WO2011122197A1 - Active energy ray-curable resin composition and cured product and film thereof - Google Patents
Active energy ray-curable resin composition and cured product and film thereof Download PDFInfo
- Publication number
- WO2011122197A1 WO2011122197A1 PCT/JP2011/054475 JP2011054475W WO2011122197A1 WO 2011122197 A1 WO2011122197 A1 WO 2011122197A1 JP 2011054475 W JP2011054475 W JP 2011054475W WO 2011122197 A1 WO2011122197 A1 WO 2011122197A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- acrylate
- resin composition
- active energy
- energy ray
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 173
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000002009 diols Chemical class 0.000 claims abstract description 26
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 14
- -1 methacryloyl group Chemical group 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229920001451 polypropylene glycol Polymers 0.000 claims description 14
- 125000004434 sulfur atom Chemical group 0.000 claims description 12
- 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
- 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 4
- 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
- 239000000178 monomer Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 33
- 239000011248 coating agent Substances 0.000 abstract description 32
- 239000000203 mixture Substances 0.000 abstract description 23
- 239000012298 atmosphere Substances 0.000 abstract description 9
- 239000007858 starting material Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 28
- 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
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 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 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 10
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- 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 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 230000000052 comparative effect Effects 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-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
- 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-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
- WNNRUOPGOIGERJ-UHFFFAOYSA-N 1-(2-hydroxyethylsulfanyl)propan-2-ol Chemical compound CC(O)CSCCO WNNRUOPGOIGERJ-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
- GAECBAMNQFGJIM-UHFFFAOYSA-N 2-(2-hydroxyethylsulfanylmethylsulfanyl)ethanol Chemical compound OCCSCSCCO GAECBAMNQFGJIM-UHFFFAOYSA-N 0.000 description 2
- LXGFOHOXYOCIDT-UHFFFAOYSA-N 2-[2-(2-hydroxyethylsulfanyl)ethoxy]ethanol Chemical compound OCCOCCSCCO LXGFOHOXYOCIDT-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
- UMCLPWBJGMCBTQ-UHFFFAOYSA-N CC(CSCO)CO Chemical compound CC(CSCO)CO UMCLPWBJGMCBTQ-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- 239000004386 Erythritol Substances 0.000 description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- 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
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 2
- 235000019414 erythritol Nutrition 0.000 description 2
- 229940009714 erythritol Drugs 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
- 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 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
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-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
- 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
- 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
- OEYNWAWWSZUGDU-UHFFFAOYSA-N 1-methoxypropane-1,2-diol Chemical compound COC(O)C(C)O OEYNWAWWSZUGDU-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-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
- YHYCMHWTYHPIQS-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol Chemical compound COC(O)COCCO YHYCMHWTYHPIQS-UHFFFAOYSA-N 0.000 description 1
- QGECTPPOVMJXOX-UHFFFAOYSA-N 2-(2-hydroxyethylsulfanylmethoxymethylsulfanyl)ethanol Chemical compound OCCSCOCSCCO QGECTPPOVMJXOX-UHFFFAOYSA-N 0.000 description 1
- RKYJPYDJNQXILT-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCCOC(=O)C=C RKYJPYDJNQXILT-UHFFFAOYSA-N 0.000 description 1
- BXPKASQEUYICBF-UHFFFAOYSA-N 2-(3-prop-2-enoyloxypropoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCCCOC(=O)C=C BXPKASQEUYICBF-UHFFFAOYSA-N 0.000 description 1
- HHGMODSKOYEYJL-UHFFFAOYSA-N 2-(3-prop-2-enoyloxypropoxycarbonyl)cyclohex-3-ene-1-carboxylic acid Chemical compound OC(=O)C1CCC=CC1C(=O)OCCCOC(=O)C=C HHGMODSKOYEYJL-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
- 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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 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
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- RUCLWVAQWOEEPY-UHFFFAOYSA-N 4-(4-hydroxybutyldisulfanyl)butan-1-ol Chemical compound OCCCCSSCCCCO RUCLWVAQWOEEPY-UHFFFAOYSA-N 0.000 description 1
- UJKICTBMGHXJPW-UHFFFAOYSA-N 5-(5-hydroxypentyldisulfanyl)pentan-1-ol Chemical compound S(SCCCCCO)CCCCCO UJKICTBMGHXJPW-UHFFFAOYSA-N 0.000 description 1
- HPKCPHUCATZKGA-UHFFFAOYSA-N 6-(6-hydroxyhexyldisulfanyl)hexan-1-ol Chemical compound OCCCCCCSSCCCCCCO HPKCPHUCATZKGA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-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
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-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
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-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
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 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
- 238000007664 blowing Methods 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
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 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
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 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
- 125000003055 glycidyl group Chemical group C(C1CO1)* 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
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- 239000000463 material 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-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
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 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
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 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 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 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
Definitions
- the present invention particularly relates to an active energy ray-curable resin composition that can be preferably used for forming a hard coat layer for protecting the touch panel surface.
- compositions 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
- Mw weight average molecular weight
- penta A photocurable 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).
- 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.
- 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.
- the present inventors have determined 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.
- Mw weight average molecular weight
- 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.
- the present inventors have found that a cured layer obtained by curing the composition exhibits high hardness and completed the present invention.
- 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.
- the present invention also provides a cured product obtained by curing the active energy ray-curable resin composition.
- the present invention provides a film characterized by having a cured layer formed by curing the active energy ray-curable resin composition on a film-like substrate.
- the active energy ray-curable resin composition of the present invention 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 and less noticeable fingerprint traces and easy to wipe off the adhered 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.
- the urethane (meth) acrylate (A) used in the present invention comprises 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. .
- 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.
- Mw weight average molecular weight
- 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.
- Those having a weight average molecular weight (MW) in the range of 700 to 4,500 are preferred, and those having a weight average molecular weight (Mw) in the range of 1,000 to 4,000 are more preferred.
- 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
- Detector RI (differential refractometer)
- Data processing Multi-station GPC-8020model 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 solid content filtered through a microfilter (100 ⁇ l)
- 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.
- Mw weight average molecular weight
- the range of 1 to 20 is preferable, and 2 to 10 A range is more preferred.
- 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.
- polyalkylene glycol (a1) examples 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.
- 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.
- the diol (a2) having an alkylene thioether structure in the molecular structure used in the present invention is, 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'-thiobis (1-propanol), 1,1'-thiobis (2-propanol), 5-methyl-3-thiahexane-1,6-diol, 3-oxa-6-thiaoctane-1,8-diol, etc.
- 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)] Ethanol, 2,2 ′-[(2-
- 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.
- R1 and R2 are each an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group.
- l, m and n are each 0 or 1
- R1, R2, R3, R4, R5 and R6 are each an alkyl group or halogenated alkyl group having 1 to 4 carbon atoms. Is a sulfur atom or an oxygen atom, and more than half of X contained in the compound is a sulfur atom.
- the compound represented by the general formula (1) examples include 2,2′-thiodiethanol, 3-thia-1,6-hexanediol, 1- (2-hydroxyethylthio) -2-propanol, for example. 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 Compounds having one sulfur atom in them; 2,2 ′-(methylenebisthio) diethanol, 1,2-bis (2-hydroxyethylthio) ethane, 2,2 ′-[oxybis (meth) Nthio)] bisethanol,
- 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 from the viewpoint of excellent fingerprint resistance of the coating film. Examples of such diisocyanates include aromatic diisocyanates and aliphatic diisocyanates.
- aromatic diisocyanate examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate (XDI), and tetramethylxylylene diisocyanate (TMXDI).
- TDI tolylene diisocyanate
- MDI diphenylmethane diisocyanate
- p-phenylene diisocyanate p-phenylene diisocyanate
- XDI naphthalene diisocyanate
- XDI xylylene diisocyanate
- TMXDI tetramethylxylylene diisocyanate
- 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.
- HMDI hexamethylene diis
- the diisocyanate (a3) may be used alone or in combination of two or more.
- 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, More preferred are 4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate.
- 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.
- 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.
- 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.
- a1 polyalkylene glycol
- the method by the process (process 2) with which (meth) acrylate (a4) which has one hydroxyl group is made to react is mentioned.
- the production method of the isocyanate group-containing urethane prepolymer will be described in detail with respect to the step 1.
- 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.
- 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.
- a hard coat layer that can easily wipe off the attached fingerprint is obtained, and therefore, the range of [1.0 / 0.2] to [1.0 / 5.0] is preferable.
- a range of 0 / 0.5] to [1.0 / 2.0] is more preferable.
- 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
- 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], preferably [1 / 1.1] to [1/2].
- 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.
- 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], more preferably in the range of [1 / 1.01] to [1 / 1.05].
- 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 from the viewpoint of obtaining a coating film having an excellent balance between the performance of both the conspicuousness of attached fingerprints and ease of wiping.
- 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 mentioned.
- 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;
- (meth) acrylates in which a part of the various polyfunctional (meth) acrylates described above is substituted with an alkyl group or ⁇ -caprolactone can be used.
- 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.
- 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. A range of 5 is more preferable.
- 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.
- 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.
- polyfunctional urethane (meth) acrylate (b4) is preferable in that a coating film having higher hardness can be obtained.
- 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].
- 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. .
- 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.
- a hard coat layer having high curability, high hardness and excellent transparency can be obtained. Therefore, a monomer type polyfunctional (with a molecular weight of less than 600) ( It is preferable to use a combination of (meth) acrylate (b1) and an oligomer-type polyfunctional (meth) acrylate having a molecular weight in the range of 600 to 3,000. Furthermore, dipentaerythritol pentaacrylate (b5) and dipentaerythritol hexaacrylate (b6) are used as the monomer-type polyfunctional (meth) acrylate (b1) in terms of excellent hardness, transparency and curl resistance of the coating film.
- urethane (meth) acrylate (b4) is preferably used as the oligomer-type polyfunctional (meth) acrylate, and the mass ratio [(b56) / (b4)] is [ It is preferably in the range of 1/2] to [2 to 1].
- 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.
- 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)].
- 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.
- an organic solvent those having a boiling point of 50 to 200 ° C. are usually used to obtain a resin composition for an active energy ray-curable coating and an active energy ray-curable paint that are excellent in workability during coating and drying before and after curing.
- 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
- 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.
- the active energy ray-curable resin composition obtained in the present invention contains an organic solvent
- the active energy ray-curable resin composition for coating is applied to the support and the active energy ray-curable resin composition is applied on the support.
- a hot air dryer or the like can be used as a means for removing the organic solvent.
- 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.
- 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.
- 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.
- 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.
- polymerization inhibitors such as hydroquinone, benzoquinone, toluhydronoquinone, para tertiary butyl catechol, etc. can be added in combination with a photopolymerization initiator.
- various leveling agents such as fluorine-based, silicone-based, and hydrocarbon-based additives are added in an amount that does not impair fingerprint resistance (0.005 to 1% by mass). Can be added.
- inorganic fine particles such as silica gel (particle size 5 to 100 nm) can be added in an addition amount (0.1 to 50% by mass) within a range not impairing transparency.
- the cured product of the present invention is obtained by curing the energy beam curable resin composition.
- 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 so that the integrated light quantity is 50 to 1,000 mj / cm 2 .
- the dose is preferably 1 to 5 Mrad.
- ultraviolet curing is preferable because it is easy to handle.
- 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.
- film-like substrate examples include films made from polyethylene, polypropylene, triacetyl cellulose, polyethylene terephthalate, vinyl chloride, polycarbonate, and the like.
- 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.
- coating it is preferable to coat so that the thickness of the cured protective layer is 0.1 to 400 ⁇ m, and it is more preferable that the thickness is 1 to 50 ⁇ m.
- the organic solvent is usually removed after forming the active energy ray-curable resin composition layer on the base film.
- the organic solvent may be left standing to wait for volatilization or may be dried using a dryer or the like.
- the temperature at which the organic solvent is removed is usually 70 to
- the drying time at 130 ° C. is preferably in the range of 10 seconds to 10 minutes.
- the coating layer is irradiated with active energy rays to obtain the film 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.
- Measuring device HLC-8220GPC manufactured by Tosoh Corporation Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation + Tosoh Corporation TSK-GEL SuperHZM-M ⁇ 4 Detector: RI (differential refractometer)
- Data processing Multi-station GPC-8020model II manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 0.35 ml / min Standard; Monodisperse polystyrene Sample; Filtered 0.2% by weight tetrahydrofuran solution in terms of resin solids with a microfilter (100 ⁇ l)
- the temperature in the system was adjusted to 50 ° C. Thereafter, 261 g (3 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. Further, 260 g (2 mol) of hydroxypropyl acrylate was added, and the reaction was carried out at 80 ° C. while blowing air, until the isocyanate group completely disappeared, and urethane acrylate (A1) having a weight average molecular weight (Mw) of 24,000 was obtained.
- Mw weight average molecular weight
- 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
- Synthesis Examples 8 to 10 [Synthesis of urethane (meth) acrylate (a) for comparison] Comparative urethane acrylates (a1) to (a3) were obtained in the same manner as in Synthesis Example 1 except that the synthesis was carried out 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.
- 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
- urethane acrylate (B1) was 1,400.
- the acryloyl equivalent was 109 g / mol.
- Example 1 3 g of urethane acrylate (A1), 48.5 g of urethane acrylate (B1), 48.5 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (weight ratio 40/60), 4 g of 1-hydroxycyclohexyl phenyl ketone, butyl acetate 104 g was mixed to obtain an active energy ray-curable composition (1) having a solid content of 50% by mass.
- a hard coat layer was formed on the film under the following conditions using the composition (1), 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.
- composition (1) A PET film (125 ⁇ m) was coated using a bar coater so that the dry film thickness was 5 ⁇ m. 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.
- 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.
- 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.
- Examples 2 to 9 and Comparative Examples 1 to 3 Active energy ray curable resin compositions 2 to 9 and comparative active energy ray curable resin compositions 1 ′ to 3 ′ were prepared in the same manner as in Example 1 except that the formulations shown in Tables 3 and 4 were used. Prepared. The same evaluation as in Example 1 was performed, and the results are shown in Tables 5-7.
- 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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Abstract
Description
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 comprises 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. .
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 × 4
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020model 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 solid content filtered through a microfilter (100 μl)
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 × 4
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent Tetrahydrofuran Flow rate 0.35 ml / min Standard; Monodisperse polystyrene Sample; Filtered 0.2% by weight tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)
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91g(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261g(3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)]
A flask was charged with 4,000 g (2 mol) of polypropylene glycol having a weight average molecular weight (Mw) of 2,000 and 91 g (1 mol) of 1,2-bis (2hydroxyethylthio) ethane, and tin octoate (1 mol) as a catalyst. II) and zinc octoate (II) each 200 ppm, dibutylhydroxytoluene 3,000 ppm as a polymerization inhibitor, methoquinone 300 ppm, and normal butyl acetate as a solvent in an amount such that the solid content in the flask is 80%, and mixed well. The temperature in the system was adjusted to 50 ° C. Thereafter, 261 g (3 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. Further, 260 g (2 mol) of hydroxypropyl acrylate was added, and the reaction was carried out at 80 ° C. while blowing air, until the isocyanate group completely disappeared, and urethane acrylate (A1) having a weight average molecular weight (Mw) of 24,000 was obtained.
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.
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
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 urethane (meth) acrylate (a) for comparison]
Comparative urethane acrylates (a1) to (a3) were obtained in the same manner as in Synthesis Example 1 except that the synthesis was carried out 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.
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
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 tin (II) octoate and zinc (II) octoate as catalysts, dibutylhydroxytoluene 3,000 ppm as an antioxidant, and 300 ppm methoquinone as a polymerization inhibitor, and add normal butyl acetate to the solid. The mixture was mixed so that the content became 80%, and the temperature in the system was adjusted to 50 ° C.
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
3 g of urethane acrylate (A1), 48.5 g of urethane acrylate (B1), 48.5 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (weight ratio 40/60), 4 g of 1-hydroxycyclohexyl phenyl ketone, butyl acetate 104 g was mixed to obtain an active energy ray-curable composition (1) having a solid content of 50% by mass. A hard coat layer was formed on the film under the following conditions using the composition (1), 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.
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 disappeared completely. The smaller the number of reciprocations, the better the wiping of fingerprint marks.
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.
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 to 9 and Comparative Examples 1 to 3
Active energy ray curable resin compositions 2 to 9 and comparative active energy ray curable resin compositions 1 ′ to 3 ′ were prepared in the same manner as in Example 1 except that the formulations shown in Tables 3 and 4 were used. Prepared. The same evaluation as in Example 1 was performed, and the results are shown in Tables 5-7.
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
Claims (12)
- 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。 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, a diisocyanate (a3) having a molecular weight of 500 or less, A urethane having a weight average molecular weight (Mw) in the range of 10,000 to 100,000 obtained by reacting (meth) acrylate (a4) having one hydroxyl group in the molecular structure as an essential raw material component ( An active energy ray-curable resin composition comprising a (meth) acrylate (A) and a polyfunctional (meth) acrylate (B).
- 前記ポリアルキレングリコール(a1)がポリプロピレングリコールである請求項1記載の活性エネルギー線硬化型樹脂組成物。 The active energy ray-curable resin composition according to claim 1, wherein the polyalkylene glycol (a1) is polypropylene glycol.
- 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)が、下記一般式(1)又は一般式(2)で示される化合物である請求項1記載の活性エネルギー線硬化型樹脂組成物。
- 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)が、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-オールからなる群から選ばれる1種類以上の化合物である請求項1記載の活性エネルギー線硬化型樹脂組成物。 The diol (a2) having the alkylene thioether structure in the molecular structure is 2,2′-thiobis (1-propanol), 1,2-bis (2-hydroxyethylthio) ethane, 2- [2- [2- (2-hydroxyethylthio) propylthio] -1-methylethylthio] ethanol, 1- (2- [2- (2-hydroxypropylsulfanyl) propylsulfanyl] 1-methyl-ethylsulfanyl) propan-2-ol The active energy ray-curable resin composition according to claim 1, which is one or more compounds selected from the group.
- 前記ウレタン(メタ)アクリレート(A)の原料中の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)〕が1/0.2~1/5となる範囲である請求項1記載の活性エネルギー線硬化型樹脂組成物。 The molar ratio [(a1) / (a2)] of the content of the polyalkylene glycol (a1) in the raw material of the urethane (meth) acrylate (A) and the diol (a2) having an alkylene thioether structure in the molecular structure is 2. The active energy ray-curable resin composition according to claim 1, which is in a range of 1 / 0.2 to 1/5.
- 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)が、分子構造中にメタアクリロイル基を1つ有するモノヒドロキシモノ(メタ)アクリレートである請求項1記載の活性エネルギー線硬化型樹脂組成物。 The active energy ray curable type according to claim 1, wherein the (meth) acrylate (a4) having one hydroxyl group in the molecular structure is a monohydroxy mono (meth) acrylate having one methacryloyl group in the molecular structure. Resin composition.
- 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)との質量比〔(A)/(B)〕が0.1/99.9~15/85の範囲である請求項1記載の活性エネルギー線硬化型樹脂組成物。 The mass ratio [(A) / (B)] of the urethane (meth) acrylate (A) and the polyfunctional (meth) acrylate (B) is in the range of 0.1 / 99.9 to 15/85. 1. The active energy ray-curable resin composition according to 1.
- 前記多官能(メタ)アクリレート(B)として、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多官能(メタ)アクリレート(b2)とを併用することを特徴とする請求項1記載の活性エネルギー線硬化型樹脂組成物。 As the polyfunctional (meth) acrylate (B), 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. The active energy ray-curable resin composition according to claim 1, wherein (b2) is used in combination.
- 前記分子量が600~3,000の範囲であるオリゴマー型多官能(メタ)アクリレート(b2)が多官能ウレタン(メタ)アクリレートである請求項8記載の活性エネルギー線硬化型樹脂組成物。 The active energy ray-curable resin composition according to claim 8, wherein the oligomer type polyfunctional (meth) acrylate (b2) having a molecular weight in the range of 600 to 3,000 is a polyfunctional urethane (meth) acrylate.
- 前記分子量が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多官能(メタ)アクリレート(b2)との質量比[(b1)/(b2)]が1/2~2/1の範囲である請求項8記載の活性エネルギー線硬化型樹脂組成物。 Mass ratio of the monomer-type polyfunctional (meth) acrylate (b1) having a molecular weight of less than 600 and the oligomer-type polyfunctional (meth) acrylate (b2) having a molecular weight in the range of 600 to 3,000 [(b1) The active energy ray-curable resin composition according to claim 8, wherein / (b2)] is in the range of 1/2 to 2/1.
- 請求項1~10のいずれか1つに記載の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。 A cured product obtained by curing the active energy ray-curable resin composition according to any one of claims 1 to 10.
- 請求項1~10のいずれか1つに記載の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。 A film comprising a cured layer formed by curing the active energy ray-curable resin composition according to any one of claims 1 to 10 on a film-like substrate.
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WO2015045200A1 (en) * | 2013-09-25 | 2015-04-02 | ハリマ化成株式会社 | Photocurable resin composition and cured film thereof |
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JP7287357B2 (en) * | 2019-07-16 | 2023-06-06 | 荒川化学工業株式会社 | Active energy ray-curable resin composition, active energy ray-curable hydrous resin composition, coating agent composition, cured film and film |
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TWI303652B (en) * | 2001-07-18 | 2008-12-01 | Dainippon Ink & Chemicals | |
EP1302514B1 (en) * | 2001-10-09 | 2009-07-15 | Mitsubishi Chemical Corporation | Active energy ray-curable antistatic coating composition |
US20080021174A1 (en) * | 2004-07-29 | 2008-01-24 | Dainipoon Ink And Chemicals Inc. | Radiation-Curable Resin Composition for Shape-Replication, Sheet for Shape-Replication, and Shape-Replicated Material |
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 |
WO2008056569A1 (en) * | 2006-11-09 | 2008-05-15 | Dic Corporation | Actinic-energy-ray-curable water-based resin composition, actinic-energy-ray-curable coating material, method of forming cured coating film, and article |
JP4304643B2 (en) * | 2007-03-08 | 2009-07-29 | Dic株式会社 | Active energy ray curable resin composition, active energy ray curable coating material, and method for forming protective layer |
JP2009062423A (en) * | 2007-09-05 | 2009-03-26 | Aica Kogyo Co Ltd | Active energy ray-curable hard coating resin composition and hard coating film |
JP6084412B2 (en) * | 2012-09-20 | 2017-02-22 | ヒューグルエレクトロニクス株式会社 | Substrate case cleaning device |
-
2011
- 2011-02-28 JP JP2011548501A patent/JP4998647B2/en active Active
- 2011-02-28 CN CN201180017034.6A patent/CN102844346B/en not_active Expired - Fee Related
- 2011-02-28 KR KR1020127015382A patent/KR101802215B1/en active IP Right Grant
- 2011-02-28 WO PCT/JP2011/054475 patent/WO2011122197A1/en active Application Filing
- 2011-03-30 TW TW100110948A patent/TWI498339B/en not_active IP Right Cessation
Patent Citations (2)
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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 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI595016B (en) * | 2012-01-17 | 2017-08-11 | 迪愛生股份有限公司 | Radiation curable aqueous resin composition, radiation curable water paint, and article coated by the paint |
JP2015528040A (en) * | 2012-07-20 | 2015-09-24 | ビーエイエスエフ・ソシエタス・エウロパエアBasf Se | Quick-drying radiation-curable coating composition |
Also Published As
Publication number | Publication date |
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KR101802215B1 (en) | 2017-11-28 |
CN102844346A (en) | 2012-12-26 |
JPWO2011122197A1 (en) | 2013-07-08 |
TWI498339B (en) | 2015-09-01 |
TW201211071A (en) | 2012-03-16 |
CN102844346B (en) | 2014-10-15 |
KR20130028704A (en) | 2013-03-19 |
JP4998647B2 (en) | 2012-08-15 |
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