TW201441316A - 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
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- TW201441316A TW201441316A TW103108894A TW103108894A TW201441316A TW 201441316 A TW201441316 A TW 201441316A TW 103108894 A TW103108894 A TW 103108894A TW 103108894 A TW103108894 A TW 103108894A TW 201441316 A TW201441316 A TW 201441316A
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- TW
- Taiwan
- Prior art keywords
- acrylate
- meth
- cyclic olefin
- curable composition
- ultraviolet curable
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 88
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 64
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 63
- 239000011248 coating agent Substances 0.000 claims abstract description 49
- 238000000576 coating method Methods 0.000 claims abstract description 49
- 239000003999 initiator Substances 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 135
- 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 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011256 inorganic filler Substances 0.000 claims description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000002845 discoloration Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 91
- -1 automobiles Substances 0.000 description 27
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 24
- 235000019354 vermiculite Nutrition 0.000 description 23
- 239000010455 vermiculite Substances 0.000 description 23
- 229910052902 vermiculite Inorganic materials 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
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000010419 fine particle Substances 0.000 description 13
- 125000001931 aliphatic group Chemical group 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- WVSFUMAHZBOQGJ-UHFFFAOYSA-N phosphono 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOP(O)(O)=O WVSFUMAHZBOQGJ-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 6
- YSGPDJCRZNUFBU-UHFFFAOYSA-N 2-methylidenepentanenitrile Chemical group CCCC(=C)C#N YSGPDJCRZNUFBU-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 239000012788 optical film Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 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
- 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
- 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
- 238000005299 abrasion Methods 0.000 description 3
- 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 3
- 238000003851 corona treatment Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 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 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 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
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-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
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 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
- 229960002130 benzoin Drugs 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 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
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-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
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-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
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
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- 125000001424 substituent group Chemical group 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
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- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical compound 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
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-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
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- OHTRJOZKRSVAOX-UHFFFAOYSA-N 1,3-diisocyanato-2-methylcyclohexane Chemical compound CC1C(N=C=O)CCCC1N=C=O OHTRJOZKRSVAOX-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
- VYMSWGOFSKMMCE-UHFFFAOYSA-N 10-butyl-2-chloroacridin-9-one Chemical compound ClC1=CC=C2N(CCCC)C3=CC=CC=C3C(=O)C2=C1 VYMSWGOFSKMMCE-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
- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-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
- 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
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- UKQJDWBNQNAJHB-UHFFFAOYSA-N 2-hydroxyethyl formate Chemical compound OCCOC=O UKQJDWBNQNAJHB-UHFFFAOYSA-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
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-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
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- 125000004864 4-thiomethylphenyl group Chemical group 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
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- PAJKBYQWGBVBPE-UHFFFAOYSA-N ethene;terephthalic acid Chemical compound C=C.C=C.C=C.OC(=O)C1=CC=C(C(O)=O)C=C1 PAJKBYQWGBVBPE-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
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- 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
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VSQYNPJPULBZKU-UHFFFAOYSA-N mercury xenon Chemical compound [Xe].[Hg] VSQYNPJPULBZKU-UHFFFAOYSA-N 0.000 description 1
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- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 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
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- 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
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 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
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
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- OJNNAJJFLWBPRS-UHFFFAOYSA-N phenyl-[(2,4,6-trimethylphenyl)methyl]-[(2,4,6-trimethylphenyl)methylidene]phosphanium Chemical compound CC1=C(C=P(C2=CC=CC=C2)=CC2=C(C=C(C=C2C)C)C)C(=CC(=C1)C)C OJNNAJJFLWBPRS-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 230000001235 sensitizing effect Effects 0.000 description 1
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- 239000004332 silver Substances 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
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
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- 239000004034 viscosity adjusting agent Substances 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
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Paints Or Removers (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Polymerisation Methods In General (AREA)
- Materials Engineering (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本發明關於環狀烯烴樹脂用紫外線硬化性組成物及使用其之環狀烯烴樹脂薄膜，該環狀烯烴樹脂用紫外線硬化性組成物係可藉由塗覆於環狀烯烴樹脂之表面、使其硬化，而形成包含耐擦傷性高、與基底之密著性優異、著色少之硬化塗膜的硬塗層。 The present invention relates to an ultraviolet curable composition for a cyclic olefin resin and a cyclic olefin resin film using the same, and the ultraviolet curable composition for a cyclic olefin resin can be applied to the surface of a cyclic olefin resin. After hardening, a hard coat layer containing a cured coating film having high scratch resistance, excellent adhesion to a substrate, and little coloration is formed.
環狀烯烴樹脂薄膜係透明性、低雙折射、低吸濕性、耐熱性、電絕緣性、耐藥品性等優異，而被廣泛地用於光學構件、醫療、包裝薄膜、汽車、半導體用途等。尤其是光學構件方面，正探討配合在液晶顯示器、觸控面板用途之單元的多樣化，而使用透明性高、低吸濕性優異的環狀烯烴樹脂薄膜來取代以往所使用之聚對苯二甲酸乙二酯(PET)、三乙醯纖維素(TAC)等塑膠薄膜。 The cyclic olefin resin film is excellent in transparency, low birefringence, low moisture absorption, heat resistance, electrical insulation, chemical resistance, etc., and is widely used for optical members, medical, packaging films, automobiles, semiconductors, and the like. . In particular, in the case of optical components, we are considering the diversification of units for use in liquid crystal displays and touch panels, and using a cyclic olefin resin film having high transparency and low moisture absorption to replace the polyphenylene terephthalate used in the past. Plastic film such as ethylene glycol formate (PET) or triethylene terephthalate (TAC).
又，由於環狀烯烴樹脂薄膜其表面硬度不足，而有在加工時損傷之虞，為提升耐磨耗性、耐擦傷性，正探討在其表面上設置包含紫外線硬化性組成物之硬化塗膜的硬塗層等保護層。然而，由於環狀烯烴樹脂薄膜其主構造為脂環構造，因而薄膜表面的極性低，水接觸角則高為90°左右之故，在塗覆紫外線硬化性組成物的 情況，塗材不容易擴散塗布，而有環狀烯烴樹脂薄膜表面與硬塗層之間的密著性低等問題。 In addition, since the surface hardness of the cyclic olefin resin film is insufficient, and there is damage during processing, in order to improve abrasion resistance and scratch resistance, it is considered to provide a hard coating film containing an ultraviolet curable composition on the surface thereof. A protective layer such as a hard coat layer. However, since the cyclic olefin resin film has a main structure of an alicyclic structure, the surface of the film has a low polarity, and the water contact angle is as high as about 90°, and the ultraviolet curable composition is coated. In the case where the coating material is not easily diffused and coated, there is a problem that the adhesion between the surface of the cyclic olefin resin film and the hard coat layer is low.
作為提升環狀烯烴樹脂薄膜表面與硬塗層之間的密著性之方法，有提議在環狀烯烴樹脂薄膜表面，設置以具有極性基之改性烯烴系樹脂作為主成分之底塗層後，塗覆電離放射線硬化型樹脂、使其硬化之方法(例如，參照專利文獻1。)。此方法係可提升環狀烯烴樹脂薄膜表面與硬塗層之間的密著性，但是也有增加了塗覆、乾燥底塗層之步驟，進而發生產率降低、成本提高之問題。 As a method of improving the adhesion between the surface of the cyclic olefin resin film and the hard coat layer, it is proposed to provide a primer layer having a polar group-modified olefin resin as a main component on the surface of the cyclic olefin resin film. A method of applying an ionizing radiation-curable resin and hardening it (for example, refer to Patent Document 1). This method can improve the adhesion between the surface of the cyclic olefin resin film and the hard coat layer, but also increases the steps of coating and drying the undercoat layer, thereby causing a problem of reduced yield and increased cost.
又，作為不設置底塗層而使硬塗層密著於環狀烯烴樹脂薄膜表面之方法，有提議使用含有具脂環構造之(甲基)丙烯酸酯的硬化性組成物之硬化塗膜作為硬塗層(例如，參照專利文獻2。)。在使用此硬化性組成物的情況，為了要成為與環狀烯烴樹脂薄膜表面之密著性充分者，而有必要提高具脂環構造之(甲基)丙烯酸酯的比率。然而，若提高具脂環構造之(甲基)丙烯酸酯的比率，則會有硬化塗膜的交聯密度降低，硬化塗膜表面的耐擦傷性變得不足之問題。 Further, as a method of adhering the hard coat layer to the surface of the cyclic olefin resin film without providing the undercoat layer, it is proposed to use a hard coat film containing a curable composition of a (meth) acrylate having an alicyclic structure as a method. Hard coat layer (for example, refer to Patent Document 2). In the case of using the curable composition, in order to obtain sufficient adhesion to the surface of the cyclic olefin resin film, it is necessary to increase the ratio of the (meth) acrylate having an alicyclic structure. However, when the ratio of the (meth) acrylate having an alicyclic structure is increased, the crosslinking density of the cured coating film is lowered, and the scratch resistance of the surface of the cured coating film is insufficient.
進一步地，作為提升紫外線硬化性組成物之對於環狀烯烴樹脂成形品的密著性之方法，有提議在添加於紫外線硬化性組成物的光聚合起始劑中使用具有二苯甲酮構造之4-苯甲醯基-4-甲基二硫化物(例如，參照專利文獻3。)。然而，此紫外線硬化性組成物有硬化塗膜著色成為黃色之問題。 Further, as a method of improving the adhesion to the cyclic olefin resin molded article of the ultraviolet curable composition, it is proposed to use a benzophenone structure in the photopolymerization initiator added to the ultraviolet curable composition. 4-benzylidene-4-methyl disulfide (for example, refer to Patent Document 3). However, this ultraviolet curable composition has a problem that the cured coating film is colored yellow.
於是，謀求一種可使環狀烯烴樹脂薄膜表面為高耐擦傷性、可形成不需底塗層而與環狀烯烴樹脂薄膜表面之間有優異密著性的硬化塗膜、更進而硬化塗膜不會著色的紫外線硬化性組成物。 Then, a hardened coating film having a high abrasion resistance on the surface of the cyclic olefin resin film, an excellent adhesion between the surface of the cyclic olefin resin film and the surface of the cyclic olefin resin film, and a hardened coating film can be formed. An ultraviolet curable composition that does not stain.
[專利文獻1]日本特開2004-284158號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-284158
[專利文獻2]日本特開2010-89458號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-89458
[專利文獻3]日本特開2002-275392號公報 [Patent Document 3] Japanese Laid-Open Patent Publication No. 2002-275392
本發明欲解決之課題為提供一種環狀烯烴樹脂用紫外線硬化性組成物及使用其之環狀烯烴樹脂薄膜，該環狀烯烴樹脂用紫外線硬化性組成物係可藉由塗覆於環狀烯烴樹脂之表面、使其硬化，而形成包含耐擦傷性高、與環狀烯烴樹脂之密著性優異、著色少之硬化塗膜的硬塗層。 The object of the present invention is to provide an ultraviolet curable composition for a cyclic olefin resin and a cyclic olefin resin film using the same, which can be applied to a cyclic olefin by using an ultraviolet curable composition. The surface of the resin is hardened to form a hard coat layer containing a cured coating film having high scratch resistance, excellent adhesion to a cyclic olefin resin, and little coloration.
本發明人等為解決上述課題，進行鑽研探討之結果，發現了藉由在用於紫外線硬化性組成物之光聚合起始劑中，使用在1分子中具有2個以上特定構造之化合物，係能夠形成與環狀烯烴樹脂薄膜等環狀烯烴樹脂成形品表面之密著性優異的硬化塗膜，再者此硬化塗膜的表面具有高耐擦傷性、著色亦少，因而完成本發明。 In order to solve the above problems, the inventors of the present invention have found that a compound having two or more specific structures in one molecule is used in a photopolymerization initiator for an ultraviolet curable composition. The cured coating film having excellent adhesion to the surface of the cyclic olefin resin molded article such as the cyclic olefin resin film can be formed, and the surface of the cured coating film has high scratch resistance and less coloration, and thus the present invention has been completed.
亦即，本發明係關於一種環狀烯烴樹脂用紫外線硬化性組成物及使用其之環狀烯烴樹脂薄膜，該環狀烯烴樹脂用紫外線硬化性組成物之特徵為含有紫外線硬化性化合物(A)及作為光聚合起始劑(B)而在1分子中具有2個以上之下式(1)所表示的基之化合物，當作其必要成分。 In other words, the present invention relates to an ultraviolet curable composition for a cyclic olefin resin and a cyclic olefin resin film using the same, and the ultraviolet curable composition for a cyclic olefin resin is characterized by containing an ultraviolet curable compound (A). And a compound which has two or more groups represented by the formula (1) in one molecule as a photopolymerization initiator (B), and is an essential component.
本發明之紫外線硬化性組成物係可對環狀烯烴樹脂成形品表面賦予高耐擦傷性，可獲得與環狀烯烴樹脂成形品之密著性優異、著色亦少的硬化塗膜。因此，本發明之紫外線硬化性組成物係可用來作為在各種環狀烯烴樹脂成形品，尤其是環狀烯烴樹脂薄膜表面，形成具有高耐擦傷性之硬塗層的材料。又，具有包含本發明之紫外線硬化性組成物之硬化塗膜的硬塗層之環狀烯烴樹脂薄膜，可用來作為在液晶顯示器或觸控面板用途所使用的光學薄膜。 The ultraviolet curable composition of the present invention can impart high scratch resistance to the surface of the cyclic olefin resin molded article, and can obtain a cured coating film which is excellent in adhesion to the cyclic olefin resin molded article and has 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 on the surface of a cyclic olefin resin film. Further, the cyclic olefin resin film having a hard coat layer containing 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.
本發明之紫外線硬化性組成物，係含有紫外 線硬化性化合物(A)及作為光聚合起始劑(B)之在1分子中具有2個以上之下式(1)所表示的基之化合物。 The ultraviolet curable composition of the present invention contains ultraviolet rays The linear curable compound (A) and a compound having two or more groups represented by the formula (1) in one molecule as the photopolymerization initiator (B).
作為前述紫外線硬化性化合物(A)，可舉出例如，多官能(甲基)丙烯酸酯(A1)、胺基甲酸酯(甲基)丙烯酸酯(A2)等。此等可單獨使用，亦可併用2種以上。 The ultraviolet curable compound (A) may, for example, be a polyfunctional (meth) acrylate (A1) or a urethane (meth) acrylate (A2). These may be used alone or in combination of two or more.
又，在本發明中「(甲基)丙烯酸酯」係指丙烯酸酯與甲基丙烯酸酯之一者或兩者，「(丙基)丙烯醯基」係指丙烯醯基與甲基丙烯醯基之一者或兩者。 Further, in the present invention, "(meth)acrylate" means either or both of an acrylate and a methacrylate, and "(propyl)acryloyl group" means a propylene group and a methacryl group. One or both.
前述多官能(甲基)丙烯酸酯(A1)是在1分子中具有2個以上之(丙基)丙烯醯基的化合物。作為此多官能(甲基)丙烯酸酯(a1)之具體例，可舉出1,4-丁二醇二(甲基)丙烯酸酯、3-甲基-1,5-戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、2-甲基-1,8-辛二醇二(甲基)丙烯酸酯、2-丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯等2元醇的二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、參(2-羥基乙基)三聚異氰酸酯的二(甲基)丙烯酸酯、在新戊二醇1莫耳加成4莫耳以上之 環氧乙烷或環氧丙烷而得的二醇之二(甲基)丙烯酸酯、在雙酚A 1莫耳加成2莫耳之環氧乙烷或環氧丙烷而得的二醇之二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷改性三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷改性三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、參(2-(甲基)丙烯醯基氧基乙基)三聚異氰酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇三(甲基)丙烯酸酯、二新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等。此等多官能(甲基)丙烯酸酯(A1)可單獨使用，亦可併用2種以上。又，此等多官能(甲基)丙烯酸酯(A1)之中，由可提升本發明之紫外線硬化性組成物之硬化塗膜的耐擦傷性而言，較佳為二新戊四醇六(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯。 The polyfunctional (meth) acrylate (A1) is a compound having two or more (propyl) acryl fluorenyl groups in one molecule. Specific examples of the polyfunctional (meth) acrylate (a1) include 1,4-butanediol di(meth)acrylate and 3-methyl-1,5-pentanediol di(a). Acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylic acid Ester, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, etc. Methyl acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, di(meth) acrylate of bis(2-hydroxyethyl) trimer isocyanate, in new Pentylene glycol 1 molar addition to 4 moles a di(meth)acrylate of a diol derived from ethylene oxide or propylene oxide, a diol derived from a bisphenol A 1 molar addition of 2 moles of ethylene oxide or propylene oxide (Meth) acrylate, trimethylolpropane tri(meth) acrylate, ethylene oxide modified trimethylolpropane tri(meth) acrylate, propylene oxide modified trimethylolpropane (Meth) acrylate, di-trimethylolpropane tri(meth) acrylate, di-trimethylolpropane tetra(meth) acrylate, gin(2-(methyl) propylene decyloxy Ethyl)trimeric isocyanate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol IV (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. Further, among these polyfunctional (meth) acrylates (A1), dinopentaerythritol is preferred from the scratch resistance of the cured coating film which can improve the ultraviolet curable composition of the present invention. Methyl) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, neopentyl alcohol tri (meth) acrylate.
前述胺基甲酸酯(甲基)丙烯酸酯(A2)為使聚異氰酸酯(a2-1)與具有羥基之(甲基)丙烯酸酯(a2-2)反應而得者。 The urethane (meth) acrylate (A2) is obtained by reacting a polyisocyanate (a2-1) with a (meth) acrylate (a2-2) having a hydroxyl group.
作為前述聚異氰酸酯(a2-1)，可舉出脂肪族聚異氰酸酯與芳香族聚異氰酸酯，但由可更減低本發明之紫外線硬化性組成物之硬化塗膜的著色而言，較佳為脂肪族聚異氰酸酯。 Examples of the polyisocyanate (a2-1) include an aliphatic polyisocyanate and an aromatic polyisocyanate. However, the color of the cured coating film which can further reduce the ultraviolet curable composition of the present invention is preferably aliphatic. Polyisocyanate.
前述脂肪族聚異氰酸酯其除了異氰酸酯基以外之部位係由脂肪族烴所構成之化合物。作為此脂肪族 聚異氰酸酯之具體例，可舉出六亞甲基二異氰酸酯、離胺酸二異氰酸酯、離胺酸三異氰酸酯等脂肪族聚異氰酸酯；降莰烷二異氰酸酯、異佛酮二異氰酸酯、亞甲基雙(4-環己基異氰酸酯)、1,3-雙(異氰酸基甲基)環己烷、2-甲基-1,3-二異氰酸基環己烷、2-甲基-1,5-二異氰酸基環己烷等脂環式聚異氰酸酯等。又，亦可將前述脂肪族聚異氰酸酯或脂環式聚異氰酸酯3聚化而成之3聚物作為前述脂肪族聚異氰酸酯使用。又，此等脂肪族聚異氰酸酯可單獨使用，亦可併用2種以上。 The aliphatic polyisocyanate is a compound composed of an aliphatic hydrocarbon other than the isocyanate group. As this aliphatic Specific examples of the polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, isocyanate diisocyanate, and isocyanuric acid triisocyanate; norbornane diisocyanate, isophorone diisocyanate, and methylene bis ( 4-cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5 An alicyclic polyisocyanate such as diisocyanylcyclohexane. Further, a terpolymer obtained by polymerizing the aliphatic polyisocyanate or the alicyclic polyisocyanate 3 may be used as the aliphatic polyisocyanate. Further, these aliphatic polyisocyanates may be used singly or in combination of two or more.
前述脂肪族聚異氰酸酯之中，為使塗膜之耐擦傷性提升，在脂肪族聚異氰酸酯中，較佳為直鏈脂肪族烴之二異氰酸酯的六亞甲基二異氰酸酯、脂環式二異氰酸酯的降莰烷二異氰酸酯、異佛酮二異氰酸酯。 Among the aliphatic polyisocyanates, in order to improve the scratch resistance of the coating film, among the aliphatic polyisocyanates, hexamethylene diisocyanate or alicyclic diisocyanate of a diisocyanate of a linear aliphatic hydrocarbon is preferred. Decane diisocyanate, isophorone diisocyanate.
前述(甲基)丙烯酸酯(a2-2)為具有羥基與(丙基)丙烯醯基之化合物。作為此(甲基)丙烯酸酯(a2-2)之具體例，可舉出2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、2-羥基丁基(甲基)丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯、1,5-戊二醇單(甲基)丙烯酸酯、1,6-己二醇單(甲基)丙烯酸酯、新戊二醇單(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇單(甲基)丙烯酸酯等2元醇的單(甲基)丙烯酸酯；三羥甲基丙烷二(甲基)丙烯酸酯、環氧乙烷(EO)改性三羥甲基丙烷(甲基)丙烯酸酯、環氧丙烷(PO)改性三羥甲基丙烷二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、雙(2-(甲基)丙烯醯基氧基乙基)羥基乙基三聚異氰酸酯等3元醇的單或二(甲基)丙烯酸酯、或是具 有將此等之醇性羥基的一部分以ε-己內酯改性之羥基的單及二(甲基)丙烯酸酯；新戊四醇三(甲基)丙烯酸酯、二-三羥甲基丙烷三(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯等具有1官能羥基與3官能以上(丙基)丙烯醯基的化合物、或是具有將該化合物進一步以ε-己內酯改性之羥基的多官能(甲基)丙烯酸酯；二丙二醇單(甲基)丙烯酸酯、二乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯等具有氧基伸烷基鏈的(甲基)丙烯酸酯；聚乙二醇-聚丙二醇單(甲基)丙烯酸酯、聚氧基伸丁基-聚氧基伸丙基單(甲基)丙烯酸酯等具有嵌段構造之氧基伸烷基鏈的(甲基)丙烯酸酯；聚(乙二醇-伸丁二醇)單(甲基)丙烯酸酯、聚(丙二醇-伸丁二醇)單(甲基)丙烯酸酯等具有無規構造之氧基伸烷基鏈的(甲基)丙烯酸酯等。此等(甲基)丙烯酸酯(a2-2)可單獨使用，亦可併用2種以上。 The aforementioned (meth) acrylate (a2-2) is a compound having a hydroxyl group and a (propyl) acrylonitrile group. Specific examples of the (meth) acrylate (a2-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxy butyl ( Methyl) acrylate, 4-hydroxybutyl (meth) acrylate, 1,5-pentanediol mono(meth) acrylate, 1,6-hexanediol mono(meth) acrylate, neopentyl Mono(meth)acrylate of divalent alcohol such as diol mono(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol mono(meth)acrylate; trimethylolpropane di(meth)acrylic acid Ester, ethylene oxide (EO) modified trimethylolpropane (meth) acrylate, propylene oxide (PO) modified trimethylolpropane di(meth) acrylate, glycerol di(methyl) a mono- or di-(meth) acrylate of a trihydric alcohol such as acrylate or bis(2-(methyl) propylene decyloxyethyl) hydroxyethyl tripolyisocyanate, or Mono- and di(meth)acrylates having a hydroxyl group in which a part of the alcoholic hydroxyl group is modified with ε-caprolactone; neopentyl alcohol tri(meth)acrylate, di-trimethylolpropane a compound having a monofunctional hydroxyl group and a trifunctional or higher (propyl) acrylonitrile group such as tris(meth)acrylate or dipentaerythritol penta(meth)acrylate, or having the compound further ε-hexyl Polyfunctional (meth) acrylate of lactone-modified hydroxyl group; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene a (meth) acrylate having an alkylene chain such as a diol mono(meth)acrylate; a polyethylene glycol-polypropylene glycol mono(meth)acrylate, a polyoxybutylene-polyoxypropyl propyl group (meth) acrylate having a block structure of an alkylene chain such as mono(meth)acrylate; poly(ethylene glycol-butanediol) mono(meth)acrylate, poly(propylene glycol-extension) (Meth) acrylate having a random structure of an alkylene chain such as a mono(meth)acrylate such as a mono(meth)acrylate. These (meth) acrylates (a2-2) may be used alone or in combination of two or more.
前述胺基甲酸酯(甲基)丙烯酸酯(A2)之中，因可提升本發明之紫外線硬化性組成物的硬化塗膜之耐擦傷性，較佳為在1分子中具有4個以上(丙基)丙烯醯基者。為使前述胺基甲酸酯(甲基)丙烯酸酯(A2)成為在1分子中具有4個以上(丙基)丙烯醯基者，作為前述(甲基)丙烯酸酯(a2-2)，較佳為具有2個以上(丙基)丙烯醯基者。作為此種(甲基)丙烯酸酯(a2-2)，可舉出例如，三羥甲基丙烷二(甲基)丙烯酸酯、環氧乙烷改性三羥甲基丙烷二(甲基)丙烯酸酯、環氧丙烷改性三羥甲基丙烷二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、雙(2-(甲基)丙烯醯基 氧基乙基)羥基乙基三聚異氰酸酯、新戊四醇三(甲基)丙烯酸酯、二-三羥甲基丙烷三(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯等。此等(甲基)丙烯酸酯(a2-2)相對於前述脂肪族聚異氰酸酯(a1)之1種而言，可使用1種，亦可併用2種以上。又，此等(甲基)丙烯酸酯(a2-2)之中，新戊四醇三(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯因可提升耐擦傷性而較佳。 Among the urethane (meth) acrylates (A2), it is preferable to have four or more in one molecule because the scratch resistance of the cured coating film of the ultraviolet curable composition of the present invention can be improved ( Propyl) acrylonitrile. In order to make the urethane (meth) acrylate (A2) have four or more (propyl) acrylonitrile groups in one molecule, as the (meth) acrylate (a2-2), It is preferred to have two or more (propyl) acrylonitrile groups. Examples of such a (meth) acrylate (a2-2) include trimethylolpropane di(meth)acrylate and ethylene oxide-modified trimethylolpropane di(meth)acrylic acid. Ester, propylene oxide modified trimethylolpropane di(meth) acrylate, glycerol di(meth) acrylate, bis(2-(methyl) propylene fluorenyl Oxyethyl)hydroxyethyltrimeric isocyanate, pentaerythritol tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylic acid Ester and the like. One type of these (meth) acrylates (a2-2) may be used alone or two or more types may be used in combination with one type of the above-mentioned aliphatic polyisocyanate (a1). Further, among these (meth) acrylates (a2-2), pentaerythritol tri(meth) acrylate and dipentaerythritol penta (meth) acrylate are improved in abrasion resistance. good.
前述聚異氰酸酯(a2-1)與前述(甲基)丙烯酸酯(a2-2)之反應可藉由常法之胺基甲酸酯化反應而進行。又，為了促進胺基甲酸酯化反應之進行，較佳為在胺基甲酸酯化觸媒存在下進行胺基甲酸酯化反應。作為前述胺基甲酸酯化觸媒，可舉出例如，吡啶、吡咯、三乙基胺、二乙基胺、二丁基胺等胺化合物；三苯基膦、三乙基膦等磷化合物；二丁基錫二月桂酸酯、辛基錫三月桂酸酯、辛基錫二乙酸酯、二乙酸二丁基錫、辛基酸錫等有機錫化合物、辛基酸鋅等有機鋅化合物等。 The reaction of the above polyisocyanate (a2-1) with the above (meth) acrylate (a2-2) can be carried out by a conventional urethanation reaction. Further, in order to promote the progress of the urethanization reaction, it is preferred to carry out the urethanization reaction in the presence of a urethanization catalyst. Examples of the urethane-based catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; and phosphorus compounds such as triphenylphosphine and triethylphosphine. An organotin compound such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate or tin octylate, or an organic zinc compound such as zinc octylate.
又，視需要，作為上述多官能(甲基)丙烯酸酯(A1)、胺基甲酸酯(甲基)丙烯酸酯(A2)以外之紫外線硬化性化合物(A)，可使用環氧基(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯等較高分子量的(甲基)丙烯酸酯(A3)。作為前述環氧基(甲基)丙烯酸酯，可舉出例如，藉由在雙酚型環氧樹脂、酚醛型環氧樹脂、聚環氧丙基甲基丙烯酸酯等，使(甲基)丙烯酸反應且酯化而得者。又，作為前述聚酯(甲基)丙烯酸酯，可舉出例如，藉由在將多元羧酸與多元醇聚縮合而得之兩末 端為羥基的聚酯、使(甲基)丙烯酸反應且酯化而得者；或是藉由在將環氧烷加成於多元羧酸者、使(甲基)丙烯酸反應且酯化而得者。再者，作為前述聚醚(甲基)丙烯酸酯，可舉出例如，藉由在聚醚聚醇使(甲基)丙烯酸反應且酯化而得者。又，前述(甲基)丙烯酸酯(A3)可單獨使用，亦可併用2種以上。 Further, if necessary, an epoxy group (A) can be used as the ultraviolet curable compound (A) other than the polyfunctional (meth)acrylate (A1) or the urethane (meth)acrylate (A2). Higher molecular weight (meth) acrylate (A3) such as acrylate, polyester (meth) acrylate, or polyether (meth) acrylate. Examples of the epoxy group (meth) acrylate include (meth)acrylic acid by a bisphenol epoxy resin, a novolac epoxy resin, a polyepoxypropyl methacrylate, or the like. Reacted and esterified. Further, the polyester (meth) acrylate may, for example, be obtained by polycondensation of a polyvalent carboxylic acid and a polyhydric alcohol. a polyester having a hydroxyl group at the end, which is obtained by reacting and esterifying (meth)acrylic acid; or by reacting and esterifying (meth)acrylic acid by adding an alkylene oxide to a polycarboxylic acid; By. In addition, as the polyether (meth) acrylate, for example, a (meth)acrylic acid is reacted and esterified with a polyether polyol. Further, the (meth) acrylate (A3) may be used singly or in combination of two or more.
進一步地，本發明之紫外線硬化性組成物中，除上述作為紫外線硬化性化合物(A)所例示的(A1)~(A3)以外，若摻合具有磷酸基之(甲基)丙烯酸酯(A4)，則因可更提升對基材之密著性而較佳。前述具有磷酸基之(甲基)丙烯酸酯(A4)是在1分子中具有至少1個磷酸基之(甲基)丙烯酸酯。作為此具有磷酸基之(甲基)丙烯酸酯(A4)，可舉出例如，磷酸(甲基)丙烯醯基氧基乙酯、磷酸二(甲基)丙烯醯基氧基乙酯、磷酸三(甲基)丙烯醯基氧基乙酯、己內酯改性磷酸(甲基)丙烯醯基氧基乙酯等，亦可使用在1分子中具有2個以上(丙基)丙烯醯基之化合物。又，此等具有磷酸基之(甲基)丙烯酸酯(A4)可單獨使用，亦可併用2種以上。 Further, in the ultraviolet curable composition of the present invention, in addition to (A1) to (A3) exemplified as the ultraviolet curable compound (A), a (meth) acrylate having a phosphate group (A4) is blended. Therefore, it is preferable because the adhesion to the substrate can be further improved. The (meth) acrylate (A4) having a phosphoric acid group is a (meth) acrylate having at least one phosphate group in one molecule. Examples of the (meth) acrylate (A4) having a phosphoric acid group include, for example, (meth) acryloyloxyethyl phosphate, di(methyl) propylene decyloxyethyl phosphate, and phosphoric acid (Methyl) propylene decyloxyethyl ester, caprolactone-modified phosphoric acid (meth) propylene decyloxyethyl ester, etc., and it is also possible to use two or more (propyl) acryl fluorenyl groups in one molecule. Compound. Further, these (meth) acrylates (A4) having a phosphoric acid group may be used singly or in combination of two or more kinds.
在本發明之紫外線硬化性組成物摻合前述具有磷酸基之(甲基)丙烯酸酯(A4)時其摻合量，從可更提升對基材之密著性、可更提升硬化塗膜表面之耐擦傷性而言，於前述紫外線硬化性化合物(A)中較佳為0.1~30質量%，更佳為0.5~20質量%。 When the ultraviolet curable composition of the present invention is blended with the (meth) acrylate (A4) having a phosphoric acid group, the blending amount thereof can further enhance the adhesion to the substrate, and the surface of the hardened coating film can be further improved. The scratch resistance is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 20% by mass, based on the ultraviolet curable compound (A).
本發明之紫外線硬化性組成物係作為必要成分，而在含有上述紫外線硬化性化合物(A)之同時，含有 作為光聚合起始劑(B)之在1分子中具有2個以上之下式(1)所表示的基之化合物(B1)。又，下式(1)中的苯基亦可為具有烷基、烷氧基、鹵基等之置換基者。 The ultraviolet curable composition of the present invention contains, as an essential component, the ultraviolet curable compound (A), and contains The compound (B1) having two or more groups represented by the following formula (1) in one molecule, as the photopolymerization initiator (B). Further, the phenyl group in the following formula (1) may be a substituent having a substituent such as an alkyl group, an alkoxy group or a halogen group.
藉由將前述化合物(B1)作為光聚合起始劑使用，本發明之紫外線硬化性組成物的硬化塗膜係變得耐擦傷性高、與環狀烯烴樹脂之密著性優異、著色少，而可形成優異之硬塗層。 When the compound (B1) is used as a photopolymerization initiator, the cured coating film of the ultraviolet curable composition of the present invention has high scratch resistance, excellent adhesion to a cyclic olefin resin, and less coloration. An excellent hard coat layer can be formed.
作為前述化合物(B1)，可舉出例如，下式(2)所表示之氧基苯基乙酸2-(2-側氧-2-苯基乙醯氧基乙氧基)乙基酯等。 The compound (B1), for example, 2-(2-oxo-2-phenylethenyloxyethoxy)ethyl oxyphenylacetate represented by the following formula (2).
作為本發明之紫外線硬化性組成物中所含的前述光聚合起始劑(B)，將前述化合物(B1)作為必要成分，但可使用其以外的光聚合起始劑(B2)。作為前述光聚合起始劑(B2)，可舉出例如，二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、低聚{2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮}、苄基二甲基縮酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、4-(2-羥基乙氧基)苯基-(2- 羥基-2-丙基)酮、1-羥基環己基苯基酮、2-甲基-2-啉基(4-硫甲基苯基)丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-啉基苯基)-丁酮等苯乙酮系化合物；苯偶姻、苯偶姻甲基醚、苯偶姻異丙基醚等苯偶姻系化合物；2,4,6-三甲基苯偶姻二苯基膦氧化物、雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物等醯基膦氧化物系化合物；苄基(二苯甲醯基)、甲基苯基乙醛醯基酯、氧基苯基乙酸2-(2-羥基乙氧基)乙基酯等苄基系化合物；二苯甲酮、o-苯甲醯基安息香酸甲基-4-苯基二苯甲酮、4,4’-二氯二苯甲酮、羥基二苯甲酮、4-苯甲醯基-4’-甲基-二苯硫醚、丙烯醯化二苯甲酮、3,3’,4,4’-四(t-丁基過氧基羰基)二苯甲酮、3,3’-二甲基-4-甲氧基二苯甲酮、2,4,6-三甲基二苯甲酮、4-甲基二苯甲酮等二苯甲酮系化合物；2-異丙基9-氧硫、2,4-二甲基9-氧硫、2,4-二乙基9-氧硫、2,4-二氯9-氧硫等9-氧硫系化合物；米其勒酮、4,4’-二乙基胺基二苯甲酮等胺基二苯甲酮系化合物；10-丁基-2-氯吖啶酮、2-乙基蒽醌、9,10-菲醌、樟腦醌、1-[4-(4-苯甲醯基苯基磺醯基)苯基]-2-甲基-2-(4-甲基苯基碸基)丙烷-1-酮等。 The photopolymerization initiator (B) contained in the ultraviolet curable composition of the present invention contains the compound (B1) as an essential component, but a photopolymerization initiator (B2) other than the above may be used. The photopolymerization initiator (B2) may, for example, be diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, or oligomeric {2-hydroxy- 2-methyl-1-[4-(1-methylvinyl)phenyl]acetone}, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2- Methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- Phytyl (4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Acetophenone-based compound such as phenylphenyl)-butanone; benzoin-based compound such as benzoin, benzoin methyl ether, benzoin isopropyl ether; 2,4,6-trimethylbenzene a mercaptophosphine oxide compound such as diphenylphosphine oxide or bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide; benzyl (diphenylmethylhydrazine), a benzyl compound such as methylphenylacetaldehyde decyl ester or 2-(2-hydroxyethoxy)ethyl oxyphenylacetate; benzophenone, o-benzylidene benzoic acid methyl- 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide, propylene deuterated diphenyl Methyl ketone, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2, a benzophenone compound such as 4,6-trimethylbenzophenone or 4-methylbenzophenone; 2-isopropyl 9-oxosulfur 2,4-dimethyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 9-oxosulfur Compound; amino benzophenone-based compound such as rice ketone, 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylhydrazine , 9,10-phenanthrenequinone, camphorquinone, 1-[4-(4-benzylidenephenylsulfonyl)phenyl]-2-methyl-2-(4-methylphenylindenyl) Propane-1-one and the like.
本發明之紫外線硬化性組成物中之前述化合物(B1)的摻合量，從硬化性變得良好、與環狀聚烯烴之密著性更為提升而言，相對於上述紫外線硬化性化合物(A)100質量份，較佳為0.1~20質量份，更佳為0.5~10質量%。 The blending amount of the compound (B1) in the ultraviolet curable composition of the present invention is improved from the curable property and the adhesion to the cyclic polyolefin is improved with respect to the ultraviolet curable compound ( A) 100 parts by mass, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10% by mass.
又，在本發明之紫外線硬化性組成物中所含 有之光聚合起始劑(B)中前述化合物(B1)的比率，較佳為50質量%以上，更佳為65質量%以上，進一步更佳為80質量%以上。 Further, it is contained in the ultraviolet curable composition of the present invention. The ratio of the compound (B1) in the photopolymerization initiator (B) is preferably 50% by mass or more, more preferably 65% by mass or more, and still more preferably 80% by mass or more.
本發明之紫外線硬化性組成物中，除上述紫外線硬化性化合物(A)及光聚合起始劑(B)以外，可視用途、要求特性，而摻合光增感劑、有機溶劑、聚合抑制劑、表面調整劑、抗靜電劑、消泡劑、黏度調整劑、耐光安定劑、耐候安定劑、耐熱安定劑、紫外線吸收劑、抗氧化劑、調平劑、有機顏料、無機顏料、顏料分散劑、有機珠粒等添加劑；氧化矽(矽石粒子)、氧化鋁、氧化鈦、氧化鋯、五氧化銻等之無機填充劑等。此等其他摻合物可單獨使用，亦可併用2種以上。 In addition to the ultraviolet curable compound (A) and the photopolymerization initiator (B), the ultraviolet curable composition of the present invention may be blended with a photosensitizer, an organic solvent, or a polymerization inhibitor depending on the intended use and desired characteristics. Surface conditioning agent, antistatic agent, antifoaming agent, viscosity modifier, light stabilizer, weathering stabilizer, heat stabilizer, ultraviolet absorber, antioxidant, leveling agent, organic pigment, inorganic pigment, pigment dispersant, Additives such as organic beads; inorganic fillers such as cerium oxide (vermiculite particles), aluminum oxide, titanium oxide, zirconium oxide, and antimony pentoxide. These other blends may be used singly or in combination of two or more.
前述無機填充劑之中，藉由摻合矽石粒子，可更提升本發明之紫外線硬化性組成物之硬化塗膜表面的耐擦傷性、可更提升對基材之密著性。作為前述矽石粒子，可為其表面以有機基表面修飾者、亦可為未經表面修飾者。又，前述矽石粒子從可更提升本發明之紫外線線硬化性組成物之硬化塗膜的透明性及表面的耐擦傷性而言，較佳為奈米等級之尺寸的矽石微粒子，更佳為膠態矽石。前述矽石微粒子的平均粒徑較佳為5~200nm之範圍，更佳為5~100nm之範圍。又，此平均粒徑係以動態光散射法測定之值。 Among the inorganic fillers, by blending the vermiculite particles, 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. The vermiculite particles may be those whose surface is modified with an organic surface or which may not be surface-modified. Further, the vermiculite particles are preferably fine-grained fine particles of a nanometer size from the viewpoint of improving the transparency of the cured coating film of the ultraviolet curable composition of the present invention and the scratch resistance of the surface. It is a colloidal vermiculite. The average particle diameter of the fine particles of the vermiculite is preferably in the range of 5 to 200 nm, more preferably in the range of 5 to 100 nm. Further, the average particle diameter is a value measured by a dynamic light scattering method.
摻合前述無機填充劑時之其摻合量，從更提升本發明之紫外線硬化性組成物之硬化塗膜表面的耐擦傷性、亦更提升對基材之密著性而言，相對於前述紫外 線硬化性化合物(A)100質量份，係較佳為1~150質量份，更佳為5~100質量份。 When the blending amount of the inorganic filler is blended, the scratch resistance of the surface of the cured coating film of the ultraviolet curable composition of the present invention is further improved, and the adhesion to the substrate is further improved. Ultraviolet The linear curable compound (A) is preferably 1 to 150 parts by mass, more preferably 5 to 100 parts by mass, per 100 parts by mass.
作為前述光增感劑，可舉出例如，二乙醇胺、N-甲基二乙醇胺、三丁基胺等3級胺化合物、o-甲苯基硫尿素等尿素化合物、二乙基二硫代磷酸鈉、s-苄基異硫脲-p-甲苯磺酸鹽等硫化合物等。摻合光增感劑時之其摻合量，相對於上述紫外線硬化性化合物(A)100質量份，係較佳為0.01~20質量份，更佳為0.5~10質量%。 Examples of the photosensitizer include a tertiary amine compound such as diethanolamine, N-methyldiethanolamine or tributylamine, a urea compound such as o-tolylsulfuric acid, and sodium diethyldithiophosphate. And a sulfur compound such as s-benzylisothiourea-p-toluenesulfonate. The blending amount of the light sensitizing agent is preferably 0.01 to 20 parts by mass, more preferably 0.5 to 10% by mass, based on 100 parts by mass of the ultraviolet curable compound (A).
前述有機溶媒在適宜調整本發明之活性能量線硬化性組成物的溶液黏度方面為有用，尤其是為了進行薄膜塗布，調整膜厚係變得容易。作為能在此使用之有機溶媒，可舉出例如甲苯、二甲苯等芳香族烴；甲醇、乙醇、異丙醇、t-丁醇等醇類；乙酸乙酯、乙酸丁酯、丙二醇單甲基醚乙酸酯等酯類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮類等。此等溶劑可單獨使用，亦可併用2種以上。 The organic solvent is useful for suitably adjusting the solution viscosity of the active energy ray-curable composition of the present invention, and in particular, for film coating, it is easy to adjust the film thickness. Examples of the organic solvent that can be used herein include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and t-butanol; ethyl acetate, butyl acetate, and propylene glycol monomethyl. Esters such as ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used singly or in combination of two or more.
本發明之紫外線硬化性組成物，因可獲得尤其是對環狀烯烴樹脂具有優異密著性的硬化塗膜，所以作為塗覆本發明之紫外線硬化性組成物的基材，較佳為環狀烯烴樹脂成形品，尤其是環狀烯烴樹脂薄膜。又，作為環狀烯烴樹脂，只要是聚合環狀烯烴者，單獨聚合物、共聚物都可無特別限制地使用。作為環狀烯烴樹脂之市售品，可舉出例如，日本ZEON股份有限公司製之「ZEONOR」、「ZEONEX」；JSR股份有限公司製之「ARTON」；POLYPLASTICS股份有限公司製之「TOPAS」等。 In the ultraviolet curable composition of the present invention, since a cured coating film having excellent adhesion to a cyclic olefin resin is obtained, the substrate to which the ultraviolet curable composition of the present invention is applied is preferably a ring. An olefin resin molded article, particularly a cyclic olefin resin film. In addition, as the cyclic olefin resin, any polymer or copolymer may be used without particular limitation as long as it is a polymerized cyclic olefin. For example, "ZEONOR" and "ZEONEX" manufactured by Japan ZEON Co., Ltd.; "ARTON" manufactured by JSR Co., Ltd.; "TOPAS" manufactured by POLYPLASTICS Co., Ltd., etc., etc. .
前述環狀烯烴樹脂薄膜係將環狀烯烴樹脂在薄膜上成形者。又，環狀烯烴樹脂薄膜的表面，為提升與本發明之紫外線硬化性組成物之硬化塗膜的密著性，較佳為藉由以噴砂法法、溶劑處理法等之表面凹凸化處理、電處理(電暈放電處理、大氣壓電漿處理)、鉻酸處理、火焰處理、熱風處理、臭氧．紫外線．電子線照射處理、氧化處理等處理者，此等中更佳為經電暈放電處理、大氣壓電漿處理等電氣的處理者。 The cyclic olefin resin film is one in which a cyclic olefin resin is formed on a film. In addition, the surface of the cyclic olefin resin film is improved in adhesion to the cured coating film of the ultraviolet curable composition of the present invention, and is preferably subjected to surface unevenness treatment by a sand blast method or a solvent treatment method. Electrical treatment (corona discharge treatment, atmospheric piezoelectric slurry treatment), chromic acid treatment, flame treatment, hot air treatment, ozone. Ultraviolet light. The processor such as the electron beam irradiation treatment or the oxidation treatment is more preferably an electric processor such as a corona discharge treatment or an atmospheric piezoelectric slurry treatment.
又，前述環狀烯烴樹脂薄膜的厚度，較佳為50~200μm之範圍，更佳為80~150μm之範圍，進一步更佳為90~130μm之範圍。藉由使薄膜基材的厚度在該範圍內，在環狀烯烴樹脂薄膜的單面上，藉由本發明之紫外線硬化性組成物設置硬塗層時，亦容易抑制捲曲發生。 Further, the thickness of the cyclic olefin resin film is preferably in the range of 50 to 200 μm, more preferably in the range of 80 to 150 μm, still more preferably in the range of 90 to 130 μm. When the thickness of the film substrate is within this range, when a hard coat layer is provided on the single surface of the cyclic olefin resin film by the ultraviolet curable composition of the present invention, curling can be easily suppressed.
本發明之環狀烯烴樹脂薄膜，係藉由在該薄膜的至少1面上塗覆本發明之紫外線硬化性組成物，然後照射紫外線作為硬化塗膜而得者。作為在環狀烯烴樹脂薄膜塗覆本發明之紫外線硬化性組成物的方法，可舉出例如，模具塗布、微凹版塗布、凹版塗布、輥塗布、刮刀式塗布、空氣刀塗布、吻合式塗布、噴灑塗布、通過式塗布(pass coat)、浸漬塗布、旋轉塗布、輪式塗布(Wheeler coat)、刷毛塗布、藉由絲版印刷之全版塗布、線棒塗布、流動塗布等。 The cyclic olefin resin film of the present invention is obtained by coating the ultraviolet curable composition of the present invention on at least one side of the film and then irradiating ultraviolet rays as a cured coating film. The method of applying the ultraviolet curable composition of the present invention to the cyclic olefin resin film may, for example, die coating, micro gravure coating, gravure coating, roll coating, doctor blade coating, air knife coating, and conformal coating. Spray coating, pass coating, dip coating, spin coating, Wheeler coating, brush coating, full-plate coating by screen printing, wire bar coating, flow coating, and the like.
又，為了將紫外線硬化性組成物硬化，作為照射紫外線的裝置，可舉出例如，低壓水銀燈、高壓水 銀燈、超高壓水銀燈、金屬鹵化物燈、無電極燈(Fusion燈)、化學燈、黑光燈、水銀-氙燈、短電弧燈、氦．鎘雷射、氬雷射、太陽光、LED等。 Moreover, in order to cure the ultraviolet curable composition, as a means for irradiating ultraviolet rays, for example, a low pressure mercury lamp and high pressure water are mentioned. Silver lamp, ultra-high pressure mercury lamp, metal halide lamp, electrodeless lamp (Fusion lamp), chemical lamp, black light, mercury-xenon lamp, short arc lamp, 氦. Cadmium laser, argon laser, sunlight, LED, etc.
具有本發明之紫外線硬化性組成物之硬化塗膜的環狀烯烴樹脂薄膜，由於其基材之優異光學特性、尺寸穩定性、耐熱性、透明性以外，其表面耐擦傷性亦為優異，所以可適用於各種用途，但特別有用於作為液晶顯示器(LCD)、有機EL顯示器(OLED)等之影像顯示裝置之影像顯示部中所用之光學薄膜。尤其是因為即使為薄型亦具有優異耐擦傷性，所以可較佳合用於作為例如電子筆記本、行動電話、智慧型手機、攜帶聲訊播放機、行動個人電腦、攜帶終端機等小型化或薄型化要求高的攜帶電子終端機的影像顯示裝置之影像顯示部的光學薄膜。又，作為光學薄膜使用時，可作為影像顯示裝置之影像顯示部的最表面所用之保護薄膜、觸控面板之基材使用。再者，作為保護薄膜使用時，例如在LCD模組、OLED模組等影像顯示模組的上部設有保護該影像顯示模組的透明面板之結構的影像顯示裝置中，係藉由貼付在該透明面板的表面或背面使用，而在損傷防止或透明面板破損之際之飛散防止上有效。 The cyclic olefin resin film having the cured coating film of the ultraviolet curable composition of the present invention is excellent in surface scratch resistance due to excellent optical properties, dimensional stability, heat resistance and transparency of the substrate. It can be applied to various applications, but is particularly useful as an optical film used in an image display unit of an image display device such as a liquid crystal display (LCD) or an organic EL display (OLED). In particular, since it has excellent scratch resistance even in a thin shape, it can be preferably used in combination as a miniaturization or thinning requirement such as an electronic notebook, a mobile phone, a smart phone, a portable audio player, a mobile personal computer, and a portable terminal. A high optical film of an image display portion of an image display device that carries an electronic terminal. Further, when used as an optical film, it can be used as a protective film for the outermost surface of the image display portion of the image display device or a substrate of the touch panel. Further, when used as a protective film, for example, an image display device having a structure for protecting a transparent panel of the image display module on an upper portion of an image display module such as an LCD module or an OLED module is attached thereto. It is used on the surface or the back surface of the transparent panel, and is effective in preventing scattering damage or scattering of the transparent panel.
以下藉由實施例更具體地說明本發明。 The invention will be more specifically described below by way of examples.
(合成例1：胺基甲酸酯丙烯酸酯(A2-1)之合成) (Synthesis Example 1: Synthesis of urethane acrylate (A2-1))
在具備攪拌機、氣體導入管、冷卻管及溫度計的燒 瓶中裝入乙酸丁酯254質量份、異佛酮二異氰酸酯222質量份、p-甲氧基酚0.5質量份及二乙酸二丁基錫0.5質量份，一邊吹入空氣一邊升溫至70℃後，花費1小時滴入新戊四醇三丙烯酸酯(以下簡稱為「PE3A」)及新戊四醇四丙烯酸酯(以下簡稱為「PE4A」)之混合物(PE3A/PE4A=75/25(質量比))400質量份與異三聚氰酸環氧乙烷改性二丙烯酸酯497質量份。滴入結束後，在70℃反應3小時，進一步進行反應直到顯示異氰酸酯基的2250cm-1之紅外線吸收光譜消失為止，獲得含有在1分子中具有6個丙烯醯基的胺基甲酸酯丙烯酸酯(A2-1)之不揮發分80質量%之溶液。又，在此溶液中，不揮發分中除了胺基甲酸酯丙烯酸酯(A2-1)以外，含有19.5質量%之PE4A。 245 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 placed in a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer. After raising the temperature to 70 ° C while blowing air, a mixture of pentaerythritol triacrylate (hereinafter referred to as "PE3A") and pentaerythritol tetraacrylate (hereinafter referred to as "PE4A") was added dropwise for 1 hour. (PE3A/PE4A=75/25 (mass ratio)) 400 parts by mass and 497 parts by mass of isomeric cyanuric acid-modified diacrylate. After the completion of the dropwise addition, the reaction was carried out at 70 ° C for 3 hours, and the reaction was further carried out until the infrared absorption spectrum of 2250 cm -1 showing the isocyanate group disappeared, and a urethane acrylate having 6 propylene groups in one molecule was obtained. A solution of (A2-1) having a nonvolatile content of 80% by mass. Further, in this solution, the nonvolatile matter contained 19.5% by mass of PE4A in addition to the urethane acrylate (A2-1).
(實施例1) (Example 1)
均勻地攪拌二新戊四醇六丙烯酸酯(以下簡稱為「DPHA」)及二新戊四醇五丙烯酸酯(以下簡稱為「DPPA」)之混合物(DPHA/DPPA=65/35(質量比))35質量份、聚酯丙烯酸酯(4官能、分子量1,800)65質量份、矽石微粒子(日產化學工業股份有限公司製「MEK-ST」、平均粒徑10~20nm、有機矽石溶膠之30質量%甲基乙基酮分散液；以下簡稱為「矽石微粒子分散液(1)」)25質量份(以矽石微粒子計7.5質量份)、及氧基苯基乙酸2-(2-側氧-2-苯基乙醯氧基乙氧基)乙基酯(以下簡稱為「光聚合起始劑(B1-1)」)3質量份後，以甲基乙基酮稀釋，而調製不揮發分25質量%之紫外線硬化性組成物(1)。 A mixture of dipentaerythritol hexaacrylate (hereinafter abbreviated as "DPHA") and dipentaerythritol pentaacrylate (hereinafter referred to as "DPPA") was uniformly stirred (DPHA/DPPA = 65/35 (mass ratio) 35 parts by mass, polyester acrylate (4-functional, molecular weight 1,800), 65 parts by mass, vermiculite fine particles ("MEK-ST" manufactured by Nissan Chemical Industries, Ltd., average particle diameter 10-20 nm, organic vermiculite sol 30 Mass % methyl ethyl ketone dispersion; hereinafter referred to as "fine stone fine particle dispersion (1)") 25 parts by mass (7.5 parts by mass of vermiculite particles), and 2-(2- side of oxyphenylacetic acid) 3 parts by mass of oxy-2-phenylethenyloxyethoxy)ethyl ester (hereinafter referred to as "photopolymerization initiator (B1-1)"), diluted with methyl ethyl ketone, and not prepared An ultraviolet curable composition (1) having 25% by mass of volatile matter.
[評估用薄膜之製作] [Production of evaluation film]
將上述所得紫外線硬化性組成物(1)用線棒塗布在預先將表面電處理(電暈放電處理；出力100W、速度1.0m/分鐘)之環狀烯烴樹脂薄膜(日本ZEON股份有限公司製「ZeonorFilm ZF16-100」、厚度100μm)上，在60℃加熱90秒後，在空氣環境下使用紫外線照射裝置(iGrafx股份有限公司製「MIDN-042-C1」、燈：120W/cm、高壓水銀燈)，以照射光量0.3J/cm2照射紫外線，而獲得具有厚度4μm之硬化塗膜的評估用薄膜。 The ultraviolet curable composition (1) obtained above was applied to a cyclic olefin resin film (manufactured by Japan ZEON Co., Ltd.) by electroplating (corona discharge treatment; output of 100 W, speed: 1.0 m/min) in advance. After heating at 60 ° C for 90 seconds on ZeonorFilm ZF16-100" and thickness 100 μm), an ultraviolet irradiation device ("MIDN-042-C1" manufactured by iGrafx Co., Ltd., lamp: 120 W/cm, high-pressure mercury lamp) was used in an air atmosphere. The ultraviolet light was irradiated with an irradiation light amount of 0.3 J/cm 2 to obtain a film for evaluation having a cured coating film having a thickness of 4 μm.
[耐擦傷性之評估] [Evaluation of scratch resistance]
針對上述所得之評估用薄膜的硬化塗膜表面，用Crock Meter型摩擦試驗器(直徑1.0cm圓形摩擦子、不鏽鋼棉#0000、負重300g、來回10次)進行試驗，以目視觀察試驗後的硬化塗膜表面，並依照下記基準評估耐擦傷性。 The surface of the cured coating film of the evaluation film obtained above was tested by a Crock Meter type friction tester (diameter 1.0 cm circular friction, stainless steel cotton #0000, weight 300 g, back and forth 10 times) to visually observe the test. The surface of the coating film was hardened, and the scratch resistance was evaluated in accordance with the following criteria.
A：損傷數目為9條以下。 A: The number of injuries is 9 or less.
B：損傷數目為10條以上。 B: The number of injuries is more than 10.
[密著性之評估] [Evaluation of adhesion]
在上述所得之評估用薄膜上，於薄膜的硬化被膜表面以1mm間隔劃下縱、橫11條的切痕，製作100個格子。接著，重複2次使市售賽珞玢膠帶密著在其表面後，一口氣剝除之操作。計算未剝而殘留的格子數目，依照以下基準評估密著性。 On the evaluation film obtained above, 11 slits of vertical and horizontal were cut at intervals of 1 mm on the surface of the cured film of the film to prepare 100 lattices. Next, the operation of peeling off the commercially available celluloid tape on the surface thereof was repeated twice. The number of unremoved lattices was counted, and the adhesion was evaluated according to the following criteria.
A：殘留的格子數目為100個。 A: The number of remaining grids is 100.
B：殘留的格子數目為80個以上99個以下。 B: The number of remaining lattices is 80 or more and 99 or less.
C：殘留的格子數目為60個以上80個以下。 C: The number of remaining lattices is 60 or more and 80 or less.
D：殘留的格子數目為59個以下。 D: The number of remaining lattices is 59 or less.
[厚膜密著性之評估] [Evaluation of Thick Film Adhesion]
除了變更紫外線硬化性組成物(1)塗布量以外，係與上述評估用薄膜之製作同樣地進行，而獲得具有厚度6μm之硬化塗膜的厚膜密著性評估用薄膜。針對所得之薄膜，係與上述密著性之評估同樣地進行，而評估厚膜密著性。 In the same manner as the production of the evaluation film described above, a film for evaluating a thick film adhesion having a cured coating film having a thickness of 6 μm was obtained, except that the coating amount of the ultraviolet curable composition (1) was changed. The obtained film was evaluated in the same manner as the above evaluation of the adhesion, and the thick film adhesion was evaluated.
[塗膜著色之評估] [Evaluation of film coloring]
將上述所得之評估用薄膜切割成50mm×80mm的大小，並將薄膜捲繞在外徑8mm的棒上，以賽珞玢膠帶固定。接著，拉出棒後，以目視觀察輥狀之評估用薄膜的色調，並依照以下基準評估塗膜著色。 The evaluation film obtained above was cut into a size of 50 mm × 80 mm, and the film was wound around a rod having an outer diameter of 8 mm and fixed with a cellophane tape. Next, after the rod was pulled out, the color tone of the film for evaluation of the roll shape was visually observed, and the coloring of the coating film was evaluated in accordance with the following criteria.
A：無色。 A: No color.
B：有黃色調之著色。 B: There is a yellow color.
(實施例2) (Example 2)
除了將光聚合起始劑(B1-1)的摻合量從3質量份變更為6質量份以外，係與實施例1同樣地進行，調製紫外線硬化性組成物(2)。 The ultraviolet curable composition (2) was prepared in the same manner as in Example 1 except that the blending amount of the photopolymerization initiator (B1-1) was changed from 3 parts by mass to 6 parts by mass.
(實施例3) (Example 3)
除了將光聚合起始劑(B1-1)的摻合量從3質量份變更為9質量份以外，係與實施例1同樣地進行，調製不揮發分25質量%之紫外線硬化性組成物(3)。 An ultraviolet curable composition having a nonvolatile content of 25% by mass was prepared in the same manner as in Example 1 except that the blending amount of the photopolymerization initiator (B1-1) was changed from 3 parts by mass to 9 parts by mass. 3).
(實施例4) (Example 4)
均勻地攪拌在合成例1所獲得之多官能胺基甲酸酯丙烯酸酯(A2-1)(不揮發分80質量%)125質量份(以多官 能丙烯酸酯計為100質量份)、矽石微粒子分散液(1)25質量份(以矽石微粒子計為7.5質量份)及光聚合起始劑(B1-1)3質量份後，以甲基乙基酮稀釋，而調製不揮發分25質量%之紫外線硬化性組成物(4)。 The polyfunctional urethane acrylate (A2-1) (nonvolatile matter 80% by mass) obtained in Synthesis Example 1 was uniformly stirred in an amount of 125 parts by mass. 100 parts by mass of the acrylate, and 25 parts by mass of the vermiculite fine particle dispersion (1) (7.5 parts by mass of the vermiculite particles) and 3 parts by mass of the photopolymerization initiator (B1-1), The ethyl ethyl ketone was diluted to prepare an ultraviolet curable composition (4) having a nonvolatile content of 25% by mass.
(實施例5) (Example 5)
除了將光聚合起始劑(B1-1)的摻合量從3質量份變更為6質量份以外，係與實施例4同樣地進行，調製不揮發分25質量%之紫外線硬化性組成物(5)。 An ultraviolet curable composition having a nonvolatile content of 25% by mass was prepared in the same manner as in Example 4 except that the blending amount of the photopolymerization initiator (B1-1) was changed from 3 parts by mass to 6 parts by mass. 5).
(實施例6) (Example 6)
除了將光聚合起始劑(B1-1)的摻合量從3質量份變更為9質量份以外，係與實施例4同樣地進行，調製不揮發分25質量%之紫外線硬化性組成物(6)。 An ultraviolet curable composition having a nonvolatile content of 25% by mass was prepared in the same manner as in Example 4 except that the blending amount of the photopolymerization initiator (B1-1) was changed from 3 parts by mass to 9 parts by mass. 6).
(實施例7) (Example 7)
均勻地攪拌在合成例1所獲得之多官能胺基甲酸酯丙烯酸酯(A2-1)(不揮發分80質量%)125質量份(以多官能丙烯酸酯計為100質量份)、矽石微粒子(日產化學工業股份有限公司製「MEK-ST40」、平均粒徑10~20nm、有機矽石溶膠之40質量%甲基乙基酮分散液；以下簡稱為「矽石微粒子分散液(2)」)62.5質量份(以矽石微粒子計為25質量份)、及光聚合起始劑(B1-1)6質量份後，以甲基乙基酮稀釋，而調製不揮發分25質量%之紫外線硬化性組成物(7)。 125 parts by mass of the polyfunctional urethane acrylate (A2-1) (nonvolatile content: 80% by mass) obtained in Synthesis Example 1 (100 parts by mass based on the polyfunctional acrylate), vermiculite Microparticles (MEK-ST40, manufactured by Nissan Chemical Industries, Ltd.), 40% by mass of methyl ethyl ketone dispersion with an average particle diameter of 10 to 20 nm and an organic vermiculite sol; hereinafter referred to as "fine particles of fine particles (2) ”62.5 parts by mass (25 parts by mass of vermiculite particles) and 6 parts by mass of photopolymerization initiator (B1-1), and then diluted with methyl ethyl ketone to prepare a nonvolatile content of 25% by mass. Ultraviolet curable composition (7).
(實施例8) (Example 8)
均勻地攪拌多官能胺基甲酸酯丙烯酸酯(A2-1)(不揮發分80質量%)123.75質量份(以多官能丙烯酸酯計為 99質量份)、具有磷酸基之甲基丙烯酸酯(MIWON公司製「MIRAMER SC1400」；以下簡稱為「磷酸甲基丙烯酸酯(1)」)1質量份、矽石微粒子分散液(2)62.5質量份(以矽石微粒子計為25質量份)、及光聚合起始劑(B1-1)6質量份後，以甲基乙基酮稀釋，而調製不揮發分25質量%之紫外線硬化性組成物(8)。 Uniformly stirring the polyfunctional urethane acrylate (A2-1) (nonvolatile matter 80% by mass) 123.75 parts by mass (based on the polyfunctional acrylate) 99 parts by mass), methacrylate having a phosphate group ("MIRAMER SC1400" manufactured by MIWON Co., Ltd.; hereinafter referred to as "phosphoric acid methacrylate (1)"), 1 part by mass, vermiculite fine particle dispersion (2) 62.5 mass A part (25 parts by mass of vermiculite particles) and 6 parts by mass of a photopolymerization initiator (B1-1) were diluted with methyl ethyl ketone to prepare a UV curable composition having a nonvolatile content of 25% by mass. (8).
(實施例9) (Example 9)
均勻地攪拌多官能胺基甲酸酯丙烯酸酯(A2-1)(不揮發分80質量%)118.75質量份(以多官能丙烯酸酯計為95質量份)、磷酸甲基丙烯酸酯(1)5質量份、矽石微粒子分散液(2)62.5質量份(以矽石微粒子計為25質量份)、及光聚合起始劑(B1-1)6質量份後，以甲基乙基酮稀釋，而調製不揮發分25質量%之紫外線硬化性組成物(9)。 The polyfunctional urethane acrylate (A2-1) (nonvolatile matter 80% by mass) was uniformly stirred, 118.75 parts by mass (95 parts by mass based on the polyfunctional acrylate), and phosphoric acid methacrylate (1) 5 The mass fraction, the vermiculite fine particle dispersion (2), 62.5 parts by mass (25 parts by mass in terms of vermiculite particles), and 6 parts by mass of the photopolymerization initiator (B1-1) are diluted with methyl ethyl ketone. Further, an ultraviolet curable composition (9) having a nonvolatile content of 25% by mass was prepared.
(實施例10) (Embodiment 10)
均勻地攪拌多官能胺基甲酸酯丙烯酸酯(A2-1)(不揮發分80質量%)113.75質量份(以多官能丙烯酸酯計為91質量份)、磷酸甲基丙烯酸酯(1)9質量份、矽石微粒子分散液(2)62.5質量份(以矽石微粒子計為25質量份)、及光聚合起始劑(B1-1)6質量份後，以甲基乙基酮稀釋，而調製不揮發分25質量%之紫外線硬化性組成物(10)。 The polyfunctional urethane acrylate (A2-1) (nonvolatile matter 80% by mass) was uniformly stirred, 113.75 parts by mass (91 parts by mass based on the polyfunctional acrylate), and phosphoric acid methacrylate (1) 9 The mass fraction, the vermiculite fine particle dispersion (2), 62.5 parts by mass (25 parts by mass in terms of vermiculite particles), and 6 parts by mass of the photopolymerization initiator (B1-1) are diluted with methyl ethyl ketone. Further, an ultraviolet curable composition (10) having a nonvolatile content of 25% by mass was prepared.
(實施例11) (Example 11)
除了未摻合矽石微粒子分散液(2)以外，係與實施例7同樣地進行，調製不揮發分25質量%之紫外線硬化性組成物(11)。 The ultraviolet curable composition (11) having a nonvolatile content of 25% by mass was prepared in the same manner as in Example 7 except that the vermiculite fine particle dispersion (2) was not blended.
(實施例12) (Embodiment 12)
除了未摻合矽石微粒子分散液(2)以外，係與實施例9同樣地進行，調製成不揮發分25質量%之紫外線硬化性組成物(12)。 An ultraviolet curable composition (12) having a nonvolatile content of 25% by mass was prepared in the same manner as in Example 9 except that the vermiculite fine particle dispersion (2) was not blended.
(比較例1) (Comparative Example 1)
除了用4-(4-甲基苯基硫)二苯甲酮(以下簡稱為「光聚合起始劑(R1)」)代替實施例1所用之光聚合起始劑(B1-1)以外，係與實施例1同樣地進行，調製紫外線硬化性組成物(R1)。 In addition to 4-(4-methylphenylthio)benzophenone (hereinafter referred to as "photopolymerization initiator (R1)"), instead of the photopolymerization initiator (B1-1) used in Example 1, The ultraviolet curable composition (R1) was prepared in the same manner as in Example 1.
(比較例2) (Comparative Example 2)
除了用光聚合起始劑(R1)9質量份代替實施例1所用之光聚合起始劑(B1-1)3質量份以外，與實施例1同樣地進行，調製成紫外線硬化性組成物(R2)。 An ultraviolet curable composition was prepared in the same manner as in Example 1 except that 9 parts by mass of the photopolymerization initiator (R1) was used in place of 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1. R2).
(比較例3) (Comparative Example 3)
除了用1-羥基環己基苯基酮(以下簡稱為「光聚合起始劑(R2)」)6質量份代替實施例1所用之光聚合起始劑(B1-1)3質量份以外，係與實施例1同樣地進行，調製紫外線硬化性組成物(R3)。 Except that 6 parts by mass of 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to 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.
(比較例4) (Comparative Example 4)
除了用2-苄基-2-二甲基胺基-1-(4-啉基苯基)-1-丁酮(以下簡稱為「光聚合起始劑(R3)」)6質量份代替實施例1所用之光聚合起始劑(B1-1)3質量份以外，係與實施例1同樣地進行，調製紫外線硬化性組成物(R4)。 In addition to 2-benzyl-2-dimethylamino-1-(4- 6 parts by mass of the morphylphenyl)-1-butanone (hereinafter referred to as "photopolymerization initiator (R3)"), in place of 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1, The ultraviolet curable composition (R4) was prepared in the same manner as in Example 1.
(比較例5) (Comparative Example 5)
除了用2-甲基-1-(4-甲基硫苯基)-2-啉基丙烷-1-酮(以下簡稱為「光聚合起始劑(R4)」)6質量份代替實施 例1所用之光聚合起始劑(B1-1)3質量份以外，係與實施例1同樣地進行，調製紫外線硬化性組成物(R5)。 In addition to 2-methyl-1-(4-methylthiophenyl)-2- 6 parts by mass of the morphyl propan-1-one (hereinafter referred to as "photopolymerization initiator (R4)"), in place of 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1, 1 was carried out in the same manner to prepare an ultraviolet curable composition (R5).
(比較例6) (Comparative Example 6)
除了用2-羥基-1-[4-(2-羥基乙氧基)-苯基]-2-甲基-1-丙烷-1-酮(以下簡稱為「光聚合起始劑(R5)」)6質量份代替實施例1所用之光聚合起始劑(B1-1)3質量份以外，係與實施例1同樣地進行，調製紫外線硬化性組成物(R6)。 In addition to 2-hydroxy-1-[4-(2-hydroxyethoxy)-phenyl]-2-methyl-1-propan-1-one (hereinafter referred to as "photopolymerization initiator (R5)" In the same manner as in Example 1, except that 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1 was used, the ultraviolet curable composition (R6) was prepared.
(比較例7) (Comparative Example 7)
除了用二苯基(2,4,6-三甲基苯甲醯基)膦氧化物(以下簡稱為「光聚合起始劑(R6)」)6質量份代替實施例1所用之光聚合起始劑(B1-1)3質量份以外，係與實施例1同樣地進行，調製紫外線硬化性組成物(R7)。 In place of 6 parts by mass of diphenyl(2,4,6-trimethylbenzylidene)phosphine oxide (hereinafter referred to as "photopolymerization initiator (R6)"), instead of the photopolymerization used in Example 1, The ultraviolet curable composition (R7) was prepared in the same manner as in Example 1 except that the starting agent (B1-1) was used in an amount of 3 parts by mass.
(比較例8) (Comparative Example 8)
除了用2-羥基-2-甲基-1-苯基-1-丙酮(以下簡稱為「光聚合起始劑(R7)」)6質量份代替實施例1所用之光聚合起始劑(B1-1)3質量份以外，係與實施例1同樣地進行，調製紫外線硬化性組成物(R8)。 In place of 6 parts by mass of 2-hydroxy-2-methyl-1-phenyl-1-propanone (hereinafter referred to as "photopolymerization initiator (R7)"), the photopolymerization initiator (B1) used in Example 1 was replaced. In the same manner as in Example 1, except that the amount of -1) was 3 parts by mass, the ultraviolet curable composition (R8) was prepared.
(比較例9) (Comparative Example 9)
除了用2-羥基-1-{4-[4-(2-羥基-2-甲基-丙醯基)-苄基]苯基}-2-甲基-1-丙酮(以下簡稱為「光聚合起始劑(R8)」)6質量份代替實施例1所用之光聚合起始劑(B1-1)3質量份以外，係與實施例1同樣地進行，調製紫外線硬化性組成物(R9)。 In addition to 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-1-propanone (hereinafter referred to as "light" In the same manner as in Example 1, except that 3 parts by mass of the photopolymerization initiator (B1-1) used in Example 1 was used, the ultraviolet curable composition (R9) was prepared. ).
(比較例10) (Comparative Example 10)
除了用2,4-二乙基9-氧硫(以下簡稱為「光聚合起始劑(R9)」)6質量份代替實施例1所用之光聚合起始劑(B1-1)3質量份以外，係與實施例1同樣地進行，調製紫外線硬化性組成物(R10)。 In addition to 2,4-diethyl 9-oxosulfur In the same manner as in Example 1, except that 6 parts by mass of the photopolymerization initiator (B1-1) used in Example 1 was used instead of 3 parts by mass of the photopolymerization initiator (R9), ultraviolet rays were prepared. Hardenable composition (R10).
針對在上述實施例2~12及比較例1~10所得之紫外線硬化性組成物(2)~(12)及(R1)~(R10)，與實施例1同樣地評估耐擦傷性、密著性、厚膜密著性、及塗膜著色。 The ultraviolet curable compositions (2) to (12) and (R1) to (R10) obtained in the above Examples 2 to 12 and Comparative Examples 1 to 10 were evaluated for scratch resistance and adhesion in the same manner as in Example 1. Sex, thick film adhesion, and film coloring.
將上述實施例1~12及比較例1~10所用之紫外線硬化性組成物的組成及評估結果示於表1~4。又，表1~4中的組成皆以不揮發分量記載。 The compositions and evaluation results of the ultraviolet curable compositions used in the above Examples 1 to 12 and Comparative Examples 1 to 10 are shown in Tables 1 to 4. Further, the compositions in Tables 1 to 4 are described as non-volatile components.
由表1所示評估結果可知，本發明之紫外線硬化性組成物的實施例1~12之物，其硬化塗膜表面的耐擦傷性優異、與基材之環狀聚烯烴樹脂薄膜的密著性亦高、再者亦未觀察到塗膜之著色。尤其是摻合有具磷酸基之丙烯酸酯及矽石微粒子的實施例8~10之紫外線硬化性組成物(8)~(10)，係即使厚膜亦具有優異密著性。 As a result of the evaluation shown in Table 1, it is understood that the materials of Examples 1 to 12 of the ultraviolet curable composition of the present invention have excellent scratch resistance on the surface of the cured coating film and are adhered to the cyclic polyolefin resin film of the substrate. The sex was also high, and the color of the film was not observed. In particular, the ultraviolet curable compositions (8) to (10) of Examples 8 to 10 in which a phosphoric acid group-containing acrylate and vermiculite fine particles are blended have excellent adhesion even with a thick film.
另一方面，比較例1~10之紫外線硬化性組成物，係使用不包含本發明中作為必要成分之化合物的光聚合起始劑的例子。此等紫外線硬化性組成物沒有完全滿足該硬化塗膜表面之足夠的耐擦傷性、與基材之環狀聚烯烴樹脂薄膜的足夠的密著性及塗膜的無著色之評估者。 On the other hand, the ultraviolet curable composition of Comparative Examples 1 to 10 is an example of a photopolymerization initiator which does not contain a compound which is an essential component in the present invention. These ultraviolet curable compositions do not fully satisfy the sufficient scratch resistance of the surface of the cured coating film, sufficient adhesion to the cyclic polyolefin resin film of the substrate, and evaluation of the coloring of the coating film.
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