CN113383024A - Curable composition for hard coating - Google Patents
Curable composition for hard coating Download PDFInfo
- Publication number
- CN113383024A CN113383024A CN202080012524.6A CN202080012524A CN113383024A CN 113383024 A CN113383024 A CN 113383024A CN 202080012524 A CN202080012524 A CN 202080012524A CN 113383024 A CN113383024 A CN 113383024A
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- CN
- China
- Prior art keywords
- meth
- acrylate
- poly
- curable composition
- group
- 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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- 239000000203 mixture Substances 0.000 title claims abstract description 76
- 238000000576 coating method Methods 0.000 title claims description 44
- 239000011248 coating agent Substances 0.000 title claims description 40
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 42
- 229920000193 polymethacrylate Polymers 0.000 claims abstract description 25
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 16
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 claims abstract description 12
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 12
- 238000005259 measurement Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 230000003373 anti-fouling effect Effects 0.000 abstract description 15
- 239000011247 coating layer Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 83
- 239000010410 layer Substances 0.000 description 47
- 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 19
- -1 acrylate compound Chemical class 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 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 12
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 12
- 238000001723 curing Methods 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- LOUICXNAWQPGSU-UHFFFAOYSA-N 2,2,3,3-tetrafluorooxirane Chemical compound FC1(F)OC1(F)F LOUICXNAWQPGSU-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- IYRWEQXVUNLMAY-UHFFFAOYSA-N carbonyl fluoride Chemical compound FC(F)=O IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 231100000241 scar Toxicity 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- QASBHTCRFDZQAM-UHFFFAOYSA-N (2-isocyanato-2-methyl-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(C)(COC(=O)C=C)N=C=O QASBHTCRFDZQAM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 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
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- NTKBNCABAMQDIG-UHFFFAOYSA-N 3-butoxypropan-1-ol Chemical compound CCCCOCCCO NTKBNCABAMQDIG-UHFFFAOYSA-N 0.000 description 1
- GBSGXZBOFKJGMG-UHFFFAOYSA-N 3-propan-2-yloxypropan-1-ol Chemical compound CC(C)OCCCO GBSGXZBOFKJGMG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- IXAUCVOJRVFRBJ-UHFFFAOYSA-N 4-(trichloromethyl)triazine Chemical class ClC(Cl)(Cl)C1=CC=NN=N1 IXAUCVOJRVFRBJ-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
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- 238000003848 UV Light-Curing Methods 0.000 description 1
- INXWLSDYDXPENO-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CO)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C INXWLSDYDXPENO-UHFFFAOYSA-N 0.000 description 1
- NNVDGGDSRRQJMV-UHFFFAOYSA-L [dioctyl(2,2,5,5-tetramethylhexanoyloxy)stannyl] 2,2,5,5-tetramethylhexanoate Chemical compound CCCCCCCC[Sn](OC(=O)C(C)(C)CCC(C)(C)C)(OC(=O)C(C)(C)CCC(C)(C)C)CCCCCCCC NNVDGGDSRRQJMV-UHFFFAOYSA-L 0.000 description 1
- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 description 1
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- 238000007611 bar coating method Methods 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
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- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 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 1
- 239000006227 byproduct Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
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- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
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- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 description 1
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- 150000008282 halocarbons Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
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- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229960004065 perflutren Drugs 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 208000001072 type 2 diabetes mellitus Diseases 0.000 description 1
- 238000001195 ultra high performance liquid chromatography Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
- C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
- C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- General Physics & Mathematics (AREA)
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- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention provides a curable composition capable of forming a hard coating layer with excellent scratch resistance and antifouling durability. A curable composition comprising: (a) 100 parts by mass of dipentaerythritol poly (meth) acrylate; (b) a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at both ends of the molecular chain thereof via a urethane bond being 0.05 to 10 parts by mass (except for the perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond); and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, wherein a ratio of hexamer of the (a) dipentaerythritol poly (meth) acrylate as a proportion of hexa (meth) acrylate to the total amount of penta (meth) acrylate and hexa (meth) acrylate is 50 mol% or more and 100 mol% or less, which is calculated from a measurement result of liquid chromatography mass spectrometry.
Description
Technical Field
The present invention relates to a curable composition useful as a material for forming a hard coat layer applied to the surface of various display elements such as touch panel displays and liquid crystal displays. More particularly, the present invention relates to a curable composition capable of forming a hard coat layer having excellent durability such as scratch resistance and stain resistance even when cured in the air.
Background
Resin molded articles are often used for portable information terminal devices such as mobile phones and touch-controlled computers, notebook-size personal computers, household electric appliances, and automobile interior and exterior components. These resin molded articles are usually provided with a hard coat layer having scratch resistance on the outermost surface thereof for surface protection.
In general, as a method for imparting scratch resistance to a hard coat layer, for example, a method of improving surface hardness and providing resistance to external force by forming a high-density crosslinked structure, that is, a crosslinked structure having low molecular mobility is employed. As these hard coat layer forming materials, multifunctional acrylate-based materials that undergo three-dimensional crosslinking by radicals are most commonly used at present.
On the other hand, it is known that radical polymerization is inhibited by oxygen in the atmosphere. Therefore, in curing the above-mentioned material, the irradiation with active energy rays is generally performed in an inert gas atmosphere such as nitrogen gas.
Further, a portable information terminal device represented by a mobile phone is operated by being held by a hand and touched by a finger. Therefore, the following problems arise: every time when touching with a hand, fingerprints adhere to the screen and the frame, and the appearance is damaged. The fingerprint contains moisture derived from spontaneous perspiration and oil derived from sebum, and it is strongly desired to impart water repellency and oil repellency to the hard coat layer on the surface of the frame body in order to make both of them less likely to adhere.
From such a viewpoint, the surface of the housing of the portable information terminal device is desired to have antifouling properties against fingerprints and the like. However, even if the initial antifouling property reaches a high level, the function thereof is often degraded by daily touching with the hands of a person during use. Therefore, durability of antifouling property during use becomes a problem.
In addition, conventionally, as a method for imparting antifouling property to the surface of the hard coat layer, a method of adding a fluorine-based surface modifier in a small amount to a coating liquid for forming the hard coat layer has been used. The added fluorine-based compound segregates on the surface of the hard coat layer due to its low surface energy, and imparts water repellency and oil repellency. As the fluorine-based compound, an oligomer having a number average molecular weight of about 1000 to 5000, called perfluoropolyether having a poly (oxyperfluoroalkylene) chain, is used from the viewpoint of water repellency and oil repellency. However, the perfluoropolyether has a high fluorine concentration and is therefore not easily dissolved in an organic solvent used for a coating liquid for forming a hard coat layer in general. In addition, the perfluoropolyether causes coagulation in the formed hard coat layer.
In order to impart solubility in an organic solvent and dispersibility in a hard coat layer to such perfluoropolyether, a method of adding an organic site to the perfluoropolyether can be used. In addition, a method of bonding an active energy ray-curable portion represented by a (meth) acrylate group can be used in order to impart scratch resistance.
To date, a technique is disclosed: as a component for imparting stain resistance to the surface of the hard coat layer, a compound having a (meth) acryloyl group at both ends of a poly (oxyperfluoroalkylene) chain via a poly (oxyalkylene) group and one urethane bond is used as a surface modifier as a stain resistant hard coat layer having scratch resistance (patent document 1).
Documents of the prior art
Patent document
Patent document 1: international publication No. 2016/163479
Disclosure of Invention
Problems to be solved by the invention
The hard coat layer described in patent document 1 has the following problems because it is photo-cured in a nitrogen atmosphere: requires equipment for photocuring, and is labor-consuming and cost-intensive.
On the other hand, a hard coat layer obtained by photocuring under the atmosphere may not have sufficient scratch resistance as compared with a hard coat layer obtained by curing the composition under a nitrogen atmosphere, and may have a problem that the durability of antifouling property is deteriorated.
Means for solving the problems
As a result of intensive studies to achieve the above object, the present inventors have found that a hard coat layer having excellent scratch resistance and durability of stain resistance can be formed by a curable composition containing dipentaerythritol poly (meth) acrylate containing dipentaerythritol hexa (meth) acrylate in a specific ratio and a specific perfluoropolyether, and have completed the present invention.
That is, the present invention relates to, as a first aspect, a curable composition comprising: (a) 100 parts by mass of dipentaerythritol poly (meth) acrylate; (b) a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at both ends of the molecular chain thereof via a urethane bond being 0.05 to 10 parts by mass (except for the perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond); and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, wherein a ratio of hexamer of the (a) dipentaerythritol poly (meth) acrylate, which is a ratio of hexa (meth) acrylate to the total amount of penta (meth) acrylate and hexa (meth) acrylate, is 50 mol% or more and 100 mol% or less, calculated from a measurement result of liquid chromatography-mass spectrometry according to the following formula.
The ratio of six bodies [ mol%]＝(AH1+AH2)÷(AP1+AP2+AH1+AH2)×100
AP1: peak area of extracted ion chromatogram of proton adduct of dipentaerythritol penta (meth) acrylate.
AP2: peak area of extracted ion chromatogram of ammonium adduct of dipentaerythritol penta (meth) acrylate.
AH1: peak area of extracted ion chromatogram of proton adduct of dipentaerythritol hexa (meth) acrylate.
AH2: peak area of extracted ion chromatogram of ammonium adduct of dipentaerythritol hexa (meth) acrylate.
A second aspect relates to the curable composition according to the first aspect, wherein the perfluoropolyether (b) has at least two active energy ray-polymerizable groups at each end of the molecular chain thereof via a urethane bond.
A third aspect relates to the curable composition according to the second aspect, wherein the perfluoropolyether (b) has at least three active energy ray-polymerizable groups at each end of the molecular chain thereof via a urethane bond.
A fourth aspect of the present invention relates to the curable composition according to any one of the first to third aspects, wherein the poly (oxyperfluoroalkylene) group has a repeating unit- [ OCF ]2]-and a repeating unit- [ OCF2CF2]Both of them are groups in which these repeating units are bonded in a block bonding, a random bonding, or a block bonding and a random bonding.
A fifth aspect relates to the curable composition according to the fourth aspect, wherein the perfluoropolyether (b) has a partial structure represented by the following formula [1 ].
(the above formula[1]In which n represents a repeating unit- [ OCF ]2CF2]Number and repeating Unit- [ OCF ]2]-a total number of numbers of 5 to 30, said repeating units- [ OCF2CF2]-and said recurring unit- [ OCF2]The bonding is performed by block bonding, random bonding, or any of block bonding and random bonding. )
A sixth aspect relates to the curable composition according to any one of the first to fifth aspects, further comprising (d) a solvent.
A seventh aspect relates to a cured film formed from a cured product of the curable composition according to any one of the first to sixth aspects.
An eighth aspect relates to a hard coat film comprising a hard coat layer formed from the cured film according to the seventh aspect on at least one side of a film substrate.
A ninth aspect of the present invention relates to a hard coat film comprising a hard coat layer on at least one surface of a film base, the hard coat layer being formed by a method comprising: a step of applying the curable composition according to any one of the first to sixth aspects to a film substrate to form a coating film; and a step of irradiating the coating film with an active energy ray to cure the coating film.
A tenth aspect relates to the hard coat film according to the eighth or ninth aspect, wherein the hard coat layer has a layer thickness of 1 μm to 10 μm.
An eleventh aspect relates to a method for producing a hard coat film having a hard coat layer on at least one surface of a film base material, the method comprising: a step of applying the curable composition according to any one of the first to sixth aspects to a film substrate to form a coating film; and a step of curing the coating film by irradiating the coating film with an active energy ray in the air.
A twelfth aspect relates to the production method according to the eleventh aspect, wherein the hard coat layer has a layer thickness of 1 μm to 10 μm.
Effects of the invention
According to the present invention, a curable composition can be provided which is useful for forming a cured film and a hard coat layer having excellent scratch resistance and antifouling durability even when cured in the atmosphere and having excellent appearance even when formed into a thin film having a thickness of about 1 μm to 10 μm.
Further, according to the present invention, a cured film formed from a cured product of the curable composition or a hard coat film provided with a hard coat layer formed from the cured film on the surface can provide a hard coat film having excellent scratch resistance and appearance, and having antifouling durability.
Detailed Description
< curable composition >
More specifically, the curable composition of the present invention relates to a curable composition comprising: (a) 100 parts by mass of dipentaerythritol poly (meth) acrylate; (b) a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at both ends of the molecular chain thereof via a urethane bond being 0.05 to 10 parts by mass (except for the perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond); and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays
Hereinafter, the respective components (a) to (c) will be described first.
[ (a) dipentaerythritol poly (meth) acrylate ]
Examples of the (a) dipentaerythritol poly (meth) acrylate include: a mixture of one or more compounds selected from the group consisting of dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, and dipentaerythritol mono (meth) acrylate, preferably a mixture of dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol tetra (meth) acrylate, more preferably a mixture of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate.
In the present invention, the (meth) acrylate compound means both of an acrylate compound and a methacrylate compound. The term (meth) acrylic acid refers to both acrylic acid and methacrylic acid.
In the dipentaerythritol poly (meth) acrylate of the present invention, the ratio of dipentaerythritol hexa (meth) acrylate to the total amount of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate (hereinafter, also simply referred to as "hexamer ratio") contained in the dipentaerythritol poly (meth) acrylate is 50 mol% or more and 100 mol% or less.
By setting the proportion of dipentaerythritol hexa (meth) acrylate to 50 mol% or more, a cured film formed by curing the curable composition in the air has sufficient scratch resistance.
In addition, the dipentaerythritol poly (meth) acrylate of the present invention contains 50 mol% or more of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate in total, preferably 55 mol% or more in total, more preferably 60 mol% or more in total, and further preferably 80 mol% or more in total, based on the total amount of dipentaerythritol poly (meth) acrylate. By setting the content ratio of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate to 50 mol% or more in dipentaerythritol poly (meth) acrylate, a cured film obtained by curing the curable composition in the air has sufficient scratch resistance.
The ratio of the hexamer can be determined by a conventional method, and for example, in the case of dipentaerythritol hexaacrylate, the ratio can be calculated from the measurement result of liquid chromatography mass spectrometry (hereinafter referred to as "LC-MS") by the following formula.
The ratio of six bodies [ mol%]＝(AH1+AH2)÷(AP1+AP2+AH1+AH2)×100
AP1: peak area of extracted ion chromatogram (hereinafter, referred to as "XIC") of proton adduct of dipentaerythritol pentaacrylate (m/z ═ 525.197).
AP2: peak area of XIC of ammonium adduct of dipentaerythritol pentaacrylate (m/z-542.223).
AH1: peak area of XIC of proton adduct of dipentaerythritol hexaacrylate (m/z-579.207).
AH2: peak area of XIC of ammonium adduct of dipentaerythritol hexaacrylate (m/z-596.234).
The method for producing the dipentaerythritol poly (meth) acrylate is not particularly limited, and examples thereof include a method in which dipentaerythritol and (meth) acrylic acid are subjected to an esterification reaction. When the product is produced by this method, a high molecular weight component such as an addition reaction of dipentaerythritol poly (meth) acrylate may be produced as a by-product other than dipentaerythritol poly (meth) acrylate. The curable composition of the present invention may contain the high molecular weight component, but it is preferable to use a composition obtained by purifying and removing the high molecular weight component.
[ (b) perfluoropolyether having a poly (oxyperfluoroalkylene) group and an active energy ray-polymerizable group at both ends of the molecular chain via urethane bonds (except for the perfluoropolyether having a poly (oxyperfluoroalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond) ]
In the present invention, as the component (b), a perfluoropolyether containing a poly (oxyperfluoroalkylene) group having an active energy ray-polymerizable group via a urethane bond without via the poly (oxyalkylene) group at both ends of the molecular chain thereof (hereinafter, also simply referred to as "(b) a perfluoropolyether having a polymerizable group at both ends of the molecular chain) is used. (b) The component (a) functions as a surface modifier in a hard coat layer to which the curable composition of the present invention is applied.
Further, the hard coat layer having a transparent appearance can be formed by suppressing the generation of white turbidity by the excellent compatibility of the component (b) and the component (a).
The poly (oxyalkylene) group is a group in which the number of repeating units of an oxyalkylene group is 2 or more and an alkylene group in the oxyalkylene group is an unsubstituted alkylene group.
The number of carbon atoms of the alkylene group in the poly (oxyperfluoroalkylene) group is not particularly limited, but is preferably 1 to 4. That is, the poly (oxyperfluoroalkylene) group means a group having a structure in which a divalent fluorocarbon group having 1 to 4 carbon atoms and an oxygen atom are alternately bonded, and the oxyperfluoroalkylene group means a group having a structure in which a divalent fluorocarbon group having 1 to 4 carbon atoms and an oxygen atom are bonded. Specifically, there may be mentioned: - [ OCF2]- (perfluoromethylene oxide), - [ OCF2CF2]- (perfluoroethylene oxide), - [ OCF2CF2CF2]- (Oxoperfluoropropane-1, 3-diyl), [ OCF2C(CF3)F]- (perfluoropropane oxide-1, 2-diyl), and the like.
The above-mentioned oxyperfluoroalkylene group may be used singly or in combination of two or more, and in this case, the bonding of the multiple oxyperfluoroalkylene groups may be either of a block bonding and a random bonding.
Among them, it is preferable to use a poly (oxyperfluoroalkylene) group having- [ OCF ] as a poly (oxyperfluoroalkylene) group from the viewpoint of obtaining a cured film having good scratch resistance2]- (perfluoromethylene oxide) and- [ OCF2CF2]Both of (perfluoroethylene oxide) and (perfluoroethylene oxide) are groups of the repeating unit.
Among them, as the poly (oxyperfluoroalkylene) group, preferred is a poly (oxyperfluoroalkylene) group in which: - [ OCF2]And- [ OCF2CF2]-as [ repeating units: - [ OCF2]－]: [ repeating unit: - [ OCF2CF2]－]2: 1-1: 2, more preferably, in a ratio of about 1: the ratio of 1 comprises the groups of the above repeating units. The bonding of these repeating units may be block bonding andany of random linkages.
The number of the repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, more preferably in the range of 7 to 21, in terms of the total number of the repeating units.
The poly (oxyperfluoroalkylene) group has a weight average molecular weight (Mw) of 1000 to 5000, preferably 1500 to 3000, as measured in terms of polystyrene by Gel Permeation Chromatography (GPC).
Examples of the active energy ray-polymerizable group include a (meth) acryloyl group, a vinyl group and the like.
(b) The perfluoropolyether having polymerizable groups at both ends of the molecular chain is not limited to those having active energy ray-polymerizable groups such as one (meth) acryloyl group at both ends of the molecular chain, and may have two or more active energy ray-polymerizable groups at both ends of the molecular chain, and examples of the terminal structure including active energy ray-polymerizable groups include structures represented by the following formulas [ a1] to [ a5], and structures in which acryloyl groups in these structures are substituted with methacryloyl groups.
Examples of the perfluoropolyether having a polymerizable group at both ends of the molecular chain (b) include compounds represented by the following formula [2 ].
(formula [2]]Wherein A represents the formula [ A1]]-formula [ A5]PFPE represents one of the structures shown and structures in which an acryloyl group in their structures is substituted with a methacryloyl group, and the poly (oxyperfluoroalkylene) group (wherein, with L, a group represented by formula1The side directly bonded is an oxy terminal, and the side bonded to an oxygen atom is a perfluoroalkylene terminal. ) L is1Represents an alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms, m independently represents an integer of 1 to 5, L2Represents a residue of valence m +1 with OH removed from m +1 polyol. )
Examples of the alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms include: -CH2CHF－、－CH2CF2－、－CHFCF2－、－CH2CH2CHF－、－CH2CH2CF2－、－CH2CHFCF2-etc., preferably-CH2CF2－。
As the above formula [2]Partial structure of the shown compound (A-NHC (═ O)mL2Examples thereof include the following formula [ B1]-formula [ B12]The structure shown, etc.
(in the formulae [ B1] to [ B12], A represents one of the structures represented by the formulae [ A1] to [ A5] and a structure in which an acryloyl group in the structures is replaced by a methacryloyl group.)
In the structures represented by formulas [ B1] to [ B12], formula [ B1] and formula [ B2] correspond to the case where m is 1, formula [ B3] to formula [ B6] correspond to the case where m is 2, formula [ B7] to formula [ B9] correspond to the case where m is 3, and formula [ B10] to formula [ B12] correspond to the case where m is 5.
Among them, the structure represented by the formula [ B3] is preferable, and the combination of the formula [ B3] and the formula [ A3] is particularly preferable.
Preferable (b) perfluoropolyether having a polymerizable group at both ends of the molecular chain includes a compound having a partial structure represented by the following formula [1 ].
The partial structure represented by the above formula [1] corresponds to a portion where a — NHC (═ O) is removed from the compound represented by the above formula [2 ].
The above formula [1]Wherein n represents a repeating unit- [ OCF ]2CF2]Number and repeating Unit- [ OCF ]2]The total number of (a) is preferably an integer in the range of 5 to 30, more preferably an integer in the range of 7 to 21. Furthermore, the repeating unit- [ OCF ]2CF2]The number of-and the repeating unit- [ OCF ]2]The ratio of the quantities of-is preferably 2: 1-1: 2, more preferably about 1: 1, in the above range. The bonding of these repeating units may be either block bonding or random bonding.
In the present invention, (b) a perfluoropolyether having a polymerizable group at both ends of the molecular chain is used in a proportion of 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the aforementioned (a) dipentaerythritol poly (meth) acrylate.
By using (b) perfluoropolyether having polymerizable groups at both ends of the molecular chain in a proportion of 0.05 parts by mass or more, the hard coat layer has sufficient antifouling properties (water repellency and oil repellency). Further, by using (b) perfluoropolyether having polymerizable groups at both ends of the molecular chain in a proportion of 10 parts by mass or less, the (a) dipentaerythritol poly (meth) acrylate can be sufficiently compatible with the perfluoropolyether, and a hard coat layer with less white turbidity can be obtained.
The perfluoropolyether (b) having polymerizable groups at both ends of the molecular chain can be obtained by reacting hydroxyl groups present at both ends of the compound represented by the following formula [3], for example, with an isocyanate compound having polymerizable groups, that is, a compound having isocyanate groups bonded to bonding bonds in the structures represented by the formulae [ a1] to [ a5] and structures in which acryl groups in the structures are replaced with methacryl groups (for example, 2- (meth) acryloyloxyethyl isocyanate, 1- ((meth) acryloyloxymethyl) ethyl isocyanate, and the like) to form urethane bonds.
(HO)mL2-O-L1-PFPF-O-L1-O-L2(OH)m [3]
(formula [3]]Middle, PFPE, L1、L2And m represents the formula [2]]The same meaning is used. )
The curable composition of the present invention may contain: (b) a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, which has an active energy ray-polymerizable group at both ends of the molecular chain via a urethane bond (wherein no poly (oxyalkylene) group is present between the poly (oxyperfluoroalkylene) group and the urethane bond), may further contain: a perfluoropolyether that contains a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at one end (one end terminal) of its molecular chain via a urethane bond and a hydroxyl group at the other end (the other end terminal) of the molecular chain (wherein there is no poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond and between the poly (oxyperfluoroalkylene) group and the hydroxyl group.); a perfluoropolyether containing a poly (oxyperfluoroalkylene) group as represented by the above formula [3], the perfluoropolyether having hydroxyl groups at both ends of the molecular chain thereof (wherein no poly (oxyperfluoroalkylene) group is present between the poly (oxyperfluoroalkylene) group and the hydroxyl group) [ a compound having no active energy ray-polymerizable group ].
As described above, the curable composition of the present invention has excellent compatibility between the perfluoropolyether compound and the component (a), and thus exhibits an excellent effect of suppressing the occurrence of white turbidity in the hard coat layer and forming a hard coat layer having a transparent appearance.
[ (c) polymerization initiator generating free radical by active energy ray ]
In the curable composition of the present invention, the polymerization initiator which generates radicals by irradiation with an active energy ray such as an electron ray, an ultraviolet ray, or an X-ray (hereinafter, also simply referred to as "polymerization initiator (c)") is preferably a polymerization initiator which generates radicals by irradiation with an active energy ray.
Examples of the polymerization initiator (c) include: benzoins, alkylbenzones, thioxanthones, azos, azines, diazos, o-quinonediazines, acylphosphine oxides, oxime esters, organic peroxides, benzophenones, biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salts and sulfonium salts. These may be used alone or in combination of two or more.
Among them, in the present invention, alkylbenzophenones are preferably used as the polymerization initiator (c) from the viewpoint of transparency, surface curability, and film curability. By using the alkylphenones, a cured film having further improved scratch resistance can be obtained.
Examples of the above-mentioned alkylphenones include: α -hydroxyalkylbenzones such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one, and 2-hydroxy-1- (4- (2-hydroxy-2-methylpropanoyl) benzyl) phenyl) -2-methylpropan-1-one; α -aminoalkylbenzones such as 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one; 2, 2-dimethoxy-1, 2-diphenylethan-1-one; methyl phenylglyoxylate, and the like.
In the present invention, the polymerization initiator (c) is used in a proportion of 1 to 20 parts by mass, preferably 2 to 10 parts by mass, based on 100 parts by mass of the pentaerythritol poly (meth) acrylate (a).
[ (d) solvent ]
The curable composition of the present invention may further contain (d) a solvent, and may be in the form of a varnish (film-forming material).
The solvent may be appropriately selected in consideration of workability in coating for forming a cured film (hard coat layer) described later, drying properties before and after curing, and the like, and examples thereof include: aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetrahydronaphthalene; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits, and cyclohexane; halogenated substances such as methyl chloride, methyl bromide, methyl iodide, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene and the like; esters or ester ethers such as ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate; ethers such as diethyl ether, tetrahydrofuran, 1, 4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, and propylene glycol mono-n-butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexanol, benzyl alcohol and ethylene glycol; amides such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide; and mixing two or more of these solvents.
(d) The amount of the solvent used is not particularly limited, but is used, for example, at a concentration of 1 to 70% by mass, preferably 5 to 50% by mass, of the solid content in the curable composition of the present invention. The solid content concentration (also referred to as nonvolatile content concentration) herein means the content of a solid content (a portion where a solvent component is removed from all components) with respect to the total mass (total mass) of the components (a) to (d) (and other additives as needed) of the curable composition of the present invention.
[ other additives ]
In the curable composition of the present invention, additives such as a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant, an adhesion imparting agent, a plasticizer, an ultraviolet absorber, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, a dye, and the like may be added as needed as long as the effects of the present invention are not impaired.
< cured film >
The curable composition of the present invention is applied (coating) to a substrate to form a coating film, and the coating film is irradiated with active energy rays to polymerize (cure) the coating film, whereby a cured film can be formed. The cured film is also an object of the present invention. In addition, a hard coat layer in a hard coat film described later may be a layer formed of the cured film.
Examples of the base material in this case include: various resins (polyesters such AS polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET), and polyethylene naphthalate (PEN), polyurethane, Thermoplastic Polyurethane (TPU), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, triacetyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), and norbornene-based resin), metal, wood, paper, glass, slate, and the like. The shape of these substrates may be a plate, a film or a three-dimensional molded body.
The coating method on the substrate may be appropriately selected from a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, a die coating method, an ink jet method, a printing method (a relief printing method, a gravure printing method, a planographic printing method, a screen printing method, and the like), and among these methods, a relief printing method is preferably used from the viewpoint of applicability to a roll-to-roll method and also from the viewpoint of film coatability, and a gravure coating method is particularly preferably used. It is preferable that the curable composition is filtered in advance using a filter having a pore size of about 0.2 μm or the like and then applied. In the case of coating, a solvent may be added to the curable composition as needed to prepare a varnish. Examples of the solvent in this case include various solvents listed in the above-mentioned [ (d) solvent ].
After a curable composition is applied to a substrate to form a coating film, the coating film is pre-dried by a heating means such as a hot plate or an oven as necessary to remove a solvent (solvent removal step). The conditions for the heat drying at this time are preferably, for example, about 30 seconds to 10 minutes at 40 to 120 ℃.
After drying, the coating film is cured by irradiation with active energy rays such as ultraviolet rays. The active energy ray includes ultraviolet rays, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferable. As a light source for ultraviolet irradiation, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used.
The irradiation with the active energy ray may be performed under the atmosphere, or may be performed under an inert gas atmosphere such as nitrogen. Since the curable composition of the present invention can obtain a sufficient effect even when cured in the air, it is sufficient to perform irradiation in the air from the viewpoint of labor and cost.
Then, the polymerization can be completed by baking, specifically, heating using a hot plate, an oven, or the like.
After drying and curing, the thickness of the cured film formed is usually 0.01 to 50 μm, preferably 0.05 to 20 μm.
< hard coating film >
A hard coat film having a hard coat layer on at least one surface (surface) of a film substrate can be produced using the curable composition of the present invention. The hard coat film is also an object of the present invention, and is preferably used for protecting the surface of various display elements such as a touch panel and a liquid crystal display.
The hard coat layer in the hard coat film of the present invention is formed by a method comprising the steps of: a step of applying the curable composition of the present invention to a film substrate to form a coating film; and a step of curing the coating film by irradiating the coating film with active energy rays such as ultraviolet rays.
As the film substrate, various transparent resin films that can be used for optical applications among the substrates listed as < cured film > above can be used. Preferred resin films include, for example: films of polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethanes, Thermoplastic Polyurethanes (TPU), polycarbonates, polymethacrylates, polystyrene, polyolefins, polyamides, polyimides, and triacetyl cellulose.
In addition, as the method of applying the curable composition to the film base material (coating film forming step) and the method of irradiating the coating film with active energy rays (curing step), the methods listed under the above-mentioned < cured film > can be used. In the case where the curable composition of the present invention contains a solvent (in the form of a varnish), the coating film forming step may be followed by a step of drying the coating film to remove the solvent, if necessary. In this case, the coating film drying method (solvent removal step) listed as the above-mentioned < cured film > can be used.
The layer thickness of the hard coat layer thus obtained is preferably 1 to 20 μm, more preferably 1 to 10 μm.
Industrial applicability
According to the present invention, a curable composition having a surface on which a cured film having abrasion resistance and stain resistance (water repellency and oil repellency) is formed can be obtained. The curable composition of the present invention is preferably used as a material for a scratch-resistant hard coating layer on the surface of various displays such as Liquid Crystal Displays (LCDs), Plasma Displays (PDPs), organic EL displays (OLEDs), and touch panels.
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples.
In the examples, the apparatus and conditions for sample preparation and physical property analysis were as follows.
(1) Coating with a rod coater
The device comprises the following steps: PM-9050 MC (strain) prepared by SMT.
Stick: A-BarOSP-22 manufactured by OSG SYSTEM PRODUCTS, Inc., and a maximum wet film thickness of 22 μm (equivalent to WIRE BAR # 9).
Coating speed: 4 m/min.
(2) Baking oven
The device comprises the following steps: DRY DRYER DRC433FA, manufactured by ADVANTEC TOYOU (LTD.) CORPORATION.
(3) UV curing
The device comprises the following steps: CV-110 QC-G was manufactured by Heraeus.
Lamp: high pressure mercury lamp H-bulb manufactured by Heraeus.
Nitrogen purging box: heraeus (strain).
(4)LC－MS
[ LC ] device: UFLCXR series of ultra high performance liquid chromatography (registered trademark) manufactured by Shimadzu corporation.
A chromatographic column: xbridge BEH C manufactured by Japanese Waters18(2.1mm×75mm，2.5μm)。
Temperature of the column: at 40 ℃.
A detector: UV (210 nm).
Mobile phase A: 0.1% by mass of an ultrapure aqueous formic acid solution.
A mobile phase B: 0.1 mass% formic acid acetonitrile solution.
Flow rate: 0.3 mL/min.
Gradient: 0 min [ mobile phase a: mobile phase B98: 2 (volume ratio) ].
12 minutes [ mobile phase a: mobile phase B ═ 2: 98 (volume ratio) ].
15 minutes [ mobile phase a: mobile phase B ═ 2: 98 (volume ratio) ].
Sample concentration: 0.5mg/mL (acetonitrile solution).
Injection amount: 1 μ L.
[ MS ] device: TripleTOF 5600+ manufactured by AB Sciex.
Ionization: ESI.
Mode (2): positive type.
Scanning range: and m/z is 50-1000.
(5) Gel Permeation Chromatography (GPC)
The device comprises the following steps: HLC-8220 GPC, manufactured by Tosoh corporation.
A chromatographic column: shodex (registered trademark) GPC K-804L and GPC K-805L manufactured by Shorey electrician.
Temperature of the column: at 40 ℃.
Eluent: tetrahydrofuran.
A detector: and RI.
(6) Scratch resistance test
The device comprises the following steps: the reciprocating abrasion tester TRIBOGEAR TYPE manufactured by Xindong science (strain): and (6) 30S.
Scanning speed: 5000 mm/min.
Scanning distance: 50 mm.
(7) Contact Angle determination
The device comprises the following steps: DropMaster DM-501, manufactured by Kyowa interface science (Inc.).
Measuring temperature: at 23 ℃.
In addition, the abbreviation indicates the following meaning.
PFPE 1: perfluoropolyethers having two hydroxyl groups at both ends of the molecular chain without a poly (oxyalkylene) group [ Fomblin (registered trademark) T4, product of Solvay Specialty Polymers ].
PFPE 2: perfluoropolyether having hydroxyl groups at both ends of the molecular chain via poly (oxyalkylene) groups (repeating number of units: 8 or 9) [ Fluorolink 5147X manufactured by Solvay Specialty Polymers ].
BEI: 1, 1-bis (acryloyloxymethyl) ethyl isocyanate [ Karenz (registered trademark) BEI, manufactured by Showa Denko K.K. ].
DOTDD: dioctyltin dineodecanoate [ NEOSTAN (registered trademark) U-830, available from NIDDM CHEMICAL CRYSTAL CO., LTD.).
SM 3: perfluoropolyether having a (meth) acryloyl group at one end of the molecular chain [ MEK/MIBK solution having a nonvolatile content of 20 mass% as a fluorine-containing antifouling additive KY-1203, manufactured by shin-Etsu chemical Co., Ltd ].
SM 4: perfluoropolyether having a (meth) acryloyl group at one end of the molecular chain [ fingerprint adhesion preventive agent OPTPPL (registered trademark) DAC-HP, manufactured by Dajin industries, Ltd., nonvolatile matter 20% by mass solution ].
DPHA 80: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [ NK ESTER A-DPH, manufactured by Newzhongcun chemical industry Co., Ltd., a hexamer ratio of 80 mol% (LC-MS) ].
DPHA 66: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [ aronex (registered trademark) M-406, a pentamer, manufactured by east asia corporation, 25-35% (table of contents), a hexamer ratio of 66 mol% (LC-MS) ].
DPHA 51: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [ ARONIX (registered trademark) M-404, manufactured by Toyo Seisaku-sho., pentamer 30-40% (table of contents), and hexamer 51 mol% (LC-MS) ].
DPHA 47: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture KAYARAD DPHA, manufactured by Nippon Kagaku K.K., a hexamer ratio of 47 mol% (LC-MS).
DPHA 33: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [ ARONIX (registered trademark) M-403, manufactured by TOYOBA SYNTHESIS, Inc. ], pentad content 50-60% (table of contents), and hexamer content 33 mol% (LC-MS) ].
O2959: 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one [ OMNIRAD (registered trademark) 2959, manufactured by IGM Resins Co., Ltd ].
MEK: methyl ethyl ketone.
PGME: propylene glycol monomethyl ether.
The ratio of the hexamer in dipentaerythritol penta/hexaacrylate used was calculated from the measurement results of LC-MS by the following formula, and the average value of 4 measurements was used.
The ratio of six bodies [ mol%]＝(AH1+AH2)÷(AP1+AP2+AH1+AH2)×100
AP1: peak area of XIC of proton adduct of dipentaerythritol pentaacrylate (m/z-525.197).
AP2: peak area of XIC of ammonium adduct of dipentaerythritol pentaacrylate (m/z-542.223).
AH1: peak area of XIC of proton adduct of dipentaerythritol hexaacrylate (m/z-579.207).
AH2: peak area of XIC of ammonium adduct of dipentaerythritol hexaacrylate (m/z-596.234).
Production example 1 production of perfluoropolyether (SM1) having four acryloyl groups at each end of the molecular chain via urethane bonds
Into the spiral tube were charged 1.19g (0.5mmol) of PFPE1, 0.52g (2.0mmol) of BEI, 0.017g (an amount of 0.01 times the total mass of PFPE1 and BEI) of DOTDD, and 1.67g of MEK. The mixture was stirred at room temperature (about 23 ℃) for 24 hours using a stirrer Chip (starter Chip), to obtain a 50 mass% MEK solution of SM1 as a target compound.
Weight average molecular weight of the obtained SM1 in terms of polystyrene based on GPC: mw of 3000, dispersity: mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.
Comparative production example 1 production of perfluoropolyether (SM2) having acryloyl groups at both ends of the molecular chain via poly (oxyalkylene) groups and one urethane bond
Into the spiral tube were charged 1.05g (0.5mmol) of PFPE2, 0.26g (1.0mmol) of BEI, 0.013g (an amount of 0.01 times the total mass of PFPE2 and BEI) of DOTDD, and 1.30g of MEK. The mixture was stirred at room temperature (about 23 ℃) for 24 hours using a stirrer chip to obtain a 50 mass% MEK solution of SM2 as a target compound.
Weight average molecular weight of the obtained SM2 in terms of polystyrene based on GPC: mw 3100, dispersity: Mw/Mn was 1.1.
Examples 1 to 3 and comparative examples 1 to 5
The following components were mixed according to the description in table 1 to prepare a curable composition having the solid content concentration described in table 1. Here, the solid component means a component other than the solvent. In addition, in table 1, [ parts ] indicates [ parts by mass ].
(1) A polyfunctional monomer: 100 parts by mass of the polyfunctional monomer described in Table 1.
(2) Surface modifier: the amounts of the surface-modifying agents shown in Table 1 are shown in Table 1 (in terms of solid content).
(3) Polymerization initiator: 2.5 parts by mass of O2959.
(4) Solvent: PGME in the amounts reported in table 1.
[ Table 1]
The curable composition was applied to an easily adhesive PET film (Lumirror (registered trademark) U403 manufactured by Toray corporation) having a thickness of 100 μm, which was a size of A4, using a bar coater]Thus, a coating film was obtained. The coating film was dried in an oven at 120 ℃ for 3 minutes to remove the solvent. The obtained film was irradiated with an exposure of 1300mJ/cm in the air2The hard coat film was formed by exposure to UV light, and the hard coat film was provided with a hard coat layer (cured film) having a layer (film) thickness of about 5 μm.
Further, the curing conditions were adjusted from the atmospheric air to an exposure of 1300mJ/cm2The exposure was changed to 300mJ/cm in a nitrogen atmosphere2Otherwise, a hard coat film having a hard coat layer (cured film) with a layer (film) thickness of about 5 μm was produced in the same manner.
The hard coat films were evaluated for scratch resistance. In addition, the hard coat films obtained in examples 1 to 3 (exposed to the air) were further evaluated for antifouling durability. The procedure for evaluating the scratch resistance and the antifouling durability is shown below. The results are shown in Table 2.
[ scratch resistance ]
On the surface of the hard coat layer, steel wool (BONSTAR (registered trademark) #0000 (ultra-fine) manufactured by BONSTAR Kabushiki Kaisha) mounted on a reciprocating abrasion tester was used]Applying 1kg/cm2The test piece was rubbed 1000 times in a reciprocating manner under the load of (1), and the degree of the scratch was visually observed under a white light source, and evaluated according to the following criteria (A) and (C).
A: has no scar.
C: a scar is produced.
[ antifouling durability ]
The maintenance rate [% ] (═ contact angle after test ÷ contact angle before test × 100) was calculated from the water contact angles of the hard coat surface before and after the above-described scratch test, and evaluated as antifouling durability. In addition, the contact angle was measured at 5 points with respect to the contact angle, which was measured by attaching 1 μ L of water to the surface of the hard coat layer and measuring the contact angle θ 5 seconds later, and the average value thereof was set as the contact angle value.
[ Table 2]
As shown in table 2, the hard coat films produced using the curable compositions of examples 1 to 3 in which a dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture having a six-mer ratio of 50 mol% or more was blended as a dipentaerythritol polyacrylate had excellent scratch resistance even when the curable compositions were cured in the air.
On the other hand, hard coating films produced using the curable compositions of comparative examples 1 and 2 in which a dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture having a hexamer ratio of less than 50 mol% was incorporated as a dipentaerythritol polyacrylate did not have excellent scratch resistance when the curable compositions were cured in the air.
As shown in table 2, the hard coat films produced using the curable compositions of comparative examples 3 to 5, which were composed of: a dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture having a hexaacrylate ratio of 50 mol% or more as dipentaerythritol polyacrylate; perfluoropolyethers having two acryloyl groups via a poly (oxyalkylene) group and one urethane bond (SM2), or perfluoropolyethers having a (meth) acryloyl group at one end of the molecular chain (SM3, SM4) as general-purpose surface modifiers.
As shown in table 2, the hard coat films produced using the curable compositions of examples 1 to 3 had excellent antifouling durability.
As described above, as shown in the results of examples, a hard coat film having excellent scratch resistance even when cured under atmospheric conditions can be obtained only by using a curable composition in which dipentaerythritol poly (meth) acrylate and a specific perfluoropolyether are combined in an amount of 50 mol% or more in terms of a ratio of hexamer of dipentaerythritol poly (meth) acrylate to the total amount of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate.
Claims (12)
1. A curable composition comprising:
(a) 100 parts by mass of dipentaerythritol poly (meth) acrylate;
(b) a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at both ends of a molecular chain thereof via a urethane bond being 0.05 to 10 parts by mass, excluding the perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond; and
(c) 1 to 20 parts by mass of a polymerization initiator that generates radicals using active energy rays,
a hexamer ratio of the (a) dipentaerythritol poly (meth) acrylate, which is a ratio of hexa (meth) acrylate to the total amount of penta (meth) acrylate and hexa (meth) acrylate, calculated according to the following formula based on the measurement result of liquid chromatography-mass spectrometry, is 50 mol% or more and 100 mol% or less,
the ratio of six bodies [ mol%]＝(AH1+AH2)÷(AP1+AP2+AH1+AH2)×100
AP1: peak area of extracted ion chromatogram of proton adduct of dipentaerythritol penta (meth) acrylate,
AP2: peak area of the extracted ion chromatogram of the ammonium adduct of dipentaerythritol penta (meth) acrylate,
AH1: peak area of the extracted ion chromatogram of the proton adduct of dipentaerythritol hexa (meth) acrylate,
AH2: peak area of extracted ion chromatogram of ammonium adduct of dipentaerythritol hexa (meth) acrylate。
2. The curable composition according to claim 1,
the perfluoropolyether (b) has at least two active energy ray-polymerizable groups at both ends of the molecular chain thereof via urethane bonds.
3. The curable composition according to claim 2,
the perfluoropolyether (b) has at least three active energy ray-polymerizable groups at each end of the molecular chain thereof via a urethane bond.
4. The curable composition according to any one of claims 1 to 3,
the poly (oxyperfluoroalkylene) group is a poly (oxyalkylene) group having a repeating unit- [ OCF ]2]-and a repeating unit- [ OCF2CF2]Both of them are groups in which these repeating units are bonded in a block bonding, a random bonding, or a block bonding and a random bonding.
5. The curable composition according to claim 4,
the perfluoropolyether (b) has a partial structure represented by the following formula [1],
the above formula [1]In which n represents a repeating unit- [ OCF ]2CF2]Number and repeating Unit- [ OCF ]2]-the total number of the number of (a) is an integer of 5 to 30,
said repeating unit- [ OCF ]2CF2]-and said recurring unit- [ OCF2]The bonding is performed by block bonding, random bonding, or any of block bonding and random bonding.
6. The curable composition according to any one of claims 1 to 5,
further comprising (d) a solvent.
7. A cured film formed from a cured product of the curable composition according to any one of claims 1 to 6.
8. A hard coat film comprising a hard coat layer formed from the cured film according to claim 7 on at least one surface of a film substrate.
9. A hard coat film comprising a hard coat layer on at least one surface of a film base, wherein the hard coat layer is formed by a method comprising:
a step of applying the curable composition according to any one of claims 1 to 6 to a film substrate to form a coating film; and
and a step of irradiating the coating film with an active energy ray to cure the coating film.
10. The hard coating film according to claim 8 or 9, wherein,
the hard coat layer has a layer thickness of 1 μm to 10 μm.
11. A method for producing a hard coat film having a hard coat layer on at least one surface of a film substrate, the method comprising:
a step of applying the curable composition according to any one of claims 1 to 6 to a film substrate to form a coating film; and
and curing the coating film by irradiating the coating film with an active energy ray in the air.
12. The manufacturing method according to claim 11,
the hard coat layer has a layer thickness of 1 μm to 10 μm.
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| JP2019-020181 | 2019-02-06 | ||
| PCT/JP2020/003506 WO2020162329A1 (en) | 2019-02-06 | 2020-01-30 | Curable composition for hard coating |
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- 2020-01-30 CN CN202080012524.6A patent/CN113383024A/en active Pending
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| KR20210124349A (en) | 2021-10-14 |
| WO2020162329A1 (en) | 2020-08-13 |
| KR102622176B1 (en) | 2024-01-08 |
| JP7311844B2 (en) | 2023-07-20 |
| TWI828853B (en) | 2024-01-11 |
| TW202045554A (en) | 2020-12-16 |
| JPWO2020162329A1 (en) | 2021-12-09 |
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