is satisfied. From the viewpoint of toughness of the resin thin film, the content thereof is preferably 40% by mass or less, more preferably 30% by mass or less, and from the viewpoint of improving the water resistance of the obtained resin thin film, preferably 1% by mass or more It is more preferably 5% by mass or more, still more preferably 10% by mass or more, and still more preferably 15% by mass or more.
本実施形態の組成物は、樹脂薄膜の基材への密着性、耐熱性等の向上等を目的として、上述の単官能（メタ）アクリレート及び２官能以上の（メタ）アクリレートと共重合できる極性基含有モノマーを含んでいてもよい。 The composition of this embodiment has a polarity that can be copolymerized with the above-mentioned monofunctional (meth) acrylate and bifunctional or more (meth) acrylate for the purpose of improving the adhesion of the resin thin film to the substrate, heat resistance, etc. It may contain a group-containing monomer.
極性基含有モノマーとしては、例えば、（メタ）アクリル酸、（メタ）アクリルアミド、（メタ）アクリロイルモルホリン、（メタ）アクリロニトリル等が挙げられる。 As a polar group containing monomer, (meth) acrylic acid, (meth) acrylamide, (meth) acryloyl morpholine, (meth) acrylonitrile etc. are mentioned, for example.
本実施形態の組成物が極性基含有モノマーを含む場合、その含有量は、単官能（メタ）アクリレートと２官能以上の（メタ）アクリレートの合計含有量を超えない。もし極性基含有モノマーの比率が高くなると、得られる樹脂薄膜の耐水性が低下し、その結果、剥離性等が低下することがある。 When the composition of the present embodiment contains a polar group-containing monomer, the content does not exceed the total content of monofunctional (meth) acrylate and bifunctional or higher (meth) acrylate. If the proportion of the polar group-containing monomer is increased, the water resistance of the resulting resin thin film may be reduced, and as a result, the peelability may be reduced.
本実施形態の組成物は、放射線ラジカル重合開始剤、熱ラジカル重合開始剤等のラジカル重合開始剤を含むものであり、これらのラジカル重合開始剤であって、分子末端に水酸基を有しないラジカル重合開始剤又は分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤を適用できる。 The composition of the present embodiment contains a radical polymerization initiator such as a radiation radical polymerization initiator and a thermal radical polymerization initiator, and these radical polymerization initiators are radical polymerizations having no hydroxyl group at the molecular terminal. An initiator or a radical polymerization initiator having a hydroxyl group at a molecular end and a hindered structure can be applied.
ここで、分子末端に水酸基を有しないラジカル重合開始剤とは、例えば下記式（１）で表される２−メチル−１−（４−メチルチオフェニル）−２−モルホリノプロパン−１−オンや、下記式（２）で表される２−ジメチルアミノ−１−（４−モルホリノフェニル）−２−（ｐ−トリルメチル）ブタン−１−オンのように、構造中に水酸基を有しないものである。一方、分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤とは、例えば下記式（３）で表される１−ヒドロキシシクロヘキシル＝フェニル＝ケトンのように、構造中の水酸基がｔｅｒｔ−ブチル基やシクロヘキシル基といった嵩高い置換基に隣接し、該水酸基の反応性が低下しているものである。
Here, the radical polymerization initiator having no hydroxyl group at the molecular terminal is, for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one represented by the following formula (1), Like 2-dimethylamino-1- (4-morpholinophenyl) -2- (p-tolylmethyl) butan-1-one represented by the following formula (2), it has no hydroxyl group in the structure. On the other hand, a radical polymerization initiator having a hydroxyl group at the molecular terminal and a hindered structure is, for example, a tert-butyl hydroxyl group in the structure like 1-hydroxycyclohexyl phenyl ketone represented by the following formula (3) It is adjacent to a bulky substituent such as a group or a cyclohexyl group, and the reactivity of the hydroxyl group is lowered.
本実施形態の組成物は、分子末端に水酸基を有しないラジカル重合開始剤又は分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤を含むことにより、ガラス基板に対する優れた剥離性を付与できる。なお、これらのラジカル重合開始剤を用いることで、優れた剥離性が阻害されないメカニズムは明らかにされていないが、ガラス基材と本実施形態の組成物とが水素結合を形成しないためと考えられる。 The composition of the present embodiment can impart excellent peelability to a glass substrate by including a radical polymerization initiator having no hydroxyl group at the molecular end or a radical polymerization initiator having a hydroxyl group at the molecular end and a hindered structure. . In addition, although the mechanism in which the outstanding peelability is not inhibited is not clarified by using these radical polymerization initiators, it is thought that a glass base material and the composition of this embodiment do not form a hydrogen bond. .
放射線ラジカル重合開始剤であって、分子末端に水酸基を有しないラジカル重合開始剤の具体例としては、ジアセチル等のα−ジケトン類；ベンゾイン等のアシロイン類；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等のアシロインエーテル類；チオキサントン、２，４−ジエチルチオキサントン、チオキサントン−４−スルホン酸、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）ベンゾフェノン等のベンゾフェノン類；アセトフェノン、ｐ−ジメチルアミノアセトフェノン、α，α−ジメトキシ−α−アセトキシアセトフェノン、α，α−ジメトキシ−α−フェニルアセトフェノン、ｐ−メトキシアセトフェノン、２−メチル−１−（４−メチルチオフェニル）−２−モルホリノプロパン−１−オン、１−（２−メチル−４−メチルチオフェニル）−２−モルホリノ−１−プロパノン、α，α−ジメトキシ−α−（４−モルホリノメチルチオフェニル）アセトフェノン、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、２−ジメチルアミノ−１−（４−モルホリノフェニル）−２−（ｐ−トリルメチル）ブタン−１−オン等のアセトフェノン類；アントラキノン、１，４−ナフトキノン等のキノン類；フェナシルクロリド、トリブロモメチルフェニルスルホン、トリス（トリクロロメチル）−ｓ−トリアジン等のハロゲン化合物；［１，２’−ビスイミダゾール］−３，３’，４，４’−テトラフェニル、［１，２’−ビスイミダゾール］−１，２’−ジクロロフェニル−３，３’，４，４’−テトラフェニル等のビスイミダゾール類；ジ−ｔｅｒｔ−ブチルパ−オキシド等の過酸化物；ジフェニル（２，４，６−トリメチルベンゾイル）ホスフィンオキシド等のアシルホスフィンオキシド類；ｐ−ジメチルアミノ安息香酸エチル等のｐ−ジメチルアミノ安息香酸エステル等が挙げられる。 Specific examples of a radical polymerization initiator which is a radiation radical polymerization initiator and does not have a hydroxyl group at its molecular terminal include α-diketones such as diacetyl; acyloins such as benzoin; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Acyloin ethers such as ether; thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and the like Benzophenones; acetophenone, p-dimethylaminoacetophenone, α, α-dimethoxy-α-acetoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1- (4) Methylthiophenyl) -2-morpholinopropan-1-one, 1- (2-methyl-4-methylthiophenyl) -2-morpholino-1-propanone, α, α-dimethoxy-α- (4-morpholinomethylthiophenyl) acetophenone , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (p-tolylmethyl) butan-1-one Acetophenones such as: anthraquinone, quinones such as 1,4-naphthoquinone; halogen compounds such as phenacyl chloride, tribromomethyl phenyl sulfone, tris (trichloromethyl) -s-triazine; [1,2′-bisimidazole] -3,3 ', 4,4'-tetraphenyl, [1,2'-bisimidazole] Bisimidazoles such as -1,2'-dichlorophenyl-3,3 ', 4,4'-tetraphenyl; peroxides such as di-tert-butyl peroxide; diphenyl (2,4,6-trimethyl benzoyl) Acyl phosphine oxides such as phosphine oxide; p-dimethylaminobenzoic acid esters such as ethyl p-dimethylaminobenzoate; and the like.
放射線ラジカル重合開始剤であって、分子末端に水酸基を有しないラジカル重合開始剤の市販品としては、ＩＲＧＡＣＵＲＥ（登録商標）６５１、同９０７、同３６９、同３７９ＥＧ、同８１９、同ＴＰＯ、同ＭＢＦ（以上、ＢＡＳＦジャパン（株）製）、ＫＡＹＡＣＵＲＥ ＤＥＴＸ−Ｓ、同ＥＰＡ（以上、日本化薬（株）製）等が挙げられるが、これらに限定されない。 As commercial products of radical polymerization initiators which are radiation radical polymerization initiators and have no hydroxyl group at the molecular terminal, IRGACURE (registered trademark) 651, 907, 369, 379 EG, 819, TPO, and MBF (The above, BASF Japan Ltd. product), KAYACURE DETX-S, the same EPA (above, Nippon Kayaku Co., Ltd. product) etc. are mentioned, However, It is not limited to these.
放射線ラジカル重合開始剤であって、分子末端に水酸基を有しヒンダード構造を有するラジカル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＝ケトン等が挙げられる。 As a radical polymerization initiator which is a radiation radical polymerization initiator and has a hydroxyl group at a molecular terminal and a hindered structure, 1-hydroxycyclohexyl phenyl ketone and the like can be mentioned.
放射線ラジカル重合開始剤であって、分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤の市販品としては、ＩＲＧＡＣＵＲＥ（登録商標）１８４（以上、ＢＡＳＦジャパン（株）製）等が挙げられるが、これらに限定されない。 As a commercial item of a radical polymerization initiator which is a radiation radical polymerization initiator and has a hydroxyl group at the molecular terminal and a hindered structure, IRGACURE (registered trademark) 184 (manufactured by BASF Japan Ltd.) and the like can be mentioned. However, it is not limited to these.
熱ラジカル重合開始剤としては、過酸化水素類、アゾ化合物、レドックス系開始剤等が挙げられる。 As a thermal radical polymerization initiator, hydrogen peroxides, an azo compound, a redox type initiator etc. are mentioned.
過酸化水素類であって、分子末端に水酸基を有しないラジカル重合開始剤の具体例としては、ｔｅｒｔ−ブチル（３，５，５−トリメチルヘキサノイル）ペルオキシド、ペルオキシ酢酸ｔｅｒｔ−ブチル、ペルオキシ安息香酸ｔｅｒｔ−ブチル、ペルオキシオクタン酸ｔｅｒｔ−ブチル、ペルオキシネオデカン酸ｔｅｒｔ−ブチル、ペルオキシイソ酪酸ｔｅｒｔ−ブチル、過酸化ラウロイル、ペルオキシピバル酸ｔｅｒｔ−アミル、ペルオキシピバル酸ｔｅｒｔ−ブチル、過酸化ジクミル、過酸化ベンゾイル、過硫酸カリウム、過硫酸アンモニウム等が挙げられる。 Hydrogen peroxides, which are specific examples of radical polymerization initiators having no hydroxyl group at the molecular end, include tert-butyl (3,5,5-trimethylhexanoyl) peroxide, tert-butyl peroxyacetate, peroxybenzoic acid tert-butyl, tert-butyl peroxyoctanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxyisobutyrate, lauroyl peroxide, tert-amyl peroxypivalate, tert-butyl peroxypivalate, dicumyl peroxide, peroxypivalate Examples include benzoyl oxide, potassium persulfate, ammonium persulfate and the like.
アゾ化合物であって、分子末端に水酸基を有しないラジカル重合開始剤の具体例としては、２，２’−アゾビス（２−メチルプロピオン酸）ジメチル、２，２’−アゾビス（イソブチロニトリル）、２，２’−アゾビス（２−ブタンニトリル）、１，１’−アゾビス（シクロヘキサンカルボニトリル）、２−（ｔｅｒｔ−ブチルアゾ）−２−シアノプロパン、２，２’−アゾビス（Ｎ，Ｎ’−ジメチレンイソブチルアミジン）ジクロリド、２，２’−アゾビス（２−アミジノプロパン）ジクロリド、２，２’−アゾビス（Ｎ，Ｎ−ジメチレンイソブチルアミド）、２，２’−アゾビス（イソブチルアミド）二水和物等が挙げられる。 Specific examples of the radical polymerization initiator which is an azo compound and does not have a hydroxyl group at its molecular terminal include 2,2'-azobis (2-methylpropionic acid) dimethyl and 2,2'-azobis (isobutyronitrile) 2,2'-azobis (2-butanenitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2- (tert-butylazo) -2-cyanopropane, 2,2'-azobis (N, N ') Dimethylene isobutyl amidine) dichloride, 2,2′-azobis (2-amidinopropane) dichloride, 2,2′-azobis (N, N-dimethylene isobutyramide), 2,2′-azobis (isobutylamido) di Hydrate etc. are mentioned.
レドックス系開始剤であって、分子末端に水酸基を有しないラジカル重合開始剤としては、過酸化水素、過酸化アルキル、過酸化エステル、過炭酸塩等と、鉄塩、第一チタン塩、亜鉛ホルムアルデヒドスルホキシレート、ナトリウムホルムアルデヒドスルホキシレート等との混合物が挙げられる。また、過硫酸、過ホウ酸、過塩素酸のアルカリ金属塩、過塩素酸のアンモニウム塩等と、メタ重亜硫酸ナトリウムのような重亜硫酸アルカリ金属塩等との混合物が挙げられる。更に、過硫酸アルカリ金属塩と、ベンゼンホスホン酸等のアリールホスホン酸のような他の同様の酸等との混合物等を挙げることができる。 It is a redox initiator, and as a radical polymerization initiator having no hydroxyl group at the molecular terminal, hydrogen peroxide, alkyl peroxide, peroxide ester, percarbonate, etc., iron salt, titanium oxide, zinc formaldehyde A mixture with sulfoxylate, sodium formaldehyde sulfoxylate and the like can be mentioned. Further, a mixture of persulfuric acid, perboric acid, alkali metal salt of perchloric acid, ammonium salt of perchloric acid and the like, and alkali metal bisulfite salt and the like such as sodium metabisulfite and the like can be mentioned. Further, mixtures of alkali metal persulfates and other similar acids such as arylphosphonic acids such as benzenephosphonic acid can be mentioned.
熱ラジカル重合開始剤であって、分子末端に水酸基を有しないラジカル重合開始剤の市販品としては、パーヘキサ（登録商標）ＨＣ（日油（株）製）、ＭＡＩＢ（大塚化学（株）製）が挙げられる。 As a commercial product of a radical polymerization initiator which is a thermal radical polymerization initiator and has no hydroxyl group at the molecular terminal, Perhexa (registered trademark) HC (manufactured by NOF Corporation), MAIB (manufactured by Otsuka Chemical Co., Ltd.) Can be mentioned.
分子末端に水酸基を有しないラジカル重合開始剤又は分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤は、１種単独で又は２種以上を組み合わせて用いてもよい。また、本実施形態の組成物は、メルカプトベンゾチアゾール、メルカプトベンゾオキサゾールのような水素供与性を有する化合物や、放射線増感剤をラジカル重合開始剤と共に含んでいてもよい。なお、メルカプトベンゾチアゾール及びメルカプトベンゾオキサゾールは、その化学構造式中に水酸基を有しないものである。 The radical polymerization initiator having no hydroxyl group at the molecular terminal or the radical polymerization initiator having a hydroxyl group at the molecular terminal and having a hindered structure may be used singly or in combination of two or more. Further, the composition of the present embodiment may contain a compound having a hydrogen donating property such as mercaptobenzothiazole and mercaptobenzoxazole, or a radiation sensitizer together with a radical polymerization initiator. In addition, mercaptobenzothiazole and mercaptobenzoxazole do not have a hydroxyl group in their chemical structural formulas.
なお、本実施形態の組成物に、分子末端に水酸基を有しヒンダード構造を有しないラジカル重合開始剤を含んだ場合には、ガラス基板に対する剥離性を阻害するので好ましくない。 In the case where the composition of the present embodiment contains a radical polymerization initiator having a hydroxyl group at the molecular terminal and not having a hindered structure, it is not preferable because it inhibits the removability to the glass substrate.
一方、分子末端に水酸基を有しヒンダード構造を有しないラジカル重合開始剤は、例えば下記式（４）で表される２−ヒドロキシ−１−（４−（２−ヒドロキシエトキシ）フェニル）−２−メチルプロパン−１−オンのように、水酸基に隣接した置換基が水素原子やメチル基等の小さい置換基であり、水酸基の反応性が制限されていないものである。 On the other hand, a radical polymerization initiator having a hydroxyl group at the molecular end and having no hindered structure is, for example, 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2- represented by the following formula (4) As in methylpropan-1-one, the substituent adjacent to the hydroxyl group is a small substituent such as a hydrogen atom or a methyl group, and the reactivity of the hydroxyl group is not limited.
分子末端に水酸基を有しヒンダード構造を有しないラジカル重合開始剤の具体例としては、上述の２−ヒドロキシ−１−（４−（２−ヒドロキシエトキシ）フェニル）−２−メチルプロパン−１−オンの他、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、ｔｅｒｔ−ブチルヒドロペルオキシド、クメンヒドロペルオキシド、４，４’−アゾビス（４−ペンタン酸）、２，２’−アゾビス（２−メチル−Ｎ−（１，１−ビス（ヒドロキシメチル）−２−ヒドロキシエチル）プロピオンアミド）、２，２’−アゾビス（２−メチル−Ｎ−（１，１−ビス（ヒドロキシメチル）エチル）プロピオンアミド）、２，２’−アゾビス（２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオンアミド）等が挙げられる。 As a specific example of the radical polymerization initiator which has a hydroxyl group at the molecular terminal and does not have a hindered structure, the above-mentioned 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one is mentioned. Besides, 2-hydroxy-2-methyl-1-phenylpropan-1-one, tert-butyl hydroperoxide, cumene hydroperoxide, 4,4′-azobis (4-pentanoic acid), 2,2′-azobis ( 2-Methyl-N- (1,1-bis (hydroxymethyl) -2-hydroxyethyl) propionamide), 2,2'-azobis (2-methyl-N- (1,1-bis (hydroxymethyl) ethyl) And propionamide), 2,2'-azobis (2-methyl-N- (2-hydroxyethyl) propionamide) and the like.
また、分子末端に水酸基を有しヒンダード構造を有しないラジカル重合開始剤の市販品としては、ＩＲＧＡＣＵＲＥ（登録商標）２９５９、同１２７、ＤＡＲＯＣＵＲ（登録商標）１１７３（以上、ＢＡＳＦジャパン（株）製）等が挙げられる。 Moreover, as a commercial item of a radical polymerization initiator which has a hydroxyl group at the molecular terminal and does not have a hindered structure, IRGACURE (registered trademark) 2959, 127, DAROCUR (registered trademark) 1173 (all, manufactured by BASF Japan Ltd.) Etc.
本実施形態の組成物全体に対するラジカル重合開始剤の含有量は、酸素によるラジカルの失活の影響を抑制する観点、保存安定性確保の観点等から、ウレタン（メタ）アクリレート化合物、（メタ）アクリレート（単官能（メタ）アクリレート又は単官能（メタ）アクリレート及び２官能以上の（メタ）アクリレート）総量１００質量部に対して、好ましくは０．１質量部〜５０質量部、より好ましくは１質量部〜３０質量部、より一層好ましくは２質量部〜３０質量部である。 The content of the radical polymerization initiator with respect to the whole composition of the present embodiment is a urethane (meth) acrylate compound, (meth) acrylate from the viewpoint of suppressing the influence of deactivation of radicals by oxygen, from the viewpoint of securing storage stability, etc. The amount is preferably 0.1 parts by mass to 50 parts by mass, more preferably 1 part by mass with respect to 100 parts by mass in total of (monofunctional (meth) acrylate or monofunctional (meth) acrylate and (meth) acrylate having two or more functions). -30 parts by mass, and even more preferably 2 parts by mass to 30 parts by mass.
本実施形態の組成物は、溶媒を含んでいてもよい。溶媒は、組成物の各成分を均一に溶解させることができ、これらと反応しないものが用いられる。 The composition of the present embodiment may contain a solvent. The solvent can uniformly dissolve the components of the composition, and a solvent which does not react with them is used.
このような溶媒の具体例としては、炭酸エチレン、炭酸プロピレン等の炭酸エステル類；カプロン酸、カプリル酸等の脂肪酸；１−オクタノール、１−ノナノール、ベンジルアルコール等のアルコール類；エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）等の多価アルコールのアルキルエーテル類；エチレングリコール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（ＰＧＭＥＡ）等の多価アルコールのアルキルエーテルアセテート類；フェニルセロソルブアセテート等の多価アルコールのアリールエーテルアセテート類；３−エトキシプロピオン酸エチル、３−メトキシプロピオン酸メチル、２−ヒドロキシプロピオン酸エチル、乳酸エチル、γ−ブチロラクトン等のエステル類；ジアセトンアルコール等のケトール類等が挙げられる。なお、溶媒は、１種単独で又は２種以上を組み合わせて用いることができる。 Specific examples of such solvents include carbonates such as ethylene carbonate and propylene carbonate; fatty acids such as caproic acid and caprylic acid; alcohols such as 1-octanol, 1-nonanol and benzyl alcohol; ethylene glycol monoethyl ether Alkyl ethers of polyhydric alcohols such as diethylene glycol monomethyl ether and propylene glycol monomethyl ether (PGME); alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether acetate and propylene glycol monomethyl ether acetate (PGMEA); phenyl cellosolve acetate And other polyhydric alcohol aryl ether acetates; ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 2-hydroxypropionate Ethyl propionate, ethyl lactate, esters such as γ- butyrolactone; ketols diacetone alcohol and the like. In addition, a solvent can be used individually by 1 type or in combination of 2 or more types.
本実施形態の組成物が溶媒を含む場合、その含有量は、組成物全体に対して、５質量％〜３０質量％程度である。 When the composition of this embodiment contains a solvent, the content is about 5 mass%-about 30 mass% with respect to the whole composition.
本実施形態の組成物は、塗布性、消泡性、レベリング性等を向上させる目的で、界面活性剤を含んでいてもよい。 The composition of the present embodiment may contain a surfactant for the purpose of improving coating properties, defoaming properties, leveling properties, and the like.
界面活性剤の具体例としては、ＢＭ−１０００、ＢＭ−１１００（以上、ＢＭケミー社製）、メガファック（登録商標）Ｆ１４２Ｄ、同Ｆ１７２、同Ｆ１７３、同Ｆ１８３、同Ｆ５７０（以上、ＤＩＣ（株）製）、フロラードＦＣ−１３５、同ＦＣ−１７０Ｃ、同ＦＣ−４３０、同ＦＣ−４３１（以上、スリーエムジャパン（株）製）、サーフロンＳ−１１２、同Ｓ−１１３、同Ｓ−１３１、同Ｓ−１４１、同Ｓ−１４５（以上、ＡＧＣセイミケミカル（株）製）、ＳＨ−２８ＰＡ、同−１９０、同−１９３、ＳＺ−６０３２、ＳＦ−８４２８（以上、東レ・ダウコーニング（株）製）等の商品名で市販されているフッ素系界面活性剤、シリコーン系界面活性剤等が挙げられる。 Specific examples of the surfactant include BM-1000, BM-1100 (above, BM Chemie Co., Ltd.), Megafuck (registered trademark) F142D, F172, F173, F183, F570 (all, DIC (stock) ), Florard FC-135, FC-170C, FC-430, FC-431 (all available from 3M Japan Co., Ltd.), Surfron S-112, S-113, S-131, and the like. S-141, S-145 (above, AGC Seimi Chemical Co., Ltd. product), SH-28 PA, I-190, I-193, SZ-6032, SF-8428 (above, Toray Dow Corning Co., Ltd. product And fluorosurfactants commercially available under trade names such as) and silicone surfactants.
本実施形態の組成物が界面活性剤を含む場合、その含有量は、樹脂薄膜からの析出を防ぐ観点から、組成物全体の５質量％以下が好ましい。 When the composition of the present embodiment contains a surfactant, the content thereof is preferably 5% by mass or less of the whole composition from the viewpoint of preventing precipitation from the resin thin film.
本実施形態の組成物は、熱重合禁止剤を含んでいてもよい。 The composition of the present embodiment may contain a thermal polymerization inhibitor.
熱重合禁止剤の具体例としては、ピロガロール、ベンゾキノン、ヒドロキノン、メチレンブルー、ｔｅｒｔ−ブチルカテコール、ヒドロキノンモノベンジルエーテル、メチルヒドロキノン、アミルオキシヒドロキノン、ｎ−ブチルフェノール、フェノール、ヒドロキノンモノプロピルエーテル、４，４’−（１−メチルエチリデン）ビス（２−メチルフェノール）、４，４’−（１−メチルエチリデン）ビス（２，６−ジメチルフェノール）、４，４’−（１−（４−（１−（４−ヒドロキシフェニル）−１−メチルエチル）フェニル）エチリデン）ビスフェノール、４，４’，４’’−エチリデントリス（２−メチルフェノール）、４，４’，４’’−エチリデントリスフェノール、１，１，３−トリス（２，５−ジメチル−４−ヒドロキシフェニル）−３−フェニルプロパン等を挙げることができる。 Specific examples of the thermal polymerization inhibitor include pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butyl catechol, hydroquinone monobenzyl ether, methyl hydroquinone, amyl oxyhydroquinone, n-butyl phenol, phenol, hydroquinone monopropyl ether, 4,4 ' -(1-methylethylidene) bis (2-methylphenol), 4,4 '-(1-methylethylidene) bis (2,6-dimethylphenol), 4,4'-(1- (4- (1- (1- (1- (1-methylethylidene))) (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol, 4,4 ′, 4 ′ ′-ethylidene tris (2-methylphenol), 4,4 ′, 4 ′ ′-ethylidene trisphenol, 1 , 1,3-tris (2,5-dimethyl-4-hydroxy) Phenyl) -3-phenyl-propane and the like.
本実施形態の組成物が熱重合禁止剤を含む場合、その含有量は、ラジカル重合性の過度な低下を防ぎ、適切なラジカル重合性を確保する観点から、組成物全体の５質量％以下が好ましい。 When the composition of the present embodiment contains a thermal polymerization inhibitor, the content thereof is 5% by mass or less of the whole composition from the viewpoint of preventing an excessive decrease in radical polymerization and securing appropriate radical polymerization. preferable.
本実施形態の組成物は、ピーリング剥離性を向上させる目的で、剥離剤を含んでいてもよい。 The composition of the present embodiment may contain a release agent in order to improve the peelability.
剥離剤としては、ワックス系化合物、シリコーン系化合物、フッ素系化合物の何れも使用できるが、中でも、耐熱性、耐湿性、経時安定性の観点から、シリコーン系化合物（シロキサン結合を主骨格とするシリコーンオイル、エマルジョン等）が好ましい。 As the release agent, any of wax compounds, silicone compounds and fluorine compounds can be used. Among them, silicone compounds (silicone having a siloxane bond as a main skeleton from the viewpoints of heat resistance, moisture resistance, and stability over time) Oils, emulsions, etc.) are preferred.
剥離剤は、市販品として入手可能である。そのような市販品としては、信越シリコーン（登録商標）ＫＦ−９６−１０ＣＳ、同ＫＦ−６０１２、同Ｘ−２２−２４２６、同Ｘ−２２−１６４Ｅ（以上、信越化学工業（株）製）、ＴＥＧＯ（登録商標）ＲＡＤ ２２００Ｎ、同２７００（以上、エボニックジャパン（株）製）、ＢＹＫ−３３３（以上、ビックケミー・ジャパン（株）製）等が挙げられる。 Release agents are commercially available. As such commercial products, Shin-Etsu Silicone (registered trademark) KF-96-10CS, KF-6012, X-22-2426, X-22-164E (all manufactured by Shin-Etsu Chemical Co., Ltd.), TEGO (registered trademark) RAD 2200 N, 2700 (above, Evonik Japan Co., Ltd.), BYK-333 (above, Big Chemie Japan Co., Ltd.), and the like.
本実施形態の組成物が剥離剤を含む場合、その含有量は、樹脂薄膜からの析出を防ぐ観点から、組成物全体に対して、５質量％以下が好ましい。 When the composition of the present embodiment contains a release agent, the content is preferably 5% by mass or less with respect to the entire composition, from the viewpoint of preventing the deposition from the resin thin film.
その他、本実施形態の組成物は、レベリング剤、消泡剤等その他の成分を含んでいてもよい。 In addition, the composition of the present embodiment may contain other components such as a leveling agent and an antifoamer.
上述した通りの組成物を調製する工程を経て、本発明の実施形態にかかる易剥離性保護用樹脂薄膜形成組成物が得られる。本実施形態の組成物は、ポリカプロラクトン骨格又はポリテトラメチレングリコール骨格を主骨格とするウレタン（メタ）アクリレート化合物と、単官能（メタ）アクリレートを少なくとも含む（メタ）アクリレートと、分子末端に水酸基を有しないラジカル重合開始剤又は分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤とを含む組成物である。特に、かかる組成物は、ウレタン（メタ）アクリレート化合物として、ポリカプロラクトン骨格又はポリテトラメチレングリコール骨格を主骨格とするウレタン（メタ）アクリレート化合物を用い、ラジカル重合開始剤として、分子末端に水酸基を有しないラジカル重合開始剤又は分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤を含むことで、当該組成物を用いて、後述するガラス基板に対する剥離性に優れた易剥離性保護用樹脂薄膜を形成することができる。なお、本実施形態の組成物の各成分やその配合比等の詳細については、上述した通りであるので説明を省略する。 Through the steps of preparing the composition as described above, the easily releasable protective resin film-forming composition according to the embodiment of the present invention is obtained. The composition of the present embodiment has a urethane (meth) acrylate compound having a polycaprolactone skeleton or a polytetramethylene glycol skeleton as a main skeleton, a (meth) acrylate containing at least a monofunctional (meth) acrylate, and a hydroxyl group at a molecular terminal. It is a composition containing a radical polymerization initiator which does not have a radical polymerization initiator or a radical polymerization initiator which has a hydroxyl group at a molecular terminal and a hindered structure. In particular, such a composition uses a urethane (meth) acrylate compound having a polycaprolactone skeleton or a polytetramethylene glycol skeleton as a main skeleton as a urethane (meth) acrylate compound, and has a hydroxyl group at a molecular terminal as a radical polymerization initiator. A resin film for easy peeling protection having excellent releasability with respect to a glass substrate to be described later by using the composition by containing a radical polymerization initiator having no hydroxyl group or a radical polymerization initiator having a hindered structure having a hydroxyl group at the molecular terminal Can be formed. In addition, since it is as having mentioned above about details, such as each component of a composition of this embodiment, and its compounding ratio, description is abbreviate | omitted.
次に、易剥離性保護用樹脂薄膜を形成する工程について説明する。この工程では、上述の組成物を調製する工程で得られた組成物（樹脂液）を、ガラス基板（例えば、ソーダガラス等）に塗布し、光照射及び／又は加熱により硬化させることで、樹脂薄膜を形成することができる。即ち、得られた樹脂薄膜は、組成物の硬化物からなっている。 Next, the process of forming the peelable protective resin thin film will be described. In this step, the composition (resin liquid) obtained in the step of preparing the composition described above is applied to a glass substrate (for example, soda glass etc.) and cured by light irradiation and / or heating to obtain a resin. A thin film can be formed. That is, the obtained resin thin film consists of a cured product of the composition.
組成物（樹脂液）の塗布方法としては、スピンコート法、スリットコート法、ロールコート法、スクリーン印刷法、アプリケーター法、ディスペンサー法等が挙げられるが、これらに限定されない。 Examples of the method of applying the composition (resin liquid) include spin coating method, slit coating method, roll coating method, screen printing method, applicator method, dispenser method and the like, but are not limited thereto.
樹脂薄膜の膜厚は、耐水性、剥離性等の各特性を再現性よく実現する観点から、好ましくは５μｍ〜２５０μｍ、又は５μｍ〜１５０μｍ、又は１０μｍ〜５０μｍである。 The film thickness of the resin thin film is preferably 5 μm to 250 μm, or 5 μm to 150 μm, or 10 μm to 50 μm from the viewpoint of realizing each property such as water resistance and peelability with good reproducibility.
樹脂薄膜の膜厚を変化させる方法としては、例えば、組成物中の固形分の濃度を変化させたり、ガラス基板上への塗布量を変化させたりする方法がある。 As a method of changing the film thickness of the resin thin film, for example, there is a method of changing the concentration of solid content in the composition or changing the amount of application on the glass substrate.
本実施形態の易剥離性保護用樹脂薄膜の形成方法は、易剥離性保護用樹脂薄膜形成組成物を調製する工程と、易剥離性保護用樹脂薄膜を形成する工程とを経ることにより、ガラス基板上に易剥離性保護用樹脂薄膜を形成することができる。かかる形成方法において、上述のラジカル重合開始剤を用いることにより、得られた易剥離性保護用樹脂薄膜は、ガラス基板に対する剥離性に優れており、当該樹脂薄膜の形成時にはガラス基板から剥離しないが、必要期間経過後には手で容易にガラス基板から剥離することができる。このような易剥離性保護用樹脂薄膜は、ストリッパブルペイントとして好適である。 The method of forming the resin film for easy releasability protection of the present embodiment is a method of preparing a resin film-forming composition for easy releasability protection and a process for forming a resin film for easy releasability protection. An easily peelable protective resin thin film can be formed on a substrate. In this formation method, by using the above-mentioned radical polymerization initiator, the easily releasable protective resin film obtained is excellent in releasability to the glass substrate, and does not separate from the glass substrate when the resin thin film is formed. After the required period, it can be easily peeled off from the glass substrate by hand. Such a peelable protective resin thin film is suitable as a strippable paint.
以下、実施例に基づいて本発明を具体的に説明するが、本発明は下記実施例に限定されるものではない。なお、実施例において使用した略記号は、以下の意味を表す。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples. The abbreviations used in the examples have the following meanings.
ＵＮ−３５２：ポリカプロラクトン系ウレタンアクリレート［根上工業（株）製 アートレジンＵＮ−３５２］
ＩＢＸＡ：イソボルニルアクリレート［東京化成工業（株）製］
Ａ−ＴＭＰＴ：トリメチロールプロパントリアクリレート［新中村化学工業（株）製 ＮＫエステルＡ−ＴＭＰＴ］
Ｉｒｇ．９０７：２−メチル−１−（４−メチルチオフェニル）−２−モルホリノプロパン−１−オン［ＢＡＳＦジャパン（株）製 ＩＲＧＡＣＵＲＥ（登録商標）９０７］
ＤＥＴＸ−Ｓ：２，４−ジエチルチオキサントン［日本化薬（株）製 ＫＡＹＡＣＵＲＥ ＤＥＴＸ−Ｓ］
Ｉｒｇ．１８４：１−ヒドロキシシクロヘキシル＝フェニル＝ケトン［ＢＡＳＦジャパン（株）製 ＩＲＧＡＣＵＲＥ（登録商標）１８４］
Ｉｒｇ．２９５９：２−ヒドロキシ−１−（４−（２−ヒドロキシエトキシ）フェニル）−２−メチルプロパン−１−オン［ＢＡＳＦジャパン（株）製 ＩＲＧＡＣＵＲＥ（登録商標）２９５９］UN-352: Polycaprolactone-based urethane acrylate [Kegami Kogyo Co., Ltd. product Art resin UN-352]
IBXA: Isobornyl acrylate [made by Tokyo Chemical Industry Co., Ltd.]
A-TMPT: trimethylolpropane triacrylate (Shin Nakamura Chemical Industry Co., Ltd. NK ester A-TMPT)
Irg. 907: 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [BASF Japan KK IRGACURE (registered trademark) 907]
DETX-S: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd. KAYACURE DETX-S)
Irg. 184: 1-hydroxycyclohexyl phenyl ketone [BASF Japan KK IRGACURE (registered trademark) 184]
Irg. 2959: 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one [BASF Japan KK IRGACURE (registered trademark) 2959]
（１）易剥離性保護用樹脂薄膜形成組成物の調製
ポリカプロラクトンを主骨格とするウレタン（メタ）アクリレート化合物としてＵＮ−３５２を用いて、下記表１に記載の質量比（質量％）で、各原料をガラス製サンプル瓶に量りとり、５０℃程度に加温しながらマグネチックスターラーを用いて均一になるまで撹拌して混合し、実施例１，２及び比較例１の易剥離性保護用樹脂薄膜形成組成物（以下、「組成物」という）をそれぞれ調製した。(1) Preparation of resin thin film-forming composition for easy releasability protection Using UN-352 as a urethane (meth) acrylate compound having polycaprolactone as a main skeleton, at a mass ratio (mass%) described in Table 1 below Each raw material is weighed in a glass sample bottle, mixed while stirring to uniform using a magnetic stirrer while heating to about 50 ° C., for easy peelability protection of Examples 1, 2 and Comparative Example 1. Resin thin film forming compositions (hereinafter referred to as "compositions") were prepared.
なお、ＵＮ−３５２は、構造解析により、ポリカプロラクトン骨格を主骨格として有するとともに、その両端にウレタン部位を有し、分子内にシクロヘキシル環を有し、且つ、分子内に２つのアクリレート基を有するものであると認められた。 According to structural analysis, UN-352 has a polycaprolactone skeleton as a main skeleton, has urethane moieties at both ends, has a cyclohexyl ring in the molecule, and has two acrylate groups in the molecule It was recognized as a thing.
（２）易剥離性保護用樹脂薄膜の作製と評価
（２−１）易剥離性保護用樹脂薄膜の作製
実施例１，２及び比較例１の組成物を、それぞれガラス基板（ソーダガラス）上にアプリケーター（ヨシミツ精機（株）製ベーカーアプリケーターＹＢＡ−３型、ウエット膜厚１２５μｍ設定）を用いて塗布し、続いてＵＶ露光（照度５０ｍＷ／ｃｍ２，照射量５００ｍＪ／ｃｍ２）することで、膜厚９０μｍ程度の易剥離性保護用樹脂薄膜（以下、「硬化物」という）を得た。何れも容易に硬化可能であり、各硬化物は、ガラス基板から自然に脱落することなく密着していた。なお、得られた硬化物を、手でガラス基板から剥離できるか否かを確かめたところ、全ての硬化物について剥離できたが、実施例１，２の組成物から得られた硬化物の方が剥離し易かった。(2) Preparation and evaluation of easily releasable protective resin film (2-1) Preparation of easily releasable protective resin film The compositions of Examples 1 and 2 and Comparative Example 1 were respectively coated on a glass substrate (soda glass) By applying using an applicator (Yoshimitsu Seiki Co., Ltd. product Baker applicator YBA-3 type, wet film thickness 125 μm setting), followed by UV exposure (illuminance 50 mW / cm 2 , irradiation amount 500 mJ / cm 2 ), An easily releasable protective resin thin film (hereinafter referred to as “cured product”) having a film thickness of about 90 μm was obtained. All were easily curable, and each cured product was in close contact with the glass substrate without falling off naturally. In addition, when it was confirmed whether the obtained cured product could be peeled off from the glass substrate by hand, all the cured products could be removed, but the cured products obtained from the compositions of Examples 1 and 2 Was easy to peel off.
（２−２）剥離性の評価
また、得られた各硬化物を、ガラス基板から剥離せずに、長さ１０ｃｍ、幅３ｃｍの短冊状に切り込んだ。ガラス基板を試験機に水平に固定し、短冊状に切り込んだ硬化物の一端を少し剥がし、これをチャックで保持した。このチャックを１ｃｍ／ｓｅｃの速度で上方へ移動させることで、ガラス基板から硬化物を剥離角度９０°で剥離したときの抵抗力（Ｎ）を測定した。抵抗力を剥離させた硬化物の幅（３ｃｍ）で除して剥離力（Ｎ／ｃｍ）を算出し、その結果を下記表２に示した。なお、測定には（株）島津製作所製の卓上型精密万能試験機オートグラフＡＧＳ−５００ＮＸを用いた。(2-2) Evaluation of releasability Each obtained cured product was cut into a strip having a length of 10 cm and a width of 3 cm without peeling from the glass substrate. The glass substrate was horizontally fixed to a testing machine, and one end of the cured material cut into strips was slightly peeled off and held by a chuck. This chuck was moved upward at a speed of 1 cm / sec to measure the resistance (N) when the cured product was peeled from the glass substrate at a peeling angle of 90 °. The peel strength (N / cm) was calculated by dividing the resistance by the width (3 cm) of the cured product, and the results are shown in Table 2 below. In addition, the table-type precision universal testing machine autograph AGS-500NX made from Shimadzu Corp. was used for the measurement.
表２に示される通り、実施例１，２の組成物から得られた硬化物と、比較例１の組成物から得られた硬化物とを比較すると、実施例１，２の方が、ガラス基板に対する良好な剥離性を維持したままだった。 As shown in Table 2, when the cured products obtained from the compositions of Examples 1 and 2 and the cured products obtained from the composition of Comparative Example 1 are compared, Good releasability to the substrate was maintained.
即ち、実施例１は、本発明に好適な、分子末端に水酸基を有しないラジカル重合開始剤を、同様に、実施例２は、分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤を用いて硬化物を形成したため、ガラス基板からの剥離力は、両者とも０．０４Ｎ／ｃｍと低い値が得られた。一方、比較例１は、分子末端に水酸基を有するラジカル重合開始剤を用いて硬化物を形成したため、ガラス基板からの剥離力は、０．０８Ｎ／ｃｍと比較的高い値となった。一般に、この剥離力は低ければ低いほど好ましく、実用上は０．１０Ｎ／ｃｍを超えると問題となる可能性が高いので、比較例１は用途によっては、剥離力の高さが問題となる可能性がある。 That is, Example 1 is a radical polymerization initiator having no hydroxyl group at the molecular end, which is suitable for the present invention, and Example 2 is a radical polymerization initiator having a hydroxyl group at the molecular end and a hindered structure. As a cured product was formed to use, the peeling force from the glass substrate was both as low as 0.04 N / cm. On the other hand, in Comparative Example 1, a cured product was formed using a radical polymerization initiator having a hydroxyl group at the molecular terminal, so the peel strength from the glass substrate was a relatively high value of 0.08 N / cm. In general, the lower the peeling force, the better, and practically it is more likely to cause problems if it exceeds 0.10 N / cm. Therefore, the height of the peeling force may become a problem in Comparative Example 1 depending on the application There is sex.
Claims (11)
単官能（メタ）アクリレートを少なくとも含む（メタ）アクリレートと、
分子末端に水酸基を有しないラジカル重合開始剤又は分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤と
を含む易剥離性保護用樹脂薄膜形成組成物を調製する工程と、
前記易剥離性保護用樹脂薄膜形成組成物をガラス基板上に塗布して易剥離性保護用樹脂薄膜を形成する工程と
を有することを特徴とする易剥離性保護用樹脂薄膜の形成方法。A urethane (meth) acrylate compound,
(Meth) acrylate containing at least monofunctional (meth) acrylate,
Preparing an easily releasable protective resin film-forming composition comprising a radical polymerization initiator having no hydroxyl group at the molecular terminal or a radical polymerization initiator having a hydroxyl group at the molecular terminal and having a hindered structure;
And a step of forming the easily releasable protective resin thin film-forming composition on a glass substrate to form an easily releasable protective resin thin film.
２官能以上の（メタ）アクリレートと
を含むことを特徴とする請求項１〜請求項５の何れか１項に記載の易剥離性保護用樹脂薄膜の形成方法。The (meth) acrylate is the monofunctional (meth) acrylate;
A method for forming the easily releasable protective resin thin film according to any one of claims 1 to 5, comprising a (meth) acrylate having two or more functional groups.
単官能（メタ）アクリレートを少なくとも含む（メタ）アクリレートと、
分子末端に水酸基を有しないラジカル重合開始剤又は分子末端に水酸基を有しヒンダード構造を有するラジカル重合開始剤と
を含むことを特徴とする易剥離性保護用樹脂薄膜形成組成物。
A urethane (meth) acrylate compound having a polycaprolactone skeleton or a polytetramethylene glycol skeleton as a main skeleton,
(Meth) acrylate containing at least monofunctional (meth) acrylate,
What is claimed is: 1. A composition for easily peelable protective resin film, comprising: a radical polymerization initiator having no hydroxyl group at a molecular terminal or a radical polymerization initiator having a hydroxyl group at a molecular terminal and a hindered structure.
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| PCT/JP2017/026930 WO2018021351A1 (en) | 2016-07-26 | 2017-07-25 | Method for forming easily-peeled protective resin thin film, and composition for forming easily-peeled protective resin thin film |
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| JPWO2018021351A1 true JPWO2018021351A1 (en) | 2019-05-16 |
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| JPS62168569A (en) * | 1986-01-17 | 1987-07-24 | Hayakawa Rubber Co Ltd | Preparation of ultraviolet cured transient surface protecting film |
| JPH05125136A (en) * | 1991-09-12 | 1993-05-21 | Nippon Kayaku Co Ltd | Radiation-curable resin composition and screen printing ink composition for radiation-curable type strippable masking material |
| JPH05301935A (en) * | 1992-04-28 | 1993-11-16 | Sekisui Chem Co Ltd | Photocurable resin composition |
| JP4880417B2 (en) * | 2006-10-16 | 2012-02-22 | 電気化学工業株式会社 | Surface protection method for workpieces |
| JP5020577B2 (en) * | 2006-09-14 | 2012-09-05 | 電気化学工業株式会社 | Method for removing protective film coated on workpiece |
| EP3252119A4 (en) * | 2015-01-27 | 2018-05-16 | Nissan Chemical Industries, Ltd. | Resin thin-film-forming composition for easily-peelable protection |
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