JP4998647B2 - Active energy ray-curable resin composition, cured product and film thereof - Google Patents
Active energy ray-curable resin composition, cured product and film thereof Download PDFInfo
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- JP4998647B2 JP4998647B2 JP2011548501A JP2011548501A JP4998647B2 JP 4998647 B2 JP4998647 B2 JP 4998647B2 JP 2011548501 A JP2011548501 A JP 2011548501A JP 2011548501 A JP2011548501 A JP 2011548501A JP 4998647 B2 JP4998647 B2 JP 4998647B2
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- Prior art keywords
- acrylate
- meth
- resin composition
- active energy
- energy ray
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 129
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 27
- 150000002009 diols Chemical class 0.000 claims description 26
- -1 methacryloyl group Chemical group 0.000 claims description 23
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229920001451 polypropylene glycol Polymers 0.000 claims description 14
- 125000005442 diisocyanate group Chemical group 0.000 claims description 13
- 125000004434 sulfur atom Chemical group 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- PDHFSBXFZGYBIP-UHFFFAOYSA-N 2-[2-(2-hydroxyethylsulfanyl)ethylsulfanyl]ethanol Chemical compound OCCSCCSCCO PDHFSBXFZGYBIP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- ZDNHCMQQCSOLIX-UHFFFAOYSA-N 1-[1-[2-(2-hydroxypropylsulfanyl)propylsulfanyl]propan-2-ylsulfanyl]propan-2-ol Chemical compound CC(O)CSC(C)CSCC(C)SCC(C)O ZDNHCMQQCSOLIX-UHFFFAOYSA-N 0.000 claims description 3
- DUFCZJRMDGJQRR-UHFFFAOYSA-N 2-(1-hydroxypropan-2-ylsulfanyl)propan-1-ol Chemical group OCC(C)SC(C)CO DUFCZJRMDGJQRR-UHFFFAOYSA-N 0.000 claims description 3
- DMRWIWTZZHAWHQ-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethylsulfanyl)propylsulfanyl]propan-2-ylsulfanyl]ethanol Chemical compound OCCSC(CSCC(SCCO)C)C DMRWIWTZZHAWHQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 32
- 239000011248 coating agent Substances 0.000 description 30
- 239000010410 layer Substances 0.000 description 27
- 239000000203 mixture Substances 0.000 description 22
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 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 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 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 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 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 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004386 Erythritol Substances 0.000 description 3
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 3
- 235000019414 erythritol Nutrition 0.000 description 3
- 229940009714 erythritol Drugs 0.000 description 3
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000011158 quantitative evaluation Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- WGLYLHNRGWWZMW-UHFFFAOYSA-N 1-(2-hydroxypropylsulfanyl)propan-2-ol Chemical compound CC(O)CSCC(C)O WGLYLHNRGWWZMW-UHFFFAOYSA-N 0.000 description 2
- DPGDWQDYDTUUFA-UHFFFAOYSA-N 1-[2-(2-hydroxybutylsulfanyl)ethylsulfanyl]butan-2-ol Chemical compound CCC(O)CSCCSCC(O)CC DPGDWQDYDTUUFA-UHFFFAOYSA-N 0.000 description 2
- TVJMNKFRSJHLBL-UHFFFAOYSA-N 1-[2-(2-hydroxypropylsulfanyl)ethylsulfanyl]propan-2-ol Chemical compound CC(O)CSCCSCC(C)O TVJMNKFRSJHLBL-UHFFFAOYSA-N 0.000 description 2
- XNKBUYFJNGMIRU-UHFFFAOYSA-N 1-[2-[2-(2-hydroxypropylsulfanyl)ethoxy]ethylsulfanyl]propan-2-ol Chemical compound CC(O)CSCCOCCSCC(C)O XNKBUYFJNGMIRU-UHFFFAOYSA-N 0.000 description 2
- BHEMISMYRYZVAA-UHFFFAOYSA-N 1-chloro-3-(2-hydroxyethylsulfanyl)propan-2-ol Chemical compound OCCSCC(O)CCl BHEMISMYRYZVAA-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 2
- VZYIKHZFVOUXKE-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethylsulfanyl)ethylsulfanyl]ethylsulfanyl]ethanol Chemical compound OCCSCCSCCSCCO VZYIKHZFVOUXKE-UHFFFAOYSA-N 0.000 description 2
- NOOVYQOSAZFXKR-UHFFFAOYSA-N 2-[2-[2-[2-(2-hydroxyethylsulfanyl)ethoxy]ethylsulfanyl]ethoxy]ethanol Chemical compound OCCOCCSCCOCCSCCO NOOVYQOSAZFXKR-UHFFFAOYSA-N 0.000 description 2
- XKHKXVFJLCVBPV-UHFFFAOYSA-N 2-[2-[2-[2-[2-(2-hydroxyethylsulfanyl)ethoxy]ethylsulfanyl]ethoxy]ethylsulfanyl]ethanol Chemical compound OCCSCCOCCSCCOCCSCCO XKHKXVFJLCVBPV-UHFFFAOYSA-N 0.000 description 2
- JIJWGPUMOGBVMQ-UHFFFAOYSA-N 2-[3-(2-hydroxyethylsulfanyl)propylsulfanyl]ethanol Chemical compound OCCSCCCSCCO JIJWGPUMOGBVMQ-UHFFFAOYSA-N 0.000 description 2
- FORJWQPDKXQQOG-UHFFFAOYSA-N 2-[4-(2-hydroxyethylsulfanyl)butylsulfanyl]ethanol Chemical compound OCCSCCCCSCCO FORJWQPDKXQQOG-UHFFFAOYSA-N 0.000 description 2
- FCYBBCGIQPEFBH-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)-2-methylpropan-1-ol Chemical compound OCC(C)CSCCO FCYBBCGIQPEFBH-UHFFFAOYSA-N 0.000 description 2
- QRQVZZMTKYXEKC-UHFFFAOYSA-N 3-(3-hydroxypropylsulfanyl)propan-1-ol Chemical compound OCCCSCCCO QRQVZZMTKYXEKC-UHFFFAOYSA-N 0.000 description 2
- YJGRQEWXDDCCCV-UHFFFAOYSA-N 3-[(2-hydroxyethyl)thio]-1-propanol Chemical compound OCCCSCCO YJGRQEWXDDCCCV-UHFFFAOYSA-N 0.000 description 2
- GBZDOXLAUOJYPB-UHFFFAOYSA-N 3-[2-(3-hydroxypropylsulfanyl)ethylsulfanyl]propan-1-ol Chemical compound OCCCSCCSCCCO GBZDOXLAUOJYPB-UHFFFAOYSA-N 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
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 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
- 238000007664 blowing Methods 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 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
- 239000003973 paint Substances 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 2
- WRCITXQNXAIKLR-UHFFFAOYSA-N tiadenol Chemical compound OCCSCCCCCCCCCCSCCO WRCITXQNXAIKLR-UHFFFAOYSA-N 0.000 description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- WNNRUOPGOIGERJ-UHFFFAOYSA-N 1-(2-hydroxyethylsulfanyl)propan-2-ol Chemical compound CC(O)CSCCO WNNRUOPGOIGERJ-UHFFFAOYSA-N 0.000 description 1
- AHRDMVQGWCOCQL-UHFFFAOYSA-N 1-(2-hydroxypropyldisulfanyl)propan-2-ol Chemical compound CC(O)CSSCC(C)O AHRDMVQGWCOCQL-UHFFFAOYSA-N 0.000 description 1
- LOSYOCXOAXDAMM-UHFFFAOYSA-N 1-[2-[2-(2-hydroxypropylsulfanyl)ethylsulfanyl]ethylsulfanyl]propan-2-ol Chemical compound CC(O)CSCCSCCSCC(C)O LOSYOCXOAXDAMM-UHFFFAOYSA-N 0.000 description 1
- YLAZLRIUONOQJD-UHFFFAOYSA-N 1-ethylsulfanyl-2-[2-(2-ethylsulfanylethylsulfanyl)ethylsulfanyl]ethane Chemical compound CCSCCSCCSCCSCC YLAZLRIUONOQJD-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
- PHIITBMJGQIRSS-UHFFFAOYSA-N 2-(1-hydroxypropan-2-yldisulfanyl)propan-1-ol Chemical compound OCC(C)SSC(C)CO PHIITBMJGQIRSS-UHFFFAOYSA-N 0.000 description 1
- QGECTPPOVMJXOX-UHFFFAOYSA-N 2-(2-hydroxyethylsulfanylmethoxymethylsulfanyl)ethanol Chemical compound OCCSCOCSCCO QGECTPPOVMJXOX-UHFFFAOYSA-N 0.000 description 1
- GAECBAMNQFGJIM-UHFFFAOYSA-N 2-(2-hydroxyethylsulfanylmethylsulfanyl)ethanol Chemical compound OCCSCSCCO GAECBAMNQFGJIM-UHFFFAOYSA-N 0.000 description 1
- PPHXSUHITJENQJ-UHFFFAOYSA-N 2-[2-(2-hydroxyethyldisulfanyl)ethyldisulfanyl]ethanol Chemical compound OCCSSCCSSCCO PPHXSUHITJENQJ-UHFFFAOYSA-N 0.000 description 1
- LXGFOHOXYOCIDT-UHFFFAOYSA-N 2-[2-(2-hydroxyethylsulfanyl)ethoxy]ethanol Chemical compound OCCOCCSCCO LXGFOHOXYOCIDT-UHFFFAOYSA-N 0.000 description 1
- ZJGXRMFOGCFCAG-UHFFFAOYSA-N 2-[2-(2-hydroxysulfanylethoxy)ethylsulfanyl]ethanol Chemical compound OCCSCCOCCSO ZJGXRMFOGCFCAG-UHFFFAOYSA-N 0.000 description 1
- USCZIOPUWFKATQ-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethyldisulfanyl)ethoxy]ethylsulfanyl]ethanol Chemical class OCCSCCOCCSSCCO USCZIOPUWFKATQ-UHFFFAOYSA-N 0.000 description 1
- SYLONGMLAHNVOC-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethylsulfanyl)ethoxy]ethylsulfanyl]ethanol Chemical compound OCCSCCOCCSCCO SYLONGMLAHNVOC-UHFFFAOYSA-N 0.000 description 1
- WOIRZZXXMTVNOY-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethylsulfanyl)ethyldisulfanyl]ethylsulfanyl]ethanol Chemical compound OCCSCCSSCCSCCO WOIRZZXXMTVNOY-UHFFFAOYSA-N 0.000 description 1
- ADIYXAJQYBGPQB-UHFFFAOYSA-N 2-[2-[2-[2-(2-hydroxyethylsulfanyl)ethoxy]ethoxy]ethylsulfanyl]ethanol Chemical compound OCCSCCOCCOCCSCCO ADIYXAJQYBGPQB-UHFFFAOYSA-N 0.000 description 1
- VOSFYVRCLVTSMD-UHFFFAOYSA-N 2-[2-[2-[2-(2-hydroxyethylsulfanyl)ethylsulfanyl]ethoxy]ethylsulfanyl]ethanol Chemical compound OCCSCCOCCSCCSCCO VOSFYVRCLVTSMD-UHFFFAOYSA-N 0.000 description 1
- OMNOPAUWOXOADS-UHFFFAOYSA-N 2-[2-[2-[2-(2-hydroxyethylsulfanyl)ethylsulfanyl]ethylsulfanyl]ethylsulfanyl]ethanol Chemical compound OCCSCCSCCSCCSCCO OMNOPAUWOXOADS-UHFFFAOYSA-N 0.000 description 1
- HZYDXMRRWHMPAF-UHFFFAOYSA-N 2-[4-(2-hydroxyethylsulfanyl)-3-methylbutyl]sulfanylethanol Chemical compound OCCSCC(C)CCSCCO HZYDXMRRWHMPAF-UHFFFAOYSA-N 0.000 description 1
- OUUXMGPVGBYKHB-UHFFFAOYSA-N 2-[5-(2-hydroxyethylsulfanyl)pentylsulfanyl]ethanol Chemical compound OCCSCCCCCSCCO OUUXMGPVGBYKHB-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- RXURJOBHVPLGQU-UHFFFAOYSA-N 3-(3-hydroxypropyldisulfanyl)propan-1-ol Chemical compound OCCCSSCCCO RXURJOBHVPLGQU-UHFFFAOYSA-N 0.000 description 1
- PLCGIBRKSKWDSK-UHFFFAOYSA-N 3-[(3-hydroxy-2-methylbutan-2-yl)disulfanyl]-3-methylbutan-2-ol Chemical compound CC(O)C(C)(C)SSC(C)(C)C(C)O PLCGIBRKSKWDSK-UHFFFAOYSA-N 0.000 description 1
- NSLRXAXIPBSNQO-UHFFFAOYSA-N 3-[6-(3-hydroxypropylsulfanyl)hexylsulfanyl]propan-1-ol Chemical compound OCCCSCCCCCCSCCCO NSLRXAXIPBSNQO-UHFFFAOYSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 description 1
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- HPKCPHUCATZKGA-UHFFFAOYSA-N 6-(6-hydroxyhexyldisulfanyl)hexan-1-ol Chemical compound OCCCCCCSSCCCCCCO HPKCPHUCATZKGA-UHFFFAOYSA-N 0.000 description 1
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-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
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 1
- OQSSNGKVNWXYOE-UHFFFAOYSA-N N=C=O.N=C=O.CCC(C)CC(C)(C)C Chemical compound N=C=O.N=C=O.CCC(C)CC(C)(C)C OQSSNGKVNWXYOE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 239000007983 Tris buffer Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 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
- 125000005474 octanoate group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229960000822 tiadenol Drugs 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
Description
本発明は特にタッチパネル表面を保護するハードコート層を形成するために好ましく用いることができる活性エネルギー線硬化型樹脂組成物に関する。 The present invention particularly relates to an active energy ray-curable resin composition that can be preferably used to form a hard coat layer that protects the surface of a touch panel.
近年、携帯電話、ゲーム機、カーナビゲーション等において、タッチパネルディスプレイを搭載した機器が増えている。画面を直接指で触れることにより操作を行うタッチパネルディスプレイにおいては、表面を保護するハードコート層に対して、画面の精彩性や表面硬度に加え、指紋跡が付着しにくい、付着した指紋跡が目立ちにくい、付着した指紋跡を拭き取りやすい等のいわゆる耐指紋性が求められる。しかしながら、画面の精彩性と表面硬度とを重視した従来のハードコート層は、表面がフラットであるために指紋が付着しやすく、また、付着した指紋が目立ち易い上に拭き取り難いという問題があった。 In recent years, devices equipped with touch panel displays are increasing in mobile phones, game machines, car navigation systems, and the like. In touch panel displays that are operated by touching the screen directly with a finger, the fingerprint marks that adhere to the hard coat layer that protects the surface, in addition to the screen's clarity and surface hardness, are less likely to adhere. What is called fingerprint resistance, such as being difficult and easy to wipe off attached fingerprint marks, is required. However, the conventional hard coat layer, which emphasizes screen clarity and surface hardness, has a problem that fingerprints are easily attached because the surface is flat, and the attached fingerprints are conspicuous and difficult to wipe off. .
そこで、指紋跡が目立ちにくく、且つ、付着した指紋跡が拭き取りやすいハードコート層を得るための組成物として、例えば、重量平均分子量（Ｍｗ）が２，０００のポリプロピレングリコールと、イソホロンジイソシアネートと、ペンタエリスリトールトリアクリレートとを、それぞれ１モルずつ反応させて得られる、片末端がアクリロイル基のウレタンアクリレートを含む光硬化性樹脂組成物が知られている（例えば、特許文献１参照）。しかしながら、特許文献１に開示されている光硬化性組成物からなる塗膜は、通常のハードコートと同等の表面硬度は得られるものの、指紋の目立ち難さ、付着した指紋跡の拭き取りやすさ共に十分な性能が得られるものではなかった。特に指紋の拭き取りやすさに関しては、該光硬化性樹脂組成物を空気雰囲気下で硬化させた場合、空気中に存在する酸素から発生するペルオキシラジカルによる塗膜表面の硬化阻害の影響により、窒素雰囲気下で硬化させた場合に比べて指紋跡の拭き取りやすさが大きく低下する問題があった。 Thus, as a composition for obtaining a hard coat layer in which fingerprint marks are not easily noticeable and attached fingerprint marks are easy to wipe off, for example, polypropylene glycol having a weight average molecular weight (Mw) of 2,000, isophorone diisocyanate, and penta A photo-curable resin composition containing urethane acrylate having one acryloyl group at one end, obtained by reacting 1 mol each of erythritol triacrylate, is known (for example, see Patent Document 1). However, although the coating film made of the photocurable composition disclosed in Patent Document 1 has a surface hardness equivalent to that of a normal hard coat, both the conspicuousness of fingerprints and the ease of wiping off attached fingerprint traces are obtained. Sufficient performance was not obtained. In particular, regarding the ease of wiping off fingerprints, when the photocurable resin composition is cured in an air atmosphere, it is affected by the inhibition of curing of the coating film surface by peroxy radicals generated from oxygen present in the air, and thus a nitrogen atmosphere. There was a problem that the ease of wiping off fingerprint marks was greatly reduced as compared with the case of curing underneath.
本発明が解決しようとする課題は、硬化塗膜が耐指紋性と表面硬度とを高いレベルで兼備し、硬化時の環境が空気雰囲気下であっても、それらの性能を発現することができる活性エネルギー線硬化型樹脂組成物、該組成物を硬化してなる硬化物、及び該組成物の硬化層を有するフィルムを提供することである。 The problem to be solved by the present invention is that the cured coating film has a high level of fingerprint resistance and surface hardness, and even when the environment during curing is in an air atmosphere, the performance can be expressed. An active energy ray-curable resin composition, a cured product obtained by curing the composition, and a film having a cured layer of the composition are provided.
本発明者らは鋭意検討を行った結果、重量平均分子量（Ｍｗ）が５００〜５，０００の範囲であるポリアルキレングリコールと、アルキレンチオエーテル構造を分子構造内に有するジオールとを必須の原料成分として反応させて得られるウレタン（メタ）アクリレートを含有する樹脂組成物を用いることにより、空気雰囲気下で硬化させた場合でも、指紋跡が目立ちにくく、しかも付着した指紋が拭き取りやすいハードコート層が得られること、該組成物を硬化させてなる硬化層は高硬度を示すこと等を見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that polyalkylene glycol having a weight average molecular weight (Mw) in the range of 500 to 5,000 and a diol having an alkylene thioether structure in the molecular structure as essential raw material components. By using a resin composition containing urethane (meth) acrylate obtained by reaction, a hard coat layer is obtained in which fingerprint traces are not noticeable even when cured in an air atmosphere, and the attached fingerprints are easy to wipe off. In addition, the present inventors have found that a cured layer obtained by curing the composition exhibits high hardness and completed the present invention.
即ち、本発明は、重量平均分子量（Ｍｗ）が５００〜５，０００の範囲であるポリアルキレングリコール（ａ１）と、アルキレンチオエーテル構造を分子構造内に有するジオール（ａ２）と、分子量が５００以下であるジイソシアネート（ａ３）と、分子構造中にヒドロキシル基を一つ有する（メタ）アクリレート（ａ４）とを必須の原料成分として反応させて得られる重量平均分子量（Ｍｗ）が１０，０００〜１００，０００の範囲であるウレタン（メタ）アクリレート（Ａ）と、多官能（メタ）アクリレート（Ｂ）とを含有することを特徴とする活性エネルギー線硬化型樹脂組成物を提供するものである。 That is, the present invention relates to a polyalkylene glycol (a1) having a weight average molecular weight (Mw) in the range of 500 to 5,000, a diol (a2) having an alkylene thioether structure in the molecular structure, and a molecular weight of 500 or less. The weight average molecular weight (Mw) obtained by reacting a certain diisocyanate (a3) with (meth) acrylate (a4) having one hydroxyl group in the molecular structure as an essential raw material component is 10,000 to 100,000. An active energy ray-curable resin composition characterized by containing a urethane (meth) acrylate (A) and a polyfunctional (meth) acrylate (B) in the above range.
また、本発明は、前記活性エネルギー線硬化型樹脂組成物を硬化させてなることを特徴とする硬化物を提供するものである。 The present invention also provides a cured product obtained by curing the active energy ray-curable resin composition.
更に、本発明は、前記活性エネルギー線硬化型樹脂組成物を硬化させてなる硬化層をフィルム状基材上に有することを特徴とするフィルムを提供するものである。 Furthermore, this invention provides the film characterized by having the cured layer formed by hardening | curing the said active energy ray hardening-type resin composition on a film-form base material.
本発明の活性エネルギー線硬化型樹脂組成物を用いることにより、表面硬度が高く、かつ、付着した指紋跡が目立ちにくく、付着した指紋を拭き取りやすいハードコート層を形成することができる。ゆえに、本発明の活性エネルギー線硬化型樹脂組成物は、タッチパネルディスプレー等の指紋跡が付着しやすい物品のハードコート層を形成するための組成物として好適である。 By using the active energy ray-curable resin composition of the present invention, it is possible to form a hard coat layer having a high surface hardness, less noticeable fingerprint marks, and easy to wipe off the attached fingerprints. Therefore, the active energy ray-curable resin composition of the present invention is suitable as a composition for forming a hard coat layer of an article to which fingerprint marks such as a touch panel display are easily attached.
本発明を以下に詳細に説明する。
本発明で用いるウレタン（メタ）アクリレート（Ａ）は、重量平均分子量（Ｍｗ）が５００〜５，０００の範囲であるポリアルキレングリコール（ａ１）と、アルキレンチオエーテル構造を分子構造内に有するジオール（ａ２）と、分子量が１００〜５００の範囲であるジイソシアネート（ａ３）と、分子構造中にヒドロキシル基を一つ有する（メタ）アクリレート（ａ４）とを必須の原料成分として反応させて得られるものである。The present invention is described in detail below.
The urethane (meth) acrylate (A) used in the present invention includes a polyalkylene glycol (a1) having a weight average molecular weight (Mw) in the range of 500 to 5,000, and a diol (a2) having an alkylene thioether structure in the molecular structure. ), Diisocyanate (a3) having a molecular weight in the range of 100 to 500, and (meth) acrylate (a4) having one hydroxyl group in the molecular structure are reacted as essential raw material components. .
ここで、前記ウレタン（メタ）アクリレート（Ａ）の原料成分である前記ポリアルキレングリコール（ａ１）は、重量平均分子量（Ｍｗ）が５００〜５，０００の範囲である。重量平均分子量（Ｍｗ）が５００未満の場合には、付着した指紋の目立ち難さの点で十分な性能が発揮されず、また、５，０００を超える場合には、付着した指紋の拭取り易さが十分に発現されない。上記ポリアルキレングリコール（ａ１）の中でも、指紋性分との馴染み易さに優れ、多官能（メタ）アクリレート（Ｂ）との相溶性が良く、かつ、より高硬度の塗膜が得られる点で、重量平均分子量（ＭＷ）が７００〜４，５００の範囲であるものが好ましく、重量平均分子量（Ｍｗ）が１，０００〜４，０００の範囲であるものがより好ましい。 Here, the polyalkylene glycol (a1) which is a raw material component of the urethane (meth) acrylate (A) has a weight average molecular weight (Mw) in the range of 500 to 5,000. When the weight average molecular weight (Mw) is less than 500, sufficient performance cannot be exhibited in terms of difficulty of conspicuous adhesion of the attached fingerprint, and when it exceeds 5,000, the attached fingerprint can be easily wiped off. Is not fully expressed. Among the polyalkylene glycols (a1), the compatibility with the fingerprint component is excellent, the compatibility with the polyfunctional (meth) acrylate (B) is good, and a coating film with higher hardness can be obtained. The weight average molecular weight (MW) is preferably in the range of 700 to 4,500, and the weight average molecular weight (Mw) is more preferably in the range of 1,000 to 4,000.
尚、本発明において、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）は下記条件のゲルパーミアーションクロマトグラフィー（ＧＰＣ）により測定される値である。
測定装置 ；東ソー株式会社製 ＨＬＣ−８２２０ＧＰＣ
カラム ；東ソー株式会社製 ＴＳＫ−ＧＵＡＲＤＣＯＬＵＭＮ ＳｕｐｅｒＨＺ−Ｌ
＋東ソー株式会社製 ＴＳＫ−ＧＥＬ ＳｕｐｅｒＨＺＭ−Ｍ×４
検出器 ；ＲＩ（示差屈折計）
データ処理；東ソー株式会社製 マルチステーションＧＰＣ−８０２０ｍｏｄｅｌＩＩ
測定条件 ；カラム温度 ４０℃
溶媒 テトラヒドロフラン
流速 ０．３５ｍｌ／分
標準 ；単分散ポリスチレン
試料 ；樹脂固形分換算で０．２重量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（１００μｌ）In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) under the following conditions.
Measuring device: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ Tosoh Corporation TSK-GEL SuperHZM-M x 4
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 0.35 ml / min standard; monodisperse polystyrene sample; 0.2 wt% tetrahydrofuran solution in terms of resin solids filtered through a microfilter (100 μl)
ウレタン（メタ）アクリレート（Ａ）中に含まれるポリアルキレングリコール（ａ１）由来のポリアルキレンオキシ構造ユニットの数は、用いるポリアルキレングリコールの重量平均分子量（Ｍｗ）により異なるが、指紋性分のなじみやすさ、多官能（メタ）アクリレート（Ｂ）との相溶性、及び塗膜の表面硬度のいずれにも優れる樹脂組成物が得られることから、１〜２０個の範囲が好ましく、２〜１０個の範囲がより好ましい。特に、ポリアルキレングリコール（ａ１）の重量平均分子量（Ｍｗ）が１，０００〜４，０００の範囲である場合には、２〜６個であることが好ましい。 The number of polyalkyleneoxy structural units derived from the polyalkylene glycol (a1) contained in the urethane (meth) acrylate (A) varies depending on the weight average molecular weight (Mw) of the polyalkylene glycol used, but it is easy to adapt to the fingerprint property. In addition, since a resin composition excellent in both the compatibility with the polyfunctional (meth) acrylate (B) and the surface hardness of the coating film is obtained, the range of 1 to 20 is preferable, and 2 to 10 A range is more preferred. In particular, when the weight average molecular weight (Mw) of the polyalkylene glycol (a1) is in the range of 1,000 to 4,000, it is preferably 2 to 6.
前記ポリアルキレングリコール（ａ１）は、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ポリブチレングリコール、ポリ３−クロロプロピレングリコール等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。これらの中でも、指紋跡が目立ち難いハードコート層が得られることから、ポリプロピレングリコール、ポリブチレングリコールが好ましく、ポリプロピレングリコールがより好ましい。 Examples of the polyalkylene glycol (a1) include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and poly-3-chloropropylene glycol. These may be used alone or in combination of two or more. Among these, polypropylene glycol and polybutylene glycol are preferable, and polypropylene glycol is more preferable because a hard coat layer in which fingerprint marks are hardly noticeable is obtained.
本発明では、前述の通り、ウレタン（メタ）アクリレート（Ａ）の原料成分としてアルキレンチオエーテル構造を分子構造内に有するジオール（ａ２）を用いることにより、窒素雰囲気下及び空気雰囲気下のいずれの硬化条件であっても、指紋の拭取りやすさに優れる硬化塗膜を得ることができる。 In the present invention, as described above, by using the diol (a2) having an alkylene thioether structure in the molecular structure as a raw material component of the urethane (meth) acrylate (A), any curing condition in a nitrogen atmosphere or an air atmosphere is used. Even so, it is possible to obtain a cured coating film excellent in ease of fingerprint wiping.
本発明で用いるアルキレンチオエーテル構造を分子構造中に有するジオール（ａ２）は、例えば、２，２’−チオジエタノール、３−チア−１，６−ヘキサンジオール、１−（２−ヒドロキシエチルチオ）−２−プロパノール、４−メチル−２−チアペンタン−１，５−ジオール、１−クロロ−３−（２−ヒドロキシエチルチオ）−２−プロパノール、３，３’−チオビス（１−プロパノール）、２，２’−チオビス（１−プロパノール）、１，１’−チオビス（２−プロパノール）、５−メチル−３−チアヘキサン−１，６−ジオール、３−オキサ−６−チアオクタン−１，８−ジオール等の分子構造中に硫黄原子を一つ有する化合物； Examples of the diol (a2) having an alkylene thioether structure in the molecular structure used in the present invention include 2,2′-thiodiethanol, 3-thia-1,6-hexanediol, 1- (2-hydroxyethylthio)- 2-propanol, 4-methyl-2-thiapentane-1,5-diol, 1-chloro-3- (2-hydroxyethylthio) -2-propanol, 3,3′-thiobis (1-propanol), 2, 2′-thiobis (1-propanol), 1,1′-thiobis (2-propanol), 5-methyl-3-thiahexane-1,6-diol, 3-oxa-6-thiaoctane-1,8-diol, etc. A compound having one sulfur atom in its molecular structure;
２，２’−（メチレンビスチオ）ジエタノール、１，２−ビス（２−ヒドロキシエチルチオ）エタン、３，３’−ジチオビス（１−プロパノール）、１，１’−ジチオビス（２−プロパノール）、ビス（２−ヒドロキシ−１−メチルエチル）ペルスルフィド、２，２’−［オキシビス（メチレンチオ）］ビスエタノール、３，９−ジチア−６−オキサノナン−１，９−ジオール、２，２’−（トリメチレンビスチオ）ジエタノール、２，２’−（テトラメチレンビスチオ）ジエタノール、４，４’−ジチオビス（１−ブタノール）、１，１’−（エチレンビスチオ）ビス（２−プロパノール）、３−［２−（３−ヒドロキシプロピルスルファニル）エチルスルファニル］プロパン−１−オール、２，２’−［オキシビス（エチレンチオ）］ジエタノール、２，２’−［（２−メチル−１，４−ブタンジイル）ビス（チオ）］ビスエタノール、２，２’−（ペンタメチレンビスチオ）ジエタノール、２，２’−（ヘキサメチレンビスチオ）ジエタノール、１，１’−（エチレンビスチオ）ビス（２−ブタノール）、３，３’−ジチオビス（３−メチル−２−ブタノール）、ビス（５−ヒドロキシペンチル）ペルスルフィド、４，９−ジチアドデカン−１，１２−ジオール、１−（２−［２−（２−ヒドロキシプロピルスルファニル）エトキシ］エチルスルファニル）プロパン−２−オール、２，２’−［エチレンビス（オキシエチレンチオ）］ジエタノール、２，２’−（オキシエチレンチオエチレンオキシエチレンチオ）ジエタノール、２，２’−（オクタメチレンビスチオ）ジエタノール、６，６’−ジチオビス（１−ヘキサノール）、４，１１−ジチアテトラデカン−１，１４−ジオール、ビス［１−（ヒドロキシメチル）−１−エチルプロピル］ペルスルフィド、２−［９−（２−ヒドロキシエチルチオ）ノニルチオ］エタノール、チアデノール、２，２’−（１，１０−デカンジイルビスチオ）ジエタノール等の分子構造中に硫黄原子を２つ有する化合物； 2,2 ′-(methylenebisthio) diethanol, 1,2-bis (2-hydroxyethylthio) ethane, 3,3′-dithiobis (1-propanol), 1,1′-dithiobis (2-propanol), Bis (2-hydroxy-1-methylethyl) persulfide, 2,2 ′-[oxybis (methylenethio)] bisethanol, 3,9-dithia-6-oxanonane-1,9-diol, 2,2 ′-( Trimethylenebisthio) diethanol, 2,2 ′-(tetramethylenebisthio) diethanol, 4,4′-dithiobis (1-butanol), 1,1 ′-(ethylenebisthio) bis (2-propanol), 3 -[2- (3-hydroxypropylsulfanyl) ethylsulfanyl] propan-1-ol, 2,2 '-[oxybis (ethylenethio)] di Tanol, 2,2 ′-[(2-methyl-1,4-butanediyl) bis (thio)] bisethanol, 2,2 ′-(pentamethylenebisthio) diethanol, 2,2 ′-(hexamethylenebisthio) ) Diethanol, 1,1 ′-(ethylenebisthio) bis (2-butanol), 3,3′-dithiobis (3-methyl-2-butanol), bis (5-hydroxypentyl) persulfide, 4,9- Dithiadecane-1,12-diol, 1- (2- [2- (2-hydroxypropylsulfanyl) ethoxy] ethylsulfanyl) propan-2-ol, 2,2 ′-[ethylenebis (oxyethylenethio)] diethanol, 2,2 ′-(oxyethylenethioethyleneoxyethylenethio) diethanol, 2,2 ′-(octamethylenebisthio) die Diol, 6,6′-dithiobis (1-hexanol), 4,11-dithiatetradecane-1,14-diol, bis [1- (hydroxymethyl) -1-ethylpropyl] persulfide, 2- [9- (2-hydroxyethylthio) nonylthio] a compound having two sulfur atoms in the molecular structure such as ethanol, thiadenol, 2,2 ′-(1,10-decandiylbisthio) diethanol;
２，２’−［チオビス（エチレンチオ）］ジエタノール、２，２’−［チオエチレンオキシエチレン（ジチオ）］ジエタノール、１−（２−［２−（２−ヒドロキシプロピルスルファニル）エチルスルファニル］エチルスルファニル）プロパン−２−オール、２−［２−［２−（２−ヒドロキシエチルチオ）プロピルチオ］−１−メチルエチルチオ］エタノール、６−オキサ−３，９，１２−トリチア−１，１４−テトラデカンジオール、１−（２−［２−（２−ヒドロキシプロピルスルファニル）プロピルスルファニル］１−メチル−エチルスルファニル）プロパン−２−オール、２，２’−［チオビス（エチレンオキシエチレンチオ）］ジエタノール、３，１２−ジオキサ−６，９，１５−トリチア−１，１７−ヘプタデカンジオール等の分子構造中に硫黄原子を３つ有する化合物； 2,2 ′-[thiobis (ethylenethio)] diethanol, 2,2 ′-[thioethyleneoxyethylene (dithio)] diethanol, 1- (2- [2- (2-hydroxypropylsulfanyl) ethylsulfanyl] ethylsulfanyl) Propan-2-ol, 2- [2- [2- (2-hydroxyethylthio) propylthio] -1-methylethylthio] ethanol, 6-oxa-3,9,12-trithia-1,14-tetradecanediol 1- (2- [2- (2-hydroxypropylsulfanyl) propylsulfanyl] 1-methyl-ethylsulfanyl) propan-2-ol, 2,2 ′-[thiobis (ethyleneoxyethylenethio)] diethanol, 3, 12-dioxa-6,9,15-trithia-1,17-heptadecanediol and the like Compounds having three sulfur atoms in the molecular structure;
２，２’−［１，２−エタンジイルビス（ジチオ）］ビスエタノール、２−［２−［２−（２−ヒドロキシエチルチオ）エチルジチオ］エチルチオ］エタノール、３，６，９，１２−テトラチアテトラデカン−１，１４−ジオール等の分子構造中に硫黄原子を４つ有する化合物が挙げられる。 2,2 ′-[1,2-ethanediylbis (dithio)] bisethanol, 2- [2- [2- (2-hydroxyethylthio) ethyldithio] ethylthio] ethanol, 3,6,9,12-tetrathiatetradecane Examples thereof include compounds having 4 sulfur atoms in the molecular structure such as -1,14-diol.
これらの中でも、塗膜の空気雰囲気下での硬化性と耐指紋性とのバランスに優れる点で、下記一般式（１）又は一般式（２）で示される化合物が好ましい。 Among these, the compound represented by the following general formula (1) or general formula (2) is preferable in that the balance between curability of the coating film in an air atmosphere and fingerprint resistance is excellent.
上記一般式（１）で示される化合物の具体例としては、例えば、２，２’−チオジエタノール、３−チア−１，６−ヘキサンジオール、１−（２−ヒドロキシエチルチオ）−２−プロパノール、４−メチル−２−チアペンタン−１，５−ジオール、１−クロロ−３−（２−ヒドロキシエチルチオ）−２−プロパノール、３，３’−チオビス（１−プロパノール）、２，２’−チオビス（１−プロパノール）、１，１’−チオビス（２−プロパノール）、５−メチル−３−チアヘキサン−１，６−ジオール、３−オキサ−６−チアオクタン−１，８−ジオール等の分子構造中に硫黄原子を一つ有する化合物；２，２’−（メチレンビスチオ）ジエタノール、１，２−ビス（２−ヒドロキシエチルチオ）エタン、２，２’−［オキシビス（メチレンチオ）］ビスエタノール、２，２’−（トリメチレンビスチオ）ジエタノール、２，２’−（テトラメチレンビスチオ）ジエタノール、１，１’−（エチレンビスチオ）ビス（２−プロパノール）、３−［２−（３−ヒドロキシプロピルスルファニル）エチルスルファニル］プロパン−１−オール、２，２’−［オキシビス（エチレンチオ）］ジエタノール、１，１’−（エチレンビスチオ）ビス（２−ブタノール）、４，９−ジチアドデカン−１，１２−ジオール、１−（２−［２−（２−ヒドロキシプロピルスルファニル）エトキシ］エチルスルファニル）プロパン−２−オール、２，２’−［エチレンビス（オキシエチレンチオ）］ジエタノール、２，２’−（オキシエチレンチオエチレンオキシエチレンチオ）ジエタノール等の分子構造中に硫黄原子を二つ有する化合物；２，２’−［チオビス（エチレンチオ）］ジエタノール、１−（２−［２−（２−ヒドロキシプロピルスルファニル）エチルスルファニル］エチルスルファニル）プロパン−２−オール、２−［２−［２−（２−ヒドロキシエチルチオ）プロピルチオ］−１−メチルエチルチオ］エタノール、６−オキサ−３，９，１２−トリチア−１，１４−テトラデカンジオール、１−（２−［２−（２−ヒドロキシプロピルスルファニル）プロピルスルファニル］１−メチル−エチルスルファニル）プロパン−２−オール、２，２’−［チオビス（エチレンオキシエチレンチオ）］ジエタノール、３，１２−ジオキサ−６，９，１５−トリチア−１，１７−ヘプタデカンジオール等の分子構造中に硫黄原子を三つ有する化合物；３，６，９，１２−テトラチアテトラデカン−１，１４−ジオール等の分子構造中に硫黄原子を４つ有する化合物等が挙げられる。 Specific examples of the compound represented by the general formula (1) include, for example, 2,2′-thiodiethanol, 3-thia-1,6-hexanediol, 1- (2-hydroxyethylthio) -2-propanol 4-methyl-2-thiapentane-1,5-diol, 1-chloro-3- (2-hydroxyethylthio) -2-propanol, 3,3′-thiobis (1-propanol), 2,2′- Molecular structures such as thiobis (1-propanol), 1,1′-thiobis (2-propanol), 5-methyl-3-thiahexane-1,6-diol, 3-oxa-6-thiaoctane-1,8-diol Compound having one sulfur atom in it; 2,2 ′-(methylenebisthio) diethanol, 1,2-bis (2-hydroxyethylthio) ethane, 2,2 ′-[oxybis (methyl) Thio)] bisethanol, 2,2 ′-(trimethylenebisthio) diethanol, 2,2 ′-(tetramethylenebisthio) diethanol, 1,1 ′-(ethylenebisthio) bis (2-propanol), 3 -[2- (3-hydroxypropylsulfanyl) ethylsulfanyl] propan-1-ol, 2,2 '-[oxybis (ethylenethio)] diethanol, 1,1'-(ethylenebisthio) bis (2-butanol), 4,9-dithiadecane-1,12-diol, 1- (2- [2- (2-hydroxypropylsulfanyl) ethoxy] ethylsulfanyl) propan-2-ol, 2,2 ′-[ethylenebis (oxyethylenethio) )] Diethanol, 2,2 '-(oxyethylenethioethyleneoxyethylenethio) diethanol, etc. Compound having two sulfur atoms in the structure; 2,2 ′-[thiobis (ethylenethio)] diethanol, 1- (2- [2- (2-hydroxypropylsulfanyl) ethylsulfanyl] ethylsulfanyl) propan-2-ol 2- [2- [2- (2-hydroxyethylthio) propylthio] -1-methylethylthio] ethanol, 6-oxa-3,9,12-trithia-1,14-tetradecanediol, 1- (2 -[2- (2-hydroxypropylsulfanyl) propylsulfanyl] 1-methyl-ethylsulfanyl) propan-2-ol, 2,2 '-[thiobis (ethyleneoxyethylenethio)] diethanol, 3,12-dioxa-6 , 9,15-trithia-1,17-heptadecanediol, etc. Compounds having four sulfur atoms in the molecular structure such as 3,6,9,12-tetrathiatetradecane-1,14-diol.
更に、上記化合物の中でも、塗膜の空気雰囲気下での硬化性と耐指紋性とのバランスにより優れる点で、２，２’−チオビス（１−プロパノール）、１，２−ビス（２−ヒドロキシエチルチオ）エタン、２−［２−［２−（２−ヒドロキシエチルチオ）プロピルチオ］−１−メチルエチルチオ］エタノール、１−（２−［２−（２−ヒドロキシプロピルスルファニル）プロピルスルファニル］１−メチル−エチルスルファニル）プロパン−２−オールが特に好ましい。 Furthermore, among the above compounds, 2,2′-thiobis (1-propanol) and 1,2-bis (2-hydroxy) are superior in terms of the balance between curability of the coating film in an air atmosphere and fingerprint resistance. Ethylthio) ethane, 2- [2- [2- (2-hydroxyethylthio) propylthio] -1-methylethylthio] ethanol, 1- (2- [2- (2-hydroxypropylsulfanyl) propylsulfanyl] 1 -Methyl-ethylsulfanyl) propan-2-ol is particularly preferred.
本発明で用いるジイソシアネート（ａ３）は、分子量が５００以下である。分子量が５００を超える場合には、塗膜の耐指紋性が十分に発現しない。これらの中でも、塗膜の耐指紋性に優れる点で、分子量が１５０〜４５０の範囲であるものがより好ましい。このようなジイソシアネートは例えば、芳香族ジイソシアネート、脂肪族ジイソシアネート等が挙げられる。 The diisocyanate (a3) used in the present invention has a molecular weight of 500 or less. When the molecular weight exceeds 500, fingerprint resistance of the coating film is not sufficiently exhibited. Among these, those having a molecular weight in the range of 150 to 450 are more preferable in that the coating film has excellent fingerprint resistance. Examples of such diisocyanates include aromatic diisocyanates and aliphatic diisocyanates.
前記芳香族ジイソシアネートは、例えば、トリレンジイソシアネート（ＴＤＩ）、ジフェニルメタンジイソシアネート（ＭＤＩ）、ｐ−フェニレンジイソシアネート、ナフタレンジイソシアネート、キシリレンジイソシアネート（ＸＤＩ）及びテトラメチルキシリレンジイソシアネート（ＴＭＸＤＩ）等が挙げられる。 Examples of the aromatic diisocyanate include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate (XDI), and tetramethylxylylene diisocyanate (TMXDI).
前記脂肪族ジイソシアネートは、ヘキサメチレンジイソシアネート（ＨＭＤＩ）、２，２，４−トリメチルヘキサンジイソシアネート及びリジンジイソシアネート等の鎖状ジイソシアネート；１，４−シクロヘキサンジイソシアネート（ＣＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、４，４’−ジシクロヘキシルメタンジイソシアネート（水添ＭＤＩ）、メチルシクロヘキサンジイソシアネート、イソプロピリデンジシクロヘキシル−４，４’−ジイソシアネート、１，３−ジイソシアナトメチルシクロヘキサン（水添ＸＤＩ）、４−メチル−１，３−シクロヘキシレンジイソシアナート（水添ＴＤＩ）、ノルボルナンジイソシアネート等の脂環式ジイソシアネート等が挙げられる。 The aliphatic diisocyanate is a chain diisocyanate such as hexamethylene diisocyanate (HMDI), 2,2,4-trimethylhexane diisocyanate and lysine diisocyanate; 1,4-cyclohexane diisocyanate (CDI), isophorone diisocyanate (IPDI), 4,4 '-Dicyclohexylmethane diisocyanate (hydrogenated MDI), methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, 1,3-diisocyanatomethylcyclohexane (hydrogenated XDI), 4-methyl-1,3-cyclohexyl Examples thereof include cycloaliphatic diisocyanates such as silylene isocyanate (hydrogenated TDI) and norbornane diisocyanate.
前記ジリイソシアネート（ａ３）はそれぞれ単独で用いても良いし、２種類以上を併用しても良い。中でも、得られるウレタン（メタ）アクリレート（Ａ）が多官能（メタ）アクリレート（Ｂ）との相溶性に優れる化合物となる点で芳香族ジイソシアネート又は脂環式ジイソシアネートが好ましく、トリレンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネートがより好ましい。 Each of the diisocyanates (a3) may be used alone or in combination of two or more. Among them, aromatic diisocyanate or alicyclic diisocyanate is preferable in that the obtained urethane (meth) acrylate (A) is a compound having excellent compatibility with the polyfunctional (meth) acrylate (B), tolylene diisocyanate, 4, 4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate are more preferred.
本発明で用いる分子構造中にヒドロキシル基を一つ有する（メタ）アクリレート（ａ４）は、例えば、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート等の（メタ）アクリロイル基を一つ有するヒドロキシ（メタ）アクリレート；グリセリンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ソルビトールペンタ（メタ）アクリレート等の（メタ）アクリロイル基を二つ以上有するヒドロキシ（メタ）アクリレート等が挙げられる。これらはそれぞれ単独で用いても良いし、二種類以上を併用しても良い。 The (meth) acrylate (a4) having one hydroxyl group in the molecular structure used in the present invention is, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy- Hydroxy (meth) acrylate having one (meth) acryloyl group such as 3-phenoxypropyl (meth) acrylate; glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, di Examples thereof include hydroxy (meth) acrylate having two or more (meth) acryloyl groups such as pentaerythritol penta (meth) acrylate and sorbitol penta (meth) acrylate. These may be used alone or in combination of two or more.
これらの中でも、付着した指紋跡が目立ちにくく、かつ、付着した指紋を拭き取りやすいハードコート層が得られることから（メタ）アクリロイル基を一つ有するヒドロキシ（メタ）アクリレートが好ましく、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレートがより好ましい。 Among these, hydroxy (meth) acrylate having one (meth) acryloyl group is preferable, since a hard coat layer in which the attached fingerprint trace is not noticeable and the attached fingerprint can be easily wiped off is preferable, and hydroxyethyl (meth) An acrylate and a hydroxypropyl (meth) acrylate are more preferable.
本発明で用いるウレタン（メタ）アクリレート（Ａ）を製造する方法は、例えば、前記重量平均分子量が５００〜５，０００の範囲であるポリアルキレングリコール（ａ１）と、前記アルキレンチオエーテル構造を分子構造内に有するジオール（ａ２）と、前記ジイソシアネート（ａ３）とを反応させて得られるイソシアネート基含有ウレタンプレポリマーを製造する工程（工程１）と、これに次ぐ、該ウレタンプレポリマーと前記分子構造中にヒドロキシル基を一つ有する（メタ）アクリレート（ａ４）とを反応させる工程（工程２）とによる方法が挙げられる。 The method for producing the urethane (meth) acrylate (A) used in the present invention includes, for example, a polyalkylene glycol (a1) having a weight average molecular weight in the range of 500 to 5,000 and the alkylene thioether structure in the molecular structure. In the step (Step 1) for producing an isocyanate group-containing urethane prepolymer obtained by reacting the diol (a2) having a diisocyanate (a3) with the urethane prepolymer and the molecular structure The method by the process (process 2) with which (meth) acrylate (a4) which has one hydroxyl group is made to react is mentioned.
前記工程１に関して詳述すると、前記イソシアネート基含有ウレタンプレポリマーの製造方法は、例えば、ポリアルキレングリコール（ａ１）と、アルキレンチオエーテル構造を分子構造内に有するジオール（ａ２）と、ジイソシアネート（ａ３）とを、ウレタン化触媒であるオクタン酸スズ（ＩＩ）５００ｐｐｍと、重合禁止剤メトキノン３００ｐｐｍとの存在下、７０〜１２０℃の温度条件下で反応させる方法が挙げられる。 The production method of the isocyanate group-containing urethane prepolymer will be described in detail with respect to the step 1. For example, the polyalkylene glycol (a1), the diol (a2) having an alkylene thioether structure in the molecular structure, and the diisocyanate (a3) Can be reacted in the presence of 500 ppm of tin (II) octoate as a urethanization catalyst and 300 ppm of the polymerization inhibitor methoquinone at a temperature of 70 to 120 ° C.
前記工程１において、ポリアルキレングリコール（ａ１）と、アルキレンチオエーテル構造を分子構造内に有するジオール（ａ２）との含有量のモル比〔（ａ１）／（ａ２）〕は、空気雰囲気下で硬化させた場合にも付着した指紋を拭き取りやすいハードコート層が得られることから、〔１．０／０．２〕〜〔１．０／５．０〕となる範囲であることが好ましく、〔１．０／０．５〕〜〔１．０／２．０〕の範囲であることがより好ましい。 In the step 1, the molar ratio [(a1) / (a2)] of the polyalkylene glycol (a1) and the diol (a2) having an alkylene thioether structure in the molecular structure is cured in an air atmosphere. In this case, a hard coat layer that can easily wipe off the attached fingerprint is obtained, and therefore, it is preferably in the range of [1.0 / 0.2] to [1.0 / 5.0]. The range of 0 / 0.5] to [1.0 / 2.0] is more preferable.
また、前記工程１において、ポリアルキレングリコール（ａ１）中のヒドロキシル基のモル数をＦ１、アルキレンチオエーテル構造を分子構造内に有するジオール（ａ２）中のヒドロキシル基のモル数をＦ２、ジイソシアネート（ａ３）中のイソシアネート基のモル数をＦ３とし、系中に含まれるヒドロキシル基のモル数とイソシアネート基のモル数との比〔（Ｆ１＋Ｆ２）／Ｆ３〕は、〔１／１．０５〕〜〔１／３〕の範囲であることが好ましく、〔１／１．１〕〜〔１／２〕の範囲であることがより好ましい。In Step 1, the number of moles of hydroxyl groups in the polyalkylene glycol (a1) is F 1 , the number of moles of hydroxyl groups in the diol (a2) having an alkylene thioether structure in the molecular structure is F 2 , diisocyanate ( the number of moles of isocyanate groups in a3) and F 3, the ratio of the number of moles and the isocyanate groups of the hydroxyl groups contained in the system [(F 1 + F 2) / F 3 ] is [1/1 .05] to [1/3], and more preferably [1 / 1.1] to [1/2].
前記工程２に関して詳述すると、例えば、前記イソシアネート基含有ウレタンプレポリマーと、前記分子構造中にヒドロキシル基を一つ有する（メタ）アクリレート（ａ４）とを、ウレタン化触媒であるオクタン酸スズ（ＩＩ）を３００〜８００ｐｐｍの範囲で添加し、かつ、重合禁止剤であるメトキノンを１００〜５００ｐｐｍの範囲で添加して、８０℃の温度条件下で反応させる方法が挙げられる。 The step 2 will be described in detail. For example, the isocyanate group-containing urethane prepolymer and the (meth) acrylate (a4) having one hydroxyl group in the molecular structure are mixed with octoate tin (II) which is a urethanization catalyst. ) Is added in the range of 300 to 800 ppm, and methoquinone, which is a polymerization inhibitor, is added in the range of 100 to 500 ppm, and the reaction is performed at a temperature of 80 ° C.
前期工程２において、イソシアネート基含有ウレタンプレポリマー中のイソシアネート基のモル数ＦＮＣＯと、分子構造中にヒドロキシル基を有する（メタ）アクリレート中のヒドロキシル基のモル数ＦＯＨとの比〔ＦＮＣＯ／ＦＯＨ〕は、〔１／１〕〜〔１／１．２〕の範囲であることが好ましく、〔１／１．０１〕〜〔１／１．０５〕の範囲であることがより好ましい。In the first step 2, the ratio of the number of moles F NCO of isocyanate groups in the isocyanate group-containing urethane prepolymer to the number of moles F OH of hydroxyl groups in the (meth) acrylate having a hydroxyl group in the molecular structure [F NCO / F OH ] is preferably in the range of [1/1] to [1 / 1.2], and more preferably in the range of [1 / 1.01] to [1 / 1.05].
このようにして得られる前記ウレタン（メタ）アクリレート（Ａ）は、指紋性分のなじみやすさ、塗膜の硬度、及び多官能（メタ）アクリレート（Ｂ）との相溶性のいずれにも優れる樹脂組成物が得られることから、重量平均分子量（Ｍｗ）が１０，０００〜１００，０００の範囲である。これらの中でも、付着した指紋の目立ち難さと、拭取りやすさとの両方の性能のバランスに優れる塗膜が得られる点で、２０，０００〜８０，０００の範囲であることがより好ましい。 The urethane (meth) acrylate (A) thus obtained is a resin excellent in all of compatibility with the fingerprint property, the hardness of the coating film, and the compatibility with the polyfunctional (meth) acrylate (B). Since the composition is obtained, the weight average molecular weight (Mw) is in the range of 10,000 to 100,000. Among these, the range of 20,000 to 80,000 is more preferable in that a coating film having an excellent balance between the performance of both the conspicuousness of attached fingerprints and the ease of wiping can be obtained.
本発明で用いる多官能（メタ）アクリレート（Ｂ）は、分子量が６００未満であるモノマー型の多官能（メタ）アクリレート（ｂ１）と、分子量が６００〜３，０００の範囲であるオリゴマー型の多官能（メタ）アクリレート（ｂ２）とを併用する。分子量が６００未満のモノマー型の多官能（メタ）アクリレート（ｂ１）としては、例えば、ブタンジオールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、エトキシ化ヘキサンジオールジ（メタ）アクリレート、プロポキシ化ヘキサンジオールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エトキシ化ネオペンチルグリコールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレートなどのジ（メタ）アクリレート；
The polyfunctional (meth) acrylate (B) used in the present invention includes a monomer-type polyfunctional (meth) acrylate (b1) having a molecular weight of less than 600, and an oligomer-type polyfunctional (meth) acrylate having a molecular weight in the range of 600 to 3,000. A functional (meth) acrylate (b2) is used in combination . Examples of monomer-type polyfunctional (meth) acrylate (b1) having a molecular weight of less than 600 include butanediol di (meth) acrylate, hexanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, and propoxylation Hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate Di (meth) acrylates such as hydroxypivalic acid neopentyl glycol di (meth) acrylate;
トリメチロールプロパントリ（メタ）アクリレート、エトキシ化トリメチロールプロパントリ（メタ）アクリレート、プロポキシ化トリメチロールプロパントリ（メタ）アクリレート、トリス２―ヒドロキシエチルイソシアヌレートトリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート等のトリ（メタ）アクリレート； Trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, tris 2-hydroxyethyl isocyanurate tri (meth) acrylate, glycerin tri (meth) acrylate Tri (meth) acrylates such as;
ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジトリメチロールプロパンペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジトリメチロールプロパンヘキサ（メタ）アクリレート等の４官能以上の（メタ）アクリレート； Pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) Tetrafunctional or higher functional (meth) acrylates such as acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate;
および、上記した各種多官能（メタ）アクリレートの一部をアルキル基やε−カプロラクトンで置換した（メタ）アクリレート等が挙げられる。 And the (meth) acrylate etc. which substituted a part of above-mentioned various polyfunctional (meth) acrylate with the alkyl group and (epsilon) -caprolactone, etc. are mentioned.
前記モノマー型の多官能（メタ）アクリレート（ｂ１）の中でも、より高硬度の塗膜が得られることから、４官能以上の（メタ）アクリレートが好ましく、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレートがより好ましい。更に、塗膜の表面硬度と耐カール性とに優れる点で、ジペンタエリスリトールペンタアクリレート（ｂ５）と、ジペンタエリスリトールヘキサアクリレート（ｂ６）との混合物（ｂ５６）が特に好ましく、このとき、ジペンタエリスリトールペンタアクリレート（ｂ５）とジペンタエリスリトールヘキサアクリレート（ｂ６）との質量比〔（ｂ５）／（ｂ６）］は３／７〜７／３の範囲であることが好ましく、４／６〜５／５の範囲であることがより好ましい。 Among the monomer-type polyfunctional (meth) acrylates (b1), a coating film having higher hardness can be obtained, and therefore, a tetrafunctional or higher functional (meth) acrylate is preferable. Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate Is more preferable. Furthermore, a mixture (b56) of dipentaerythritol pentaacrylate (b5) and dipentaerythritol hexaacrylate (b6) is particularly preferred from the viewpoint of excellent surface hardness and curl resistance of the coating film. The mass ratio [(b5) / (b6)] of erythritol pentaacrylate (b5) to dipentaerythritol hexaacrylate (b6) is preferably in the range of 3/7 to 7/3, and 4/6 to 5 /. A range of 5 is more preferable.
前記オリゴマー型の多官能（メタ）アクリレート（ｂ２）は、重量平均分子量（Ｍｗ）が６００〜３，０００の範囲であることで、塗膜の表面硬度と耐カール性とに優れる塗膜が得られる。該オリゴマー型の多官能（メタ）アクリレート（ｂ２）は、例えば、ポリエステル（メタ）アクリレート、ウレタン（メタ）アクリレート、エポキシ（メタ）アクリレート、アクリル（メタ）アクリレート等が挙げられる。これらの多官能（メタ）アクリレート（Ｂ）はそれぞれ単独で用いても良いし、二種類以上を併用しても良い。これらの中でも、より高硬度の塗膜が得られる点で、多官能ウレタン（メタ）アクリレート（ｂ４）が好ましい。 The oligomer type polyfunctional (meth) acrylate (b2) has a weight average molecular weight (Mw) in the range of 600 to 3,000, so that a coating film having excellent surface hardness and curl resistance can be obtained. It is done. Examples of the oligomer type polyfunctional (meth) acrylate (b2) include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, and acrylic (meth) acrylate. These polyfunctional (meth) acrylates (B) may be used alone or in combination of two or more. Among these, polyfunctional urethane (meth) acrylate (b4) is preferable in that a coating film having higher hardness can be obtained.
前記オリゴマー型の多官能（メタ）アクリレート（ｂ２）として用いる多官能ウレタン（メタ）アクリレート（ｂ４）は、例えば、ポリイソシアネートと、分子構造中に水酸基を有する多官能（メタ）アクリレートとを、ポリイソシアネート中のイソシアネート基のモル数ＦＮＣＯと、分子構造中に水酸基を有する（メタ）アクリレート中の水酸基のモル数ＦＯＨとの比〔ＦＮＣＯ／ＦＯＨ〕が、〔１／１〕〜〔１／１．２〕の範囲となるように反応させて得ることができる。The polyfunctional urethane (meth) acrylate (b4) used as the oligomer type polyfunctional (meth) acrylate (b2) is, for example, a polyisocyanate and a polyfunctional (meth) acrylate having a hydroxyl group in the molecular structure. The ratio [F NCO / F OH ] of the number of moles F NCO of isocyanate groups in the isocyanate to the number of moles F OH of hydroxyl groups in the (meth) acrylate having a hydroxyl group in the molecular structure is [1/1] to [ It can be obtained by reacting to be in the range of [1 / 1.2].
該ポリイソシアネートは、例えば、前記ジイソシアネート（ａ３）として列記した各種のジイソシアネートが挙げられる。また、該分子構造中に水酸基を有する多官能（メタ）アクリレートは、例えば、前記分子構造中にヒドロキシル基を一つ有する（メタ）アクリレート（ａ４）として列記した各種の（メタ）アクリレートが挙げられる。これらの中でも、より高硬度の塗膜が得られることから、ヘキサメチレンジイソシアネートとペンタエリスリトールトリ（メタ）アクリレートとを反応させて得られるウレタン（メタ）アクリレートが好ましい。 Examples of the polyisocyanate include various diisocyanates listed as the diisocyanate (a3). Examples of the polyfunctional (meth) acrylate having a hydroxyl group in the molecular structure include various (meth) acrylates listed as (meth) acrylate (a4) having one hydroxyl group in the molecular structure. . Among these, urethane (meth) acrylate obtained by reacting hexamethylene diisocyanate and pentaerythritol tri (meth) acrylate is preferable because a coating film having higher hardness can be obtained.
本発明で用いる多官能（メタ）アクリレート（Ｂ）の中でも、塗膜の硬度、透明性、及び耐カール性に優れる点で、前記モノマー型の多官能（メタ）アクリレート（ｂ１）として、ジペンタエリスリトールペンタアクリレート（ｂ５）とジペンタエリスリトールヘキサアクリレート（ｂ６）との混合物（ｂ５６）を用い、前記オリゴマー型の多官能（メタ）アクリレートとしてウレタン（メタ）アクリレート（ｂ４）を用いることが好ましく、これらの質量比［（ｂ５６）／（ｂ４）］は［１／２］〜［２〜１］の範囲であることが好ましい。 Among the polyfunctional (meth) acrylates (B) used in the present invention, dipentadiene is used as the monomer-type polyfunctional (meth) acrylate (b1) in that the coating film has excellent hardness, transparency, and curl resistance. It is preferable to use a urethane (meth) acrylate (b4) as the oligomer-type polyfunctional (meth) acrylate using a mixture (b56) of erythritol pentaacrylate (b5) and dipentaerythritol hexaacrylate (b6). The mass ratio [(b56) / (b4)] is preferably in the range of [1/2] to [2-1].
本発明では、前記ウレタン（メタ）アクリレート（Ａ）と多官能（メタ）アクリレート（Ｂ）とを、質量比［（Ａ）／（Ｂ）］が［０．１／９９．９］〜［１５／８５］の範囲となるように含有することを特徴とする。前記ウレタン（メタ）アクリレート（Ａ）を上記範囲で用いることによりハードコート層の硬度を下げることなく付着した指紋跡が目立ちにくく、且つ、付着した指紋を容易に拭き取ることができるハードコート層が得られる。ウレタン（メタ）アクリレート（Ａ）と多官能（メタ）アクリレート（Ｂ）は、質量比〔（Ａ）／（Ｂ）〕で０．１／９９．９〜１０／９０の範囲で含有することが好ましく、質量比〔（Ａ）／（Ｂ）〕で０．１／９９〜５／９５の範囲で含有することがより好ましい。 In the present invention, the urethane (meth) acrylate (A) and the polyfunctional (meth) acrylate (B) have a mass ratio [(A) / (B)] of [0.1 / 99.9] to [15]. / 85] to be included. By using the urethane (meth) acrylate (A) in the above range, it is possible to obtain a hard coat layer in which the attached fingerprint trace is not noticeable without lowering the hardness of the hard coat layer and the attached fingerprint can be easily wiped off. It is done. Urethane (meth) acrylate (A) and polyfunctional (meth) acrylate (B) may be contained in a mass ratio [(A) / (B)] in the range of 0.1 / 99.9 to 10/90. Preferably, it is contained in the range of 0.1 / 99 to 5/95 by mass ratio [(A) / (B)].
本発明の活性エネルギー線硬化型樹脂組成物には本発明の効果を損なわない範囲で有機溶剤を混合させても良い。有機溶剤としては、通常、沸点が５０〜２００℃のものが、塗工時の作業性、硬化前後の乾燥性に優れる活性エネルギー線硬化型塗料用樹脂組成物や活性エネルギー線硬化型塗料が得られる点から好ましく、例えば、メタノール、イソプロピルアルコール、ｎ−ブタノール、イソブタノール等のアルコール系溶剤；酢酸メチル、酢酸エチル、酢酸ブチル、エチレングリコールモノエチルエーテル、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート等のエステル系溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤；トルエン、キシレン等の芳香族系溶剤、またはこれらの混合物類等が挙げられる。 The active energy ray-curable resin composition of the present invention may be mixed with an organic solvent as long as the effects of the present invention are not impaired. As an organic solvent, those having a boiling point of 50 to 200 ° C. are usually used to obtain a resin composition for active energy ray-curable coatings and an active energy ray-curable paint that are excellent in workability during coating and drying before and after curing. For example, alcohol solvents such as methanol, isopropyl alcohol, n-butanol and isobutanol; methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether Examples thereof include ester solvents such as acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic solvents such as toluene and xylene, or mixtures thereof.
本発明で得られる活性エネルギー線硬化型樹脂組成物に有機溶剤を含ませた場合は、例えば、活性エネルギー線硬化型塗料用樹脂組成物を支持体に塗布し支持体上に活性エネルギー線硬化型樹脂組成物の層を形成した後、該層に活性エネルギー線を照射する前に有機溶剤を除去するのが好ましい。有機溶剤を除去する手段としては、例えば、熱風乾燥機等を用いることができる。また、有機溶剤の使用量は、特に限定されないが、通常は塗料の固形分濃度が１０〜７０重量％となる範囲である。 When the active energy ray-curable resin composition obtained in the present invention contains an organic solvent, for example, the active energy ray-curable resin composition for coating is applied to a support and the active energy ray-curable resin composition is applied on the support. After forming the layer of the resin composition, it is preferable to remove the organic solvent before irradiating the layer with active energy rays. As a means for removing the organic solvent, for example, a hot air dryer or the like can be used. The amount of the organic solvent used is not particularly limited, but is usually in the range where the solid content concentration of the paint is 10 to 70% by weight.
本発明の活性エネルギー線硬化型樹脂組成物には、目的に応じて、光重合開始剤を添加することが出来る。光重合開始剤としては、各種のものが使用できる。光開始剤としては、例えば、ベンゾフェノン、ベンジル、ミヒラーケトン、チオキサントン、アントラキノン等の水素引き抜きによってラジカルを発生するタイプの化合物等が挙げられる。これらの化合物は、メチルアミン、ジエタノールアミン、Ｎ−メチルジエタノールアミン、トリブチルアミン等の第三アミンと併用するのが一般的である。 A photopolymerization initiator can be added to the active energy ray-curable resin composition of the present invention depending on the purpose. Various photopolymerization initiators can be used. Examples of the photoinitiator include compounds that generate radicals by hydrogen abstraction, such as benzophenone, benzyl, Michler ketone, thioxanthone, and anthraquinone. These compounds are generally used in combination with tertiary amines such as methylamine, diethanolamine, N-methyldiethanolamine, and tributylamine.
更に、光重合開始剤として、例えば、分子内開裂によってラジカルを発生するタイプの化合物も挙げられる。具体的には、例えば、ベンゾイン、ジアルコキシアセトフェノン、アシルオキシムエステル、ベンジルケタール、ヒドロキシアルキルフェノン、ハロゲノケトン等が挙げられる。 Furthermore, examples of the photopolymerization initiator include compounds of a type that generates radicals by intramolecular cleavage. Specific examples include benzoin, dialkoxyacetophenone, acyloxime ester, benzyl ketal, hydroxyalkylphenone, halogenoketone and the like.
また、必要により、光重合開始剤と併用して、ハイドロキノン、ベンゾキノン、トルハイドノキノン、パラターシャリーブチルカテコールの如き重合禁止剤類などを添加することもできる。 Further, if necessary, a polymerization inhibitor such as hydroquinone, benzoquinone, tolhydronoquinone, paratertiary butylcatechol, etc. can be added in combination with a photopolymerization initiator.
また、塗膜表面の平滑性を向上させる目的で、フッ素系、シリコーン系、炭化水素系等の各種レベリング剤を、耐指紋性を損なわない範囲の添加量で（０．００５〜１質量％）添加することができる。更に、塗膜硬度を向上させる目的で、シリカゲル等の無機微粒子（粒径５〜１００ｎｍ）を、透明性を損なわない範囲の添加量で（０．１〜５０質量％）添加することができる。 In addition, for the purpose of improving the smoothness of the coating film surface, various leveling agents such as fluorine, silicone and hydrocarbon are added in an amount that does not impair fingerprint resistance (0.005 to 1% by mass). Can be added. Furthermore, for the purpose of improving the coating film hardness, inorganic fine particles (particle size 5 to 100 nm) such as silica gel can be added in an addition amount (0.1 to 50% by mass) within a range not impairing transparency.
本発明の硬化物は前記エネルギー線硬化型樹脂組成物を硬化させてなる。活性エネルギー線としては、例えば、電子線、紫外線、ガンマ線などを挙げることができる。照射条件は、保護層を得るのに用いた活性エネルギー線硬化型塗料の組成に応じて定められるが、紫外線照射の場合、通常積算光量が１０〜５，０００ｍｊ／ｃｍ２となるように照射するのが好ましく、積算光量が５０〜１，０００ｍｊ／ｃｍ２となるように照射するのがより好ましい。また、電子線を照射する場合には１〜５Ｍｒａｄの照射量であることが好ましい。これらの中でも、扱いが簡便な点で紫外線硬化が好ましい。The cured product of the present invention is obtained by curing the energy beam curable resin composition. Examples of active energy rays include electron beams, ultraviolet rays, and gamma rays. Irradiation conditions are determined according to the composition of the active energy ray-curable coating material used to obtain the protective layer, but in the case of ultraviolet irradiation, irradiation is usually performed so that the integrated light amount is 10 to 5,000 mj / cm 2. It is preferable to irradiate such that the integrated light quantity is 50 to 1,000 mj / cm 2 . Moreover, when irradiating an electron beam, it is preferable that it is a 1-5 Mrad irradiation amount. Among these, ultraviolet curing is preferable because it is easy to handle.
本発明のフィルムは前記活性エネルギー線硬化型樹脂組成物を硬化させてなる硬化層をフィルム状基材上に有する。 The film of the present invention has a cured layer formed by curing the active energy ray-curable resin composition on a film-like substrate.
前記フィルム状基材としては、例えば、また、プラスチックフィルムとしては、例えば、ポリエチレン、ポリプロピレン、トリアセチルセルロース、ポリエチレンテレフタレート、塩化ビニル、ポリカーボネートなどから製造されたフィルム等が挙げられる。 Examples of the film-like substrate include films made from polyethylene, polypropylene, triacetyl cellulose, polyethylene terephthalate, vinyl chloride, polycarbonate, and the like.
活性エネルギー線硬化型樹脂組成物の層をフィルム基材上に形成する為の塗装手段としては、例えば、グラビアコート法、ロールコート法、スプレーコート法、リップコート法、コンマコート法などのコート法、グラビア印刷法、スクリーン印刷法などの印刷法等が挙げられる。塗装する際には、硬化させた保護層の厚さが０．１〜４００μｍとなる様に塗装するのが好ましく、なかでも１〜５０μｍとなる様に塗装するのがより好ましい。 Examples of the coating means for forming the layer of the active energy ray-curable resin composition on the film substrate include coating methods such as gravure coating, roll coating, spray coating, lip coating, and comma coating And printing methods such as gravure printing and screen printing. At the time of coating, it is preferable that the thickness of the cured protective layer is 0.1 to 400 μm, and it is more preferable that the thickness is 1 to 50 μm.
有機溶剤を含有している活性エネルギー線硬化型樹脂組成物を用いるときは、基材フィルム上に活性エネルギー線硬化型樹脂組成物の層を形成した後、通常有機溶剤を除去する。有機溶剤を除去する方法としては、そのまま放置して揮発するのを待っても良いし、乾燥機等を用いて乾燥させても良いが、有機溶剤を除去する際の温度は、通常、７０〜１３０℃でである、乾燥時間は１０秒〜１０分の範囲であることが好ましい。 When the active energy ray-curable resin composition containing an organic solvent is used, the organic solvent is usually removed after forming the active energy ray-curable resin composition layer on the substrate film. As a method for removing the organic solvent, it may be left as it is to evaporate, or may be dried using a dryer or the like, but the temperature at the time of removing the organic solvent is usually from 70 to The drying time at 130 ° C. is preferably in the range of 10 seconds to 10 minutes.
前記方法等で活性エネルギー線硬化型塗料の層を形成した後、該塗料の層に活性エネルギー線を照射し、本発明のフィルムを得る。 After forming the active energy ray-curable coating layer by the above method or the like, the coating layer is irradiated with active energy rays to obtain the film of the present invention.
以下に実施例および比較例を示して、本発明をさらに詳しく説明する。以下において、部および％は特に断りのない限り、すべて質量基準である。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following, all parts and% are based on mass unless otherwise specified.
尚、本発明の実施例において、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）は下記条件のゲルパーミアーションクロマトグラフィー（ＧＰＣ）を用いて測定した。 In Examples of the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured using gel permeation chromatography (GPC) under the following conditions.
測定装置 ；東ソー株式会社製 ＨＬＣ−８２２０ＧＰＣ
カラム ；東ソー株式会社製 ＴＳＫ−ＧＵＡＲＤＣＯＬＵＭＮ ＳｕｐｅｒＨＺ−Ｌ
＋東ソー株式会社製 ＴＳＫ−ＧＥＬ ＳｕｐｅｒＨＺＭ−Ｍ×４
検出器 ；ＲＩ（示差屈折計）
データ処理；東ソー株式会社製 マルチステーションＧＰＣ−８０２０ｍｏｄｅｌＩＩ
測定条件 ；カラム温度 ４０℃
溶媒 テトラヒドロフラン
流速 ０．３５ｍｌ／分
標準 ；単分散ポリスチレン
試料 ；樹脂固形分換算で０．２重量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（１００μｌ）Measuring device: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ Tosoh Corporation TSK-GEL SuperHZM-M x 4
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene sample: 0.2 wt% tetrahydrofuran solution in terms of resin solids filtered through a microfilter (100 μl)
合成例１〔ウレタンアクリレート（Ａ）の合成〕
重量平均分子量（Ｍｗ）２，０００のポリプロピレングリコールを４，０００ｇ（２モル）、１，２−ビス（２ヒドロキシエチルチオ）エタン１８２ｇ（１モル）をフラスコに仕込み、さらに触媒としてオクタン酸スズ（ＩＩ）とオクタン酸亜鉛（ＩＩ）をそれぞれ２００ｐｐｍ、重合禁止剤としてジブチルヒドロキシトルエン３，０００ｐｐｍ、メトキノン３００ｐｐｍ、溶剤として酢酸ノルマルブチルをフラスコ内の固形分が８０％となる量を加えよく混合し、系内の温度を５０℃に調整した。その後、発熱に注意しながらトルエンジイソシアネート６９６ｇ（４モル）を３分割して加え、８０℃で１時間反応させた。更に、ヒドロキシプロピルアクリレート２６０ｇ（２モル）を加え、空気を吹き込みながら８０度でイソシアネート基が完全に消失するまで反応させ、重量平均分子量（Ｍｗ）２４，０００のウレタンアクリレート（Ａ１）を得た。
Synthesis Example 1 [Synthesis of Urethane Acrylate (A)]
4,000 g (2 mol) of polypropylene glycol having a weight average molecular weight (Mw) of 2,000 and 182 g (1 mol) of 1,2-bis (2hydroxyethylthio) ethane were charged into a flask, and tin octoate as a catalyst. (II) and zinc octoate (II) are each 200 ppm, dibutylhydroxytoluene is 3,000 ppm, methoquinone is 300 ppm as a polymerization inhibitor, and normal butyl acetate is added as a solvent in an amount of 80% solid content and mixed well. The temperature in the system was adjusted to 50 ° C. Thereafter, 696 g ( 4 mol) of toluene diisocyanate was added in three portions while paying attention to heat generation, and the mixture was reacted at 80 ° C. for 1 hour. Furthermore, 260 g (2 mol) of hydroxypropyl acrylate was added, and the reaction was performed at 80 ° C. while blowing air, until the isocyanate group completely disappeared to obtain urethane acrylate (A1) having a weight average molecular weight (Mw) of 24,000.
合成例２〜７（同上）
第一表に示す原料及び配合量で合成を行う以外は合成例１と同様にしてウレタンアクリレート（Ａ２）〜（Ａ７）を得た。それぞれの重量平均分子量（Ｍｗ）の値を第一表に示す。Synthesis examples 2 to 7 (same as above)
Urethane acrylates (A2) to (A7) were obtained in the same manner as in Synthesis Example 1 except that the synthesis was performed using the raw materials and blending amounts shown in Table 1. The respective weight average molecular weight (Mw) values are shown in Table 1.
第一表の脚注
ポリアルキレングリコール１：重量平均分子量が２，０００のポリプロピレングリコール
ポリアルキレングリコール２：重量平均分子量が１，０００のポリプロピレングリコール
ポリアルキレングリコール３：重量平均分子量が４，０００のポリプロピレングリコール
ポリアルキレングリコール４：重量平均分子量が７００のポリプロピレングリコールFootnotes in Table 1 Polyalkylene glycol 1: Polypropylene glycol having a weight average molecular weight of 2,000 Polyalkylene glycol 2: Polypropylene glycol having a weight average molecular weight of 1,000 Polyalkylene glycol 3: Polypropylene glycol having a weight average molecular weight of 4,000 Polyalkylene glycol 4: Polypropylene glycol having a weight average molecular weight of 700
合成例８〜１０〔比較対照用ウレタン（メタ）アクリレート（ａ）の合成〕
第二表に示す原料及び配合量で合成を行う以外は合成例１と同様にして比較対照用ウレタンアクリレート（ａ１）〜（ａ３）を得た。それぞれの重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の値を第二表に示す。Synthesis examples 8 to 10 [Synthesis of comparative urethane (meth) acrylate (a)]
Comparative comparative urethane acrylates (a1) to (a3) were obtained in the same manner as in Synthesis Example 1 except that the synthesis was performed using the raw materials and blending amounts shown in Table 2. The respective values of weight average molecular weight (Mw) and number average molecular weight (Mn) are shown in Table 2.
第二表の脚注
ポリアルキレングリコール５：重量平均分子量が４００のポリプロピレングリコール
ポリアルキレングリコール６：重量平均分子量が８，０００のポリプロピレングリコール
ポリアルキレングリコール７：重量平均分子量が２，０００のポリプロピレングリコールFootnotes in Table 2 Polyalkylene glycol 5: Polypropylene glycol having a weight average molecular weight of 400 Polyalkylene glycol 6: Polypropylene glycol having a weight average molecular weight of 8,000 Polyalkylene glycol 7: Polypropylene glycol having a weight average molecular weight of 2,000
合成例１１〔多官能（メタ）アクリレート（Ｂ）の合成〕
ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートの混合物（重量比６０／４０）５３５．５ｇをフラスコに仕込んだ。触媒としてオクタン酸スズ（ＩＩ）とオクタン酸亜鉛（ＩＩ）をそれぞれ２００ｐｐｍ、酸化防止剤としてジブチルヒドロキシトルエン３，０００ｐｐｍ、重合禁止剤としてメトキノン３００ｐｐｍとなるようにフラスコに加え、更に酢酸ノルマルブチルを固形分が８０％となるように混合し、系内の温度を５０℃に調整した。Synthesis Example 11 [Synthesis of polyfunctional (meth) acrylate (B)]
A flask was charged with 535.5 g of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (weight ratio 60/40). Add stannous octoate (II) and zinc octoate (II) as catalysts, dibutylhydroxytoluene (3,000 ppm) as an antioxidant, and methoquinone (300 ppm) as a polymerization inhibitor, and add normal butyl acetate as a solid. The mixture was mixed so that the content became 80%, and the temperature in the system was adjusted to 50 ° C.
系内に空気を吹き込みながらヘキサメチレンジイソシアネート８４ｇを３分割して加えた。系内の温度を８０℃に上げ、８０℃にて系内のイソシアネート基が完全に消失するまで反応させウレタンアクリレート（Ｂ１）を得た。ＧＰＣ分析によるとウレタンアクリレート（Ｂ１）の重量平均分子量は１，４００であった。また、アクリロイル当量は１０９ｇ／ｍｏｌであった。 While blowing air into the system, 84 g of hexamethylene diisocyanate was added in three portions. The temperature in the system was raised to 80 ° C. and reacted at 80 ° C. until the isocyanate groups in the system disappeared completely to obtain urethane acrylate (B1). According to GPC analysis, the weight average molecular weight of urethane acrylate (B1) was 1,400. The acryloyl equivalent was 109 g / mol.
実施例１
ウレタンアクリレート（Ａ１）３ｇ、ウレタンアクリレート（Ｂ１）４８．５ｇ、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（重量比４０／６０）４８．５ｇ、１−ヒドロキシシクロヘキシルフェニルケトン４ｇ、酢酸ブチル１０４ｇを混合し、固形分量が５０質量％の活性エネルギー線硬化型組成物（１）を得た。組成物（１）を用いて下記条件にてフィルム上にハードコート層を形成し、付着した指紋跡の目立ちにくさ及び付着した指紋跡の拭き取りやすさを下記基準に従って評価した。付着した指紋跡の目立ちにくさ及び付着した指紋跡の拭き取りやすさは、ハードコート層を形成した初期段階と指紋跡の付着と除去を２０回繰り返した後の段階のそれぞれについて評価した。付着した指紋跡の除去は、後述する指紋跡の拭き取りやすさの評価方法で行った。尚、ウレタンアクリレート（Ｂ１）４８．５ｇ、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（重量比４０／６０）４８．５ｇの混合物のアクリロイル当量は１０４ｇ／ｍｏｌであった。Example 1
Urethane acrylate (A1) 3 g, urethane acrylate (B1) 48.5 g, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (weight ratio 40/60) 48.5 g, 1-hydroxycyclohexyl phenyl ketone 4 g, butyl acetate 104 g was mixed to obtain an active energy ray-curable composition (1) having a solid content of 50% by mass. Using the composition (1), a hard coat layer was formed on the film under the following conditions, and the difficulty of conspicuous adhesion of the fingerprint trace and the ease of wiping off the fingerprint trace was evaluated according to the following criteria. The conspicuousness of the attached fingerprint trace and the ease of wiping off the attached fingerprint trace were evaluated in each of the initial stage in which the hard coat layer was formed and the stage after 20 times of attaching and removing the fingerprint trace. The removal of the attached fingerprint trace was performed by an evaluation method for ease of wiping off the fingerprint trace described later. The acryloyl equivalent of 48.5 g of urethane acrylate (B1) and 48.5 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (weight ratio 40/60) was 104 g / mol.
＜ハードコート層の形成方法＞
組成物（１）ＰＥＴフィルム（１２５μｍ）に乾燥膜厚が５μｍになるようにバーコーターを用いて塗工した。７０℃で５分間溶剤を乾燥させた後、高圧水銀灯（８０Ｗ／ｃｍ）で照射量が５００ｍＪ／ｃｍ２となるように紫外線を照射し、ハードコート層を得た。尚、紫外線の照射は空気雰囲気下もしくは窒素雰囲気下で行った。<Method for forming hard coat layer>
Composition (1) A PET film (125 μm) was coated using a bar coater so that the dry film thickness was 5 μm. After the solvent was dried at 70 ° C. for 5 minutes, ultraviolet rays were irradiated with a high-pressure mercury lamp (80 W / cm) so that the irradiation amount was 500 mJ / cm 2 to obtain a hard coat layer. The ultraviolet irradiation was performed in an air atmosphere or a nitrogen atmosphere.
＜指紋跡の目立ちにくさの評価（定量評価）＞
指紋跡の目立ちにくさは視認角度で定量評価した。視認角度とは、ハードコート層に付着させた指紋跡に対する目視角度を９０度から徐々に下げていき、指紋跡が確認され始める角度をいう。視認角度が小さいほど、指紋跡の目立ちにくさが良好である。<Evaluation of the difficulty of conspicuous fingerprint marks (quantitative evaluation)>
The inconspicuousness of fingerprint marks was quantitatively evaluated by the viewing angle. The viewing angle refers to an angle at which the fingerprint trace starts to be confirmed by gradually lowering the viewing angle with respect to the fingerprint trace attached to the hard coat layer from 90 degrees. The smaller the viewing angle, the better the fingerprint marks are less noticeable.
＜指紋跡の拭き取り易さの評価（定量評価）＞
指紋跡の拭き取り易さは、指紋跡をハードコート層から除去する際のふき取り回数で評価した。具体的には、ハードコート層に付着させた指紋跡の上にティッシュペーパーを１Ｋｇ（５．７平方センチメートルあたり）で往復させ、付着した指紋跡が完全に見えなくなるまでの往復回数で定量評価した。この往復回数が少ないほど、指紋跡の拭取りやすさが良好である。<Evaluation of ease of wiping off fingerprint marks (quantitative evaluation)>
The ease of wiping off the fingerprint marks was evaluated by the number of times of wiping when the fingerprint marks were removed from the hard coat layer. Specifically, the tissue paper was reciprocated at 1 Kg (per 5.7 square centimeters) on the fingerprint trace adhered to the hard coat layer, and quantitative evaluation was performed by the number of reciprocations until the adhered fingerprint trace was completely invisible. The smaller the number of reciprocations, the better the wiping of fingerprint marks.
＜塗膜硬度の評価＞
ＪＩＳ Ｋ５６００−５−４に準拠して鉛筆硬度測定を行った。１つの硬度につき５回測定を行い、４回以上傷がつかない硬度を硬化塗膜の有する硬度とした。<Evaluation of coating film hardness>
Pencil hardness was measured according to JIS K5600-5-4. The hardness was measured five times for each hardness, and the hardness that the cured coating film had was not damaged more than four times.
実施例２〜９及び比較例１〜３
第三表及び第四表に示す配合で行う以外は実施例１と同様にして活性エネルギー線硬化型樹脂組成物２〜９及び比較対照用活性エネルギー線硬化型樹脂組成物１’〜３’を調製した。実施例１と同様の評価を行い、その結果を第五表〜第七表に示す。Examples 2-9 and Comparative Examples 1-3
Active energy ray-curable resin compositions 2 to 9 and comparative active energy ray-curable resin compositions 1 'to 3' were used in the same manner as in Example 1 except that the formulations shown in Tables 3 and 4 were used. Prepared. Evaluation similar to Example 1 was performed, and the results are shown in Tables 5-7.
第三表及び第四表の脚注
多官能アクリレート（Ｂ２）：ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（重量比４０／６０）
多官能アクリレート（Ｂ１）と多官能アクリレート（Ｂ２）の混合物のアクリロイル基当量は１０４ｇ／ｍｏｌ
光開始剤：1−ヒドロキシシクロヘキシルフェニルケトン
希釈溶剤：酢酸ノルマルブチルFootnotes in Tables 3 and 4 Multifunctional acrylate (B2): Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (weight ratio 40/60)
The acryloyl group equivalent of the mixture of polyfunctional acrylate (B1) and polyfunctional acrylate (B2) is 104 g / mol.
Photoinitiator: 1-hydroxycyclohexyl phenyl ketone Diluent: normal butyl acetate
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| CN104470997B (en) * | 2012-07-20 | 2016-08-17 | 巴斯夫欧洲公司 | The coating compound of quick-drying radiation-curable |
| JP2015048459A (en) * | 2013-09-04 | 2015-03-16 | Dic株式会社 | Radically polymerizable resin composition and civil engineering building material |
| JP6031195B2 (en) * | 2013-09-25 | 2016-11-24 | ハリマ化成株式会社 | Photocurable resin composition and cured film thereof |
| JP2015200698A (en) * | 2014-04-04 | 2015-11-12 | 日東電工株式会社 | Transparent resin layer, polarizing film with adhesive layer, and image display device |
| JP5943230B2 (en) * | 2014-06-30 | 2016-07-05 | Dic株式会社 | UV-curable adhesive composition, adhesive film, and method for producing adhesive film |
| JP6766969B2 (en) * | 2017-12-18 | 2020-10-14 | Dic株式会社 | An active energy ray-curable composition and a film using the same. |
| JP6512281B1 (en) * | 2017-12-26 | 2019-05-15 | 東洋インキＳｃホールディングス株式会社 | Active energy ray-curable hard coat agent and laminate |
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| JPS61108619A (en) * | 1984-11-01 | 1986-05-27 | Sanyo Kokusaku Pulp Co Ltd | Photocurable resin composition |
| JPS6390525A (en) * | 1986-10-03 | 1988-04-21 | Sumitomo Chem Co Ltd | Curable resin composition |
| JP2009062423A (en) * | 2007-09-05 | 2009-03-26 | Aica Kogyo Co Ltd | Active energy ray-curable hard coating resin composition and hard coating film |
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| CN1989161B (en) * | 2004-07-29 | 2010-05-05 | 大日本油墨化学工业株式会社 | Actinic radiation-curable resin composition for shaping, shaping sheet, and shaped product |
| KR100864349B1 (en) * | 2005-04-25 | 2008-10-17 | 디아이씨 가부시끼가이샤 | Actinic Radiation Curable Resin Composition For Film Protection Layer and Film and Optical Sheet Made by Using the Same |
| US20100010162A1 (en) * | 2006-11-09 | 2010-01-14 | Dic Corporation | Active energy-ray-curable water- based resin composition, active energy-ray-curable coating material, method of forming cured coating film, and article |
| US8414979B2 (en) * | 2007-03-08 | 2013-04-09 | Dic Corporation | Radiation-curable resin composition, radiation-curable coating material, and method for forming protective layer |
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| JPS61108619A (en) * | 1984-11-01 | 1986-05-27 | Sanyo Kokusaku Pulp Co Ltd | Photocurable resin composition |
| JPS6390525A (en) * | 1986-10-03 | 1988-04-21 | Sumitomo Chem Co Ltd | Curable resin composition |
| JP2009062423A (en) * | 2007-09-05 | 2009-03-26 | Aica Kogyo Co Ltd | Active energy ray-curable hard coating resin composition and hard coating film |
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