JP5709706B2 - Paint for forming transparent film and substrate with transparent film - Google Patents
Paint for forming transparent film and substrate with transparent film Download PDFInfo
- Publication number
- JP5709706B2 JP5709706B2 JP2011202157A JP2011202157A JP5709706B2 JP 5709706 B2 JP5709706 B2 JP 5709706B2 JP 2011202157 A JP2011202157 A JP 2011202157A JP 2011202157 A JP2011202157 A JP 2011202157A JP 5709706 B2 JP5709706 B2 JP 5709706B2
- Authority
- JP
- Japan
- Prior art keywords
- transparent film
- substrate
- transparent
- resin
- range
- 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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- 239000000758 substrate Substances 0.000 title claims description 110
- 239000003973 paint Substances 0.000 title claims description 56
- 238000000576 coating method Methods 0.000 claims description 106
- 239000011248 coating agent Substances 0.000 claims description 104
- 239000004925 Acrylic resin Substances 0.000 claims description 69
- 239000011347 resin Substances 0.000 claims description 52
- 229920005989 resin Polymers 0.000 claims description 52
- 125000000524 functional group Chemical group 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 39
- 239000010419 fine particle Substances 0.000 claims description 31
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims description 23
- 150000004706 metal oxides Chemical class 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 22
- 238000002834 transmittance Methods 0.000 claims description 20
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 13
- 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 group 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 claims description 13
- 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 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 32
- 238000004519 manufacturing process Methods 0.000 description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 19
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 18
- 239000000377 silicon dioxide Substances 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229920001296 polysiloxane Polymers 0.000 description 9
- 230000001629 suppression Effects 0.000 description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 125000004386 diacrylate group Chemical group 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 239000002612 dispersion medium Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 4
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- -1 glycol acrylates Chemical class 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 2
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical group CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- ZODNDDPVCIAZIQ-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C=C ZODNDDPVCIAZIQ-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
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- OJXVKURLHFKLHR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol 1,6-diisocyanatohexane ethyl carbamate Chemical compound NC(=O)OCC.C(CCCCCN=C=O)N=C=O.OCC(CO)(CO)CO OJXVKURLHFKLHR-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
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- HQLKZWRSOHTERR-UHFFFAOYSA-N 2-Ethylbutyl acetate Chemical compound CCC(CC)COC(C)=O HQLKZWRSOHTERR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- OWDBMKZHFCSOOL-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)propoxy]propoxy]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(C)COC(C)COC(=O)C(C)=C OWDBMKZHFCSOOL-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-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
- UPTHZKIDNHJFKQ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OCC(O)CO UPTHZKIDNHJFKQ-UHFFFAOYSA-N 0.000 description 1
- HZHPOJPIGFWDTD-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOC(=O)C=C HZHPOJPIGFWDTD-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
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- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
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- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
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- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Description
本発明は、厚みの薄い基材であってもカーリング（湾曲）が抑制され、基材との密着性、硬度、耐擦傷性、透明性等に優れた透明被膜を形成することのできる透明被膜形成用塗料と透明被膜付基材とに関する。 The present invention provides a transparent coating that can curl (curve) even with a thin substrate and can form a transparent coating excellent in adhesion to the substrate, hardness, scratch resistance, transparency, and the like. The present invention relates to a paint for forming and a substrate with a transparent coating.
従来、ガラス、プラスチックシート、プラスチックレンズ等の基材表面の耐擦傷性を向上させるため、基材表面にハードコート機能を有する透明被膜を形成することが知られており、このような透明被膜として有機樹脂膜あるいは無機膜をガラスやプラスチック等の表面に形成することが行われている。さらに、有機樹脂膜あるいは無機膜中に樹脂粒子あるいはシリカ等の無機粒子を配合してさらに耐擦傷性を向上させることが行われている。 Conventionally, in order to improve the scratch resistance of the substrate surface such as glass, plastic sheet, plastic lens, etc., it is known to form a transparent film having a hard coat function on the substrate surface. An organic resin film or an inorganic film is formed on the surface of glass or plastic. Furthermore, it is practiced to further improve the scratch resistance by blending resin particles or inorganic particles such as silica in an organic resin film or an inorganic film.
このとき、塗料あるいは塗膜の厚さによっては透明被膜付基材がカーリング（湾曲）する問題があった。
さらに、近年、透明性を向上させるために、あるいは透明被膜付基材を使用した表示装置、携帯電話等の軽量化のために厚みの薄い基材が志向されている。
At this time, depending on the thickness of the paint or the coating film, there was a problem that the substrate with the transparent film curled (curved).
Further, in recent years, a thin base material has been aimed at in order to improve transparency, or to reduce the weight of a display device, a mobile phone or the like using a base material with a transparent coating.
従来このような樹脂製透明被膜には、アクリレート樹脂が使用されていた。たとえば、特許文献１（特開2002-055203号公報）、特許文献２（特表2007-524724号公報）などには、ウレタン系アクリレートや多官能アクリレート樹脂を用いた透明被膜が開示されている。 Conventionally, acrylate resins have been used for such resinous transparent coatings. For example, Patent Document 1 (Japanese Patent Laid-Open No. 2002-055203) and Patent Document 2 (Japanese Patent Publication No. 2007-524724) disclose transparent coatings using urethane acrylates or polyfunctional acrylate resins.
また、本発明者らも、特許文献３（特開2010-001396号公報）、特許文献４（特開2011-137097号公報）に多官能アクリレート樹脂を用いた透明被膜を開示している。 The present inventors have also disclosed a transparent film using a polyfunctional acrylate resin in Patent Document 3 (Japanese Patent Laid-Open No. 2010-001396) and Patent Document 4 (Japanese Patent Laid-Open No. 2011-137097).
しかしながら、厚みの薄い基材に従来の透明被膜形成用塗料を用いて透明被膜を形成したところ、透明被膜形成時の収縮によって、カーリング（湾曲）が顕著になり、場合によっては透明被膜が基材から剥離する場合があり、まったく使用に耐えないことが判明した。 However, when a transparent coating is formed on a thin substrate using a conventional coating for forming a transparent coating, curling (curvature) becomes conspicuous due to shrinkage during the formation of the transparent coating. It was found that it could not be used at all.
特許文献３には、導電性酸化物微粒子と、マトリックス形成成分としてグリコール系アクリレート樹脂、非グリコール系アクリレート樹脂からなる塗料が記載されている。
しかしながら、この塗料を用いても、基材が薄い場合、カーリングを抑制することが困難であった。
Patent Document 3 describes a coating composed of conductive oxide fine particles and a glycol acrylate resin or a non-glycol acrylate resin as a matrix forming component.
However, even when this paint is used, it is difficult to suppress curling when the substrate is thin.
本発明者等は、このようなカーリング（湾曲）の抑制について鋭意検討した結果、４官能以上のアクリレート樹脂（Ａ）と、２官能トリシクロデカン系アクリレート樹脂および／または３官能ペンタエリスリトール系トリアクリレート樹脂（Ｂ）とを組み合わせることにより、特に4官能以上のウレタンアクリレート樹脂オリゴマーとトリシクロデカン系２官能ないしペンタエリスリトール系３官能アクリレート樹脂を混合した樹脂にシリカなどの無機酸化物微粒子を配合した透明被膜形成用塗料を用いるとカーリング（湾曲）が抑制され、基材との密着性に優れ、硬度、耐擦傷性の高い透明被膜付基材が得られることを見出して本発明を完成するに至った。 As a result of intensive studies on the suppression of such curling (curvature), the present inventors have obtained a tetrafunctional or higher acrylate resin (A), a bifunctional tricyclodecane acrylate resin and / or a trifunctional pentaerythritol triacrylate. By combining the resin (B), a transparent resin in which inorganic oxide fine particles such as silica are mixed with a resin in which a tetrafunctional or higher urethane acrylate resin oligomer and a tricyclodecane bifunctional or pentaerythritol trifunctional acrylate resin are mixed. The use of a coating-forming coating material has found that curling (curving) is suppressed, a substrate with a transparent coating having excellent adhesion to the substrate, high hardness and scratch resistance, and the present invention has been completed. It was.
[1]官能基数が４以上のアクリレート樹脂（Ａ）と、
官能基数が２および／または３のアクリレート樹脂（Ｂ）と、
平均粒子径が５〜５００ｎｍの範囲にある金属酸化物微粒子（Ｃ）と、
有機溶媒（Ｄ）とからなり、
アクリレート樹脂（Ａ）の濃度（ＣA）とアクリレート樹脂（Ｂ）の濃度（ＣB）との濃度比（ＣB）／（ＣA）が０．０５〜０．５の範囲にある透明被膜形成用塗料。
[1] An acrylate resin (A) having 4 or more functional groups;
An acrylate resin (B) having 2 and / or 3 functional groups;
Metal oxide fine particles (C) having an average particle diameter in the range of 5 to 500 nm;
An organic solvent (D),
Transparent film having a concentration ratio (C B ) / (C A ) between the concentration (C A ) of the acrylate resin ( A ) and the concentration (C B ) of the acrylate resin (B) in the range of 0.05 to 0.5 Forming paint.
[2]前記アクリレート樹脂（Ａ）がウレタンアクリレート樹脂であり、該樹脂の平均分子量が５００〜５０００の範囲にある[1]の透明被膜形成用塗料。
[3]前記アクリレート樹脂（Ｂ）が２官能トリシクロデカン系アクリレート樹脂および／または３官能ペンタエリスリトール系トリアクリレート樹脂であり、該樹脂の平均分子量が２００〜５００の範囲にある[1]または[2]の透明被膜形成用塗料。
[2] The paint for forming a transparent film according to [1], wherein the acrylate resin (A) is a urethane acrylate resin, and the average molecular weight of the resin is in the range of 500 to 5,000.
[3] The acrylate resin (B) is a bifunctional tricyclodecane acrylate resin and / or a trifunctional pentaerythritol triacrylate resin, and the average molecular weight of the resin is in the range of 200 to 500 [1] or [ [2] Paint for forming a transparent film.
[4]前記樹脂（Ａ）の濃度（ＣA）が固形分として０．９５〜４５重量％の範囲にあり、
前記樹脂（Ｂ）の濃度（ＣB）が固形分として０．０５〜１２重量％の範囲にあり、
前記金属酸化物微粒子（Ｃ）の濃度が固形分として０．２５〜４８重量％の範囲にあり、
濃度比（Ｃ）／｛（Ａ）＋（Ｂ）＋（Ｃ）｝が０．２〜０．７の範囲にあり、合計の濃度｛（Ａ）＋（Ｂ）＋（Ｃ）｝が固形分として５〜６０重量％の範囲にある[1]〜[3]の透明被膜形成用塗料。
[4] is in the range concentration (C A) is from 0.95 to 45% by weight solid content of the resin (A), the
In the range concentration (C B) is from 0.05 to 12% by weight solids of the resin (B),
The concentration of the metal oxide fine particles (C) is in the range of 0.25 to 48% by weight as a solid content,
The concentration ratio (C) / {(A) + (B) + (C)} is in the range of 0.2 to 0.7, and the total concentration {(A) + (B) + (C)} is solid. [1] to [3] The coating material for forming a transparent film in a range of 5 to 60% by weight.
[5]基材と、基材上に形成された透明被膜とからなり、
基材の厚みが２０〜７０μｍの範囲にあり、該透明被膜が[1]〜[4]の透明被膜形成用塗料を用いて形成された透明被膜であることを特徴とする透明被膜付基材。
[5] consisting of a base material and a transparent film formed on the base material,
A substrate with a transparent coating, characterized in that the thickness of the substrate is in the range of 20 to 70 μm, and the transparent coating is a transparent coating formed by using the transparent coating forming paint of [1] to [4] .
[6]前記基材がトリアセチルセルロース（ＴＡＣ）である[5]の透明被膜付基材。
[7]前記透明被膜の膜厚が１〜１０μｍの範囲にある[5]または[6]の透明被膜付基材。
[8]前記透明被膜のカーリング性が２０ｍｍ以下である[5]〜[7]の透明被膜付基材。
[6] The substrate with a transparent coating according to [5], wherein the substrate is triacetylcellulose (TAC).
[7] The substrate with a transparent coating according to [5] or [6], wherein the thickness of the transparent coating is in the range of 1 to 10 μm.
[8] The substrate with a transparent coating according to [5] to [7], wherein the curling property of the transparent coating is 20 mm or less.
[9]前記透明被膜の鉛筆硬度が３Ｈ以上である[5]〜[8]の透明被膜付基材。
[10]透明被膜を設けた基材の光透過率が９２％以上である[5]〜[9]の透明被膜付基材。
[9] The substrate with a transparent coating according to [5] to [8], wherein the pencil hardness of the transparent coating is 3H or more.
[10] The substrate with a transparent coating according to [5] to [9], wherein the substrate having a transparent coating has a light transmittance of 92% or more.
本発明によれば、厚みの薄い基材であってもカーリング（湾曲）が抑制され、透明性、硬度、耐擦傷性等に優れた透明被膜を形成することのできる透明被膜形成用塗料と該透明被膜形成用塗料を用いて形成された透明被膜付基材とを提供することができる。 According to the present invention, the curling (curving) is suppressed even with a thin substrate, and the coating for forming a transparent film capable of forming a transparent film excellent in transparency, hardness, scratch resistance, etc. A substrate with a transparent coating formed using a coating for forming a transparent coating can be provided.
以下、まず、本発明に係る透明被膜形成用塗料について説明する。
[透明被膜形成用塗料]
本発明に係る透明被膜形成用塗料は、官能基数が４以上のアクリレート樹脂（Ａ）と官能基数が２および／または３のアクリレート樹脂（Ｂ）と平均粒子径が５〜５００ｎｍの範囲にある金属酸化物微粒子（Ｃ）と有機溶媒（Ｄ）とからなる。
Hereinafter, first, the coating material for forming a transparent film according to the present invention will be described.
[Transparent coating paint]
The coating material for forming a transparent film according to the present invention includes an acrylate resin (A) having 4 or more functional groups, an acrylate resin (B) having 2 and / or 3 functional groups, and a metal having an average particle diameter in the range of 5 to 500 nm. It consists of oxide fine particles (C) and an organic solvent (D).
官能基数が４以上のアクリレート樹脂（Ａ）
官能基数が４以上のアクリレート樹脂（Ａ）としては、ペンタエリストールテトラアクリレート等の４官能アクリレート樹脂、ペンタエリスリトールポリグリシジルエーテルアクリレート等のエポキシ基含有４官能アクリレート樹脂、ジペンタエリスルトールヘキサアクリレート等の６官能アクリレート樹脂、６官能ウレタンアクレートオリゴマー樹脂、８官能ウレタンアクレートオリゴマー樹脂、９官能ウレタンアクレートオリゴマー樹脂、１２官能ウレタンアクレートオリゴマー樹脂、クレゾールノボラック型エポキシアクリレート、ビスフェノールＡジグリシジルエーテルアクリル酸付加物等のエポキシ基を含有する４官能以上のアクリレート樹脂等が挙げられ、これらの混合物も好適に用いることができる。
Acrylate resin with four or more functional groups (A)
Examples of the acrylate resin (A) having 4 or more functional groups include tetrafunctional acrylate resins such as pentaerythritol tetraacrylate, epoxy group-containing tetrafunctional acrylate resins such as pentaerythritol polyglycidyl ether acrylate, and dipentaerythritol hexaacrylate. 6-functional acrylate resin, 6-functional urethane acrylate oligomer resin, 8-functional urethane acrylate oligomer resin, 9-functional urethane acrylate oligomer resin, 12-functional urethane acrylate oligomer resin, cresol novolac type epoxy acrylate, bisphenol A diglycidyl ether acrylic A tetrafunctional or higher functional acrylate resin containing an epoxy group such as an acid adduct can be used, and a mixture thereof can also be used suitably.
このようなアクリレート樹脂（Ａ）としては、市販されているＮＫオリゴＵＡ−３３Ｈ，ＮＫオリゴＵＡ−６ＬＲ，ＮＫオリゴＵＡ−８ＬＲ，ＮＫオリゴＵＡ−１２ＬＲ（新中村化学（株）製）等は好適に用いることができる。 As such acrylate resin (A), commercially available NK Oligo UA-33H, NK Oligo UA-6LR, NK Oligo UA-8LR, NK Oligo UA-12LR (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like are suitable. Can be used.
官能基数が４以上のアクリレート樹脂（Ａ）のなかでも、官能基数が６〜１２のアクリレート樹脂は、カーリング抑制効果が高く好適に用いることができる。
特に、このような官能基数が４以上のアクリレート樹脂（Ａ）は、ウレタンアクリレート樹脂であることが好ましい。
Among acrylate resins (A) having 4 or more functional groups, acrylate resins having 6 to 12 functional groups have a high curling suppression effect and can be suitably used.
In particular, the acrylate resin (A) having 4 or more functional groups is preferably a urethane acrylate resin.
ウレタンアクリレート樹脂を用いるとカーリング抑制効果がより高く、しかも硬度、耐擦傷性に優れた透明被膜を得ることができる。
また、前記ウレタンアクリレート樹脂（Ａ）の平均分子量が５００〜５０００、さらには６００〜４０００の範囲にあることが好ましい。
When a urethane acrylate resin is used, it is possible to obtain a transparent film having a higher curling suppression effect and excellent in hardness and scratch resistance.
Moreover, it is preferable that the average molecular weight of the said urethane acrylate resin (A) exists in the range of 500-5000, Furthermore, 600-4000.
ウレタンアクリレート樹脂（Ａ）の平均分子量が低いと、透明被膜形成時の膜の収縮が大きいためにカーリング抑制効果が不十分となる場合がある。ウレタンアクリレート樹脂（Ａ）の平均分子量が高すぎても、透明被膜の硬度、耐擦傷性が不十分となる場合がある。 When the average molecular weight of the urethane acrylate resin (A) is low, the curling suppression effect may be insufficient due to the large shrinkage of the film when the transparent film is formed. Even if the average molecular weight of the urethane acrylate resin (A) is too high, the hardness and scratch resistance of the transparent film may be insufficient.
ウレタンアクリレート樹脂（Ａ）として、平均分子量が前記範囲にあるオリゴマーを用いると、さらにカーリングが抑制され、硬度、耐擦傷性に優れた透明被膜を得ることができる。 When an oligomer having an average molecular weight within the above range is used as the urethane acrylate resin (A), curling is further suppressed, and a transparent film excellent in hardness and scratch resistance can be obtained.
官能基数が２および／または３のアクリレート樹脂（Ｂ）
２官能アクリレート樹脂としては、ポリエチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリプロピレングリコールジアクリレート、ポリプロピレングリコールジアクリレート、ポリエチレングリコールジメタクレート、ネオペンチルグリコールジメタクリレート、トリプロピレングリコールジメタクリレート、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ポリプロピレングリコールジメタクリレート等のグリコール系アクリレートが挙げられる。さらに、１．４−ブタンジオールジメタクレート、１．６−ヘキサンジオールジメタクレート、１．９−ノナンジオールジメタクレート、１．１０−デカンジオールジメタクリレート、グリセリンジメタクリレート、２ヒドロキシ−３−アクリロイロキシプロピルメタクリレート、１．６−ヘキサンジオールジアクリレート、１．９−ノナンジオールジアクレート、ジメチロール-トリシクロデカンジアクリレート、２-ヒドロキシ−３-アクリロイロキシプロピルメタクレート等の非グリコール系アクリレートが挙げられる。
Acrylate resin (B) having 2 and / or 3 functional groups
Bifunctional acrylate resins include polyethylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, tripropylene glycol dimethacrylate, ethylene glycol diacrylate. Examples thereof include glycol acrylates such as methacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and polypropylene glycol dimethacrylate. Further, 1.4-butanediol dimethacrylate, 1.6-hexanediol dimethacrylate, 1.9-nonanediol dimethacrylate, 1.10-decanediol dimethacrylate, glycerin dimethacrylate, 2hydroxy-3- Non-glycol acrylates such as acryloyloxypropyl methacrylate, 1.6-hexanediol diacrylate, 1.9-nonanediol diacrylate, dimethylol-tricyclodecane diacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate Is mentioned.
３官能アクリレート樹脂としては、ペンタエリスリトールトリアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート等の３官能アクリレート樹脂、ペンタエリスリトールヘキサメチレンジイソシアネートウレタンプレポリマー等の３官能ウレタンアクリレート樹脂、クレゾールノボラック型エポキシアクリレート、ビスフェノールＡジグリシジルエーテルアクリル酸付加物等のエポキシ基含有３官能アクリレート樹脂等が挙げられ、これらの混合物も好適に用いることができる。 Examples of trifunctional acrylate resins include trifunctional acrylate resins such as pentaerythritol triacrylate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate, trifunctional urethane acrylate resins such as pentaerythritol hexamethylene diisocyanate urethane prepolymer, and cresol novolac epoxy. Epoxy group-containing trifunctional acrylate resins such as acrylates and bisphenol A diglycidyl ether acrylic acid adducts can be used, and mixtures thereof can also be suitably used.
このような官能基数が２および／または３のアクリレート樹脂（Ｂ）を用いると、硬度、耐擦傷性を損なうことなく基材との密着性に優れた透明被膜を得ることができる。そして、前記４官能以上のアクリレート（A）と組み合わせることで、基材との密着性が向上し、カーリングが抑制され、硬度、耐擦傷性に優れた透明被膜付基材となる。 When such an acrylate resin (B) having 2 and / or 3 functional groups is used, a transparent film excellent in adhesion to the substrate can be obtained without impairing hardness and scratch resistance. By combining with the tetrafunctional or higher functional acrylate (A), adhesion to the substrate is improved, curling is suppressed, and a substrate with a transparent coating excellent in hardness and scratch resistance is obtained.
なかでも、２官能アクリレート樹脂（Ｂ）としてはトリシクロデカン系アクリレート樹脂、官能基数が３のアクリレート樹脂（Ｂ）としては、ペンタエリスリトール系トリアクリレート樹脂が好適に用いられる。これらは、前記した４官能以上のウレタンアクリレートと組み合わせることでより基材との密着性に優れ、カーリングが抑制され、硬度、耐擦傷性に優れた透明被膜付基材となる。その結果、カーリング抑制効果、硬度を低下させることなくより密着性を向上することができるので好適に用いることができる。 Among these, a tricyclodecane acrylate resin is suitably used as the bifunctional acrylate resin (B), and a pentaerythritol triacrylate resin is suitably used as the acrylate resin (B) having 3 functional groups. These are combined with the above-described tetrafunctional or higher urethane acrylates to provide a substrate with a transparent coating that is more excellent in adhesion to the substrate, curling is suppressed, and has excellent hardness and scratch resistance. As a result, the adhesiveness can be further improved without lowering the curling suppression effect and hardness, so that it can be suitably used.
また、官能基数が２、３のアクリレート樹脂（Ｂ）の平均分子量が２００〜５００の範囲にあることが好ましい。
前記アクリレート樹脂（Ｂ）の平均分子量が低すぎると、カーリング抑制が不十分となる場合があり、平均分子量が高すぎても、透明被膜の硬度、耐擦傷性が不十分となる場合がある。
The average molecular weight of the acrylate resin (B) having 2 or 3 functional groups is preferably in the range of 200 to 500.
If the average molecular weight of the acrylate resin (B) is too low, curling suppression may be insufficient, and even if the average molecular weight is too high, the hardness and scratch resistance of the transparent film may be insufficient.
金属酸化物微粒子（Ｃ）
金属酸化物微粒子（Ｃ）としては、従来公知の金属酸化物微粒子を用いることができる。
Metal oxide fine particles (C)
Conventionally known metal oxide fine particles can be used as the metal oxide fine particles (C).
金属酸化物微粒子（C）を配合して用いると、添加量によるものの、基材との密着性、膜強度、耐擦傷性に優れた透明被膜を得ることができる。
金属酸化物微粒子としては、例えば、シリカ、アルミナ、チタニア、シリカ・アルミナ、シリカ・ジルコニア等の他、酸化錫、ＳｂまたはＰがドープされた酸化錫、酸化インジウム、ＳｎまたはＦがドーピングされた酸化インジウム、酸化アンチモン、低次酸化チタン等の導電性金属酸化物微粒子も好適に用いることができる。
When the metal oxide fine particles (C) are blended and used, a transparent film excellent in adhesion to the substrate, film strength, and scratch resistance can be obtained, depending on the amount added.
Examples of the metal oxide fine particles include silica, alumina, titania, silica / alumina, silica / zirconia, etc., tin oxide, tin oxide doped with Sb or P, oxide oxidized with indium oxide, Sn or F. Conductive metal oxide fine particles such as indium, antimony oxide and low-order titanium oxide can also be suitably used.
また、金属酸化物微粒子は、従来公知の方法によりシランカップリング剤処理等の分散性を高める処理をして用いることもできる。
金属酸化物微粒子は平均粒子径が５〜５００ｎｍ、さらには１０〜２００ｎｍの範囲にあることが好ましい。
The metal oxide fine particles can also be used after being subjected to a treatment for improving dispersibility, such as a silane coupling agent treatment, by a conventionally known method.
The metal oxide fine particles preferably have an average particle diameter in the range of 5 to 500 nm, more preferably 10 to 200 nm.
金属酸化物微粒子が小さすぎると、透明被膜形成用塗料中で粒子が凝集しやすく、得られる透明被膜の基材との密着性、膜強度、耐擦傷性等が不充分になる場合があり、さらに金属酸化物微粒子が導電性微粒子である場合は粒界抵抗が大きくなるため、得られる透明被膜の帯電防止性能が不充分となる場合がある。 If the metal oxide fine particles are too small, the particles are likely to aggregate in the coating for forming a transparent coating, and the resulting transparent coating may have insufficient adhesion to the substrate, film strength, scratch resistance, Further, when the metal oxide fine particles are conductive fine particles, the grain boundary resistance increases, and thus the antistatic performance of the obtained transparent film may be insufficient.
また、金属酸化物微粒子が非伝導性微粒子である場合、なかでもシリカ微粒子を好適に用いることができる。特に球状のシリカコロイド粒子に由来するシリカ微粒子を用いると、基材との密着性に優れ、カーリングが抑制され、硬度、耐擦傷性に優れるとともに、基材がTACである場合に、基材との屈折率差のない透明被膜を形成することができ、このため、干渉縞がなく透明性に優れた透明被膜付基材を得ることができる。 Further, when the metal oxide fine particles are non-conductive fine particles, among them, silica fine particles can be suitably used. In particular, when using silica fine particles derived from spherical silica colloidal particles, excellent adhesion to the substrate, curling is suppressed, hardness and scratch resistance are excellent, and when the substrate is TAC, A transparent coating film having no difference in refractive index can be formed. For this reason, a substrate with a transparent coating film having no interference fringes and excellent transparency can be obtained.
金属酸化物微粒子が大きすぎても、得られる透明被膜の透明性が低下したり、ヘーズが高くなる場合がある。また、金属酸化物微粒子が導電性微粒子である場合は透明被膜中で導電パスを形成しにくく、帯電防止性能が不充分となる場合がある。 Even if the metal oxide fine particles are too large, the transparency of the obtained transparent film may be lowered or haze may be increased. Further, when the metal oxide fine particles are conductive fine particles, it is difficult to form a conductive path in the transparent film, and the antistatic performance may be insufficient.
有機溶媒（Ｄ）
本発明に用いる有機溶媒としては前記官能基数が４以上のアクリレート樹脂（Ａ）と官能基数が２のアクリレート樹脂（Ｂ）、重合開始剤を溶解あるいは分散できるとともに金属酸化物微粒子を均一に分散することができる従来公知の溶媒を用いることができる。
Organic solvent (D)
As the organic solvent used in the present invention, the acrylate resin (A) having 4 or more functional groups, the acrylate resin (B) having 2 functional groups, a polymerization initiator can be dissolved or dispersed, and metal oxide fine particles can be uniformly dispersed. Conventionally known solvents that can be used can be used.
具体的には、メタノール、エタノール、プロパノール、2-プロパノール（ＩＰＡ）、
ブタノール、ジアセトンアルコール、フルフリルアルコール、テトラヒドロフルフリルアルコールなどのアルコール類；酢酸メチル、酢酸エチル、酢酸イソプルピル、酢酸プルピル、酢酸イソブチル、酢酸ブチル、酢酸イソペンチル、酢酸ペンチル、酢酸３−メトキシブチル、酢酸２−エチルブチル、酢酸シクロヘキシル、エチレングリコールモノアセテート等のエステル類、エチレングリコール、ヘキシレングリコールなどのグリコール類；ジエチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールイソプルピルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プルピレングリコールものエチルエーテルなどのエーテル類を含む親水性溶媒、酢酸プルピル、酢酸イソブチル、酢酸ブチル、酢酸イソペンチル、酢酸ペンチル、酢酸３−メトキシブチル、酢酸２−エチルブチル、酢酸シクロヘキシル、エチレングリコールものアセタートなどのエステル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、ブチルメチルケトン、シクロヘキサノン、メチルシクロヘキサノン、ジプロピルケトン、メチルペンチルケトン、ジイソブチルケトン等のケトン類；トルエン等極性溶媒が挙げられる。これらは単独で使用してもよく、また２種以上混合して使用してもよい。
Specifically, methanol, ethanol, propanol, 2-propanol (IPA),
Alcohols such as butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol; methyl acetate, ethyl acetate, isopropyl, acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, acetic acid Esters such as 2-ethylbutyl, cyclohexyl acetate, ethylene glycol monoacetate, glycols such as ethylene glycol, hexylene glycol; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isoprene Pill ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol Hydrophilic solvents including ethers such as rumonomethyl ether and purpylene glycol ethyl ether, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene Esters such as glycol acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, and diisobutyl ketone; polar solvents such as toluene. These may be used singly or in combination of two or more.
重合開始剤
本発明では、必要に応じて光重合開始剤を用いることができる。
重合開始剤としては、公知のものを特に制限なく使用することが可能であり、例えば、ビス（2、4、6−トリメチルベンゾイル）フェニルフォスフィンオキサイド、ビス（2、6−ジメトキシベンゾイル）2、4、4−トリメチル-ペンチルフォスフィンオキサイド、2−ヒドロキシ-メチル-2-メチル-フェニル-プロパン-1-ケトン、2、2-ジメトキシ-1、2-ジフェニルエタン-１-オン、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン（イルガキュア１８４）、2-メチル-1-［4-(メチルチオ)フェニル］-2-モルフォリノプロパン-1-オン等が挙げられる。また、上記以外に、レベリング剤などが含まれていてよい。
Polymerization initiator In this invention, a photoinitiator can be used as needed.
As the polymerization initiator, known ones can be used without particular limitation. For example, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2, 4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-methyl-2-methyl-phenyl-propane-1-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy- Examples include cyclohexyl-phenyl-ketone (Irgacure 184), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, and the like. In addition to the above, a leveling agent or the like may be included.
組成
前記各成分を含む透明被膜形成用塗料中の樹脂（Ａ）の濃度（ＣA）は固形分として０．９５〜４５重量％、さらには２．０〜４０重量％の範囲にあることが好ましい。
Composition The concentration (C A ) of the resin (A) in the coating material for forming a transparent film containing each of the above components is 0.95 to 45% by weight, more preferably 2.0 to 40% by weight as a solid content. preferable.
透明被膜形成用塗料中の樹脂（Ａ）の濃度（ＣA）が少なすぎると、得られる透明被膜がカーリングする場合がある。透明被膜形成用塗料中の樹脂（Ａ）の濃度（ＣA）が多すぎても、得られる透明被膜の硬度が不十分となる場合がある。 If the concentration (C A ) of the resin (A) in the coating for forming a transparent film is too small, the resulting transparent film may curl. Even concentration (C A) is too large in the resin of the transparent film-forming paint (A), there is a case where the hardness of the resulting transparent coating film becomes insufficient.
また、樹脂（Ｂ）の濃度（ＣB）は固形分として０．０５〜１２重量％、さらには０．１〜１０重量％の範囲にあることが好ましい。
樹脂（Ｂ）の濃度（ＣB）が少ないと、透明被膜と基材との密着性が不十分となる場合がある。樹脂（Ｂ）の濃度（ＣB）が多すぎても、得られる透明被膜の硬度が不十分となる場合がある。
The concentration (C B) of the resin (B) is from 0.05 to 12% by weight solids, more preferably in the range of 0.1 to 10 wt%.
When the resin concentration of (B) (C B) is small, the adhesion between the transparent film and the substrate becomes insufficient. Even if the concentration of the resin (B) (C B) is too large, there is a case where the hardness of the resulting transparent coating film becomes insufficient.
透明被膜形成用塗料中の金属酸化物微粒子（Ｃ）の濃度は固形分として０．２５〜４８重量％、さらには０．５〜４２重量％の範囲にあることが好ましい。
透明被膜形成用塗料中の金属酸化物微粒子（Ｃ）が少ないと、カーリング抑制効果、硬度および耐擦傷性が不十分となる場合がある。透明被膜形成用塗料中の金属酸化物微粒子（Ｃ）が多すぎても、得られる透明被膜と基材との密着性が不十分となり、厚膜化した場合にクラックを生じる場合がある。
The concentration of the metal oxide fine particles (C) in the coating for forming a transparent film is preferably in the range of 0.25 to 48% by weight, more preferably 0.5 to 42% by weight as a solid content.
When the metal oxide fine particles (C) in the coating for forming a transparent film are small, curling suppression effect, hardness and scratch resistance may be insufficient. Even if there are too many metal oxide fine particles (C) in the paint for forming a transparent film, the adhesion between the obtained transparent film and the substrate becomes insufficient, and cracks may occur when the film is thickened.
透明被膜形成用塗料中の（A）〜（C）の合計濃度は固形分として５〜６０重量％、さらには１０〜５０重量％の範囲にあることが好ましい。
透明被膜形成用塗料の合計濃度が低すぎると、１回の塗布で膜厚が０．５μｍ以上の透明被膜を得ることが困難な場合があり、繰り返し塗布、乾燥して形成した場合、得られる透明被膜の硬度や耐擦傷性が不充分となったり、ヘーズあるいは外観が悪くなったり、生産性、製造信頼性等が低下する。透明被膜形成用塗料の合計濃度が高すぎても、塗料の粘度が高くなり、塗布性が低下したり、得られる透明被膜のヘーズが高くなったり、表面粗さが大きく耐擦傷性が不充分となる場合がある。
The total concentration of (A) to (C) in the paint for forming a transparent film is preferably in the range of 5 to 60% by weight, more preferably 10 to 50% by weight as the solid content.
If the total concentration of the coating for forming a transparent film is too low, it may be difficult to obtain a transparent film having a film thickness of 0.5 μm or more by a single application, and it is obtained when it is repeatedly applied and dried. The hardness and scratch resistance of the transparent film become insufficient, the haze or appearance deteriorates, and the productivity, production reliability, etc. are lowered. Even if the total concentration of the paint for forming a transparent film is too high, the viscosity of the paint increases, the applicability decreases, the haze of the resulting transparent film increases, the surface roughness is large, and the scratch resistance is insufficient. It may become.
前記アクリレート樹脂（Ａ）の濃度（ＣA）と前記アクリレート樹脂（Ｂ）の濃度（ＣB）との濃度比（ＣB）／（ＣA）は０．０５〜０．５０、さらには０．０５〜０．４３の範囲にあることが好ましい。
前記濃度比（ＣB）／（ＣA）が小さ過ぎると、樹脂（B）が少ないため、密着性が不十分となる場合があり、前記濃度比（ＣB）／（ＣA）が多すぎると、樹脂（A）が少ないために、カーリング抑制効果および硬度、耐擦傷性が不十分となる場合がある。
The acrylate concentration ratio between the concentration (C B) of the resin concentration of (A) (C A) and the acrylate resin (B) (C B) / (C A) is 0.05 to 0.50, more 0 It is preferable to be in the range of 0.05 to 0.43.
If the concentration ratio (C B ) / (C A ) is too small, the resin (B) is small and the adhesion may be insufficient, and the concentration ratio (C B ) / (C A ) is large. If the amount is too large, the resin (A) is small, and the curling suppression effect, hardness, and scratch resistance may be insufficient.
全固形分濃度｛（Ａ）＋（Ｂ）＋（Ｃ）｝に対する金属酸化物微粒子の濃度（Ｃ）の割合、（Ｃ）／｛（Ａ）＋（Ｂ）＋（Ｃ）｝は０．２〜０．７、０．２５〜０．６の範囲にあることが好ましい。 Ratio of concentration (C) of metal oxide fine particles to total solid content concentration {(A) + (B) + (C)}, (C) / {(A) + (B) + (C)} is 0. It is preferable that it exists in the range of 2-0.7 and 0.25-0.6.
前記（Ｃ）／｛（Ａ）＋（Ｂ）＋（Ｃ）｝が小さいと、カーリング抑制効果、硬度および耐擦傷性が不十分となる場合がある。
前記（Ｃ）／｛（Ａ）＋（Ｂ）＋（Ｃ）｝が多すぎても、得られる透明被膜と基材との密着性が不十分となり、厚膜化した場合にクラックを生じる場合がある。
When (C) / {(A) + (B) + (C)} is small, curling suppression effect, hardness and scratch resistance may be insufficient.
Even if there is too much (C) / {(A) + (B) + (C)}, the adhesion between the obtained transparent film and the substrate becomes insufficient, and cracks occur when the film is thickened. There is.
このような透明被膜形成塗料を用いた透明被膜の形成方法は、ディップ法、スプレー法、スピナー法、ロールコート法、バーコート法、グラビア印刷法、マイクログラビア印刷法等の周知の方法で基材に塗布し、乾燥し、紫外線照射する等常法によって硬化させることによって透明被膜を形成することができる。
得られた透明被膜付基材の透明被膜の膜厚は１〜１０μｍ、さらには２〜１０μｍの範囲にあることが好ましい。
次ぎに、本発明に係る透明被膜付基材について説明する。
The transparent film-forming method using such a transparent film-forming coating is a known method such as dipping, spraying, spinner, roll coating, bar coating, gravure printing, or micro gravure printing. A transparent film can be formed by applying the composition to a coating, drying, and curing by an ordinary method such as ultraviolet irradiation.
The film thickness of the transparent coating of the obtained substrate with a transparent coating is preferably in the range of 1 to 10 μm, more preferably 2 to 10 μm.
Next, the transparent film-coated substrate according to the present invention will be described.
[透明被膜付基材]
本発明に係る透明被膜付基材は、基材と、基材上に形成された前記塗料を用いてい形成された透明被膜とからなる。
[Base material with transparent coating]
The base material with a transparent film according to the present invention includes a base material and a transparent film formed using the paint formed on the base material.
基材
本発明に用いる基材としては、公知のものを特に制限なく使用することが可能であり、ポリカーボネート、アクリル樹脂、ＰＥＴ、トリアセチルセルロース（ＴＡＣ）等のプラスチックシート、プラスチックフィルム等、プラスチックパネル等があげられる。
中でも厚みの薄い基材に好適に用いることができ、特にＴＡＣ基材は基材の厚みが薄い場合にカーリングしやすく、カーリングを抑制することのできる本発明の透明被膜付基材としては好適に用いることができる。
Substrate As the substrate used in the present invention, a known substrate can be used without particular limitation, and a plastic sheet such as polycarbonate, acrylic resin, PET, triacetylcellulose (TAC), or a plastic film. Etc., and plastic panels.
Among them, it can be suitably used for a substrate having a small thickness. Particularly, a TAC substrate is easily curled when the substrate is thin, and is suitably used as a substrate with a transparent coating according to the present invention that can suppress curling. Can be used.
基材の厚みは２０〜７０μｍ、さらには３０〜６０μｍの範囲にあることが好ましい。
基材が薄いものでは、前記した本発明の透明被膜形成塗料を用いてもカーリングを抑制することが困難となることがある。
The thickness of the substrate is preferably in the range of 20 to 70 μm, more preferably 30 to 60 μm.
When the substrate is thin, curling may be difficult to suppress even when the above-described transparent film-forming paint of the present invention is used.
基材の厚いものでは、従来公知の塗料を用いても顕著にカーリングすることなく透明性、硬度、耐擦傷性等に優れた透明被膜を形成することができる。なお、このことは、本発明の透明被膜形成塗料を用いて厚みが７０μｍを越える基材上に透明被膜を形成することを排除するものではない。 When the substrate is thick, a transparent film excellent in transparency, hardness, scratch resistance and the like can be formed without significantly curling even if a conventionally known paint is used. This does not exclude the formation of a transparent film on a substrate having a thickness exceeding 70 μm using the transparent film-forming paint of the present invention.
透明被膜
本発明に係る透明被膜は、前記した官能基数が４以上のアクリレート樹脂（Ａ）と官能基数が２および／または３のアクリレート樹脂（Ｂ）とが、硬化したマトリックスと平均粒子径が５〜５００ｎｍの範囲にある金属酸化物微粒子（Ｃ）とからなっている。
Transparent coating The transparent coating according to the present invention has a matrix in which the acrylate resin (A) having 4 or more functional groups and the acrylate resin (B) having 2 and / or 3 functional groups are cured and an average particle size of 5 It consists of metal oxide fine particles (C) in the range of ˜500 nm.
塗料中の各成分（A）〜（C）の割合が通常、そのまま透明被膜中の割合となる。
透明被膜中の官能基数が４以上のアクリレート樹脂（Ａ）の含有量（ＷA）は固形分として１．５８〜７５重量％、さらには３．３３〜６６．７重量％の範囲にあることが好ましい。アクリレート樹脂（Ａ）のが少ないと、透明被膜がカーリングする場合がある。アクリレート樹脂（Ａ）が多すぎても、透明被膜の硬度、耐擦傷性が不十分となる場合がある。
The proportion of each component (A) to (C) in the paint is usually the proportion in the transparent film as it is.
The content (W A ) of the acrylate resin (A) having 4 or more functional groups in the transparent film is 1.58 to 75% by weight, more preferably 3.33 to 66.7% by weight as a solid content. Is preferred. If the amount of the acrylate resin (A) is small, the transparent film may curl. Even if the acrylate resin (A) is too much, the hardness and scratch resistance of the transparent film may be insufficient.
透明被膜中の官能基数が２および／または３のアクリレート樹脂（Ｂ）含有量（ＷB）は固形分として０．０８〜２０重量％、さらには０．１７〜１６．７重量％の範囲にあることが好ましい。アクリレート樹脂（Ｂ）が少なすぎても、基材との密着性が不十分となる場合がある。アクリレート樹脂（Ｂ）が多すぎても、硬度、耐擦傷性が不十分となる場合がある。 The content (W B ) of the acrylate resin (B) having 2 and / or 3 functional groups in the transparent film is in the range of 0.08 to 20% by weight, more preferably 0.17 to 16.7% by weight as a solid content. Preferably there is. Even if there is too little acrylate resin (B), adhesiveness with a base material may become inadequate. Even if there is too much acrylate resin (B), hardness and scratch resistance may be insufficient.
前記樹脂（Ａ）の含有量（ＷA）と前記樹脂（Ｂ）の含有量（ＷB）との含有量比（ＷB）／（ＷA）は０．０５〜０．５、さらには０．０５〜０．４３の範囲にあることが好ましい。
含有量比（ＷB）／（ＷA）が０．０５未満の場合は、密着性が不十分となる場合がある。
含有量比（ＷB）／（ＷA）が０．４を越えると、透明被膜がカーリングしたり硬度、耐擦傷性が不十分となる場合がある。
The content ratio (W B ) / (W A ) between the content (W A ) of the resin ( A ) and the content (W B ) of the resin (B) is 0.05 to 0.5, It is preferable to be in the range of 0.05 to 0.43.
When the content ratio (W B ) / (W A ) is less than 0.05, the adhesion may be insufficient.
When the content ratio (W B ) / (W A ) exceeds 0.4, the transparent film may curl or the hardness and scratch resistance may be insufficient.
透明被膜の膜厚は１〜１０μｍ、さらには２〜１０μｍの範囲にあることが好ましい。
透明被膜の膜厚が薄いと、透明被膜の硬度、耐擦傷性が不充分となる場合がある。透明被膜の膜厚が厚すぎても、基材との密着性が不十分となったり、クラックが発生する場合がある。
The film thickness of the transparent coating is preferably in the range of 1 to 10 μm, more preferably 2 to 10 μm.
If the film thickness of the transparent film is thin, the hardness and scratch resistance of the transparent film may be insufficient. Even if the film thickness of the transparent coating is too thick, adhesion to the substrate may be insufficient or cracks may occur.
本発明では、透明被膜のカーリング性が２０ｍｍ以下、さらには１０ｍｍ以下であることが好ましい。
ここで、本発明でカーリング性とは、所定の形状（１４ｃｍ×２５ｃｍ×厚み：４０μｍ）のＴＡＣフィルム基材上に所定の厚み（８μｍ）の透明被膜が形成できるように透明被膜形成用塗料を塗布し、２０時間静置し、その後、フィルムを１０ｃｍ×１０ｃｍサイズにカットし、塗布面を下にしてフィルムを平板上に置き、カーリング（湾曲）して浮上した基材の頂点の平板からの高さ（Ａｍｍ）として定義される。
In the present invention, the curling property of the transparent coating is preferably 20 mm or less, more preferably 10 mm or less.
Here, curling property in the present invention refers to a coating for forming a transparent film so that a transparent film having a predetermined thickness (8 μm) can be formed on a TAC film substrate having a predetermined shape (14 cm × 25 cm × thickness: 40 μm). Apply and let stand for 20 hours, then cut the film to 10cm x 10cm size, place the film on a flat plate with the coated surface down, curl (curve) and lift from the flat plate at the top of the substrate Defined as height (Amm).
透明被膜のカーリング性が大きいと、偏光板等の基材と接着する際にハンドリングが悪く、透明被膜が基板に均一に密着した透明被膜付基材が得られない場合がある。
また、本発明の透明被膜の鉛筆硬度は３Ｈ以上、さらには４Ｈ以上であることが好ましい。透明被膜の鉛筆硬度が３Ｈ未満の場合は、耐擦傷性が不十分である。
また、透明被膜付基材の光透過率が９２％以上、さらには９２．５％以上であることが好ましい。
When the curling property of the transparent film is large, handling may be poor when adhering to a substrate such as a polarizing plate, and a substrate with a transparent film in which the transparent film is uniformly adhered to the substrate may not be obtained.
Further, the pencil hardness of the transparent film of the present invention is preferably 3H or higher, more preferably 4H or higher. When the pencil hardness of the transparent film is less than 3H, the scratch resistance is insufficient.
Moreover, it is preferable that the light transmittance of the base material with a transparent film is 92% or more, more preferably 92.5% or more.
透明被膜付基材の光透過率が上記範囲よりも低いとの場合は、表示装置等に用いた場合、画像の鮮明度不充分となる場合がある。
このような透明被膜基材は、光電気セル、液晶表示セルや携帯電話、パソコン等の軽量化のために厚みの薄く、かつ軽量も求められる用途に好適である。
When the light transmittance of the substrate with a transparent coating is lower than the above range, the image clarity may be insufficient when used in a display device or the like.
Such a transparent coating substrate is suitable for applications where a thin and light weight is required to reduce the weight of photoelectric cells, liquid crystal display cells, mobile phones, personal computers and the like.
［実施例］
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例により限定されるものではない。
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.
［実施例１］
透明被膜形成用塗料(1)の調製
シリカオルガノゾル分散液（日揮触媒化成（株）製：ＯＳＣＡＬ１８４２；平均粒子径１２ｎｍ、ＳｉＯ2濃度４０．５重量％、分散媒：メチルイソブチルケトン、粒子屈折率１．４６）５９．２６ｇと、官能基数が９のアクリレート樹脂（Ａ）としてウレタンアクリレートオリゴマー樹脂（新中村化学（株）製：ＮＫオリゴ ＵＡ−３３Ｈ、平均分子量＝4000）１４．４０ｇと、官能基数が２のアクリレート樹脂（Ｂ）としてジメチロール-トリシクロデカンジアクリレート（共栄社化学（株）製：ライトアクリレートＤＣＰ−Ａ、平均分子量＝３０２）１．６０ｇと、アクリルシリコーン系レベリング剤（楠本化成（株）製；ディスパロンＮＳＨ−８４３０ＨＦ）０．２０ｇと光重合開始剤（チバジャパン（株））製：イルガキュア１８４、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）で固形分濃度３０％に溶解）３．２０ｇとＰＧＭＥ１１．３４ｇとアセトン１０．０ｇを充分に混合して固形分濃度４０．０重量％の透明被膜形成用塗料(1)を調製した。
[Example 1]
Preparation of paint for forming transparent film (1) Silica organosol dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: OSCAL1842; average particle size 12 nm, SiO 2 concentration 40.5% by weight, dispersion medium: methyl isobutyl ketone) , Particle refractive index 1.46) 59.26 g, urethane acrylate oligomer resin (Shin Nakamura Chemical Co., Ltd .: NK Oligo UA-33H, average molecular weight = 4000) as acrylate resin (A) having 9 functional groups. 40 g, 1.60 g of dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate DCP-A, average molecular weight = 302) as an acrylate resin (B) having 2 functional groups, and an acrylic silicone leveling agent (Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 0.20 g and photopolymerization initiator (Ciba Japan ( )) Made: Irgacure 184, dissolved in propylene glycol monomethyl ether (PGME) to a solid content concentration of 30%) 3.20 g, 11.34 g of PGME and 10.0 g of acetone were mixed well to obtain a solid content concentration of 40.0% by weight. A transparent film-forming paint (1) was prepared.
透明被膜付基材(1)の製造
透明被膜形成用塗料(1)を、ＴＡＣフィルム（富士フィルム（株）製：ＦＴ−ＰＢ４０ＵＬ−Ｍ、厚さ：４０μｍ、屈折率：１．５１）にバーコーター法（＃１４）で塗布し、８０℃で１２０秒間乾燥した後、Ｎ2雰囲気下３００ｍＪ／ｃｍ2の紫外線を照射して硬化させて透明被膜付基材(1)を得た。透明被膜の膜厚は８μｍであった。
Production of substrate with transparent coating (1) The coating for transparent coating formation (1) is placed on a TAC film (Fuji Film Co., Ltd .: FT-PB40UL-M, thickness: 40 μm, refractive index: 1.51). After coating by the coater method (# 14) and drying at 80 ° C. for 120 seconds, the substrate was coated with a transparent coating (1) by irradiating it with ultraviolet rays of 300 mJ / cm 2 in an N 2 atmosphere. The film thickness of the transparent film was 8 μm.
得られた透明被膜付基材(1)について、全光線透過率およびヘイズは、ヘーズメーター（スガ試験機（株）製）により測定した。なお、未塗布のＴＡＣフィルムは全光線透過率が９３．２％、ヘイズが０．２％であった。
また、カーリング性、耐擦傷性および鉛筆硬度を以下の方法、評価基準で評価し、結果を表に示す。
About the obtained base material (1) with a transparent film, the total light transmittance and haze were measured with the haze meter (made by Suga Test Instruments Co., Ltd.). The uncoated TAC film had a total light transmittance of 93.2% and a haze of 0.2%.
Further, curling property, scratch resistance and pencil hardness were evaluated by the following methods and evaluation criteria, and the results are shown in the table.
カーリング性評価
１４ｃｍ×２５ｃｍ×４０μｍ（厚み）のＴＡＣフィルム基材上に厚みが８μｍの透明被膜が形成できるように透明被膜形成用塗料(1)を塗布し、２０時間静置し、その後、フィルムを１０ｃｍ×１０ｃｍサイズにカットし、塗布面を下にしてフィルムを平板上に置き、カーリング（湾曲）して浮上した基材の頂点の平板からの高さを測定し、以下の基準で評価した。
Curing property evaluation A coating for forming a transparent film (1) is applied on a TAC film substrate having a thickness of 14 cm × 25 cm × 40 μm (thickness) so that a transparent film having a thickness of 8 μm can be formed. Was cut into a size of 10 cm × 10 cm, the film was placed on a flat plate with the coating surface down, the height of the apex of the substrate that was curled (curved) and floated from the flat plate was measured, and evaluated according to the following criteria: .
〈評価基準〉
１０ｍｍ未満 ：◎
１０〜２０ｍｍ未満 ：○
２０〜３０ｍｍ未満 ：△
３０ｍｍ以上 ：×
<Evaluation criteria>
Less than 10 mm: ◎
Less than 10-20mm: ○
20-30 mm or less: △
30 mm or more: ×
鉛筆硬度の測定
ＪＩＳ−Ｋ−５６００に準じて鉛筆硬度試験器により測定した。
耐擦傷性の測定
＃００００スチールウールを用い、荷重２ｋｇ／ｃｍ2で１０回摺動し、膜の表面を目視観察し、以下の基準で評価した。
評価基準：
筋条の傷が認められない ：◎
筋条に傷が僅かに認められる：○
筋条に傷が多数認められる ：△
面が全体的に削られている ：×
Measurement of pencil hardness It measured with the pencil hardness tester according to JIS-K-5600.
Measurement of scratch resistance Using # 0000 steel wool, sliding 10 times with a load of 2 kg / cm 2 , visually observing the surface of the film, and evaluating according to the following criteria.
Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×
［実施例２］
透明被膜形成用塗料(2)の調製
実施例１において、官能基数が９のアクリレート樹脂（Ａ）としてウレタンアクリレートオリゴマー樹脂（新中村化学（株）製：ＮＫオリゴ ＵＡ−３３Ｈ、平均分子量＝4000）１５．２０ｇと、官能基数が２のアクリレート樹脂（Ｂ）としてジメチロール-トリシクロデカンジアクリレート（共栄社化学（株）製：ライトアクリレートＤＣＰ−Ａ、平均分子量＝３０２）０．８ｇとを用いた以外は同様にして固形分濃度４０．０重量％の透明被膜形成用塗料(2)を調製した。
[Example 2]
Preparation of paint for forming transparent film (2) In Example 1, urethane acrylate oligomer resin (made by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H, average molecular weight = 4000) as acrylate resin (A) having 9 functional groups Other than using 15.20 g and 0.8 g of dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate DCP-A, average molecular weight = 302) as the acrylate resin (B) having 2 functional groups In the same manner, a transparent film-forming paint (2) having a solid content concentration of 40.0% by weight was prepared.
透明被膜付基材(2)の製造
実施例１において、透明被膜形成用塗料(2)を用いた以外は同様にして透明被膜付基材(2)を得た。透明被膜の膜厚は８μｍであった。得られた透明被膜付基材(2)について、全光線透過率、ヘイズ、カーリング性、耐擦傷性および鉛筆硬度を測定し、結果を表に示す。
Production of transparent film-coated substrate (2) A transparent film-coated substrate (2) was obtained in the same manner as in Production Example 1 except that the transparent film-forming paint (2) was used. The film thickness of the transparent film was 8 μm. With respect to the obtained substrate (2) with a transparent coating, the total light transmittance, haze, curling property, scratch resistance and pencil hardness were measured, and the results are shown in the table.
［実施例３］
透明被膜形成用塗料(3)の調製
実施例１において、官能基数が９のアクリレート樹脂（Ａ）としてウレタンアクリレートオリゴマー樹脂（新中村化学（株）製：ＮＫオリゴ ＵＡ−３３Ｈ、平均分子量＝4000）１１．２ｇと、官能基数が２のアクリレート樹脂（Ｂ）としてジメチロール-トリシクロデカンジアクリレート（共栄社化学（株）製：ライトアクリレートＤＣＰ−Ａ、平均分子量＝３０２）４．８ｇとを用いた以外は同様にして固形分濃度４０．０重量％の透明被膜形成用塗料(3)を調製した。
[Example 3]
Preparation of Transparent Film Forming Paint (3) In Example 1, urethane acrylate oligomer resin (made by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H, average molecular weight = 4000) as acrylate resin (A) having 9 functional groups Other than using 11.2 g and 4.8 g of dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DCP-A, average molecular weight = 302) as the acrylate resin (B) having 2 functional groups. In the same manner, a transparent film-forming paint (3) having a solid content concentration of 40.0% by weight was prepared.
透明被膜付基材(3)の製造
実施例１において、透明被膜形成用塗料(3)を用いた以外は同様にして透明被膜付基材(3)を得た。透明被膜の膜厚は８μｍであった。
得られた透明被膜付基材(3)について、全光線透過率、ヘイズ、カーリング性、耐擦傷性および鉛筆硬度を測定し、結果を表に示す。
Production of transparent film-coated substrate (3) In Example 1, a transparent film-coated substrate (3) was obtained in the same manner except that the transparent film-forming paint (3) was used. The film thickness of the transparent film was 8 μm.
With respect to the obtained substrate (3) with a transparent coating, the total light transmittance, haze, curling property, scratch resistance and pencil hardness were measured, and the results are shown in the table.
［実施例４］
透明被膜形成用塗料(4)の調製
実施例１において、官能基数が８のアクリレート樹脂（Ａ）としてウレタンアクリレートオリゴマー樹脂（新中村化学（株）製：ＮＫオリゴ ＵＡ−８ＬＲ、平均分子量＝3000）１４．４ｇを用いた以外は同様にして固形分濃度４０．０重量％の透明被膜形成用塗料(4)を調製した。
[Example 4]
Preparation of paint for forming transparent film (4) In Example 1, urethane acrylate oligomer resin (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-8LR, average molecular weight = 3000) as acrylate resin (A) having 8 functional groups A transparent film-forming paint (4) having a solid content concentration of 40.0% by weight was prepared in the same manner except that 14.4 g was used.
透明被膜付基材(4)の製造
実施例１において、透明被膜形成用塗料(4)を用いた以外は同様にして透明被膜付基材(4)を得た。透明被膜の膜厚は８μｍであった。
得られた透明被膜付基材(4)について、全光線透過率、ヘイズ、カーリング性、耐擦傷性および鉛筆硬度を測定し、結果を表に示す。
Production of transparent film-coated substrate (4) A transparent film-coated substrate (4) was obtained in the same manner as in Production Example 1 except that the transparent film-forming paint (4) was used. The film thickness of the transparent film was 8 μm.
For the obtained substrate with transparent film (4), the total light transmittance, haze, curling property, scratch resistance and pencil hardness were measured, and the results are shown in the table.
［実施例５］
透明被膜形成用塗料(5)の調製
実施例１において、官能基数が１２のアクリレート樹脂（Ａ）としてウレタンアクリレートオリゴマー樹脂（新中村化学（株）製：ＮＫオリゴ ＵＡ−１２ＬＲ、平均分子量＝4400）１４．４ｇを用いた以外は同様にして固形分濃度４０．０重量％の透明被膜形成用塗料(5)を調製した。
[Example 5]
Preparation of Transparent Film Forming Paint (5) In Example 1, urethane acrylate oligomer resin (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-12LR, average molecular weight = 4400) as acrylate resin (A) having 12 functional groups A transparent film-forming paint (5) having a solid content concentration of 40.0% by weight was prepared in the same manner except that 14.4 g was used.
透明被膜付基材(5)の製造
実施例１において、透明被膜形成用塗料(5)を用いた以外は同様にして透明被膜付基材(5)を得た。透明被膜の膜厚は８μｍであった。
得られた透明被膜付基材(5)について、全光線透過率、ヘイズ、カーリング性、耐擦傷性および鉛筆硬度を測定し、結果を表に示す。
Production of transparent film-coated substrate (5) A transparent film-coated substrate (5) was obtained in the same manner as in Production Example 1 except that the transparent film-forming paint (5) was used. The film thickness of the transparent film was 8 μm.
With respect to the obtained substrate (5) with a transparent coating, the total light transmittance, haze, curling property, scratch resistance and pencil hardness were measured, and the results are shown in the table.
［実施例６］
透明被膜形成用塗料(6)の調製
実施例１において、官能基数が３のアクリレート樹脂（Ｂ）としてペンタエリスリトールトリアクリレート（共栄社化学（株）製：ライトアクリレートＰＥ−３Ａ、平均分子量＝２９８）１．６０ｇを用いた以外は同様にして固形分濃度４０．０重量％の透明被膜形成用塗料(6)を調製した。
[Example 6]
Preparation of paint for forming transparent film (6) In Example 1, pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate PE-3A, average molecular weight = 298) as acrylate resin (B) having 3 functional groups A transparent film-forming coating material (6) having a solid content of 40.0% by weight was prepared in the same manner except that .60 g was used.
透明被膜付基材(6)の製造
実施例１において、透明被膜形成用塗料(6)を用いた以外は同様にして透明被膜付基材(6)を得た。透明被膜の膜厚は８μｍであった。
得られた透明被膜付基材(6)について、全光線透過率、ヘイズ、カーリング性、耐擦傷性および鉛筆硬度を測定し、結果を表に示す。
Production of transparent film-coated substrate (6) A transparent film-coated substrate (6) was obtained in the same manner as in Production Example 1 except that the transparent film-forming paint (6) was used. The film thickness of the transparent film was 8 μm.
With respect to the obtained substrate with transparent film (6), the total light transmittance, haze, curling property, scratch resistance and pencil hardness were measured, and the results are shown in the table.
［実施例７］
透明被膜形成用塗料(7)の調製
シリカゾル分散液（日揮触媒化成（株）製；ＳＩ−４５Ｐ；平均粒子径４５ｎｍ、ＳｉＯ2濃度４０．５重量％）１０００ｇにイオン交換水６０００ｇを加え、ついで陽イオン交換樹脂（三菱化学（株）製：ＳＫ−１ＢＨ）８００ｇを添加し、１時間攪拌して脱アルカリ処理した。
[Example 7]
Preparation of paint for forming transparent film (7) Silica sol dispersion (manufactured by JGC Catalysts &Chemicals;SI-45P; average particle size 45 nm, SiO 2 concentration 40.5 wt%) was added to 6000 g of ion-exchanged water, 800 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) was added and subjected to dealkalization by stirring for 1 hour.
ついで陽イオン交換樹脂を分離した後、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）４００ｇを添加し、１時間攪拌して脱アニオン処理した。ついで、再び陽イオン交換樹脂（三菱化学（株）製：ＳＫ−１ＢＨ）４００ｇを添加し、１時間攪拌して脱アルカリ処理してＳｉＯ2濃度５重量％のシリカ粒子（ＲＡ）分散液を調製した。 Next, after separating the cation exchange resin, 400 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added, and the mixture was stirred for 1 hour for deanion treatment. Next, 400 g of cation exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SK-1BH) was added again, and the mixture was stirred for 1 hour and dealkalized to prepare a silica particle (RA) dispersion having a SiO 2 concentration of 5% by weight. did.
この分散液を、限外濾過膜を用いてメタノールにて溶媒置換して固形分濃度４０重量％のメタノール分散液を得た。
ついで、このメタノール分散液１００ｇにγ-メタアクリロオキシプロピルトリメトキシシラン３．００ｇ（信越シリコ−ン（株）製：ＫＢＭ−５０３、ＳｉО2成分８１．２％）を混合し５０℃で２０時間攪拌して表面処理した４５ｎｍのシリカゾル分散液を得た（固形分濃度４０．５重量％）。
その後、ロータリーエバポレーターでプロピレングリコールモノプロピルエーテル（ＰＧＭＥ）に溶剤置換した（固形分４０．５％）。
This dispersion was subjected to solvent substitution with methanol using an ultrafiltration membrane to obtain a methanol dispersion having a solid concentration of 40% by weight.
Next, 3.00 g of γ-methacrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd .: KBM-503, SiO 2 component 81.2%) was mixed with 100 g of this methanol dispersion, and 20% at 50 ° C. A silica sol dispersion having a surface treatment of 45 nm was obtained by stirring for a period of time (solid content concentration: 40.5% by weight).
Thereafter, the solvent was replaced with propylene glycol monopropyl ether (PGME) by a rotary evaporator (solid content: 40.5%).
実施例１において、上記方法で調製した固形分濃度４０．５重量％のシリカゾル(1)のプロピレングリコールモノプロピルエーテル分散液５９．２６ｇを用いた以外は同様にして固形分濃度４０．０重量％の透明被膜形成用塗料(7)を調製した。 In Example 1, the solid content concentration was 40.0% by weight except that 59.26 g of the silica sol (1) propylene glycol monopropyl ether dispersion prepared by the above method was used. A transparent film-forming paint (7) was prepared.
透明被膜付基材(7)の製造
実施例１において、透明被膜形成用塗料(7)を用いた以外は同様にして透明被膜付基材(7)を得た。透明被膜の膜厚は８μｍであった。得られた透明被膜付基材(7)について、全光線透過率、ヘイズ、カーリング性、耐擦傷性および鉛筆硬度を測定し、結果を表に示す。
Production of transparent film-coated substrate (7) A transparent film-coated substrate (7) was obtained in the same manner as in Production Example 1 except that the transparent film-forming paint (7) was used. The film thickness of the transparent film was 8 μm. With respect to the obtained substrate (7) with a transparent coating, the total light transmittance, haze, curling property, scratch resistance and pencil hardness were measured, and the results are shown in the table.
［実施例８］
透明被膜形成用塗料(8)の調製
シリカオルガノゾル分散液（日揮触媒化成（株）製：ＯＳＣＡＬ１８４２；平均粒子径１２ｎｍ、ＳｉＯ2濃度４０．５重量％、分散媒：メチルイソブチルケトン、粒子屈折率１．４６）６９．１４ｇと、官能基数が９のアクリレート樹脂（Ａ）としてウレタンアクリレートオリゴマー樹脂（新中村化学（株）製：ＮＫオリゴ ＵＡ−３３Ｈ、平均分子量＝4000）１０．８ｇと、官能基数が２のアクリレート樹脂（Ｂ）としてジメチロール-トリシクロデカンジアクリレート（共栄社化学（株）製：ライトアクリレートＤＣＰ−Ａ、平均分子量＝３０２）１．２０ｇと、アクリルシリコーン系レベリング剤（楠本化成（株）製；ディスパロンＮＳＨ−８４３０ＨＦ）０．２０ｇと光重合開始剤（チバジャパン（株））製：イルガキュア１８４、ＰＧＭＥで固形分濃度３０％に溶解）２．４ｇとＰＧＭＥ６．２６ｇとアセトン１０ｇを充分に混合して固形分濃度４０．０重量％の透明被膜形成用塗料(8)を調製した。
[Example 8]
Preparation of paint for forming transparent film (8) Silica organosol dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: OSCAL1842; average particle size 12 nm, SiO 2 concentration 40.5 wt%, dispersion medium: methyl isobutyl ketone, particle refractive index 1.46) 69.14 g, urethane acrylate oligomer resin (made by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H, average molecular weight = 4000) as acrylate resin (A) having 9 functional groups, and 10.8 g functional 1.20 g of dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate DCP-A, average molecular weight = 302) as an acrylate resin (B) having 2 groups, and an acrylic silicone leveling agent (Enomoto Chemical ( Co., Ltd .; Disparon NSH-8430HF) 0.20 g and photopolymerization initiator (Ciba Japan Co., Ltd.) : Irgacure 184, dissolved to a solid content concentration of 30% with PGME) 2.4 g, 6.26 g of PGME, and 10 g of acetone were sufficiently mixed to prepare a coating material (8) for forming a transparent film having a solid content concentration of 40.0 wt%. .
透明被膜付基材(8)の製造
実施例１において、透明被膜形成用塗料(8)を用いた以外は同様にして透明被膜付基材(8)を得た。透明被膜の膜厚は８μｍであった。
得られた透明被膜付基材(8)について、全光線透過率、ヘイズ、カーリング性、耐擦傷性および鉛筆硬度を測定し、結果を表に示す。
Production of transparent film-coated substrate (8) A transparent film-coated substrate (8) was obtained in the same manner as in Production Example 1 except that the transparent film-forming paint (8) was used. The film thickness of the transparent film was 8 μm.
For the obtained substrate with transparent film (8), the total light transmittance, haze, curling property, scratch resistance and pencil hardness were measured, and the results are shown in the table.
［実施例９］
透明被膜形成用塗料(9)の調製
シリカオルガノゾル分散液（日揮触媒化成（株）製：ＯＳＣＡＬ１８４２；平均粒子径１２ｎｍ、ＳｉＯ2濃度４０．５重量％、分散媒：メチルイソブチルケトン、粒子屈折率１．４６）２９．６３ｇと、官能基数が９のアクリレート樹脂（Ａ）としてウレタンアクリレートオリゴマー樹脂（新中村化学（株）製：ＮＫオリゴ ＵＡ−３３Ｈ、平均分子量＝4000）２５．２０ｇと、官能基数が２のアクリレート樹脂（Ｂ）としてジメチロール-トリシクロデカンジアクリレート（共栄社化学（株）製：ライトアクリレートＤＣＰ−Ａ、平均分子量＝３０２）２．８ｇと、アクリルシリコーン系レベリング剤（楠本化成（株）製；ディスパロンＮＳＨ−８４３０ＨＦ）０．２ｇと光重合開始剤（チバジャパン（株））製：イルガキュア１８４、ＰＧＭＥで固形分濃度３０％に溶解）５．６ｇとＰＧＭＥ２６．５７ｇとアセトン１０ｇを充分に混合して固形分濃度４０．０重量％の透明被膜形成用塗料(9)を調製した。
[Example 9]
Preparation of paint for forming transparent film (9) Silica organosol dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: OSCAL1842; average particle size 12 nm, SiO 2 concentration 40.5% by weight, dispersion medium: methyl isobutyl ketone, particle refractive index 1.46) 29.63 g, urethane acrylate oligomer resin (made by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H, average molecular weight = 4000) as acrylate resin (A) having 9 functional groups, and functional As the acrylate resin (B) having 2 groups, 2.8 g of dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate DCP-A, average molecular weight = 302) and an acrylic silicone leveling agent (Tsubakimoto Chemical ( Co., Ltd .; Disparon NSH-8430HF) 0.2g and photopolymerization initiator (Ciba Japan Co., Ltd.) Irgacure 184, solid concentration 30% lysis) 5.6 g and PGME26.57g and acetone 10g were mixed well having a solid concentration of 40.0% by weight of the transparent film-forming coating material (9) was prepared in PGME.
透明被膜付基材(9)の製造
実施例１において、透明被膜形成用塗料(9)を用いた以外は同様にして透明被膜付基材(9)を得た。透明被膜の膜厚は８μｍであった。
得られた透明被膜付基材(9)について、全光線透過率、ヘイズ、カーリング性、耐擦傷性および鉛筆硬度を測定し、結果を表に示す。
Production of transparent film-coated substrate (9) A transparent film-coated substrate (9) was obtained in the same manner as in Production Example 1 except that the transparent film-forming paint (9) was used. The film thickness of the transparent film was 8 μm.
For the obtained substrate (9) with a transparent coating, the total light transmittance, haze, curling property, scratch resistance and pencil hardness were measured, and the results are shown in the table.
［実施例１０］
透明被膜付基材(10)の製造
実施例１において、ＴＡＣフィルム（富士フィルム（株）製：ＦＴ−ＰＢ４０ＵＬ−Ｍ、厚さ：６０μｍ、屈折率：１．５１）を用いた以外は同様にして透明被膜付基材(10)を得た。透明被膜の膜厚は８μｍであった。
得られた透明被膜付基材(12)について、全光線透過率、ヘイズ、カーリング性、耐擦傷性および鉛筆硬度を測定し、結果を表に示す。
[Example 10]
Production of substrate with transparent coating (10) In Example 1, except that a TAC film (Fuji Film Co., Ltd .: FT-PB40UL-M, thickness: 60 μm, refractive index: 1.51) was used. As a result, a substrate (10) with a transparent coating was obtained. The film thickness of the transparent film was 8 μm.
With respect to the obtained substrate (12) with a transparent coating, the total light transmittance, haze, curling property, scratch resistance and pencil hardness were measured, and the results are shown in the table.
［比較例１］
透明被膜形成用塗料(R1)の調製
シリカオルガノゾル分散液（日揮触媒化成（株）製：ＯＳＣＡＬ１８４２；平均粒子径１２ｎｍ、ＳｉＯ2濃度４０．５重量％、分散媒：メチルイソブチルケトン、粒子屈折率１．４６）５９．２６ｇと、官能基数が９のアクリレート樹脂（Ａ）としてウレタンアクリレートオリゴマー樹脂（新中村化学（株）製：ＮＫオリゴ ＵＡ−３３Ｈ、平均分子量＝4000）１６．０ｇと、アクリルシリコーン系レベリング剤（楠本化成（株）製；ディスパロンＮＳＨ−８４３０ＨＦ）０．２ｇと光重合開始剤（チバジャパン（株））製：イルガキュア１８４、ＰＧＭＥで固形分濃度３０％に溶解）３．２ｇとＰＧＭＥ１１．３４ｇとアセトン１０ｇを充分に混合して固形分濃度４０．０重量％の透明被膜形成用塗料(R1)を調製した。
[Comparative Example 1]
Preparation of paint (R1) for forming transparent film Silica organosol dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: OSCAL1842; average particle diameter 12 nm, SiO 2 concentration 40.5 wt%, dispersion medium: methyl isobutyl ketone, particle refractive index 1.46) 59.26 g, urethane acrylate oligomer resin (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H, average molecular weight = 4000) as an acrylate resin (A) having 9 functional groups, and acrylic Silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 0.2 g and photopolymerization initiator (Ciba Japan Co., Ltd.): Irgacure 184, dissolved in 30% solid content with PGME) 3.2 g PGME 11.34 g and acetone 10 g are mixed thoroughly to prepare a transparent film forming paint (R1) with a solid content concentration of 40.0% by weight. It was.
透明被膜付基材(R1)の製造
実施例１において、透明被膜形成用塗料(R1)を用いた以外は同様にして透明被膜付基材(R1)を得た。透明被膜の膜厚は８μｍであった。得られた透明被膜付基材(R1)について、全光線透過率、ヘイズ、カーリング性、耐擦傷性および鉛筆硬度を測定し、結果を表に示す。
Production of transparent film-coated substrate (R1) In Example 1, a transparent film-coated substrate (R1) was obtained in the same manner except that the transparent film-forming paint (R1) was used. The film thickness of the transparent film was 8 μm. With respect to the obtained substrate with a transparent film (R1), the total light transmittance, haze, curling property, scratch resistance and pencil hardness were measured, and the results are shown in the table.
［比較例２］
透明被膜形成用塗料(R2)の調製
シリカオルガノゾル分散液（日揮触媒化成（株）製：ＯＳＣＡＬ１８４２；平均粒子径１２ｎｍ、ＳｉＯ2濃度４０．５重量％、分散媒：メチルイソブチルケトン、粒子屈折率１．４６）５９．２６ｇと、官能基数が２のアクリレート樹脂（Ｂ）としてジメチロール-トリシクロデカンジアクリレート（共栄社化学（株）製：ライトアクリレートＤＣＰ−Ａ、平均分子量＝３０２）１６．０ｇと、アクリルシリコーン系レベリング剤（楠本化成（株）製；ディスパロンＮＳＨ−８４３０ＨＦ）０．２０ｇと光重合開始剤（チバジャパン（株））製：イルガキュア１８４、ＰＧＭＥで固形分濃度３０％に溶解）３．２０ｇとＰＧＭＥ１１．３４ｇとアセトン１０．０ｇを充分に混合して固形分濃度４０．０重量％の透明被膜形成用塗料(R2)を調製した。
[Comparative Example 2]
Preparation of paint for forming transparent film (R2) Silica organosol dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: OSCAL1842; average particle diameter 12 nm, SiO 2 concentration 40.5% by weight, dispersion medium: methyl isobutyl ketone, particle refractive index 1.46) 59.26 g, dimethylol-tricyclodecanediacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DCP-A, average molecular weight = 302) 16.0 g as an acrylate resin (B) having 2 functional groups , Acrylic silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 0.20 g and photopolymerization initiator (Ciba Japan Co., Ltd.): Irgacure 184, dissolved in solid content concentration of 30% with PGME 3 20 g, 11.34 g of PGME and 10.0 g of acetone were mixed thoroughly to obtain a transparent content of 40.0% by weight. A bright film-forming paint (R2) was prepared.
透明被膜付基材(R2)の製造
実施例１において、透明被膜形成用塗料(R2)を用いた以外は同様にして透明被膜付基材(R2)を得た。透明被膜の膜厚は８μｍであった。得られた透明被膜付基材(R2)について、全光線透過率、ヘイズ、カーリング性、耐擦傷性および鉛筆硬度を測定し、結果を表に示す。
Production of transparent film-coated substrate (R2) In Example 1, a transparent film-coated substrate (R2) was obtained in the same manner except that the transparent film-forming paint (R2) was used. The film thickness of the transparent film was 8 μm. For the obtained substrate with transparent coating (R2), the total light transmittance, haze, curling property, scratch resistance and pencil hardness were measured, and the results are shown in the table.
［比較例３］
透明被膜形成用塗料(R3)の調製
シリカオルガノゾル分散液（日揮触媒化成（株）製：ＯＳＣＡＬ１８４２；平均粒子径１２ｎｍ、ＳｉＯ2濃度４０．５重量％、分散媒：メチルイソブチルケトン、粒子屈折率１．４６）５９．２６ｇと、官能基数が６のアクリレート樹脂（共栄社化学社（株）製：ＤＰＥ−６Ａ、平均分子量＝５７８）１６．０ｇと、アクリルシリコーン系レベリング剤（楠本化成（株）製；ディスパロンＮＳＨ−８４３０ＨＦ）０．２０ｇと光重合開始剤（チバジャパン（株））製：イルガキュア１８４、ＰＧＭＥで固形分濃度３０％に溶解）３．２０ｇとＰＧＭＥ１１．３４ｇとアセトン１０ｇを充分に混合して固形分濃度４０．０重量％の透明被膜形成用塗料(R3)を調製した。
[Comparative Example 3]
Preparation of paint (R3) for forming transparent film Silica organosol dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: OSCAL1842; average particle diameter 12 nm, SiO 2 concentration 40.5 wt%, dispersion medium: methyl isobutyl ketone, particle refractive index 1.46) 59.26 g, acrylate resin having 6 functional groups (manufactured by Kyoeisha Chemical Co., Ltd .: DPE-6A, average molecular weight = 578) 16.0 g, acrylic silicone leveling agent (Enomoto Kasei Co., Ltd.) Manufactured; Disparon NSH-8430HF) 0.20 g and photopolymerization initiator (Ciba Japan Co., Ltd.): Irgacure 184, dissolved in 30% solid content with PGME) 3.20 g, PGME 11.34 g and acetone 10 g By mixing, a transparent film forming paint (R3) having a solid content concentration of 40.0% by weight was prepared.
透明被膜付基材(R3)の製造
実施例１において、透明被膜形成用塗料(R3)を用いた以外は同様にして透明被膜付基材(R3)を得た。透明被膜の膜厚は８μｍであった。得られた透明被膜付基材(R3)について、全光線透過率、ヘイズ、カーリング性、耐擦傷性および鉛筆硬度を測定し、結果を表に示す。
Production of substrate with transparent coating (R3) A substrate with transparent coating (R3) was obtained in the same manner as in Example 1 except that the coating for forming a transparent coating (R3) was used. The film thickness of the transparent film was 8 μm. With respect to the obtained substrate with a transparent film (R3), the total light transmittance, haze, curling property, scratch resistance and pencil hardness were measured, and the results are shown in the table.
［比較例４］
透明被膜形成用塗料(R4)の調製
シリカオルガノゾル分散液（日揮触媒化成（株）製：ＯＳＣＡＬ１８４２；平均粒子径１２ｎｍ、ＳｉＯ2濃度４０．５重量％、分散媒：メチルイソブチルケトン、粒子屈折率１．４６）５９．２６ｇと、ポリエステルアクリレート樹脂（大阪有機化学社（株）製：Ｖ＃１０００、平均分子量＝１０００〜２０００）１６．０ｇと、アクリルシリコーン系レベリング剤（楠本化成（株）製；ディスパロンＮＳＨ−８４３０ＨＦ）０．２０ｇと光重合開始剤（チバジャパン（株））製：イルガキュア１８４、ＰＧＭＥで固形分濃度３０％に溶解）３．２０ｇとＰＧＭＥ１１．３４ｇとアセトン１０．０ｇを充分に混合して固形分濃度４０．０重量％の透明被膜形成用塗料(R4)を調製した。
[Comparative Example 4]
Preparation of paint for forming transparent film (R4) Silica organosol dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: OSCAL1842; average particle size 12 nm, SiO 2 concentration 40.5% by weight, dispersion medium: methyl isobutyl ketone, particle refractive index 1.46) 59.26 g, polyester acrylate resin (Osaka Organic Chemical Co., Ltd .: V # 1000, average molecular weight = 1000-2000) 16.0 g, and acrylic silicone leveling agent (Enomoto Kasei Co., Ltd.) ; Disparon NSH-8430HF) 0.20 g, photopolymerization initiator (Ciba Japan Co., Ltd.): Irgacure 184, PGME dissolved in 30% solid content) 3.20 g, PGME 11.34 g, and acetone 10.0 g are sufficient. And a transparent film-forming paint (R4) having a solid content concentration of 40.0% by weight was prepared.
透明被膜付基材(R4)の製造
実施例１において、透明被膜形成用塗料(R4)を用いた以外は同様にして透明被膜付基材(R4)を得た。透明被膜の膜厚は８μｍであった。得られた透明被膜付基材(R4)について、全光線透過率、ヘイズ、カーリング性、耐擦傷性および鉛筆硬度を測定し、結果を表に示す。
Production of transparent film-coated substrate (R4) In Example 1, a transparent film-coated substrate (R4) was obtained in the same manner except that the transparent film-forming paint (R4) was used. The film thickness of the transparent film was 8 μm. For the obtained substrate with transparent coating (R4), the total light transmittance, haze, curling property, scratch resistance and pencil hardness were measured, and the results are shown in the table.
［比較例５］
透明被膜形成用塗料(R5)の調製
官能基数が９官能のアクリレート樹脂（Ａ）としてウレタンアクリレートオリゴマー樹脂（新中村化学（株）製：ＮＫオリゴ ＵＡ−３３Ｈ、平均分子量＝4000）３６．０ｇと、官能基数が２のアクリレート樹脂（Ｂ）としてジメチロール-トリシクロデカンジアクリレート（共栄社化学（株）製：ライトアクリレートＤＣＰ−Ａ、平均分子量＝３０２）４．０ｇと、アクリルシリコーン系レベリング剤（楠本化成（株）製；ディスパロンＮＳＨ−８４３０ＨＦ）０．２０ｇと光重合開始剤（チバジャパン（株））製：イルガキュア１８４、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）で固形分濃度３０％に溶解）８．０ｇとＰＧＭＥ４１．８ｇとアセトン１０．０ｇを充分に混合して固形分濃度４０．０重量％の透明被膜形成用塗料(R5)を調製した。
[Comparative Example 5]
Preparation of paint for forming transparent film (R5) As acrylate resin (A) having 9 functional groups, urethane acrylate oligomer resin (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H, average molecular weight = 4000) 36.0 g As an acrylate resin (B) having 2 functional groups, 4.0 g of dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DCP-A, average molecular weight = 302) and an acrylic silicone leveling agent (Enomoto) Kasei Co., Ltd .; Disparon NSH-8430HF 0.20 g and photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184, dissolved in 30% solid content with propylene glycol monomethyl ether (PGME)) 8.0 g PGME 41.8 g and acetone 10.0 g are mixed thoroughly to obtain a solid content concentration of 40.0. A paint (R5) for forming a transparent film with a weight% was prepared.
透明被膜付基材(R5)の製造
実施例１において、透明被膜形成用塗料(R5)を用いた以外は同様にして透明被膜付基材(R5)を得た。透明被膜の膜厚は８μｍであった。得られた透明被膜付基材(R5)について、全光線透過率、ヘイズ、カーリング性、耐擦傷性および鉛筆硬度を測定し、結果を表に示す。
Production of substrate with transparent coating (R5) A substrate with transparent coating (R5) was obtained in the same manner as in Production Example 1 except that the coating for forming a transparent coating (R5) was used. The film thickness of the transparent film was 8 μm. For the obtained substrate with transparent coating (R5), the total light transmittance, haze, curling property, scratch resistance and pencil hardness were measured, and the results are shown in the table.
Claims (7)
官能基数が２で、理論分子量が２００〜５００の範囲にあるトリシクロデカン系アクリレート樹脂および／または官能基数が３で、理論分子量が２００〜５００の範囲にあるペンタエリスリトール系トリアクリレート樹脂（Ｂ）と、
平均粒子径が５〜５００ｎｍの範囲にある金属酸化物微粒子（Ｃ）と、
有機溶媒（Ｄ）を含み、
前記樹脂（Ａ）と前記樹脂（Ｂ）が有する官能基がアクリロイル基であって、
前記樹脂（Ａ）の濃度（Ｃ A ）が固形分として０．９５〜４５重量％の範囲にあり、
前記樹脂（Ｂ）の濃度（Ｃ B ）が固形分として０．０５〜１２重量％の範囲にあり、
前記金属酸化物微粒子（Ｃ）の濃度（Ｃ C ）が固形分として０．２５〜４８重量％の範囲にあり、
（ＣB）／（ＣA）が０．０５〜０．５の範囲、（Ｃ C ）／｛（Ｃ A ）＋（Ｃ B ）＋（Ｃ C ）｝が０．２〜０．７の範囲にあり、合計の濃度｛（Ｃ A ）＋（Ｃ B ）＋（Ｃ C ）｝が固形分として５〜６０重量％の範囲
にあることを特徴とする透明被膜形成用塗料。 Urethane acrylate resin (A) having a functional group number of 4 or more and a weight average molecular weight in the range of 500 to 5000 ;
Tricyclodecane acrylate resin having 2 functional groups and a theoretical molecular weight in the range of 200 to 500 and / or pentaerythritol triacrylate resin having a functional group number of 3 and a theoretical molecular weight in the range of 200 to 500 (B) When,
Metal oxide fine particles (C) having an average particle diameter in the range of 5 to 500 nm;
Including an organic solvent (D),
The functional group of the resin (A) and the resin (B) is an acryloyl group,
In the range concentration (C A) is from 0.95 to 45% by weight solid content of the resin (A), the
In the range concentration (C B) is from 0.05 to 12% by weight solids of the resin (B),
The concentration (C C ) of the metal oxide fine particles (C) is in the range of 0.25 to 48% by weight as a solid content ,
(C B ) / (C A ) is in the range of 0.05 to 0.5, and (C C ) / {(C A ) + (C B ) + (C C )} is in the range of 0.2 to 0.7. A coating for forming a transparent film, characterized in that the total concentration {(C A ) + (C B ) + (C C )} is in the range of 5 to 60% by weight as a solid content. .
基材の厚みが２０〜７０μｍの範囲にあり、該透明被膜が請求項１に記載の透明被膜形成用塗料を用いて形成された透明被膜であることを特徴とする透明被膜付基材。 It consists of a base material and a transparent film formed on the base material,
A substrate with a transparent coating, wherein the thickness of the substrate is in the range of 20 to 70 µm, and the transparent coating is a transparent coating formed using the transparent coating forming paint according to claim 1 .
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