KR101639546B1 - Ultraviolet-ray-curable composition for cyclic olefin resins, and cyclic olefin resin film produced using same - Google Patents
Ultraviolet-ray-curable composition for cyclic olefin resins, and cyclic olefin resin film produced using same Download PDFInfo
- Publication number
- KR101639546B1 KR101639546B1 KR1020157028665A KR20157028665A KR101639546B1 KR 101639546 B1 KR101639546 B1 KR 101639546B1 KR 1020157028665 A KR1020157028665 A KR 1020157028665A KR 20157028665 A KR20157028665 A KR 20157028665A KR 101639546 B1 KR101639546 B1 KR 101639546B1
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- acrylate
- ultraviolet
- mass
- cyclic olefin
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 54
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 49
- 239000003999 initiator Substances 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 129
- 238000000576 coating method Methods 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 17
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- MQOQCTKJCVQBEU-UHFFFAOYSA-N 2-[2-(2-ethoxy-2-oxoethyl)phenyl]peroxyethyl 2-oxo-2-phenylacetate Chemical compound CCOC(=O)CC1=CC=CC=C1OOCCOC(=O)C(=O)C1=CC=CC=C1 MQOQCTKJCVQBEU-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 87
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 36
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 24
- -1 polyethylene terephthalate Polymers 0.000 description 23
- 239000005056 polyisocyanate Substances 0.000 description 17
- 229920001228 polyisocyanate Polymers 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 13
- 125000001931 aliphatic group Chemical group 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 10
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 10
- 239000010419 fine particle Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 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 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000012788 optical film Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 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 3
- 150000001298 alcohols Chemical class 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000005702 oxyalkylene group Chemical group 0.000 description 3
- WVSFUMAHZBOQGJ-UHFFFAOYSA-N phosphono 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOP(O)(O)=O WVSFUMAHZBOQGJ-UHFFFAOYSA-N 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- OHTRJOZKRSVAOX-UHFFFAOYSA-N 1,3-diisocyanato-2-methylcyclohexane Chemical compound CC1C(N=C=O)CCCC1N=C=O OHTRJOZKRSVAOX-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- SORGEQQSQGNZFI-UHFFFAOYSA-N [azido(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(N=[N+]=[N-])OC1=CC=CC=C1 SORGEQQSQGNZFI-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 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 2
- 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 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000002156 mixing Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical class NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- PJLLSZIVQKRTSE-UHFFFAOYSA-N (7-methyl-8-prop-2-enoyloxyoctyl) prop-2-enoate Chemical compound C=CC(=O)OCC(C)CCCCCCOC(=O)C=C PJLLSZIVQKRTSE-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- YXWWHNCQZBVZPV-UHFFFAOYSA-N 2'-methylacetophenone Chemical compound CC(=O)C1=CC=CC=C1C YXWWHNCQZBVZPV-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- UXCIJKOCUAQMKD-UHFFFAOYSA-N 2,4-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC(Cl)=C3SC2=C1 UXCIJKOCUAQMKD-UHFFFAOYSA-N 0.000 description 1
- VZDIRINETBAVAV-UHFFFAOYSA-N 2,4-diisocyanato-1-methylcyclohexane Chemical compound CC1CCC(N=C=O)CC1N=C=O VZDIRINETBAVAV-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- YWEJNVNVJGORIU-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-hydroxy-2-phenylacetate Chemical compound OCCOCCOC(=O)C(O)C1=CC=CC=C1 YWEJNVNVJGORIU-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- ZUEORFBIZHLZFY-UHFFFAOYSA-N 2-[2-[2-(2-oxo-2-phenylacetyl)oxyethylperoxy]phenyl]acetic acid Chemical compound O=C(C(=O)OCCOOC1=C(C=CC=C1)CC(=O)O)C1=CC=CC=C1 ZUEORFBIZHLZFY-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- AJOPUMVHMNKYCQ-UHFFFAOYSA-N 2-benzoylbenzoic acid;(2-methyl-4-phenylphenyl)-phenylmethanone Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1.CC1=CC(C=2C=CC=CC=2)=CC=C1C(=O)C1=CC=CC=C1 AJOPUMVHMNKYCQ-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- GNDOBZLRZOCGAS-JTQLQIEISA-N 2-isocyanatoethyl (2s)-2,6-diisocyanatohexanoate Chemical compound O=C=NCCCC[C@H](N=C=O)C(=O)OCCN=C=O GNDOBZLRZOCGAS-JTQLQIEISA-N 0.000 description 1
- 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 description 1
- NNAHKQUHXJHBIV-UHFFFAOYSA-N 2-methyl-1-(4-methylthiophen-2-yl)-2-morpholin-4-ylpropan-1-one Chemical compound CC1=CSC(C(=O)C(C)(C)N2CCOCC2)=C1 NNAHKQUHXJHBIV-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 1
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 1
- XHBIFXBXBOMPFS-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)C1=CC=C(C=C1)SC1=CC=C(C=C1)C(C(C)S(=O)(=O)C1=CC=C(C=C1)C)=O Chemical compound C(C1=CC=CC=C1)(=O)C1=CC=C(C=C1)SC1=CC=C(C=C1)C(C(C)S(=O)(=O)C1=CC=C(C=C1)C)=O XHBIFXBXBOMPFS-UHFFFAOYSA-N 0.000 description 1
- XHIKSLHIZYVEQI-UHFFFAOYSA-N CC1=C(C(=O)[PH2]=O)C(=CC(=C1)C)C Chemical compound CC1=C(C(=O)[PH2]=O)C(=CC(=C1)C)C XHIKSLHIZYVEQI-UHFFFAOYSA-N 0.000 description 1
- DEKKPANYKUZWJF-UHFFFAOYSA-N ClC1(CC=2C(C3=CC=CC=C3NC2C=C1)=O)Cl Chemical compound ClC1(CC=2C(C3=CC=CC=C3NC2C=C1)=O)Cl DEKKPANYKUZWJF-UHFFFAOYSA-N 0.000 description 1
- BWPYBAJTDILQPY-UHFFFAOYSA-N Methoxyphenone Chemical compound C1=C(C)C(OC)=CC=C1C(=O)C1=CC=CC(C)=C1 BWPYBAJTDILQPY-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- XSVQKCHBWGYRPA-UHFFFAOYSA-N benzylthiourea;4-methylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1.NC(=S)NCC1=CC=CC=C1 XSVQKCHBWGYRPA-UHFFFAOYSA-N 0.000 description 1
- QDVNNDYBCWZVTI-UHFFFAOYSA-N bis[4-(ethylamino)phenyl]methanone Chemical compound C1=CC(NCC)=CC=C1C(=O)C1=CC=C(NCC)C=C1 QDVNNDYBCWZVTI-UHFFFAOYSA-N 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- KQBTUOVABZLXGP-UHFFFAOYSA-N butane-1,4-diol;ethane-1,2-diol Chemical compound OCCO.OCCCCO KQBTUOVABZLXGP-UHFFFAOYSA-N 0.000 description 1
- DDPAAMHROJBRGE-UHFFFAOYSA-N butane-1,4-diol;propane-1,2-diol Chemical compound CC(O)CO.OCCCCO DDPAAMHROJBRGE-UHFFFAOYSA-N 0.000 description 1
- UIZLQMLDSWKZGC-UHFFFAOYSA-N cadmium helium Chemical compound [He].[Cd] UIZLQMLDSWKZGC-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- DUDXQIXWPJMPRQ-UHFFFAOYSA-N isocyanatomethylcyclohexane Chemical compound O=C=NCC1CCCCC1 DUDXQIXWPJMPRQ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000007759 kiss coating Methods 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VSQYNPJPULBZKU-UHFFFAOYSA-N mercury xenon Chemical compound [Xe].[Hg] VSQYNPJPULBZKU-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ACLZYRNSDLQOIA-UHFFFAOYSA-N o-tolylthiourea Chemical compound CC1=CC=CC=C1NC(N)=S ACLZYRNSDLQOIA-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- ZKDDJTYSFCWVGS-UHFFFAOYSA-M sodium;diethoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Na+].CCOP([S-])(=S)OCC ZKDDJTYSFCWVGS-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- MVQLEZWPIWKLBY-UHFFFAOYSA-N tert-butyl 2-benzoylbenzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 MVQLEZWPIWKLBY-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- JBCJMTUHAXHILC-UHFFFAOYSA-N zinc;octanoic acid Chemical compound [Zn+2].CCCCCCCC(O)=O JBCJMTUHAXHILC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C08J7/047—
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
Abstract
본 발명은 자외선 경화성 화합물 (A) 및 광 중합 개시제 (B) 로서 하기 식 (1) 로 나타내는 기를 1 분자 중에 2 개 이상 갖는 화합물을 필수 성분으로서 함유하는 것을 특징으로 하는 고리형 올레핀 수지용 자외선 경화성 조성물을 제공한다. 본 발명의 고리형 올레핀 수지용 자외선 경화성 조성물은, 고리형 올레핀 수지의 표면에 도포, 경화시킴으로써, 내찰상성이 높고, 고리형 올레핀 수지와의 밀착성이 우수하고, 착색이 적은 경화 도포막으로 이루어지는 하드 코트층을 형성할 수 있다.
Description
본 발명은 고리형 올레핀 수지의 표면에 도포, 경화시킴으로써, 내찰상성이 높고, 하지(下地)와의 밀착성이 우수하고, 착색이 적은 경화 도포막으로 이루어지는 하드 코트층을 형성할 수 있는 고리형 올레핀 수지용 자외선 경화성 조성물 및 그것을 사용한 고리형 올레핀 수지 필름에 관한 것이다.The present invention relates to a cyclic olefin resin composition capable of forming a hard coat layer composed of a cured coating film having high scratch resistance, excellent adhesion with a base (undercoat), and little coloring, by applying and curing the surface of the cyclic olefin resin And a cyclic olefin resin film using the UV-curable composition.
고리형 올레핀 수지 필름은 투명성, 저복굴절, 저흡습성, 내열성, 전기 절연성, 내약품성 등이 우수하고, 광학 부재, 의료, 포장 필름, 자동차, 반도체 용도 등으로 폭넓게 사용되고 있다. 특히, 광학 부재에 있어서는, 액정 디스플레이나 터치 패널 용도로의 유닛의 다양화에 맞추어, 종래 사용되고 있던 폴리에틸렌테레프탈레이트 (PET), 트리아세틸셀룰로오스 (TAC) 등의 플라스틱 필름 대신에 투명성이 높고, 저흡습성이 우수한 고리형 올레핀 수지 필름을 사용하는 것이 검토되고 있다.The cyclic olefin resin film is excellent in transparency, low birefringence, low hygroscopicity, heat resistance, electrical insulation, chemical resistance, and is widely used for optical members, medical treatment, packaging film, automobile and semiconductor applications. Particularly, in the optical member, in place of plastic films such as polyethylene terephthalate (PET) and triacetyl cellulose (TAC) which have been conventionally used, transparency is high and low hygroscopicity It has been studied to use this excellent cyclic olefin resin film.
또, 고리형 올레핀 수지 필름은 표면 경도가 불충분하기 때문에, 가공시에 있어서 흠집이 날 우려가 있어, 내마모성, 내찰상성의 향상을 위해 그 표면에 자외선 경화성 조성물의 경화 도포막으로 이루어지는 하드 코트층 등의 보호층을 형성하는 것이 검토되고 있다. 그러나, 고리형 올레핀 수지 필름은, 그 주구조가 지환 구조이기 때문에, 필름 표면의 극성이 낮고, 물 접촉각이 90 °정도로 높으므로, 자외선 경화성 조성물을 도포한 경우, 도재가 퍼지며 발라지기 어려워, 고리형 올레핀 수지 필름 표면과 하드 코트층 사이의 밀착성이 낮다는 문제가 있었다.Further, since the cyclic olefin resin film has insufficient surface hardness, it is likely to be scratched during processing. In order to improve abrasion resistance and scratch resistance, a hard coat layer made of a cured coating film of an ultraviolet ray- To form a protective layer. However, since the cyclic olefin resin film has an alicyclic structure in its main structure, the polarity of the film surface is low and the contact angle of water is as high as about 90 degrees. Therefore, when the ultraviolet ray curable composition is applied, the porcelain is hardly spread, Type olefin resin film surface and the hard coat layer is low.
고리형 올레핀 수지 필름 표면과 하드 코트층 사이의 밀착성을 향상시키는 방법으로서, 고리형 올레핀 수지 필름 표면에 극성기를 갖는 변성 올레핀계 수지를 주성분으로 한 프라이머층을 형성한 후, 전리 방사선 경화형 수지를 도포, 경화시키는 방법이 제안되어 있다 (예를 들어, 특허문헌 1 참조). 이 방법에서는, 고리형 올레핀 수지 필름 표면과 하드 코트층 사이의 밀착성을 향상시킬 수는 있지만, 프라이머층을 도포, 건조시키는 공정이 증가하여, 추가로 수율의 저하나 비용 상승을 일으키는 문제가 있었다.As a method for improving the adhesion between the surface of the cyclic olefin resin film and the hard coat layer, a primer layer comprising a modified olefin resin having a polar group as a main component is formed on the surface of the cyclic olefin resin film, and then an ionizing radiation curable resin is applied (For example, refer to Patent Document 1). In this method, although the adhesion between the surface of the cyclic olefin resin film and the hard coat layer can be improved, there is a problem that the process of applying and drying the primer layer increases, further causing a reduction in yield and an increase in cost.
또, 프라이머층을 형성하지 않고 하드 코트층을 고리형 올레핀 수지 필름 표면에 밀착시키는 방법으로서, 지환 구조를 갖는 (메트)아크릴레이트를 함유하는 경화성 조성물의 경화 도포막을 하드 코트층으로서 사용하는 것이 제안되어 있다 (예를 들어, 특허문헌 2 참조). 이 경화성 조성물을 사용한 경우, 고리형 올레핀 수지 필름 표면과의 밀착성을 충분한 것으로 하기 위해서는, 지환 구조를 갖는 (메트)아크릴레이트의 비율을 높일 필요가 있다. 그러나, 지환 구조를 갖는 (메트)아크릴레이트의 비율을 높이면, 경화 도포막의 가교 밀도가 저하되고, 경화 도포막 표면의 내찰상성이 불충분해지는 문제가 있었다.As a method of bringing the hard coat layer into close contact with the surface of the cyclic olefin resin film without forming a primer layer, it is proposed to use a cured coating film of a curable composition containing (meth) acrylate having an alicyclic structure as a hard coat layer (See, for example, Patent Document 2). When this curable composition is used, it is necessary to increase the proportion of the (meth) acrylate having an alicyclic structure in order to make the adhesiveness with the surface of the cyclic olefin resin film satisfactory. However, when the proportion of the (meth) acrylate having an alicyclic structure is increased, the cross-linking density of the cured coating film is lowered and the scratch resistance of the surface of the cured coating film becomes insufficient.
또한, 자외선 경화성 조성물의 고리형 올레핀 수지 성형품에 대한 밀착성을 향상시키는 방법으로서, 자외선 경화성 조성물에 첨가하는 광 중합 개시제에 벤조페논 구조를 갖는 4-벤조일-4-메틸디술파이드를 사용하는 것이 제안되어 있다 (예를 들어, 특허문헌 3 참조). 그러나, 이 자외선 경화성 조성물에서는, 경화 도포막은 황색으로 착색되는 문제가 있었다.It has also been proposed to use 4-benzoyl-4-methyldisulfide having a benzophenone structure as a photopolymerization initiator to be added to the ultraviolet ray curable composition as a method for improving the adhesion of the ultraviolet ray curable composition to a molded article of a cyclic olefin resin (See, for example, Patent Document 3). However, in this ultraviolet ray curable composition, there is a problem that the cured coating film is colored in yellow.
그래서, 고리형 올레핀 수지 필름 표면에 높은 내찰상성을 갖을 수 있고, 프라이머층 없이 고리형 올레핀 수지 필름 표면과의 사이에 우수한 밀착성을 갖는 경화 도포막을 형성할 수 있고, 또한 경화 도포막이 착색되지 않는 자외선 경화성 조성물이 요구되고 있었다.Thus, it is possible to form a cured coating film having high scratch resistance on the surface of the cyclic olefin resin film and having excellent adhesion between the surface of the cyclic olefin resin film and the primer layer, and also, A curable composition has been required.
본 발명이 해결하고자 하는 과제는, 고리형 올레핀 수지의 표면에 도포, 경화시킴으로써, 내찰상성이 높고, 고리형 올레핀 수지와의 밀착성이 우수하고, 착색이 적은 경화 도포막으로 이루어지는 하드 코트층을 형성할 수 있는 고리형 올레핀 수지용 자외선 경화성 조성물 및 그것을 사용한 고리형 올레핀 수지 필름을 제공하는 것이다.A problem to be solved by the present invention is to provide a hard coat layer having a high scratch resistance, excellent adhesion with a cyclic olefin resin, and a hardly coated color with little discoloration, by coating and curing the surface of the cyclic olefin resin Curable composition for a cyclic olefin resin and a cyclic olefin resin film using the same.
본 발명자들은, 상기 과제를 해결하기 위해 예의 연구한 결과, 자외선 경화성 조성물에 사용하는 광 중합 개시제에 특정한 구조를 1 분자 중에 2 개 이상 갖는 화합물을 사용함으로써, 고리형 올레핀 수지 필름 등의 고리형 올레핀 수지 성형품 표면과의 밀착성이 우수한 경화 도포막을 형성할 수 있고, 또한 이 경화 도포막의 표면은 높은 내찰상성을 갖고, 착색도 적은 것을 알아내어 본 발명을 완성시켰다.Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that by using a compound having two or more specific structures in one molecule of a photopolymerization initiator used in an ultraviolet curable composition, a cyclic olefin such as a cyclic olefin resin film It is possible to form a cured coating film having excellent adhesion to the surface of the resin molded article and the surface of the cured coated film has high scratch resistance and coloring property.
즉, 본 발명은 자외선 경화성 화합물 (A) 및 광 중합 개시제 (B) 로서 하기 식 (1) 로 나타내는 기를 1 분자 중에 2 개 이상 갖는 화합물을 필수 성분으로서 함유하는 것을 특징으로 하는 고리형 올레핀 수지용 자외선 경화성 조성물 및 그것을 사용한 고리형 올레핀 수지 필름에 관한 것이다.That is, the present invention relates to a cyclic olefin resin composition comprising as an essential component a compound having at least two groups represented by the following formula (1) as a UV curable compound (A) and a photopolymerization initiator (B) An ultraviolet ray curable composition and a cyclic olefin resin film using the same.
[화학식 1][Chemical Formula 1]
본 발명의 자외선 경화성 조성물은, 고리형 올레핀 수지 성형품 표면에 높은 내찰상성을 부여할 수 있고, 고리형 올레핀 수지 성형품과의 밀착성이 우수하고, 착색도 적은 경화 도포막을 얻을 수 있다. 따라서, 본 발명의 자외선 경화성 조성물은, 각종 고리형 올레핀 수지 성형품, 특히 고리형 올레핀 수지 필름 표면에 높은 내찰상성을 갖는 하드 코트층을 형성하는 재료로서 사용할 수 있다. 또, 본 발명의 자외선 경화성 조성물의 경화 도포막으로 이루어지는 하드 코트층을 갖는 고리형 올레핀 수지 필름은, 액정 디스플레이나 터치 패널 용도로 사용되는 광학 필름으로서 사용할 수 있다.The ultraviolet curable composition of the present invention can give a high scratch resistance to the surface of the molded article of the cyclic olefin resin, and can obtain a cured coated film excellent in adhesion with the molded article of the cyclic olefin resin and having little coloration. Therefore, the ultraviolet curable composition of the present invention can be used as a material for forming a hard coat layer having high scratch resistance on the surface of various cyclic olefin resin molded articles, particularly, the surface of an annular olefin resin film. The cyclic olefin resin film having a hard coat layer composed of the cured coating film of the ultraviolet curable composition of the present invention can be used as an optical film used for a liquid crystal display or a touch panel.
본 발명의 자외선 경화성 조성물은, 자외선 경화성 화합물 (A) 및 광 중합 개시제 (B) 로서 하기 식 (1) 로 나타내는 기를 1 분자 중에 2 개 이상 갖는 화합물을 함유하는 것이다.The ultraviolet curable composition of the present invention contains a compound having two or more groups represented by the following formula (1) in one molecule as the ultraviolet curable compound (A) and the photopolymerization initiator (B).
[화학식 2](2)
상기 자외선 경화성 화합물 (A) 로는, 예를 들어, 다관능 (메트)아크릴레이트 (A1), 우레탄(메트)아크릴레이트 (A2) 등을 들 수 있다. 이들은 단독으로 사용할 수도 있고, 2 종 이상 병용할 수도 있다.Examples of the ultraviolet curing compound (A) include polyfunctional (meth) acrylate (A1), urethane (meth) acrylate (A2) and the like. These may be used alone or in combination of two or more.
또한, 본 발명에 있어서,「(메트)아크릴레이트」란 아크릴레이트와 메타크릴레이트의 일방 또는 양방을 말하고,「(메트)아크릴로일기」란 아크릴로일기와 메타크릴로일기의 일방 또는 양방을 말한다.In the present invention, the term "(meth) acrylate" refers to one or both of acrylate and methacrylate, and the term "(meth) acryloyl group" means acryloyl group and methacryloyl group, It says.
상기 다관능 (메트)아크릴레이트 (A1) 은 1 분자 중에 2 개 이상의 (메트)아크릴로일기를 갖는 화합물이다. 이 다관능 (메트)아크릴레이트 (a1) 의 구체예로는, 1,4-부탄디올디(메트)아크릴레이트, 3-메틸-1,5-펜탄디올디(메트)아크릴레이트, 1,6-헥산디올디(메트)아크릴레이트, 네오펜틸글리콜디(메트)아크릴레이트, 2-메틸-1,8-옥탄디올디(메트)아크릴레이트, 2-부틸-2-에틸-1,3-프로판디올디(메트)아크릴레이트, 트리시클로데칸디메탄올디(메트)아크릴레이트, 에틸렌글리콜디(메트)아크릴레이트, 디에틸렌글리콜디(메트)아크릴레이트, 트리에틸렌글리콜디(메트)아크릴레이트, 디프로필렌글리콜디(메트)아크릴레이트, 트리프로필렌글리콜디(메트)아크릴레이트 등의 2 가 알코올의 디(메트)아크릴레이트, 폴리에틸렌글리콜디(메트)아크릴레이트, 폴리프로필렌글리콜디(메트)아크릴레이트, 트리스(2-하이드록시에틸)이소시아누레이트의 디(메트)아크릴레이트, 네오펜틸글리콜 1 몰에 4 몰 이상의 에틸렌옥사이드 혹은 프로필렌옥사이드를 부가하여 얻은 디올의 디(메트)아크릴레이트, 비스페놀 A 1 몰에 2 몰의 에틸렌옥사이드 혹은 프로필렌옥사이드를 부가하여 얻은 디올의 디(메트)아크릴레이트, 트리메틸올프로판트리(메트)아크릴레이트, 에틸렌옥사이드 변성 트리메틸올프로판트리(메트)아크릴레이트, 프로필렌옥사이드 변성 트리메틸올프로판트리(메트)아크릴레이트, 디트리메틸올프로판트리(메트)아크릴레이트, 디트리메틸올프로판테트라(메트)아크릴레이트, 트리스(2-(메트)아크릴로일옥시에틸)이소시아누레이트, 펜타에리트리톨트리(메트)아크릴레이트, 펜타에리트리톨테트라(메트)아크릴레이트, 디펜타에리트리톨트리(메트)아크릴레이트, 디펜타에리트리톨테트라(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 디펜타에리트리톨헥사(메트)아크릴레이트 등을 들 수 있다. 이들 다관능 (메트)아크릴레이트 (A1) 은 단독으로 사용할 수도 있고, 2 종 이상 병용할 수도 있다. 또, 이들 다관능 (메트)아크릴레이트 (A1) 중에서도, 본 발명의 자외선 경화성 조성물의 경화 도포막의 내찰상성이 향상되는 점에서, 디펜타에리트리톨헥사(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 펜타에리트리톨테트라(메트)아크릴레이트, 펜타에리트리톨트리(메트)아크릴레이트가 바람직하다.The polyfunctional (meth) acrylate (A1) is a compound having two or more (meth) acryloyl groups in one molecule. Specific examples of the polyfunctional (meth) acrylate (a1) include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) (Meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di Acrylate, diethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene glycol di (Meth) acrylate, diethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tris (meth) acrylate of dihydric alcohols such as glycol di (meth) acrylate and tripropylene glycol di (Meth) acrylate of di (2-hydroxyethyl) isocyanurate, neopentyl Di (meth) acrylate of a diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of glycol, di (meth) acrylate of a diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A , Trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylol propane tri (meth) acrylate, propylene oxide modified trimethylol propane tri (meth) acrylate, ditrimethylol propane tri (meth) (Meth) acrylate, pentaerythritol tetra (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, pentaerythritol tri (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These polyfunctional (meth) acrylates (A1) may be used alone or in combination of two or more. Of these polyfunctional (meth) acrylates (A1), dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable from the viewpoint that the scratch resistance of the cured coating film of the ultraviolet- (Meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol tri (meth) acrylate.
상기 우레탄(메트)아크릴레이트 (A2) 는, 폴리이소시아네이트 (a2-1) 과 수산기를 갖는 (메트)아크릴레이트 (a2-2) 를 반응시켜 얻어진 것이다.The urethane (meth) acrylate (A2) is obtained by reacting a polyisocyanate (a2-1) with a (meth) acrylate (a2-2) having a hydroxyl group.
상기 폴리이소시아네이트 (a2-1) 로는, 지방족 폴리이소시아네이트와 방향족 폴리이소시아네이트를 들 수 있지만, 본 발명의 자외선 경화성 조성물의 경화 도포막의 착색을 보다 저감시킬 수 있는 점에서, 지방족 폴리이소시아네이트가 바람직하다.Examples of the polyisocyanate (a2-1) include an aliphatic polyisocyanate and an aromatic polyisocyanate, but an aliphatic polyisocyanate is preferable in that the coloration of the cured coating film of the ultraviolet curable composition of the present invention can be further reduced.
상기 지방족 폴리이소시아네이트는, 이소시아네이트기를 제외한 부위가 지방족 탄화수소로 구성되는 화합물이다. 이 지방족 폴리이소시아네이트의 구체예로는, 헥사메틸렌디이소시아네이트, 리신디이소시아네이트, 리신트리이소시아네이트 등의 지방족 폴리이소시아네이트 ; 노르보르난디이소시아네이트, 이소포론디이소시아네이트, 메틸렌비스(4-시클로헥실이소시아네이트), 1,3-비스(이소시아나토메틸)시클로헥산, 2-메틸-1,3-디이소시아나토시클로헥산, 2-메틸-1,5-디이소시아나토시클로헥산 등의 지환식 폴리이소시아네이트 등을 들 수 있다. 또, 상기 지방족 폴리이소시아네이트 또는 지환식 폴리이소시아네이트를 3 량화한 3 량화물도 상기 지방족 폴리이소시아네이트로서 사용할 수 있다. 또, 이들 지방족 폴리이소시아네이트는 단독으로 사용할 수도 있고, 2 종 이상 병용할 수도 있다.The aliphatic polyisocyanate is a compound in which a moiety other than an isocyanate group is composed of an aliphatic hydrocarbon. Specific examples of the aliphatic polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate and lysine triisocyanate; (Isocyanatomethyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2- Methyl-1,5-diisocyanatocyclohexane, and other alicyclic polyisocyanates. Also, a trihydrate obtained by trimerizing the aliphatic polyisocyanate or alicyclic polyisocyanate can be used as the aliphatic polyisocyanate. These aliphatic polyisocyanates may be used alone or in combination of two or more.
상기 지방족 폴리이소시아네이트 중에서도 도포막의 내찰상성을 향상시키려면, 지방족 폴리이소시아네이트 중에서도, 직사슬 지방족 탄화수소의 디이소시아네이트인 헥사메틸렌디이소시아네이트, 지환식 디이소시아네이트인 노르보르난디이소시아네이트, 이소포론디이소시아네이트가 바람직하다.Among aliphatic polyisocyanates, hexamethylene diisocyanate, which is a diisocyanate of a straight chain aliphatic hydrocarbon, norbornadiisocyanate, which is an alicyclic diisocyanate, and isophorone diisocyanate, are preferable among the aliphatic polyisocyanates in order to improve the scratch resistance of the coating film.
상기 (메트)아크릴레이트 (a2-2) 는, 수산기와 (메트)아크릴로일기를 갖는 화합물이다. 이 (메트)아크릴레이트 (a2-2) 의 구체예로는, 2-하이드록시에틸(메트)아크릴레이트, 2-하이드록시프로필(메트)아크릴레이트, 2-하이드록시부틸(메트)아크릴레이트, 4-하이드록시부틸(메트)아크릴레이트, 1,5-펜탄디올모노(메트)아크릴레이트, 1,6-헥산디올모노(메트)아크릴레이트, 네오펜틸글리콜모노(메트)아크릴레이트, 하이드록시피발산네오펜틸글리콜모노(메트)아크릴레이트 등의 2 가 알코올의 모노(메트)아크릴레이트 ; 트리메틸올프로판디(메트)아크릴레이트, 에틸렌옥사이드 (EO) 변성 트리메틸올프로판(메트)아크릴레이트, 프로필렌옥사이드 (PO) 변성 트리메틸올프로판디(메트)아크릴레이트, 글리세린디(메트)아크릴레이트, 비스(2-(메트)아크릴로일옥시에틸)하이드록시에틸이소시아누레이트 등의 3 가의 알코올의 모노 또는 디(메트)아크릴레이트, 혹은, 이들 알코올성 수산기의 일부를 ε-카프로락톤으로 변성한 수산기를 갖는 모노 및 디(메트)아크릴레이트 ; 펜타에리트리톨트리(메트)아크릴레이트, 디트리메틸올프로판트리(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트 등의 1 관능의 수산기와 3 관능 이상의 (메트)아크릴로일기를 갖는 화합물, 혹은, 그 화합물을 다시 ε-카프로락톤으로 변성한 수산기를 갖는 다관능 (메트)아크릴레이트 ; 디프로필렌글리콜모노(메트)아크릴레이트, 디에틸렌글리콜모노(메트)아크릴레이트, 폴리프로필렌글리콜모노(메트)아크릴레이트, 폴리에틸렌글리콜모노(메트)아크릴레이트 등의 옥시알킬렌 사슬을 갖는 (메트)아크릴레이트 ; 폴리에틸렌글리콜-폴리프로필렌글리콜모노(메트)아크릴레이트, 폴리옥시부틸렌-폴리옥시프로필렌모노(메트)아크릴레이트 등의 블록 구조의 옥시알킬렌 사슬을 갖는 (메트)아크릴레이트 ; 폴리(에틸렌글리콜-테트라메틸렌글리콜)모노(메트)아크릴레이트, 폴리(프로필렌글리콜-테트라메틸렌글리콜)모노(메트)아크릴레이트 등의 랜덤 구조의 옥시알킬렌 사슬을 갖는 (메트)아크릴레이트 등을 들 수 있다. 이들 (메트)아크릴레이트 (a2-2) 는 단독으로 사용할 수도 있고, 2 종 이상 병용할 수도 있다.The (meth) acrylate (a2-2) is a compound having a hydroxyl group and a (meth) acryloyl group. Specific examples of the (meth) acrylate (a2-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, hydroxypentyl glycol mono Mono (meth) acrylates of dihydric alcohols such as di-n-pentyl glycol mono (meth) acrylate; (Meth) acrylate, trimethylolpropane di (meth) acrylate, ethylene oxide (EO) modified trimethylolpropane (meth) acrylate, propylene oxide Mono or di (meth) acrylate of a trivalent alcohol such as (2- (meth) acryloyloxyethyl) hydroxyethylisocyanurate, or a mono- or di (meth) acrylate of a hydroxyl group in which a part of these alcoholic hydroxyl groups is modified with? -Caprolactone Mono and di (meth) acrylates having a hydroxyl group; (Meth) acrylate, trifunctional or more (meth) acryloyl groups such as ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylol propane tri , Or a polyfunctional (meth) acrylate having a hydroxyl group in which the compound is further modified with? -Caprolactone; (Meth) acrylate having an oxyalkylene chain such as dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol mono Rate; (Meth) acrylate having an oxyalkylene chain having a block structure such as polyethylene glycol-polypropylene glycol mono (meth) acrylate and polyoxybutylene-polyoxypropylene mono (meth) acrylate; (Meth) acrylate having a random oxyalkylene chain such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono . These (meth) acrylates (a2-2) may be used alone or in combination of two or more.
상기 우레탄(메트)아크릴레이트 (A2) 중에서도, 본 발명의 자외선 경화성 조성물의 경화 도포막의 내찰상성을 향상시킬 수 있기 때문에, 1 분자 중에 4 개 이상의 (메트)아크릴로일기를 갖는 것이 바람직하다. 상기 우레탄(메트)아크릴레이트 (A2) 를 1 분자 중에 4 개 이상의 (메트)아크릴로일기를 갖는 것으로 하기 위해, 상기 (메트)아크릴레이트 (a2-2) 로는, (메트)아크릴로일기는 2 개 이상 갖는 것이 바람직하다. 이와 같은 (메트)아크릴레이트 (a2-2) 로는, 예를 들어, 트리메틸올프로판디(메트)아크릴레이트, 에틸렌옥사이드 변성 트리메틸올프로판디(메트)아크릴레이트, 프로필렌옥사이드 변성 트리메틸올프로판디(메트)아크릴레이트, 글리세린디(메트)아크릴레이트, 비스(2-(메트)아크릴로일옥시에틸)하이드록시에틸이소시아누레이트, 펜타에리트리톨트리(메트)아크릴레이트, 디트리메틸올프로판트리(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트 등을 들 수 있다. 이들 (메트)아크릴레이트 (a2-2) 는, 상기 지방족 폴리이소시아네이트 (a1) 의 1 종에 대해, 1 종을 사용할 수도 있고, 2 종 이상 병용할 수도 있다. 또, 이들 (메트)아크릴레이트 (a2-2) 중에서도, 펜타에리트리톨트리(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트는 내찰상성을 향상시킬 수 있기 때문에 바람직하다.Among the above urethane (meth) acrylates (A2), it is preferable to have at least 4 (meth) acryloyl groups in one molecule because the scratch resistance of the cured coating film of the ultraviolet curable composition of the present invention can be improved. In order to make the urethane (meth) acrylate (A2) have 4 or more (meth) acryloyl groups in one molecule, the (meth) acryloyl group is preferably 2 Or more. Examples of such (meth) acrylate (a2-2) include trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane di (meth) acrylate, propylene oxide modified trimethylolpropane di ) Acrylate, glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylol propane tri ) Acrylate, dipentaerythritol penta (meth) acrylate, and the like. These (meth) acrylates (a2-2) may be used alone or in combination of two or more in one kind of the aliphatic polyisocyanate (a1). Among these (meth) acrylates (a2-2), pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable because they can improve scratch resistance.
상기 폴리이소시아네이트 (a2-1) 과 상기 (메트)아크릴레이트 (a2-2) 의 반응은, 통상적인 방법의 우레탄화 반응에 의해 실시할 수 있다. 또, 우레탄화 반응의 진행을 촉진시키기 위해, 우레탄화 촉매의 존재하에서 우레탄화 반응을 실시하는 것이 바람직하다. 상기 우레탄화 촉매로는, 예를 들어, 피리딘, 피롤, 트리에틸아민, 디에틸아민, 디부틸아민 등의 아민 화합물 ; 트리페닐포스핀, 트리에틸포스핀 등의 인 화합물 ; 디부틸주석디라우레이트, 옥틸주석트리라우레이트, 옥틸주석디아세테이트, 디부틸주석디아세테이트, 옥틸산주석 등의 유기 주석 화합물, 옥틸산아연 등의 유기 아연 화합물 등을 들 수 있다.The reaction between the polyisocyanate (a2-1) and the (meth) acrylate (a2-2) can be carried out by a conventional urethanation reaction. In order to promote the progress of the urethanation reaction, it is preferable to carry out the urethanation reaction in the presence of the urethanation catalyst. Examples of the urethanization catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; Phosphorus compounds such as triphenylphosphine and triethylphosphine; Organic tin compounds such as dibutyltin dilaurate, octyltin tris laurate, octyltin diacetate, dibutyltin diacetate and tin octylate, and organic zinc compounds such as zinc octylate.
또, 필요에 따라 상기의 다관능 (메트)아크릴레이트 (A1), 우레탄(메트)아크릴레이트 (A2) 이외의 자외선 경화성 화합물 (A) 로서, 에폭시(메트)아크릴레이트, 폴리에스테르(메트)아크릴레이트, 폴리에테르(메트)아크릴레이트 등의 비교적 고분자량의 (메트)아크릴레이트 (A3) 을 사용할 수 있다. 상기 에폭시(메트)아크릴레이트로는, 예를 들어, 비스페놀형 에폭시 수지, 노볼락형 에폭시 수지, 폴리글리시딜메타크릴레이트 등에 (메트)아크릴산을 반응시켜 에스테르화함으로써 얻어지는 것을 들 수 있다. 또, 상기 폴리에스테르(메트)아크릴레이트로는, 예를 들어, 다가 카르복실산과 다가 알코올을 중축합하여 얻어진 양 말단이 수산기인 폴리에스테르에 (메트)아크릴산을 반응시켜 에스테르화함으로써 얻어진 것, 혹은 다가 카르복실산에 알킬렌옥사이드를 부가한 것에 (메트)아크릴산을 반응시켜 에스테르화함으로써 얻어진 것을 들 수 있다. 또한, 상기 폴리에테르(메트)아크릴레이트로는, 예를 들어, 폴리에테르폴리올에 (메트)아크릴산을 반응시켜 에스테르화함으로써 얻어진 것을 들 수 있다. 또, 상기 (메트)아크릴레이트 (A3) 은 단독으로 사용할 수도 있고, 2 종 이상 병용할 수도 있다.As the ultraviolet curable compound (A) other than the above-mentioned polyfunctional (meth) acrylate (A1) and urethane (meth) acrylate (A2), epoxy (meth) acrylate, polyester (Meth) acrylate (A3) having a relatively high molecular weight such as polyether (meth) acrylate can be used. Examples of the epoxy (meth) acrylate include those obtained by reacting (meth) acrylic acid with a bisphenol-type epoxy resin, a novolak-type epoxy resin, polyglycidyl methacrylate or the like to produce an ester. Examples of the polyester (meth) acrylate include those obtained by reacting (meth) acrylic acid with a polyester having a hydroxyl group at both terminals obtained by polycondensation of a polyvalent carboxylic acid and a polyhydric alcohol to obtain an ester, Those obtained by reacting (meth) acrylic acid with an alkylene oxide added to a carboxylic acid to effect esterification. Examples of the polyether (meth) acrylate include those obtained by reacting a polyether polyol with (meth) acrylic acid to effect esterification. The (meth) acrylate (A3) may be used alone or in combination of two or more.
또한, 본 발명의 자외선 경화성 조성물에는, 상기 자외선 경화성 화합물 (A) 로서 예시한 (A1) ∼ (A3) 이외에, 인산기를 갖는 (메트)아크릴레이트 (A4) 를 배합하면, 기재에 대한 밀착성을 보다 향상시킬 수 있는 점에서 바람직하다. 상기 인산기를 갖는 (메트)아크릴레이트 (A4) 는, 1 분자 중에 적어도 1 개의 인산기를 갖는 (메트)아크릴레이트이다. 이 인산기를 갖는 (메트)아크릴레이트 (A4) 로는, 예를 들어, 인산(메트)아크릴로일옥시에틸, 인산디(메트)아크릴로일옥시에틸, 인산트리(메트)아크릴로일옥시에틸, 카프로락톤 변성 인산(메트)아크릴로일옥시에틸 등을 들 수 있고, 1 분자 중에 2 이상의 (메트)아크릴로일기를 갖는 화합물도 사용할 수 있다. 또, 이들 인산기를 갖는 (메트)아크릴레이트 (A4) 는 단독으로 사용할 수도 있고, 2 종 이상 병용할 수도 있다.When the (meth) acrylate (A4) having a phosphoric acid group is added to the ultraviolet curable composition of the present invention in addition to the above-mentioned (A1) to (A3) exemplified as the ultraviolet curable compound (A) It is preferable from the viewpoint of improvement. The (meth) acrylate (A4) having a phosphoric acid group is a (meth) acrylate having at least one phosphoric acid group in one molecule. Examples of the (meth) acrylate (A4) having a phosphoric acid group include (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tri (meth) acryloyloxyethyl phosphate, Caprolactone-modified (meth) acryloyloxyethyl, and the like, and compounds having two or more (meth) acryloyl groups in one molecule can also be used. The (meth) acrylate (A4) having these phosphoric acid groups may be used alone or in combination of two or more.
본 발명의 자외선 경화성 조성물에 상기 인산기를 갖는 (메트)아크릴레이트 (A4) 를 배합하는 경우의 그 배합량은, 기재에 대한 밀착성을 보다 향상시킬 수 있고, 경화 도포막 표면의 내찰상성도 보다 향상시킬 수 있는 점에서, 상기 자외선 경화성 화합물 (A) 중에 0.1 ∼ 30 질량％ 가 바람직하고, 0.5 ∼ 20 질량％ 가 보다 바람직하다.When the (meth) acrylate (A4) having a phosphoric acid group is blended in the ultraviolet curable composition of the present invention, the compounding amount thereof can further improve the adhesion to the substrate and improve the scratch resistance of the surface of the cured coating film It is preferably from 0.1 to 30 mass%, more preferably from 0.5 to 20 mass%, in the ultraviolet curable compound (A).
본 발명의 자외선 경화성 조성물에서는, 상기 자외선 경화성 화합물 (A) 와 함께, 광 중합 개시제 (B) 로서 하기 식 (1) 로 나타내는 기를 1 분자 중에 2 개 이상 갖는 화합물 (B1) 을 필수 성분으로서 함유한다. 또한, 하기 식 (1) 중의 페닐기가 알킬기, 알콕시기, 할로겐기 등의 치환기를 갖는 것이어도 상관없다.The ultraviolet curable composition of the present invention contains, as an essential component, a compound (B1) having two or more groups represented by the following formula (1) as a photopolymerization initiator (B) . The phenyl group in the following formula (1) may have a substituent such as an alkyl group, an alkoxy group or a halogen group.
[화학식 3](3)
상기 화합물 (B1) 을 광 중합 개시제로서 사용함으로써, 본 발명의 자외선 경화성 조성물의 경화 도포막은, 내찰상성이 높고, 고리형 올레핀 수지와의 밀착성이 우수하고, 착색이 적은 것이 되어 우수한 하드 코트층을 형성할 수 있다.By using the above compound (B1) as a photopolymerization initiator, the cured coating film of the ultraviolet-curable composition of the present invention has high scratch resistance, excellent adhesion with the cyclic olefin resin and less coloring, .
상기 화합물 (B1) 로는, 예를 들어, 하기 식 (2) 로 나타내는 옥시페닐아세트산2-(2-옥소-2-페닐아세톡시에톡시)에틸에스테르 등을 들 수 있다.Examples of the compound (B1) include oxyphenylacetic acid 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester represented by the following formula (2).
[화학식 4][Chemical Formula 4]
본 발명의 자외선 경화성 조성물 중에 함유되는 상기 광 중합 개시제 (B) 로서 상기 화합물 (B1) 을 필수 성분으로 하지만, 그 이외의 광 중합 개시제 (B2) 를 사용할 수 있다. 상기 광 중합 개시제 (B2) 로는, 예를 들어, 디에톡시아세토페논, 2-하이드록시-2-메틸-1-페닐프로판-1-온, 올리고{2-하이드록시-2-메틸-1-[4-(1-메틸비닐)페닐]프로파논}, 벤질디메틸케탈, 1-(4-이소프로필페닐)-2-하이드록시-2-메틸프로판-1-온, 4-(2-하이드록시에톡시)페닐-(2-하이드록시-2-프로필)케톤, 1-하이드록시시클로헥실페닐케톤, 2-메틸-2-모르폴리노(4-티오메틸페닐)프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-부타논 등의 아세토페논계 화합물 ; 벤조인, 벤조인메틸에테르, 벤조인이소프로필에테르 등의 벤조인계 화합물 ; 2,4,6-트리메틸벤조인디페닐포스핀옥사이드, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드 등의 아실포스핀옥사이드계 화합물 ; 벤질(디벤조일), 메틸페닐글리옥시에스테르, 옥시페닐아세트산2-(2-하이드록시에톡시)에틸에스테르 등의 벤질계 화합물 ; 벤조페논, o-벤조일벤조산메틸-4-페닐벤조페논, 4,4'-디클로로벤조페논, 하이드록시벤조페논, 4-벤조일-4'-메틸-디페닐술파이드, 아크릴화벤조페논, 3,3',4,4'-테트라(t-부틸퍼옥시카르보닐)벤조페논, 3,3'-디메틸-4-메톡시벤조페논, 2,4,6-트리메틸벤조페논, 4-메틸벤조페논 등의 벤조페논계 화합물 ; 2-이소프로필티오크산톤, 2,4-디메틸티오크산톤, 2,4-디에틸티오크산톤, 2,4-디클로로티오크산톤 등의 티오크산톤계 화합물 ; 미힐러케톤, 4,4'-디에틸아미노벤조페논 등의 아미노벤조페논계 화합물 ; 10-부틸-2-클로로아크리돈, 2-에틸안트라퀴논, 9,10-페난트렌퀴논, 캄파퀴논, 1-[4-(4-벤조일페닐술파닐)페닐]-2-메틸-2-(4-메틸페닐술포닐)프로판-1-온 등을 들 수 있다.As the photopolymerization initiator (B) contained in the ultraviolet-curable composition of the present invention, the above-mentioned compound (B1) is an essential component, but other photopolymerization initiator (B2) may be used. Examples of the photopolymerization initiator (B2) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo {2-hydroxy- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyphenyl) propanone, benzyldimethylketal, 1- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl- Acetophenone-based compounds such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone; Benzoin compounds such as benzoin, benzoin methyl ether and benzoin isopropyl ether; Acylphosphine oxide-based compounds such as 2,4,6-trimethylbenzoindienylphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Benzyl compounds such as benzyl (dibenzoyl), methylphenylglyoxyester, and oxyphenylacetic acid 2- (2-hydroxyethoxy) ethyl ester; Benzophenone, o-benzoylbenzoic acid methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, Benzophenone based compounds; Thioxanthone compounds such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; Aminobenzophenone compounds such as Michler's ketone and 4,4'-diethylaminobenzophenone; 2-chloro-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1- [4- (4-benzoylphenylsulfanyl) phenyl] (4-methylphenylsulfonyl) propan-1-one.
본 발명의 자외선 경화성 조성물에서의 상기 화합물 (B1) 의 배합량은, 경화성이 양호해지고, 고리형 폴리올레핀과의 밀착성이 보다 향상되는 점에서, 상기 자외선 경화성 화합물 (A) 100 질량부에 대해 0.1 ∼ 20 질량부가 바람직하고, 0.5 ∼ 10 질량부가 보다 바람직하다.The compounding amount of the compound (B1) in the ultraviolet-curing composition of the present invention is preferably from 0.1 to 20 parts by mass per 100 parts by mass of the ultraviolet-curing compound (A) because the curing property is improved and the adhesion with the cyclic polyolefin is further improved. Mass part is more preferable, and 0.5 to 10 mass part is more preferable.
또, 본 발명의 자외선 경화성 조성물 중에 함유되는 광 중합 개시제 (B) 중의 상기 화합물 (B1) 의 비율은 50 질량％ 이상이 바람직하고, 65 질량％ 이상이 보다 바람직하고, 80 질량％ 이상이 더욱 바람직하다.The proportion of the compound (B1) in the photopolymerization initiator (B) contained in the ultraviolet-curable composition of the present invention is preferably 50% by mass or more, more preferably 65% by mass or more, further preferably 80% Do.
본 발명의 자외선 경화성 조성물에는, 상기 자외선 경화성 화합물 (A) 및 광 중합 개시제 (B) 이외에, 용도, 요구 특성에 따라 광 증감제, 유기 용제, 중합 금지제, 표면 조정제, 대전 방지제, 소포제, 점도 조정제, 내광 안정제, 내후 안정제, 내열 안정제, 자외선 흡수제, 산화 방지제, 레벨링제, 유기 안료, 무기 안료, 안료 분산제, 유기 비즈 등의 첨가제 ; 산화규소 (실리카 입자), 산화알루미늄, 산화티탄, 지르코니아, 오산화안티몬 등의 무기 충전제 등을 배합할 수 있다. 이들 그 밖의 배합물은 단독으로 사용할 수도 있고, 2 종 이상 병용할 수도 있다.The ultraviolet curable composition of the present invention may contain, in addition to the ultraviolet curable compound (A) and the photopolymerization initiator (B), a photosensitizer, an organic solvent, a polymerization inhibitor, a surface control agent, an antistatic agent, Additives such as an antioxidant, an antioxidant, a leveling agent, an organic pigment, an inorganic pigment, a pigment dispersant, and an organic bead; Inorganic fillers such as silicon oxide (silica particles), aluminum oxide, titanium oxide, zirconia, antimony pentoxide, and the like. These other compounds may be used alone or in combination of two or more.
상기 무기 충전제 중에서도 실리카 입자를 배합함으로써, 본 발명의 자외선 경화성 조성물의 경화 도포막 표면의 내찰상성을 보다 향상시킬 수 있고, 기재에 대한 밀착성도 보다 향상시킬 수 있다. 상기 실리카 입자로는, 그 표면이 유기기로 표면 수식된 것이어도 되고, 표면 수식되어 있지 않은 것이어도 된다. 또, 상기 실리카 입자는, 본 발명의 자외선 경화성 조성물의 경화 도포막의 투명성 및 표면의 내찰상성을 보다 향상시킬 수 있는 점에서, 나노미터 오더 사이즈의 실리카 미립자가 바람직하고, 콜로이달 실리카가 보다 바람직하다. 상기 실리카 미립자의 평균 입자 직경으로는 5 ∼ 200 ㎚ 의 범위가 바람직하고, 5 ∼ 100 ㎚ 의 범위가 보다 바람직하다. 또한, 이 평균 입자 직경은 동적 광 산란법으로 측정한 값이다.By incorporating the silica particles in the inorganic filler, the scratch resistance of the surface of the cured coating film of the ultraviolet-curable composition of the present invention can be further improved, and the adhesion to the substrate can be further improved. As the silica particles, the surface of the silica particles may be surface-modified with an organic group, or may not be surface-modified. The silica particles are preferably fine silica particles of nanometer order size and more preferably colloidal silica because they can further improve transparency and scratch resistance of the cured coating film of the ultraviolet ray curable composition of the present invention . The average particle diameter of the fine silica particles is preferably in the range of 5 to 200 nm, more preferably in the range of 5 to 100 nm. The average particle diameter is a value measured by a dynamic light scattering method.
상기 무기 충전제를 배합하는 경우의 그 배합량은, 본 발명의 자외선 경화성 조성물의 경화 도포막 표면의 내찰상성을 보다 향상시킬 수 있고, 기재에 대한 밀착성도 보다 향상할 수 있는 점에서, 상기 자외선 경화성 화합물 (A) 100 질량부에 대해 1 ∼ 150 질량부가 바람직하고, 5 ∼ 100 질량부가 보다 바람직하다.When the inorganic filler is blended, the blending amount of the ultraviolet-curable compound of the present invention can be improved by improving the scratch resistance of the surface of the cured coating film of the present invention and further improving the adhesion to the substrate. Is preferably 1 to 150 parts by mass, more preferably 5 to 100 parts by mass, per 100 parts by mass of the component (A).
상기 광 증감제로는, 예를 들어, 디에탄올아민, N-메틸디에탄올아민, 트리부틸아민 등의 3 급 아민 화합물, o-톨릴티오우레아 등의 우레아 화합물, 나트륨디에틸디티오포스페이트, s-벤질이소티오우로늄-p-톨루엔술포네이트 등의 황 화합물 등을 들 수 있다. 광 증감제를 배합하는 경우의 그 배합량은, 상기 자외선 경화성 화합물 (A) 100 질량부에 대해 0.01 ∼ 20 질량부가 바람직하고, 0.5 ∼ 10 질량부가 보다 바람직하다.Examples of the photosensitizer include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, s- And sulfur compounds such as benzyl isothiouronium-p-toluenesulfonate. When the photosensitizer is blended, the blending amount thereof is preferably 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the ultraviolet curing compound (A).
상기 유기 용매는, 본 발명의 활성 에너지선 경화성 조성물의 용액 점도를 적절히 조정하는 데에 있어서 유용하고, 특히 박막 코팅을 실시하기 위해서는, 막 두께를 조정하는 것이 용이해진다. 여기서 사용할 수 있는 유기 용매로는, 예를 들어, 톨루엔, 자일렌 등의 방향족 탄화수소 ; 메탄올, 에탄올, 이소프로판올, t-부탄올 등의 알코올류 ; 아세트산에틸, 아세트산부틸, 프로필렌글리콜모노메틸에테르아세테이트 등의 에스테르류 ; 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 시클로헥사논 등의 케톤류 등을 들 수 있다. 이들 용제는 단독으로 사용할 수도 있고, 2 종 이상을 병용할 수도 있다.The organic solvent is useful in appropriately adjusting the solution viscosity of the active energy ray curable composition of the present invention, and in particular, in order to perform thin film coating, it is easy to adjust the film thickness. Examples of the organic solvent usable herein include aromatic hydrocarbons such as toluene and xylene; Alcohols such as methanol, ethanol, isopropanol and t-butanol; Esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; And ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used alone or in combination of two or more.
본 발명의 자외선 경화성 조성물은, 특히 고리형 올레핀 수지에 대해 우수한 밀착성을 갖는 경화 도포막이 얻어지는 점에서, 본 발명의 자외선 경화성 조성물을 도포하는 기재로는, 고리형 올레핀 수지 성형품이고, 특히 고리형 올레핀 수지 필름이 바람직하다. 또, 고리형 올레핀 수지로는, 고리형 올레핀을 중합한 것이면, 단독 중합체나 공중합체여도 특별히 제한 없이 사용할 수 있다. 고리형 올레핀 수지의 시판품으로는, 예를 들어, 닛폰 제온 주식회사 제조의「ZEONOR」,「ZEONEX」; JSR 주식회사 제조의「ARTON」; 폴리플라스틱스 주식회사 제조의「TOPAS」등을 들 수 있다.The ultraviolet-curable composition of the present invention is a molded article of a cyclic olefin resin, in particular, a substrate to which the ultraviolet-curable composition of the present invention is applied since a cured coating film having excellent adhesion to the cyclic olefin resin can be obtained, A resin film is preferable. As the cyclic olefin resin, a homopolymer or a copolymer may be used without particular limitation, provided that the cyclic olefin is polymerized. Commercially available products of the cyclic olefin resin include, for example, "ZEONOR", "ZEONEX" manufactured by Nippon Zeon Co., Ltd.; "ARTON" manufactured by JSR Corporation; TOPAS " manufactured by Polyplastics Co., Ltd., and the like.
상기 고리형 올레핀 수지 필름은, 고리형 올레핀 수지를 필름 상에 성형한 것이다. 또, 고리형 올레핀 수지 필름의 표면은, 본 발명의 자외선 경화성 조성물의 경화 도포막과의 밀착성을 향상시키기 위해, 샌드 블라스트법, 용제 처리법 등에 의한 표면의 요철화 처리, 전기적 처리 (코로나 방전 처리, 대기압 플라즈마 처리), 크롬산 처리, 화염 처리, 열풍 처리, 오존·자외선·전자선 조사 처리, 산화 처리 등에 의해 처리를 한 것이 바람직하고, 이들 중에서도 코로나 방전 처리, 대기압 플라즈마 처리 등의 전기적 처리를 한 것이 보다 바람직하다.The cyclic olefin resin film is obtained by molding a cyclic olefin resin into a film. The surface of the cyclic olefin resin film is preferably subjected to a surface unevenness treatment by a sandblasting method, a solvent treatment method or the like, an electric treatment (corona discharge treatment, The atmospheric pressure plasma treatment), the chromic acid treatment, the flame treatment, the hot air treatment, the ozone, the ultraviolet ray, the electron beam irradiation treatment, the oxidation treatment and the like. Among them, the electric treatment such as the corona discharge treatment and the atmospheric pressure plasma treatment desirable.
또, 상기 고리형 올레핀 수지 필름의 두께는 50 ∼ 200 ㎛ 의 범위가 바람직하고, 80 ∼ 150 ㎛ 의 범위가 보다 바람직하고, 90 ∼ 130 ㎛ 의 범위가 더욱 바람직하다. 필름 기재의 두께를 당해 범위로 함으로써, 고리형 올레핀 수지 필름의 편면에 본 발명의 자외선 경화성 조성물에 의해 하드 코트층을 형성한 경우에도 컬을 억제하기 쉬워진다.The thickness of the cyclic olefin resin film is preferably in the range of 50 to 200 占 퐉, more preferably in the range of 80 to 150 占 퐉, and further preferably in the range of 90 to 130 占 퐉. By setting the thickness of the film base material to the above range, curl can be easily suppressed even when the hard coat layer is formed on one side of the annular olefin resin film with the ultraviolet curable composition of the present invention.
본 발명의 고리형 올레핀 수지 필름은, 당해 필름의 적어도 1 면에 본 발명의 자외선 경화성 조성물을 도포하고, 그 후 자외선을 조사하여 경화 도포막으로 함으로써 얻어진 것이다. 고리형 올레핀 수지 필름에 본 발명의 자외선 경화성 조성물을 도포하는 방법으로는, 예를 들어, 다이 코트, 마이크로 그라비아 코트, 그라비아 코트, 롤 코트, 콤마 코트, 에어 나이프 코트, 키스 코트, 스프레이 코트, 커튼 플로 코트, 딥 코트, 스피너 코트, 휠러 코트, 브러시 도포, 실크 스크린에 의한 베타 코트, 와이어 바 코트, 플로 코트 등을 들 수 있다.The cyclic olefin resin film of the present invention is obtained by applying the ultraviolet curable composition of the present invention to at least one surface of the film, and then irradiating ultraviolet rays to form a cured coating film. Examples of the method of applying the ultraviolet ray curable composition of the present invention to the cyclic olefin resin film include a die coating method, a micro gravure coating method, a gravure coating method, a roll coating method, a comma coating method, an air knife coating method, a kiss coating method, A dip coat, a spinner coat, a wheeler coat, a brush coat, a beta coat by a silk screen, a wire bar coat, and a float coat.
또, 자외선 경화성 조성물을 경화시키기 위해, 자외선을 조사하는 장치로는, 예를 들어, 저압 수은 램프, 고압 수은 램프, 초고압 수은 램프, 메탈 할라이드 램프, 무전극 램프 (퓨전 램프), 케미컬 램프, 블랙 라이트 램프, 수은-크세논 램프, 쇼트 아크등, 헬륨·카드뮴 레이저, 아르곤 레이저, 태양광, LED 등을 들 수 있다.Examples of a device for irradiating ultraviolet rays for curing the ultraviolet ray curable composition include a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), a chemical lamp, Light lamps, mercury-xenon lamps, short arc lamps, helium-cadmium lasers, argon lasers, solar light, LEDs and the like.
본 발명의 자외선 경화성 조성물의 경화 도포막을 갖는 고리형 올레핀 수지 필름은, 그 기재의 우수한 광학 특성, 치수 안정성, 내열성, 투명성에 더하여, 그 표면의 내찰상성이 우수한 점에서 각종 용도에 적용할 수 있지만, 특히 액정 디스플레이 (LCD), 유기 EL 디스플레이 (OLED) 등의 화상 표시 장치의 화상 표시부에 사용하는 광학 필름으로서 유용하다. 특히, 박형이어도 우수한 내찰상성을 갖는 점에서, 예를 들어, 전자 수첩, 휴대 전화, 스마트 폰, 휴대 오디오 플레이어, 모바일 PC, 태블릿 단말 등의 소형화나 박형화의 요청이 높은 휴대 전자 단말의 화상 표시 장치의 화상 표시부의 광학 필름으로서 바람직하게 사용할 수 있다. 또, 광학 필름으로서 사용하는 경우, 화상 표시 장치의 화상 표시부의 최표면에 사용하는 보호 필름, 터치 패널의 기재로서 사용할 수 있다. 또한, 보호 필름으로서 사용한 경우에는, 예를 들어, LCD 모듈이나 OLED 모듈 등의 화상 표시 모듈의 상부에 당해 화상 표시 모듈을 보호하는 투명 패널이 형성된 구성의 화상 표시 장치에 있어서는, 당해 투명 패널의 표면 또는 이면에 첩부하여 사용함으로써, 흠집 방지나 투명 패널이 파손되었을 때의 비산 방지에 유효하다.The cyclic olefin resin film having the cured coating film of the ultraviolet ray curable composition of the present invention can be applied to various applications because of its excellent optical properties, dimensional stability, heat resistance and transparency, , And is particularly useful as an optical film used in an image display portion of an image display device such as a liquid crystal display (LCD), an organic EL display (OLED) and the like. Particularly, in view of having excellent scratch resistance even though it is thin, there is a demand for miniaturization and thinning of electronic notebooks, mobile phones, smart phones, portable audio players, mobile PCs, tablet terminals, As an optical film of an image display portion of a liquid crystal display device. When used as an optical film, it can be used as a base material of a protective film or a touch panel used for an outermost surface of an image display unit of an image display apparatus. Further, in the case of using as a protective film, for example, in an image display apparatus having a structure in which a transparent panel for protecting the image display module is formed on an image display module such as an LCD module or an OLED module, Or the back surface of the transparent panel is used to prevent scratches and to prevent scattering when the transparent panel is broken.
실시예Example
이하에 실시예에 의해 본 발명을 보다 구체적으로 설명한다.Hereinafter, the present invention will be described more specifically with reference to Examples.
(합성예 1 : 우레탄아크릴레이트 (A2-1) 의 합성)(Synthesis Example 1: Synthesis of urethane acrylate (A2-1)
교반기, 가스 도입관, 냉각관 및 온도계를 구비한 플라스크에 아세트산부틸 254 질량부, 이소포론디이소시아네이트 222 질량부, p-메톡시페놀 0.5 질량부 및 디부틸주석디아세테이트 0.5 질량부를 주입하고, 공기를 분사하면서 70 ℃ 로 승온시킨 후, 펜타에리트리톨트리아크릴레이트 (이하,「PE3A」라고 약기한다) 및 펜타에리트리톨테트라아크릴레이트 (이하,「PE4A」라고 약기한다) 의 혼합물 (PE3A/PE4A ＝ 75/25 (질량비)) 400 질량부와 이소시아누르산에틸렌옥사이드 변성 디아크릴레이트 497 질량부를 1 시간에 걸쳐 적하하였다. 적하 종료 후, 70 ℃ 에서 3 시간 반응시키고, 또한 이소시아네이트기를 나타내는 2250 ㎝-1 의 적외선 흡수 스펙트럼이 소실될 때까지 반응을 실시하여, 1 분자 중에 6 개의 아크릴로일기를 갖는 우레탄아크릴레이트 (A2-1) 을 함유하는 불휘발분 80 질량％ 용액을 얻었다. 또한, 이 용액에는, 불휘발분 중에 우레탄아크릴레이트 (A2-1) 외에 PE4A 가 19.5 질량％ 함유된다.254 parts by mass of butyl acetate, 222 parts by mass of isophorone diisocyanate, 0.5 parts by mass of p-methoxyphenol and 0.5 parts by mass of dibutyltin diacetate were charged into a flask equipped with a stirrer, a gas introducing tube, a cooling tube and a thermometer, (PE3A / PE4A) (hereinafter abbreviated as PE3A) and pentaerythritol tetraacrylate (hereinafter abbreviated as " PE4A ") after raising the temperature to 70 deg. 75/25 (mass ratio)) and 497 parts by mass of isocyanuric acid ethylene oxide-modified diacrylate were added dropwise over 1 hour. After completion of the dropwise addition, the reaction was carried out at 70 DEG C for 3 hours, and the reaction was continued until the infrared absorption spectrum at 2250 cm < -1 > indicating the isocyanate group disappeared. As a result, the urethane acrylate having 6 acryloyl groups 1) as a non-volatile fraction. In this solution, 19.5 mass% of PE4A is contained in the nonvolatile matter in addition to urethane acrylate (A2-1).
(실시예 1)(Example 1)
디펜타에리트리톨헥사아크릴레이트 (이하,「DPHA」라고 약기한다) 및 디펜타에리트리톨펜타아크릴레이트 (이하,「DPPA」라고 약기한다) 의 혼합물 (DPHA/DPPA ＝ 65/35 (질량비)) 35 질량부, 폴리에스테르아크릴레이트 (4 관능, 분자량 1,800) 65 질량부, 실리카 미립자 (닛산 화학 공업 주식회사 제조의「MEK-ST」, 평균 입자 직경 10 ∼ 20 ㎚, 오르가노실리카졸의 30 질량％ 메틸에틸케톤 분산액 ; 이하,「실리카 미립자 분산액 (1)」이라고 약기한다) 25 질량부 (실리카 미립자로서 7.5 질량부), 및 옥시페닐아세트산2-(2-옥소-2-페닐아세톡시에톡시)에틸에스테르 (이하,「광 중합 개시제 (B1-1)」이라고 약기한다) 3 질량부를 균일하게 교반한 후, 메틸에틸케톤으로 희석하여 불휘발분 25 질량％ 의 자외선 경화성 조성물 (1) 을 조제하였다.A mixture (DPHA / DPPA = 65/35 (mass ratio)) of dipentaerythritol hexaacrylate (hereinafter abbreviated as DPHA) and dipentaerythritol pentaacrylate (hereinafter abbreviated as DPPA) (MEK-ST, manufactured by Nissan Chemical Industries, Ltd., average particle diameter of 10 to 20 nm, 30 mass% of organosilica sol, methyl (meth) acrylate 25 parts by mass (hereinafter referred to as " silica fine particle dispersion (1) ") (7.5 parts by mass as fine silica particles) and 2- (2-oxo-2-phenylacetoxyethoxy) oxyphenylacetic acid (Hereinafter abbreviated as " photo polymerization initiator (B1-1) ") were uniformly stirred and then diluted with methyl ethyl ketone to prepare an ultraviolet curable composition (1) having a nonvolatile content of 25 mass%.
[평가용 필름의 제조][Production of evaluation film]
상기에서 얻어진 자외선 경화성 조성물 (1) 을, 미리 그 표면을 전기적 처리 (코로나 방전 처리 ; 출력 100 W, 속도 1.0 m/분) 한 고리형 올레핀 수지 필름 (닛폰 제온 주식회사 제조의「제오노아 필름 ZF16-100」, 두께 100 ㎛) 상에 와이어 바를 사용하여 도포하고, 60 ℃ 에서 90 초간 가열 후, 공기 분위기하에서 자외선 조사 장치 (아이그래픽스 주식회사 제조의「MIDN-042-C1」, 램프 : 120 W/㎝, 고압 수은등) 를 사용하여 조사광량 0.3 J/㎠ 로 자외선을 조사하여, 두께 4 ㎛ 의 경화 도포막을 갖는 평가용 필름을 얻었다.The ultraviolet-curable composition (1) obtained above was coated on a surface of a cyclic olefin resin film ("Zeonoafil ZF16-Z" manufactured by Nippon Zeon Co., Ltd.) whose surface was previously subjected to an electric treatment (corona discharge treatment: output of 100 W, speed of 1.0 m / min) (MIDN-042-C1 manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm < 2 >) under air atmosphere, , High-pressure mercury lamp, etc.) was irradiated with ultraviolet light at an irradiation light quantity of 0.3 J / cm 2 to obtain an evaluation film having a cured coating film having a thickness of 4 탆.
[내찰상성의 평가][Evaluation of scratch resistance]
상기에서 얻어진 평가용 필름의 경화 도포막의 표면에 대해, 클락 미터형 마찰 시험기 (직경 1.0 ㎝ 원형 마찰자, 스틸울 ＃0000, 하중 300 g, 10 왕복) 를 사용하여 시험을 실시하고, 시험 후의 경화 도포막 표면을 육안으로 관찰하여, 하기 기준에 의해 내찰상성을 평가하였다.The test was performed on the surface of the cured coating film of the evaluation film obtained above using a clammeter type friction tester (diameter 1.0 cm circular rubber, steel wool # 0000, load 300 g, 10 reciprocating) The surface of the coating film was visually observed and scratch resistance was evaluated according to the following criteria.
A : 흠집의 수가 9 개 이하이다.A: The number of scratches is 9 or less.
B : 흠집의 수가 10 개 이상이다.B: The number of scratches is 10 or more.
[밀착성의 평가][Evaluation of adhesion]
상기에서 얻어진 평가용 필름에, 필름의 경화 피막 표면에 1 ㎜ 간격으로 세로, 가로 11 개의 새김눈을 넣어 100 개의 모눈을 제조하였다. 이어서, 시판되는 셀로판 테이프를 그 표면에 밀착시킨 후, 단번에 벗기는 조작을 2 회 반복하였다. 박리되지 않고 남은 모눈의 수를 세어, 하기 기준에 의해 밀착성을 평가하였다.In the evaluation film obtained above, 11 pieces of vertically and horizontally inscribed nicks were placed on the surface of the cured film of the film at intervals of 1 mm to prepare 100 squares. Subsequently, a commercially available cellophane tape was brought into close contact with the surface thereof, and then peeling at once was repeated twice. The number of remaining grits without peeling was counted, and the adhesion was evaluated by the following criteria.
A : 남은 모눈의 수가 100 개이다.A: The number of remaining grids is 100.
B : 남은 모눈의 수가 80 개 이상 99 개 이하이다.B: The number of remaining grids is 80 or more and 99 or less.
C : 남은 모눈의 수가 60 개 이상 80 개 이하이다.C: The number of remaining grids is 60 or more and 80 or less.
D : 남은 모눈의 수가 59 개 이하이다.D: The number of remaining grids is 59 or less.
[후막 밀착성의 평가][Evaluation of thick film adhesion]
자외선 경화성 조성물 (1) 도포량을 변경한 것 이외에는, 상기 평가용 필름의 제조와 동일하게 실시하여, 두께 6 ㎛ 의 경화 도포막을 갖는 후막 밀착성 평가용 필름을 얻었다. 얻어진 필름에 대해, 상기 밀착성의 평가와 동일하게 실시하여 후막 밀착성을 평가하였다.Except that the application amount of the ultraviolet-curable composition (1) was changed, the same procedure as in the preparation of the evaluation film was carried out to obtain a film for evaluating thick film adhesion having a cured coating film having a thickness of 6 占 퐉. The resulting film was evaluated in the same manner as in the evaluation of the adhesion to evaluate the adhesion of the thick film.
[도포막 착색의 평가][Evaluation of Coating Film Coloring]
상기에서 얻어진 평가용 필름을 50 ㎜ × 80 ㎜ 의 크기로 컷하고, 외경 8 ㎜ 의 로드에 필름을 감아 셀로판 테이프로 고정시켰다. 이어서, 로드를 발출한 후, 롤상의 평가용 필름의 색미를 육안으로 관찰하여, 하기 기준에 의해 도포막 착색을 평가하였다.The evaluation film obtained above was cut into a size of 50 mm x 80 mm and the film was wound on a rod having an outer diameter of 8 mm and fixed with a cellophane tape. Subsequently, after the rod was taken out, the color taste of the evaluation film on the roll was visually observed, and the coloring of the coating film was evaluated according to the following criteria.
A : 무색이다.A: It is colorless.
B : 황색의 착색이 있다.B: There is yellow coloration.
(실시예 2)(Example 2)
광 중합 개시제 (B1-1) 의 배합량을 3 질량부에서 6 질량부로 변경한 것 이외에는, 실시예 1 과 동일하게 실시하여 자외선 경화성 조성물 (2) 를 조제하였다.An ultraviolet-curable composition (2) was prepared in the same manner as in Example 1 except that the amount of the photopolymerization initiator (B1-1) was changed from 3 parts by mass to 6 parts by mass.
(실시예 3)(Example 3)
광 중합 개시제 (B1-1) 의 배합량을 3 질량부에서 9 질량부로 변경한 것 이외에는, 실시예 1 과 동일하게 실시하여 불휘발분 25 질량％ 의 자외선 경화성 조성물 (3) 을 조제하였다.An ultraviolet curable composition (3) having a nonvolatile content of 25% by mass was prepared in the same manner as in Example 1 except that the amount of the photopolymerization initiator (B1-1) was changed from 3 parts by mass to 9 parts by mass.
(실시예 4)(Example 4)
합성예 1 에서 얻어진 다관능 우레탄아크릴레이트 (A2-1) (불휘발분 80 질량％) 125 질량부 (다관능 아크릴레이트로서 100 질량부), 실리카 미립자 분산액 (1) 25 질량부 (실리카 미립자로서 7.5 질량부) 및 광 중합 개시제 (B1-1) 3 질량부를 균일하게 교반한 후, 메틸에틸케톤으로 희석하여 불휘발분 25 질량％ 의 자외선 경화성 조성물 (4) 를 조제하였다.125 parts by mass (100 parts by mass as polyfunctional acrylate) of the polyfunctional urethane acrylate (A2-1) (nonvolatile matter 80% by mass) obtained in Synthesis Example 1, 25 parts by mass (7.5 as silica fine particles) Mass part) and 3 parts by mass of the photopolymerization initiator (B1-1) were uniformly stirred and then diluted with methyl ethyl ketone to prepare an ultraviolet curable composition (4) having a nonvolatile content of 25 mass%.
(실시예 5)(Example 5)
광 중합 개시제 (B1-1) 의 배합량을 3 질량부에서 6 질량부로 변경한 것 이외에는, 실시예 4 와 동일하게 실시하여 불휘발분 25 질량％ 의 자외선 경화성 조성물 (5) 를 조제하였다.An ultraviolet curable composition (5) having a nonvolatile content of 25% by mass was prepared in the same manner as in Example 4 except that the amount of the photopolymerization initiator (B1-1) was changed from 3 parts by mass to 6 parts by mass.
(실시예 6)(Example 6)
광 중합 개시제 (B1-1) 의 배합량을 3 질량부에서 9 질량부로 변경한 것 이외에는, 실시예 4 와 동일하게 실시하여 불휘발분 25 질량％ 의 자외선 경화성 조성물 (6) 을 조제하였다.An ultraviolet curable composition (6) having a nonvolatile content of 25% by mass was prepared in the same manner as in Example 4 except that the amount of the photopolymerization initiator (B1-1) was changed from 3 parts by mass to 9 parts by mass.
(실시예 7)(Example 7)
합성예 1 에서 얻어진 다관능 우레탄아크릴레이트 (A2-1) (불휘발분 80 질량％) 125 질량부 (다관능 아크릴레이트로서 100 질량부), 실리카 미립자 (닛산 화학 공업 주식회사 제조의「MEK-ST40」, 평균 입자 직경 10 ∼ 20 ㎚, 오르가노실리카졸의 40 질량％ 메틸에틸케톤 분산액 ; 이하,「실리카 미립자 분산액 (2)」라고 약기한다) 62.5 질량부 (실리카 미립자로서 25 질량부), 및 광 중합 개시제 (B1-1) 6 질량부를 균일하게 교반한 후, 메틸에틸케톤으로 희석하여 불휘발분 25 질량％ 의 자외선 경화성 조성물 (7) 을 조제하였다., 125 parts by mass (100 parts by mass as polyfunctional acrylate) of the polyfunctional urethane acrylate (A2-1) (nonvolatile matter 80% by mass) obtained in Synthesis Example 1, 10 parts by mass of silica fine particles ("MEK-ST40" manufactured by Nissan Chemical Industries, , 62.5 parts by mass (25 parts by mass as fine silica particles) of an organosilica sol, an average particle diameter of 10 to 20 nm, a 40 mass% methyl ethyl ketone dispersion of organosilica sol; hereinafter abbreviated as "silica fine particle dispersion (2)") 6 parts by mass of the polymerization initiator (B1-1) was uniformly stirred and then diluted with methyl ethyl ketone to prepare an ultraviolet curable composition (7) having a nonvolatile content of 25% by mass.
(실시예 8)(Example 8)
다관능 우레탄아크릴레이트 (A2-1) (불휘발분 80 질량％) 123.75 질량부 (다관능 아크릴레이트로서 99 질량부), 인산기를 갖는 메타크릴레이트 (MIWON 사 제조의「미라머 SC1400」; 이하,「인산메타크릴레이트 (1)」이라고 약기한다) 1 질량부, 실리카 미립자 분산액 (2) 62.5 질량부 (실리카 미립자로서 25 질량부), 및 광 중합 개시제 (B1-1) 6 질량부를 균일하게 교반한 후, 메틸에틸케톤으로 희석하여 불휘발분 25 질량％ 의 자외선 경화성 조성물 (8) 을 조제하였다., 123.75 parts by mass of polyfunctional urethane acrylate (A2-1) (nonvolatile matter 80 mass%) (99 parts by mass as polyfunctional acrylate), methacrylate having a phosphoric acid group ("Miramer SC1400" 1 part by mass of "phosphoric acid methacrylate (1)"), 62.5 parts by mass of the fine silica particle dispersion (2) (25 parts by mass as fine silica particles) and 6 parts by mass of the photopolymerization initiator (B1-1) And then diluted with methyl ethyl ketone to prepare an ultraviolet curable composition (8) having a nonvolatile content of 25 mass%.
(실시예 9)(Example 9)
다관능 우레탄아크릴레이트 (A2-1) (불휘발분 80 질량％) 118.75 질량부 (다관능 아크릴레이트로서 95 질량부), 인산메타크릴레이트 (1) 5 질량부, 실리카 미립자 분산액 (2) 62.5 질량부 (실리카 미립자로서 25 질량부), 및 광 중합 개시제 (B1-1) 6 질량부를 균일하게 교반한 후, 메틸에틸케톤으로 희석하여 불휘발분 25 질량％ 의 자외선 경화성 조성물 (9) 를 조제하였다.(95 parts by mass as polyfunctional acrylate), 5 parts by mass of phosphoric acid methacrylate (1), 62.5 parts by mass of silica fine particle dispersion (2) (25 parts by mass as a silica fine particle) and 6 parts by mass of a photopolymerization initiator (B1-1) were uniformly stirred and then diluted with methyl ethyl ketone to prepare an ultraviolet curable composition (9) having a nonvolatile content of 25% by mass.
(실시예 10)(Example 10)
다관능 우레탄아크릴레이트 (A2-1) (불휘발분 80 질량％) 113.75 질량부 (다관능 아크릴레이트로서 91 질량부), 인산메타크릴레이트 (1) 9 질량부, 실리카 미립자 분산액 (2) 62.5 질량부 (실리카 미립자로서 25 질량부), 및 광 중합 개시제 (B1-1) 6 질량부를 균일하게 교반한 후, 메틸에틸케톤으로 희석하여 불휘발분 25 질량％ 의 자외선 경화성 조성물 (10) 을 조제하였다.(91 parts by mass as polyfunctional acrylate), 9 parts by mass of phosphoric acid methacrylate (1), 62.5 parts by mass of silica fine particle dispersion (2) (25 parts by mass as a silica fine particle) and 6 parts by mass of a photopolymerization initiator (B1-1) were uniformly stirred and then diluted with methyl ethyl ketone to prepare an ultraviolet curable composition (10) having a nonvolatile content of 25% by mass.
(실시예 11)(Example 11)
실리카 미립자 분산액 (2) 를 배합하지 않은 것 이외에는, 실시예 7 과 동일하게 실시하여 불휘발분 25 질량％ 의 자외선 경화성 조성물 (11) 을 조제하였다.An ultraviolet-curable composition (11) having a nonvolatile content of 25 mass% was prepared in the same manner as in Example 7 except that the silica fine particle dispersion (2) was not compounded.
(실시예 12)(Example 12)
실리카 미립자 분산액 (2) 를 배합하지 않은 것 이외에는, 실시예 9 와 동일하게 실시하여 불휘발분 25 질량％ 의 자외선 경화성 조성물 (12) 를 조제하였다.An ultraviolet curable composition (12) having a nonvolatile content of 25 mass% was prepared in the same manner as in Example 9 except that the silica fine particle dispersion (2) was not added.
(비교예 1)(Comparative Example 1)
실시예 1 에서 사용한 광 중합 개시제 (B1-1) 대신에, 4-(4-메틸페닐티오)벤조페논 (이하,「광 중합 개시제 (R1)」이라고 약기한다) 을 사용한 것 이외에는, 실시예 1 과 동일하게 실시하여 자외선 경화성 조성물 (R1) 을 조제하였다.Except that the 4- (4-methylphenylthio) benzophenone (hereinafter abbreviated as "photopolymerization initiator (R1)") was used in place of the photopolymerization initiator (B1-1) used in Example 1, The UV curable composition (R1) was prepared in the same manner.
(비교예 2)(Comparative Example 2)
실시예 1 에서 사용한 광 중합 개시제 (B1-1) 3 질량부 대신에, 광 중합 개시제 (R1) 9 질량부를 사용한 것 이외에는, 실시예 1 과 동일하게 실시하여 자외선 경화성 조성물 (R2) 를 조제하였다.An ultraviolet curable composition (R2) was prepared in the same manner as in Example 1 except that 9 parts by mass of the photopolymerization initiator (R1) was used instead of 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1.
(비교예 3)(Comparative Example 3)
실시예 1 에서 사용한 광 중합 개시제 (B1-1) 3 질량부 대신에, 1-하이드록시시클로헥실페닐케톤 (이하,「광 중합 개시제 (R2)」라고 약기한다) 6 질량부를 사용한 것 이외에는, 실시예 1 과 동일하게 실시하여 자외선 경화성 조성물 (R3) 을 조제하였다.Except that 6 parts by mass of 1-hydroxycyclohexyl phenyl ketone (hereinafter abbreviated as "photopolymerization initiator (R2)") was used instead of 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1 The ultraviolet curable composition (R3) was prepared in the same manner as in Example 1.
(비교예 4)(Comparative Example 4)
실시예 1 에서 사용한 광 중합 개시제 (B1-1) 3 질량부 대신에, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-1-부타논 (이하,「광 중합 개시제 (R3)」이라고 약기한다) 6 질량부를 사용한 것 이외에는, 실시예 1 과 동일하게 실시하여 자외선 경화성 조성물 (R4) 를 조제하였다.Except that 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1 was replaced by 2 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) (Hereinafter abbreviated as " R < 3 >) ") was used in place of the ultraviolet ray-curable composition (R4).
(비교예 5)(Comparative Example 5)
실시예 1 에서 사용한 광 중합 개시제 (B1-1) 3 질량부 대신에, 2-메틸-1-(4-메틸티오페닐)-2-모르폴리노프로판-1-온 (이하,「광 중합 개시제 (R4)」라고 약기한다) 6 질량부를 사용한 것 이외에는, 실시예 1 과 동일하게 실시하여 자외선 경화성 조성물 (R5) 를 조제하였다.Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (hereinafter, referred to as " photopolymerization initiator (B1-1) (Hereinafter, abbreviated as " R < 4 > ") were used in place of the ultraviolet curable composition (R5).
(비교예 6)(Comparative Example 6)
실시예 1 에서 사용한 광 중합 개시제 (B1-1) 3 질량부 대신에, 2-하이드록시-1-[4-(2-하이드록시에톡시)-페닐]-2-메틸-1-프로판-1-온 (이하,「광 중합 개시제 (R5)」라고 약기한다) 6 질량부를 사용한 것 이외에는, 실시예 1 과 동일하게 실시하여 자외선 경화성 조성물 (R6) 을 조제하였다.Instead of 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1, 2-hydroxy-1- [4- (2-hydroxyethoxy) -phenyl] (R6) was prepared in the same manner as in Example 1, except that 6 parts by mass of a photo-polymerization initiator
(비교예 7)(Comparative Example 7)
실시예 1 에서 사용한 광 중합 개시제 (B1-1) 3 질량부 대신에, 디페닐(2,4,6-트리메틸벤조일)포스핀옥사이드 (이하,「광 중합 개시제 (R6)」이라고 약기한다) 6 질량부를 사용한 것 이외에는, 실시예 1 과 동일하게 실시하여 자외선 경화성 조성물 (R7) 을 조제하였다.(2,4,6-trimethylbenzoyl) phosphine oxide (hereinafter referred to as " photopolymerization initiator (R6) ") was used in place of 3 parts by mass of the photopolymerization initiator (B1-1) Mass part was used in place of the ultraviolet ray-curable composition (R7).
(비교예 8)(Comparative Example 8)
실시예 1 에서 사용한 광 중합 개시제 (B1-1) 3 질량부 대신에, 2-하이드록시-2-메틸-1-페닐-1-프로파논 (이하,「광 중합 개시제 (R7)」이라고 약기한다) 6 질량부를 사용한 것 이외에는, 실시예 1 과 동일하게 실시하여 자외선 경화성 조성물 (R8) 을 조제하였다.Instead of 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1, 2-hydroxy-2-methyl-1-phenyl-1-propanone ) Was used in place of 6 parts by mass of the ultraviolet ray-curable composition (R8).
(비교예 9)(Comparative Example 9)
실시예 1 에서 사용한 광 중합 개시제 (B1-1) 3 질량부 대신에, 2-하이드록시-1-{4-[4-(2-하이드록시-2-메틸-프로피오닐)-벤질]페닐}-2-메틸-1-프로파논 (이하,「광 중합 개시제 (R8)」이라고 약기한다) 6 질량부를 사용한 것 이외에는, 실시예 1 과 동일하게 실시하여 자외선 경화성 조성물 (R9) 를 조제하였다.Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} propanoate was used in place of 3 parts by mass of the photopolymerization initiator (B1-1) (R9) was prepared in the same manner as in Example 1, except that 6 parts by mass of a photopolymerization initiator (hereinafter abbreviated as " photopolymerization initiator (R8) ") was used.
(비교예 10)(Comparative Example 10)
실시예 1 에서 사용한 광 중합 개시제 (B1-1) 3 질량부 대신에, 2,4-디에틸티오크산톤 (이하,「광 중합 개시제 (R9)」라고 약기한다) 6 질량부를 사용한 것 이외에는, 실시예 1 과 동일하게 실시하여 자외선 경화성 조성물 (R10) 을 조제하였다.Except that 6 parts by mass of 2,4-diethylthioxanthone (hereinafter abbreviated as "photopolymerization initiator (R9)") was used in place of 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1, The ultraviolet curable composition (R10) was prepared in the same manner as in Example 1.
상기 실시예 2 ∼ 12 및 비교예 1 ∼ 10 에서 얻어진 자외선 경화성 조성물 (2) ∼ (12) 및 (R1) ∼ (R10) 에 대해, 실시예 1 과 동일하게 내찰상성, 밀착성, 후막 밀착성 및 도포막 착색을 평가하였다.The ultraviolet curable compositions (2) to (12) and (R1) to (R10) obtained in Examples 2 to 12 and Comparative Examples 1 to 10 were evaluated for scratch resistance, adhesion, thick film adhesion, The film coloring was evaluated.
상기 실시예 1 ∼ 12 및 비교예 1 ∼ 10 에서 사용한 자외선 경화성 조성물의 조성 및 평가 결과를 표 1 ∼ 4 에 나타낸다. 또한, 표 1 ∼ 4 중의 조성은 모두 불휘발분량으로 기재하고 있다.The compositions and evaluation results of the ultraviolet-curable compositions used in Examples 1 to 12 and Comparative Examples 1 to 10 are shown in Tables 1 to 4. In addition, the compositions in Tables 1 to 4 are described in terms of non-volatile content.
표 1 에 나타낸 평가 결과로부터, 본 발명의 자외선 경화성 조성물인 실시예 1 ∼ 12 의 것은, 그 경화 도포막 표면의 내찰상성이 우수하고, 기재인 고리형 폴리올레핀 수지 필름과의 밀착성도 높고, 또한 도포막의 착색도 보이지 않았다. 특히, 인산기를 갖는 아크릴레이트 및 실리카 미립자를 배합한 실시예 8 ∼ 10 의 자외선 경화성 조성물 (8) ∼ (10) 은, 후막에 있어서도 우수한 밀착성을 갖고 있었다.From the evaluation results shown in Table 1, it can be seen that Examples 1 to 12, which are the ultraviolet ray curable compositions of the present invention, have excellent scratch resistance on the surface of the cured coating film and have high adhesion with the cyclic polyolefin resin film as a substrate, No discoloration of the film was seen. In particular, the ultraviolet curable compositions (8) to (10) of Examples 8 to 10, in which acrylate having a phosphoric acid group and fine silica particles were blended, had excellent adhesion even in a thick film.
한편, 비교예 1 ∼ 10 의 자외선 경화성 조성물은, 본 발명에서 필수 성분으로 하고 있는 화합물을 함유하지 않는 광 중합 개시제를 사용한 예이다. 이들 자외선 경화성 조성물은, 그 경화 도포막 표면의 충분한 내찰상성, 기재인 고리형 폴리올레핀 수지 필름과의 충분한 밀착성 및 도포막의 착색이 없다는 평가를 모두 만족시키는 것이 없었다.On the other hand, the ultraviolet curable compositions of Comparative Examples 1 to 10 are examples using a photopolymerization initiator that does not contain a compound as an essential component in the present invention. These ultraviolet ray curable compositions did not satisfy both of the sufficient scratch resistance of the surface of the cured coating film, the sufficient adhesion property with the cyclic polyolefin resin film as the substrate, and the evaluation that there was no discoloration of the coating film.
Claims (8)
[화학식 1]
[Chemical Formula 1]
상기 화합물 (B1) 이 옥시페닐아세트산2-(2-옥소-2-페닐아세톡시에톡시)에틸에스테르인 고리형 올레핀 수지 필름.The method according to claim 1,
Wherein the compound (B1) is 2- (2-oxo-2-phenylacetoxyethoxy) oxyphenylacetic acid ethylester.
상기 자외선 경화성 화합물 (A) 가 다관능 (메트)아크릴레이트 (A1) 을 함유하는 것인 고리형 올레핀 수지 필름.3. The method according to claim 1 or 2,
Wherein the ultraviolet-curable compound (A) contains a polyfunctional (meth) acrylate (A1).
상기 다관능 (메트)아크릴레이트 (A1) 이 디펜타에리트리톨헥사(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 펜타에리트리톨테트라(메트)아크릴레이트 및 펜타에리트리톨트리(메트)아크릴레이트로 이루어지는 군에서 선택되는 1 종 이상의 것인 고리형 올레핀 수지 필름.The method of claim 3,
Wherein the polyfunctional (meth) acrylate (A1) is at least one selected from the group consisting of dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate and pentaerythritol tri ) Acrylate. ≪ / RTI >
상기 자외선 경화성 화합물이, 추가로 무기 충전제를 함유하는 고리형 올레핀 수지 필름.The method according to claim 1,
Wherein the ultraviolet-curable compound further contains an inorganic filler.
상기 고리형 올레핀 수지 필름의 적어도 1 면이 미리 전기적 처리가 실시되어 있고, 그 처리면에 상기 자외선 경화성 조성물을 도포하고, 그 후 자외선을 조사하여 경화 도포막으로 함으로써 얻어지는 고리형 올레핀 수지 필름.The method according to claim 1,
Wherein at least one surface of the cyclic olefin resin film is subjected to electric treatment in advance and the ultraviolet curable composition is applied to the treated surface and then irradiated with ultraviolet rays to form a cured coating film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP-P-2013-051793 | 2013-03-14 | ||
| JP2013051793 | 2013-03-14 | ||
| PCT/JP2014/055831 WO2014142006A1 (en) | 2013-03-14 | 2014-03-06 | Ultraviolet-ray-curable composition for cyclic olefin resins, and cyclic olefin resin film produced using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20150121250A KR20150121250A (en) | 2015-10-28 |
| KR101639546B1 true KR101639546B1 (en) | 2016-07-13 |
Family
ID=51536669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020157028665A KR101639546B1 (en) | 2013-03-14 | 2014-03-06 | Ultraviolet-ray-curable composition for cyclic olefin resins, and cyclic olefin resin film produced using same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5773099B2 (en) |
| KR (1) | KR101639546B1 (en) |
| CN (1) | CN105102488B (en) |
| TW (1) | TWI586767B (en) |
| WO (1) | WO2014142006A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6870222B2 (en) * | 2016-06-24 | 2021-05-12 | Dic株式会社 | Active energy ray-curable composition for cyclic olefin resin and cyclic olefin resin film using the same |
| KR102065717B1 (en) * | 2016-12-26 | 2020-01-13 | 주식회사 엘지화학 | Polarizer protecting film, polarizer plate comprising the same, liquid crystal display comprising the polarizer plate, and coating composition for polarizer protecting film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007016215A (en) * | 2005-06-09 | 2007-01-25 | Nippon Synthetic Chem Ind Co Ltd:The | Active energy ray curing type resin composition and coating agent composition |
| US20070099119A1 (en) * | 2004-09-20 | 2007-05-03 | Rach Joe F | Photosensitive composition with low yellowing under UV-light and sunlight exposure |
| JP2012173698A (en) * | 2011-02-24 | 2012-09-10 | Dic Corp | Composition for anti-reflection coating, article using the same, and anti-reflection film |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002275392A (en) | 2001-03-19 | 2002-09-25 | Dainippon Ink & Chem Inc | Uv-setting composition and resin molded item coated with the composition |
| JP2004284158A (en) | 2003-03-20 | 2004-10-14 | Dainippon Printing Co Ltd | Hard coating film |
| JP5262549B2 (en) | 2008-10-10 | 2013-08-14 | Ｊｓｒ株式会社 | Laminated film having an inorganic vapor deposition layer and method for producing the same |
-
2014
- 2014-03-06 CN CN201480014865.1A patent/CN105102488B/en active Active
- 2014-03-06 JP JP2015505435A patent/JP5773099B2/en active Active
- 2014-03-06 WO PCT/JP2014/055831 patent/WO2014142006A1/en active Application Filing
- 2014-03-06 KR KR1020157028665A patent/KR101639546B1/en active IP Right Grant
- 2014-03-13 TW TW103108894A patent/TWI586767B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070099119A1 (en) * | 2004-09-20 | 2007-05-03 | Rach Joe F | Photosensitive composition with low yellowing under UV-light and sunlight exposure |
| JP2007016215A (en) * | 2005-06-09 | 2007-01-25 | Nippon Synthetic Chem Ind Co Ltd:The | Active energy ray curing type resin composition and coating agent composition |
| JP2012173698A (en) * | 2011-02-24 | 2012-09-10 | Dic Corp | Composition for anti-reflection coating, article using the same, and anti-reflection film |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI586767B (en) | 2017-06-11 |
| JPWO2014142006A1 (en) | 2017-02-16 |
| CN105102488B (en) | 2017-03-15 |
| TW201441316A (en) | 2014-11-01 |
| KR20150121250A (en) | 2015-10-28 |
| CN105102488A (en) | 2015-11-25 |
| JP5773099B2 (en) | 2015-09-02 |
| WO2014142006A1 (en) | 2014-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4003800B2 (en) | Active energy ray-curable resin composition for film protective layer and film using the same | |
| KR101784239B1 (en) | Active energy ray-curable composition and film using same | |
| JP2014189566A (en) | Active energy ray-curable composition for cyclic olefin resin and cyclic olefin resin film using the composition | |
| KR20160037097A (en) | Ultraviolet-curable coating composition, hard coat film and process for producing the same | |
| JP6372685B2 (en) | Active energy ray-curable composition and film using the same | |
| KR20180133229A (en) | Active Energy Ray-Curable Composition for Forming Cured Film on Cyclic Olefin-Based Resin Substrate, and Hard Coat Film and Laminate Comprising Cyclic Olefin-Based Resin Substrate | |
| JP6531969B2 (en) | Active energy ray curable composition and hard coat film | |
| JP6135234B2 (en) | Active energy ray-curable composition for cyclic olefin resin and cyclic olefin resin film using the same | |
| KR101639546B1 (en) | Ultraviolet-ray-curable composition for cyclic olefin resins, and cyclic olefin resin film produced using same | |
| JPWO2018100929A1 (en) | Active energy ray-curable composition and film using the same | |
| KR20160088000A (en) | Multi-functional (meta)acryl alkoxy silane oligomer, method for preparing thereof and composition for optical film comprising the same and its use | |
| JP5892799B2 (en) | Urethane (meth) acrylate that forms a cured product having elongation and excellent scratch resistance, and a photocurable resin composition containing the same | |
| JP7140187B2 (en) | Active energy ray-curable composition and film using the same | |
| CN108350204B (en) | Cyclic olefin resin film | |
| JP6870222B2 (en) | Active energy ray-curable composition for cyclic olefin resin and cyclic olefin resin film using the same | |
| JP6651821B2 (en) | Method of manufacturing hard coat film, method of manufacturing polarizing plate including hard coat film, method of manufacturing transmission type liquid crystal display including hard coat film | |
| JP2022085047A (en) | Active energy ray-curable hard coat agent, hard coat layer, optical member, and electronic device | |
| CN117777773A (en) | Active energy ray-curable composition, cured product, and film | |
| JP2023173047A (en) | Active energy ray curable hard coat agent, hard coat layer, optical member, and electronic device | |
| JP2022180796A (en) | Active energy ray-curable composition, cured product and film | |
| JP2007291217A (en) | Conductive hard coat resin composition for film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| A302 | Request for accelerated examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20190617 Year of fee payment: 4 |