JP2009035595A - Substrate with hard coat film and coating liquid for forming hard coat film - Google Patents
Substrate with hard coat film and coating liquid for forming hard coat film Download PDFInfo
- Publication number
- JP2009035595A JP2009035595A JP2007199151A JP2007199151A JP2009035595A JP 2009035595 A JP2009035595 A JP 2009035595A JP 2007199151 A JP2007199151 A JP 2007199151A JP 2007199151 A JP2007199151 A JP 2007199151A JP 2009035595 A JP2009035595 A JP 2009035595A
- Authority
- JP
- Japan
- Prior art keywords
- hard coat
- coat film
- organic resin
- resin matrix
- metal oxide
- 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.)
- Granted
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 42
- 238000000576 coating method Methods 0.000 title claims description 64
- 239000011248 coating agent Substances 0.000 title claims description 63
- 239000007788 liquid Substances 0.000 title claims description 42
- 239000002245 particle Substances 0.000 claims abstract description 164
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 124
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 124
- 229920005989 resin Polymers 0.000 claims abstract description 109
- 239000011347 resin Substances 0.000 claims abstract description 109
- 239000011159 matrix material Substances 0.000 claims abstract description 98
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims description 70
- 239000002612 dispersion medium Substances 0.000 claims description 49
- 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 claims description 25
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 239000003513 alkali Substances 0.000 abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 238000005299 abrasion Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 204
- 239000002585 base Substances 0.000 description 59
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 42
- 239000006185 dispersion Substances 0.000 description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 36
- 238000002360 preparation method Methods 0.000 description 33
- 239000002904 solvent Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 24
- 238000002834 transmittance Methods 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- 229910004298 SiO 2 Inorganic materials 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 14
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 11
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 11
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 10
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000010419 fine particle Substances 0.000 description 9
- 150000003961 organosilicon compounds Chemical class 0.000 description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 230000001678 irradiating effect Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 8
- 229910052753 mercury Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 5
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- -1 ITO Chemical compound 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-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
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 2
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 2
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 239000002253 acid Substances 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-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
- 150000002148 esters Chemical class 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 2
- MLXDKRSDUJLNAB-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F MLXDKRSDUJLNAB-UHFFFAOYSA-N 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- YYJIYUNJTKCRHL-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC(=O)C=C YYJIYUNJTKCRHL-UHFFFAOYSA-N 0.000 description 1
- IIMPKTUJEFLZNY-UHFFFAOYSA-N (3-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(O)OC(=O)C=C IIMPKTUJEFLZNY-UHFFFAOYSA-N 0.000 description 1
- UUGXDEDGRPYWHG-UHFFFAOYSA-N (dimethylamino)methyl 2-methylprop-2-enoate Chemical compound CN(C)COC(=O)C(C)=C UUGXDEDGRPYWHG-UHFFFAOYSA-N 0.000 description 1
- JVJVAVWMGAQRFN-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JVJVAVWMGAQRFN-UHFFFAOYSA-N 0.000 description 1
- YUTHQCGFZNYPIG-UHFFFAOYSA-N 1-[2-(2-methylprop-2-enoyloxy)ethyl]cyclohexane-1,2-dicarboxylic acid Chemical compound CC(=C)C(=O)OCCC1(C(O)=O)CCCCC1C(O)=O YUTHQCGFZNYPIG-UHFFFAOYSA-N 0.000 description 1
- IFWOFRICKCJBGV-UHFFFAOYSA-N 1-butoxy-2-(2-hydroxyethoxy)ethanol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCCCOC(O)COCCO IFWOFRICKCJBGV-UHFFFAOYSA-N 0.000 description 1
- JLBXCKSMESLGTJ-UHFFFAOYSA-N 1-ethoxypropan-1-ol Chemical compound CCOC(O)CC JLBXCKSMESLGTJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- LAWVXAWNJLTVJE-UHFFFAOYSA-N 2-(3-oxopent-4-enyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCC(=O)C=C LAWVXAWNJLTVJE-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-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
- LBNDGEZENJUBCO-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethyl]butanedioic acid Chemical compound CC(=C)C(=O)OCCC(C(O)=O)CC(O)=O LBNDGEZENJUBCO-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- PSLRXNFNXYNXEK-UHFFFAOYSA-N 2-triethoxysilylethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCOC(=O)C=C PSLRXNFNXYNXEK-UHFFFAOYSA-N 0.000 description 1
- BUJVPKZRXOTBGA-UHFFFAOYSA-N 2-trimethoxysilylethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCOC(=O)C=C BUJVPKZRXOTBGA-UHFFFAOYSA-N 0.000 description 1
- HJIMAFKWSKZMBK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HJIMAFKWSKZMBK-UHFFFAOYSA-N 0.000 description 1
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- 150000002334 glycols Chemical class 0.000 description 1
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- 150000002367 halogens Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
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- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
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- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
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- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
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- 239000003973 paint Substances 0.000 description 1
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- 239000005011 phenolic resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
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- 229920000647 polyepoxide Polymers 0.000 description 1
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- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 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
- 239000005060 rubber Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
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- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
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- WDUXKFKVDQRWJN-UHFFFAOYSA-N triethoxysilylmethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C=C WDUXKFKVDQRWJN-UHFFFAOYSA-N 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- QNKXRZAXBKSFQC-UHFFFAOYSA-N trimethoxy-[3-[2-(oxiran-2-ylmethoxy)ethoxy]propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCCOCC1CO1 QNKXRZAXBKSFQC-UHFFFAOYSA-N 0.000 description 1
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 1
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、基材と、基材上に形成されたハードコート膜とからなる基材であって、耐アルカリ性に優れ、且つ、基材との密着性、耐擦傷性、スクラッチ強度、鉛筆硬度、耐水性等に優れハードコート膜付基材および該ハードコート膜の形成に用いる塗布液に関する。 The present invention is a base material comprising a base material and a hard coat film formed on the base material, and has excellent alkali resistance, adhesion to the base material, scratch resistance, scratch strength, pencil hardness The present invention relates to a substrate with a hard coat film that has excellent water resistance and the like, and a coating solution used for forming the hard coat film.
ガラス、プラスチックシート、プラスチックレンズ、樹脂フィルム、表示装置前面板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膜を形成することが知られており、このようなハードコート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。 It is known that a hard coat film is formed on the surface of the base material in order to improve the scratch resistance of the surface of the base material such as glass, plastic sheet, plastic lens, resin film, and display device front plate. An organic resin film or an inorganic film is formed as a coat film on the surface of glass, plastic or the like. 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.
また、ハードコート膜付の樹脂基材を表示装置前面板等に貼り付けて使用される場合があるが、この時、接着剤との接着性を向上させるためにハードコート膜付基材をアルカリ処理してハードコート膜の反対側の基材表面の平滑性を低下させたり表面に粗さを設けることが行われる。また、ハードコート膜上に他の被膜、例えば高屈折率膜、反射防止膜等を設ける場合、同様にアルカリ処理することが行われることがある。 In addition, a resin base material with a hard coat film may be used by being attached to a display device front plate or the like. At this time, in order to improve the adhesiveness with the adhesive, the base material with a hard coat film is alkalinized. Treatment is performed to reduce the smoothness of the substrate surface on the opposite side of the hard coat film or to provide roughness to the surface. Further, when another film such as a high refractive index film or an antireflection film is provided on the hard coat film, an alkali treatment may be performed in the same manner.
しかしながら、従来のシリカ等の無機酸化物粒子を含むハードコート膜では少なくともこの無機酸化物粒子の一部がアルカリに溶解し、ハードコート機能が低下したり、透明性が低下して白化する等の問題があった。
このようなハードコート膜のアルカリによる浸食を防ぐためにハードコート膜上に耐アルカリ性の保護薄膜を形成することが行われているが、保護膜を形成する工程およびこれを剥離する工程を必要とし経済性が問題となることから耐アルカリ性を有するハードコート膜の開発が求められていた。
However, in the conventional hard coat film containing inorganic oxide particles such as silica, at least a part of the inorganic oxide particles is dissolved in alkali, the hard coat function is lowered, the transparency is lowered and whitening occurs. There was a problem.
In order to prevent the hard coat film from being eroded by alkali, an alkali-resistant protective thin film is formed on the hard coat film. However, a process for forming the protective film and a process for removing the protective film are required. Therefore, development of a hard coat film having alkali resistance has been demanded.
また、ハードコート膜に五酸化アンチモン、ジルコニア、ＩＴＯ、ＡＴＯ等の無機酸化物粒子を用いる場合、耐アルカリ性はある程度改良されるものの、粒子の屈折率が高く、このためハードコート膜の屈折率も高くなるため、屈折率の低い基材を用いる場合は干渉縞を生じる場合があった。 In addition, when inorganic oxide particles such as antimony pentoxide, zirconia, ITO, and ATO are used for the hard coat film, although the alkali resistance is improved to some extent, the refractive index of the particles is high, and therefore the refractive index of the hard coat film is also high. Therefore, when using a substrate having a low refractive index, interference fringes may occur.
このため、基材との密着性、耐擦傷性、スクラッチ強度、鉛筆硬度、耐水性等に優れるとともに耐アルカリ性に優れたハードコート膜付基材および該ハードコート膜形成用塗布液の出現が望まれていた。 For this reason, it is hoped that a substrate with a hard coat film having excellent adhesion to the substrate, scratch resistance, scratch strength, pencil hardness, water resistance, etc., and excellent alkali resistance, and the coating solution for forming the hard coat film will be expected. It was rare.
このような状況の下、本発明者は、上記問題点を解消すべく鋭意検討した結果、ハードコート膜形成用塗布液のマトリックス形成性分に疎水性の有機樹脂を用い、金属酸化物粒子に親水性の粒子を用いることによってハードコート膜の表面に露出する粒子がなくなり、このためアルカリ処理の際にアルカリと直接接触することが抑制され、耐アルカリ性が向上することを見いだして本発明を完成するに至った。 Under such circumstances, the present inventor has intensively studied to solve the above problems, and as a result, a hydrophobic organic resin is used for the matrix-forming component of the coating liquid for forming the hard coat film, and the metal oxide particles are used. By using hydrophilic particles, there are no particles exposed on the surface of the hard coat film, and thus the direct contact with the alkali is suppressed during the alkali treatment, and the alkali resistance is improved, thereby completing the present invention. It came to do.
本発明の構成は以下の通りである。
[1]基材と、基材の一方の表面上に形成されたハードコート膜とからなり、
該ハードコート膜が有機樹脂マトリックス成分と、表面処理金属酸化物粒子とを含んでなり、該ハードコート膜が有機樹脂マトリックス成分と、表面処理金属酸化物粒子とを含んでなり、前記有機樹脂マトリックス成分が疎水性有機樹脂マトリックス成分であり、前記表面処理金属酸化物粒子の表面電荷量（ＱP）が１５〜６０μｅｑ／ｇの範囲にあり、
かつハードコート膜表面に、金属酸化物粒子が露出していないことを特徴とするハードコート膜付基材。
[2]さらに親水性有機樹脂マトリックス成分を含み、ハードコート膜内で、親水性有機樹脂マトリックス成分が下層に偏在し、疎水性有機樹脂マトリックス成分が上層に偏在する[1]のハードコート膜付基材。
[3]親水性有機樹脂マトリックス成分と、疎水性有機樹脂マトリックス成分との混合比（重量比、疎水性マトリックス成分／親水性マトリックス成分の重量（WMB）／（WMA））が０．０１〜２の範囲にある[2]のハードコート膜付基材。
[4]前記疎水性有機樹脂マトリックス成分がビニル基、ウレタン基、エポキシ基、（メタ）アクリロイル基、ＣＦ2基等の疎水性官能基を有する多官能(メタ)アクリル酸エステル樹脂から選ばれる1種以上であり、前記親水性有機樹脂マトリックス成分が水酸基（ＯＨ基）、アミノ基、カルボキシル基、スルホ基等の親水性官能基を有する(メタ)アクリル酸エステル樹脂から選ばれる1種以上である[1]〜[3]のハードコート膜付基材。
[5]前記金属酸化物粒子の平均粒子径が５〜５００ｎｍの範囲にあり、透明被膜中の表面処理された金属酸化物粒子の含有量が５〜８０重量％の範囲にある[1]〜[4]のハードコート膜付基材。
[6]前記基材がトリアセチルセルロース（ＴＡＣ）からなるものである[1]〜[5]のハードコート膜付基材。
[7]有機樹脂マトリックス形成成分と表面処理された金属酸化物粒子と分散媒とを含んでなり、有機樹脂マトリックス形成成分が疎水性有機樹脂マトリックス形成成分であり、金属酸化物粒子の表面電荷量（ＱP）が１５〜６０μｅｑ／ｇの範囲にあることを特徴とするハードコート膜形成用塗布液。
[8]さらに親水性有機樹脂マトリックス形成成分を含み、親水性有機樹脂マトリックス形成成分の固形分としての濃度（ＣMA）と疎水性有機樹脂マトリックス形成成分の固形分としての濃度（ＣMB）との比（ＣMB）／（ＣMA）が０．０１〜２の範囲にある[7]のハード
コート膜形成用塗布液。
[9]前記疎水性有機樹脂マトリックス成分がビニル基、ウレタン基、エポキシ基、（メタ）アクリロイル基、ＣＦ2基等の疎水性官能基を有する多官能(メタ)アクリル酸エステル樹脂から選ばれる１種以上であり、前記親水性有機樹脂マトリックス成分が水酸基（ＯＨ基）、アミノ基、カルボキシル基、スルホ基等の親水性官能基を有する(メタ)アクリル酸エステル樹脂から選ばれる１種以上である[7]または[8]のハードコート膜形成用塗布液。
[10]前記分散媒が、沸点の異なる２種以上の混合分散媒である[7]〜[9]のハードコート膜形成用塗布液。
[11]前記混合分散媒の最高沸点の分散媒が疎水性分散媒である[7]〜[10]のハードコート膜形成用塗布液。
The configuration of the present invention is as follows.
[1] A base material and a hard coat film formed on one surface of the base material,
The hard coat film comprises an organic resin matrix component and surface-treated metal oxide particles, and the hard coat film comprises an organic resin matrix component and surface-treated metal oxide particles, The component is a hydrophobic organic resin matrix component, the surface charge amount (Q P ) of the surface-treated metal oxide particles is in the range of 15 to 60 μeq / g,
And the base material with a hard-coat film | membrane characterized by the metal-oxide particle | grains not being exposed on the hard-coat film | membrane surface.
[2] Further comprising a hydrophilic organic resin matrix component, and within the hard coat film, the hydrophilic organic resin matrix component is unevenly distributed in the lower layer and the hydrophobic organic resin matrix component is unevenly distributed in the upper layer. Base material.
[3] The mixing ratio of the hydrophilic organic resin matrix component to the hydrophobic organic resin matrix component (weight ratio, hydrophobic matrix component / weight of hydrophilic matrix component (W MB ) / (W MA )) is 0.01. The base material with a hard coat film of [2] in the range of ~ 2.
[4] The hydrophobic organic resin matrix component is selected from polyfunctional (meth) acrylic ester resins having a hydrophobic functional group such as vinyl group, urethane group, epoxy group, (meth) acryloyl group, CF 2 group, etc. It is at least one kind, and the hydrophilic organic resin matrix component is at least one kind selected from (meth) acrylic acid ester resins having a hydrophilic functional group such as a hydroxyl group (OH group), an amino group, a carboxyl group, and a sulfo group. [1] to [3] A substrate with a hard coat film.
[5] The average particle diameter of the metal oxide particles is in the range of 5 to 500 nm, and the content of the surface-treated metal oxide particles in the transparent film is in the range of 5 to 80% by weight. [4] A substrate with a hard coat film.
[6] The substrate with a hard coat film according to [1] to [5], wherein the substrate is made of triacetylcellulose (TAC).
[7] An organic resin matrix-forming component, surface-treated metal oxide particles, and a dispersion medium, wherein the organic resin matrix-forming component is a hydrophobic organic resin matrix-forming component, and the surface charge amount of the metal oxide particles (Q P ) is in the range of 15 to 60 μeq / g, a hard coat film forming coating solution.
[8] Further comprising a hydrophilic organic resin matrix forming component, the concentration of the hydrophilic organic resin matrix forming component as a solid content (C MA ) and the concentration of the hydrophobic organic resin matrix forming component as a solid content (C MB ) [7] The hard coat film forming coating solution having a ratio (C MB ) / (C MA ) in the range of 0.01 to 2.
[9] The hydrophobic organic resin matrix component is selected from polyfunctional (meth) acrylic acid ester resins having a hydrophobic functional group such as a vinyl group, a urethane group, an epoxy group, a (meth) acryloyl group, or a CF 2 group 1 And the hydrophilic organic resin matrix component is at least one selected from (meth) acrylic acid ester resins having a hydrophilic functional group such as a hydroxyl group (OH group), an amino group, a carboxyl group, and a sulfo group. [7] or [8] A coating solution for forming a hard coat film.
[10] The coating liquid for forming a hard coat film according to [7] to [9], wherein the dispersion medium is a mixed dispersion medium having two or more different boiling points.
[11] The coating liquid for forming a hard coat film according to [7] to [10], wherein the dispersion medium having the highest boiling point of the mixed dispersion medium is a hydrophobic dispersion medium.
本発明によれば、該ハードコート膜に含まれる表面処理された金属酸化物粒子がハードコート膜表面に露出していないので耐アルカリ性に優れ、且つ、基材との密着性、耐擦傷性、スクラッチ強度、鉛筆硬度、耐水性等に優れたハードコート膜付基材の提供が可能となる。 According to the present invention, the surface-treated metal oxide particles contained in the hard coat film are not exposed on the hard coat film surface, so that the alkali resistance is excellent, and the adhesion to the substrate, the scratch resistance, It is possible to provide a substrate with a hard coat film that is excellent in scratch strength, pencil hardness, water resistance, and the like.
以下、本発明について説明する。
［ハードコート膜付基材］
本発明のハードコート膜付基材は、基材と、基材上に形成されたハードコート膜とからな
る。
基材
本発明に用いる基材としては、従来公知のガラス、ポリカーボネート、アクリル樹脂、ＰＥＴ、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を用いることができるが、なかでも屈折率が低く耐アルカリ性を要求されるトリアセチルセルロース（ＴＡＣ）基材、ポリオレフィン系樹脂基材、ポリビニルアルコール系樹脂基材、ポリエーテルスルフォン系樹脂機材等が好適に用いられる。
The present invention will be described below.
[Base material with hard coat film]
The base material with a hard coat film of the present invention comprises a base material and a hard coat film formed on the base material.
Substrate As the substrate used in the present invention, conventionally known glass, polycarbonate, acrylic resin, plastic sheets such as PET and TAC, plastic films, plastic panels, etc. can be used. A triacetyl cellulose (TAC) base material, a polyolefin resin base material, a polyvinyl alcohol resin base material, a polyether sulfone resin material, and the like that are required to be alkaline are preferably used.
これらの基材は表示装置前面板等に貼り付けて使用する際にアルカリ処理をすることによって接着性よく貼り付けることができる。
なかでも、ＴＡＣは透明性高く、機械的強度に優れ、且つ、温度、湿度等の変化に対する寸法安定性がよく、また、屈折率が低く汎用性の高い基材であるので好ましい。
このような基材は、屈折率が１．４５〜１．５５、さらには１．４８〜１．５２の範囲にあることが好ましい。
ハードコート膜
ハードコート膜は、有機樹脂マトリックス成分と表面処理された金属酸化物粒子とを含んでなり、ハードコート膜表面に露出した金属酸化物粒子が存在しないことを特徴としている。
金属酸化物粒子
本発明に用いる金属酸化物粒子は、得られるハードコート膜が透明性を有し、耐擦傷性を向上できれば特に制限はなく従来公知の金属酸化物粒子を用いることができる。例えば、シリカ、アルミナ、ジルコニア、チタニア、マグネシア、酸化アンチモン、ボリア、およびこれら金属酸化物からなるシリカ・アルミナ、シリカ・ジルコニア、シリカ・チタニア、シリカ・酸化アンチモン等の複合酸化物粒子、コアシェル構造を有する粒子が挙げられる。さらに、これら粒子は鎖状に連結した鎖状粒子であってもよい。また、シリカを主成分とし、内部に空洞を有する中空粒子は屈折率が低く好適に用いることができる。このような中空粒子としては本願出願人の出願による特開２００１−１６７６３７号公報、特開２００１−２３３６１１号公報等に開示した内部に空洞を有するシリカ系粒子は屈折率が低く好適に用いることができる。さらに、特開２００５−１１９９０９号公報に開示した、反射防止・帯電防止膜に用いた表面を酸化アンチモンで被覆した多孔質シリカ系微粒子または内部に空洞を有するシリカ系微粒子は好適に採用することができる。
These substrates can be attached with good adhesiveness by applying an alkali treatment when attached to a display device front plate or the like.
Among these, TAC is preferable because it is highly transparent, excellent in mechanical strength, has good dimensional stability against changes in temperature, humidity, and the like, and has a low refractive index and high versatility.
Such a substrate preferably has a refractive index in the range of 1.45 to 1.55, more preferably 1.48 to 1.52.
Hard Coat Film The hard coat film comprises an organic resin matrix component and surface-treated metal oxide particles, and is characterized in that there are no metal oxide particles exposed on the hard coat film surface.
Metal oxide particles The metal oxide particles used in the present invention are not particularly limited as long as the obtained hard coat film has transparency and can improve scratch resistance, and conventionally known metal oxide particles can be used. For example, silica, alumina, zirconia, titania, magnesia, antimony oxide, boria, and composite oxide particles such as silica / alumina, silica / zirconia, silica / titania, silica / antimony oxide, and core / shell structures made of these metal oxides. Particles having the same. Further, these particles may be chain particles connected in a chain. Further, hollow particles containing silica as a main component and having cavities inside can be suitably used because of their low refractive index. As such hollow particles, silica-based particles having cavities therein disclosed in Japanese Patent Application Laid-Open Nos. 2001-167737 and 2001-233611 filed by the applicant of the present application have a low refractive index and are preferably used. it can. Furthermore, the porous silica-based fine particles disclosed in JP-A-2005-119909, which are coated with antimony oxide on the surface used for the antireflection / antistatic film, or the silica-based fine particles having cavities inside can be suitably employed. it can.
ハードコート膜に用いる金属酸化物粒子は、基材の屈折率、得られるハードコート膜の屈折率（有機樹脂マトリックス成分の屈折率、金属酸化物の配合割合）等によって適宜選択して用いるが、この時、基材の屈折率とハードコート膜の屈折率との差が小さいことが好ましい。具体的には屈折率差が０．３以下であることが好ましく、屈折率差が大きいと干渉縞を生じることがある。 The metal oxide particles used for the hard coat film are appropriately selected and used depending on the refractive index of the substrate, the refractive index of the obtained hard coat film (refractive index of the organic resin matrix component, blending ratio of the metal oxide), etc. At this time, it is preferable that the difference between the refractive index of the substrate and the refractive index of the hard coat film is small. Specifically, the refractive index difference is preferably 0.3 or less. If the refractive index difference is large, interference fringes may occur.
本発明に用いる金属酸化物粒子の平均粒子径は５〜５００ｎｍ、さらには１０〜２００ｎｍの範囲にあることが好ましい。平均粒子径が小さいと、金属酸化物粒子が凝集することがあり、ハードコート膜中に均一に分散しない場合があり、このためハードコート膜表面に露出し、後述するアルカリ処理の際に直接アルカリと接触して溶出したり、ハードコート膜が白化して透明性が損なわれたり、さらに耐擦傷性が不充分となる、即ち、耐アルカリ性が不充分となることがある。また、平均粒子径が大きいと、ハードコート膜のヘーズが悪化する傾向にある。 The average particle diameter of the metal oxide particles used in the present invention is preferably in the range of 5 to 500 nm, more preferably 10 to 200 nm. If the average particle size is small, the metal oxide particles may agglomerate and may not be uniformly dispersed in the hard coat film. For this reason, the metal oxide particles are exposed on the hard coat film surface, and are directly alkalinized during the alkali treatment described later. In some cases, the hard coat film is whitened and the transparency is impaired, and the scratch resistance is insufficient, that is, the alkali resistance is insufficient. Further, when the average particle size is large, the haze of the hard coat film tends to deteriorate.
なお、本発明の平均粒子径は電子顕微鏡写真を撮影し、１００個の粒子について粒子径を測定し、その平均値として、測定される。
ハードコート膜中の金属酸化物粒子の含有量が５〜８０重量％、さらには１０〜６０重量％の範囲にあることが好ましい。この金属酸化物粒子を含むことで、ハードコート膜の
硬度や密着性、耐擦傷性などが高められる。金属酸化物粒子の含有量が少ないと、ハードコート膜の硬度が不充分であったり、耐擦傷性が不充分となることがある。金属酸化物粒子の含有量が多すぎると、ヘーズが高くなったり、マトリックス成分が少ないために基材との密着性、耐擦傷性、スクラッチ強度、鉛筆硬度等に優れたハードコート膜を得ることが困難である。
The average particle size of the present invention is measured as an average value obtained by taking an electron micrograph and measuring the particle size of 100 particles.
The content of metal oxide particles in the hard coat film is preferably in the range of 5 to 80% by weight, more preferably 10 to 60% by weight. By including these metal oxide particles, the hardness, adhesion, scratch resistance and the like of the hard coat film are enhanced. If the content of the metal oxide particles is small, the hardness of the hard coat film may be insufficient or the scratch resistance may be insufficient. If the content of the metal oxide particles is too large, a hard coat film excellent in adhesion to the substrate, scratch resistance, scratch strength, pencil hardness and the like due to high haze and low matrix components is obtained. Is difficult.
なお、本発明では、金属酸化物粒子は必ずしも球状である必要はなく前記金属酸化物粒子が鎖状に連結した金属酸化物粒子も好適に用いることができる。鎖状に連結した金属酸化物粒子を用いると硬度の高いハードコート膜を得ることができる。 In the present invention, the metal oxide particles do not necessarily have to be spherical, and metal oxide particles in which the metal oxide particles are linked in a chain can also be suitably used. When metal oxide particles connected in a chain are used, a hard coat film with high hardness can be obtained.
本発明に用いる金属酸化物粒子は表面処理されている。かかる表面処理することよって、ハードコート膜表面から。金属酸化物粒子が突出しないようにすることができる。特に、下記式（１）で表される有機ケイ素化合物で表面処理されて、かつ、後述するマトリックス成分と組みあわせることで、
Ｒn-ＳiＸ4-n （１）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、水酸基、ハロゲン、水素、ｎ：０〜３の整数）
このような式（１）で表される有機珪素化合物としてはテトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシシラン、テトラブトキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ジフェニルジエトキシシラン、イソブチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（βメトキシエトキシ）シラン、3,3,3−トリフルオロプロピルトリメトキシシラン、メチル-3,3,3−トリフルオロプ
ロピルジメトキシシラン、β−（3,4-エポキシシクロヘキシル）エチルトリメトキシシラン、γ-グリシドキシメチルトリメトキシシラン、γ-グリシドキシメチルトリエキシシラン、γ-グリシドキシエチルトリメトキシシラン、γ-グリシドキシエチルトリエトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ−（β−グリシドキシエトキシ）プロピルトリメトキシシラン、γ-（メタ）アクリロオキシメチルトリメトキシシラン、γ-（メタ）アクリロオキシメチルトリエキシシラン、γ-（メタ）アクリロオキシエチルトリメトキシシラン、γ-（メタ）アクリロオキシエチルトリエトキシシラン、γ-（メタ）アクリロオキシプロピルトリメトキシシラン、γ-（メタ）アクリロオキシプロピルトリメトキシシラン、γ-（メタ）アクリロオキシプロピルトリエトキシシラン、γ-（メタ）アクリロオキシプロピルトリエトキシシラン、ブチルトリメトキシシラン、イソブチルトリエトキシシラン、ヘキシルトリエトキシシラオクチルトリエトキシシラン、デシルトリエトキシシラン、ブチルトリエトキシシラン、イソブチルトリエトキシシラン、ヘキシルトリエトキシシラン、オクチルトリエトキシシラン、デシルトリエトキシシラン、3-ウレイドイソプロピルプロピルトリエトキシシラン、パーフルオロオクチルエチルトリメトキシシラン、パーフルオロオクチルエチルトリエトキシシラン、パーフルオロオクチルエチルトリイソプロポキシシラン、トリフルオロプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ-アミノプロピルメチルジメトキシシラン、Ｎ−β（アミノエチル）γ-アミノプロピルトリメトキシシラン、Ｎ-フェニル-γ-アミノプロピルトリメトキシシラン、γ-メルカプトプロピルトリメトキシシラン、トリメチルシラノール、メチルトリクロロシラン等、およびこれらの混合物が挙げられる。
The metal oxide particles used in the present invention are surface-treated. By such surface treatment, from the hard coat film surface. The metal oxide particles can be prevented from protruding. In particular, by being surface-treated with an organosilicon compound represented by the following formula (1) and combining with a matrix component described later,
R n -SiX 4-n (1 )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 0 to 3)
Examples of the organosilicon compound represented by the formula (1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane. , Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3- Trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxy Silane, γ-glycidoxymethyltriexisilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxy Silane, γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meth) a Acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyl Triethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriiso Propoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β ( Minoechiru) .gamma.-aminopropyltrimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, trimethylsilanol, methyl trichlorosilane or the like, and mixtures thereof.
金属酸化物粒子がこのような有機ケイ素化合物で表面処理されていると有機樹脂マトリックス成分への分散性に優れるとともに前記炭化水素基が金属酸化物粒子の表面を覆うために仮にハードコート膜表面に露出してもアルカリ溶解性を抑制することができ、このため耐アルカリ性が向上し好適に用いることができる。 When the metal oxide particles are surface-treated with such an organosilicon compound, the dispersibility in the organic resin matrix component is excellent and the hydrocarbon group covers the surface of the metal oxide particles. Even if exposed, alkali solubility can be suppressed, so that alkali resistance can be improved and it can be suitably used.
なかでも、ｎが０または１の有機珪素化合物で金属酸化物粒子が表面処理されていると金属酸化物粒子の表面電荷量（ＱP）が１５〜６０μｅｑ／ｇの範囲となり、疎水性有機
樹脂マトリックス成分へ凝集することなく分散することができ、さらに、後述する下層に偏在する親水性有機樹脂マトリックス成分へ高分散し、ハードコート膜表面に露出することがないので耐アルカリ性が向上し好適に用いることができる。
In particular, when the metal oxide particles are surface-treated with an organic silicon compound having n of 0 or 1, the surface charge amount (Q P ) of the metal oxide particles is in the range of 15 to 60 μeq / g, and the hydrophobic organic resin It can be dispersed without agglomerating into the matrix component, and further highly dispersed in the hydrophilic organic resin matrix component that is unevenly distributed in the lower layer, which will be described later. Can be used.
金属酸化物粒子の表面処理は従来公知の方法を採用することができ、金属酸化物粒子のアルコール分散液に前記有機ケイ素化合物を所定量加え、これに水を加え、必要に応じて有機ケイ素化合物の加水分解用触媒として酸またはアルカリを加え、有機ケイ素化合物を加水分解する。この時の有機ケイ素化合物の使用量は前記式(1)のｎの値によっても異な
るが、Ｒn-ＳiＯ(4-n)/2として金属酸化物粒子の概ね２〜５０重量％、さらには５〜３０重量％の範囲にあることが好ましい。
For the surface treatment of the metal oxide particles, a conventionally known method can be adopted. A predetermined amount of the organosilicon compound is added to an alcohol dispersion of the metal oxide particles, water is added thereto, and an organosilicon compound is added if necessary. An acid or alkali is added as a catalyst for hydrolysis of the compound to hydrolyze the organosilicon compound. The amount of the organosilicon compound used at this time varies depending on the value of n in the formula (1), but is generally 2 to 50% by weight of the metal oxide particles as R n —SiO 2 (4-n) / 2 , It is preferably in the range of 5 to 30% by weight.
金属酸化物粒子が前記範囲で表面処理されていると有機樹脂系マトリックス成分へ凝集することなく分散し、さらに前記炭化水素基が金属酸化物粒子の表面を覆うためにアルカリ溶解性を抑制することができ、このため耐アルカリ性が向上し好適に用いることができる。 When the metal oxide particles are surface-treated within the above range, they are dispersed without agglomerating into the organic resin matrix component, and further the alkali solubility is suppressed because the hydrocarbon groups cover the surface of the metal oxide particles. For this reason, alkali resistance is improved and it can be suitably used.
つぎに、本発明に用いる表面処理金属酸化物粒子は表面電荷量（ＱP）が１５〜６０μ
ｅｑ／ｇ、さらには２０〜５０μｅｑ／ｇの範囲にあることが好ましい。表面電荷量（ＱP）が小さいと、疎水性が強いために、後述する疎水性マトリックス成分へ高分散し、こ
のためハードコート膜表面に露出する金属酸化物粒子が存在するようになり耐アルカリ性が不充分となることがある。表面電荷量（ＱP）が大きいと、親水性が強くなるために疎
水性マトリックス成分中に高分散できず凝集する傾向があり、基材との密着性、耐擦傷性、スクラッチ強度、鉛筆硬度等が不充分となることがある。
Next, the surface-treated metal oxide particles used in the present invention have a surface charge amount (Q P ) of 15 to 60 μm.
It is preferably in the range of eq / g, more preferably 20 to 50 μeq / g. When the surface charge amount (Q P ) is small, the hydrophobicity is strong, so that it is highly dispersed in the hydrophobic matrix component described later, so that metal oxide particles exposed on the surface of the hard coat film are present and the alkali resistance is increased. May be insufficient. When the surface charge amount (Q P ) is large, the hydrophilicity becomes strong, so that there is a tendency that it cannot be highly dispersed in the hydrophobic matrix component and aggregates, adhesion to the substrate, scratch resistance, scratch strength, pencil hardness. Etc. may be insufficient.
金属酸化物粒子の表面電荷量の測定方法は、表面電位滴定装置（Mutek(株) pcd-03）を用いて、粒子の分散液を０．００１Ｎのpoly-塩化ジアリルジメチルアンモニウムを用い
て滴定し、粒子単位グラム当たりの表面電荷量(μeq/g)求めることができる。
The method for measuring the surface charge of metal oxide particles is to titrate the dispersion of particles using 0.001N poly-diallyldimethylammonium chloride using a surface potential titrator (Mutek Co., Ltd. pcd-03). The amount of surface charge per gram of particle (μeq / g) can be determined.
なお、表面電荷量は、例えば、有機ケイ素化合物の種類、表面処理量の変更などによって調整することが可能である。具体的には、ｎが０の場合は比較的表面電荷量の高い粒子が得られ、ｎが２、３の場合は、表面電荷量の低い粒子が得られる。
マトリックス成分
ハードコート膜に含まれているマトリックス成分としては、有機樹脂マトリックスが用いられる。有機樹脂マトリックス成分として、たとえば、従来から用いられているポリエステル樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリフェニレンオキサイド樹脂、熱可塑性アクリル樹脂、塩化ビニル樹脂、フッ素樹脂、酢酸ビニル樹脂、シリコーンゴムなどの熱可塑性樹脂、ウレタン樹脂、メラミン樹脂、ケイ素樹脂、ブチラール樹脂、反応性シリコーン樹脂、フェノール樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、熱硬化性アクリル樹脂、紫外線硬化型アクリル樹脂などの熱硬化性樹脂、紫外線硬化型アクリル樹脂などが挙げられる。さらにはこれら樹脂の２種以上の共重合体や変性体であってもよい。
The surface charge amount can be adjusted, for example, by changing the kind of the organosilicon compound, the surface treatment amount, or the like. Specifically, when n is 0, particles having a relatively high surface charge amount are obtained, and when n is 2 or 3, particles having a low surface charge amount are obtained.
As a matrix component contained in the matrix component hard coat film, an organic resin matrix is used. As organic resin matrix components, for example, conventionally used polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, silicone rubbers, and other thermoplastic resins , Urethane resin, melamine resin, silicon resin, butyral resin, reactive silicone resin, phenol resin, epoxy resin, unsaturated polyester resin, thermosetting acrylic resin, UV curable acrylic resin, etc., UV curable type An acrylic resin etc. are mentioned. Further, it may be a copolymer or modified body of two or more of these resins.
これらの樹脂は、エマルジョン樹脂、水溶性樹脂、親水性樹脂であってもよい。さらに、熱硬化性樹脂の場合、紫外線硬化型のものであっても、電子線硬化型のものであってもよく、熱硬化性樹脂の場合、硬化触媒が含まれていてもよい。 These resins may be emulsion resins, water-soluble resins, and hydrophilic resins. Further, in the case of a thermosetting resin, it may be an ultraviolet curable type or an electron beam curable type, and in the case of a thermosetting resin, a curing catalyst may be included.
なお、熱硬化性樹脂の場合、マトリックス成分は通常硬化物で重合体または変性体となっている。
本発明では、有機樹脂マトリックスとして疎水性有機樹脂マトリックスが好適に用いられる。疎水性有機樹脂マトリックス成分としては、ビニル基、ウレタン基、エポキシ基、（メタ）アクリロイル基、ＣＦ2基等の疎水性官能基を有する多官能(メタ)アクリル酸エ
ステル樹脂が挙げられ、具体的にはペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラアクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサアクリレート、メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート、イソブチルメタクリレート、２−エチルヘキシルメテクリレート、イソデシルメテクリレート、n-ラウリルアクリレート、ｎ−ステアリルアクリレート、１，６−ヘ、サンジオールジメタクリレート、パーフルオロオクチルエチルメタクリレート、トリフロロエチルメテクリレート、ウレタンアクリレート等の多官能(メタ)アクリル酸エステル等の前駆体から誘導される重合体である。なお、２種の共重合体であっても、２種以上の樹脂の混合物であってもさらに変性体であってもよい。
In the case of a thermosetting resin, the matrix component is usually a cured product that is a polymer or a modified product.
In the present invention, a hydrophobic organic resin matrix is suitably used as the organic resin matrix. Examples of the hydrophobic organic resin matrix component include polyfunctional (meth) acrylate resins having a hydrophobic functional group such as a vinyl group, a urethane group, an epoxy group, a (meth) acryloyl group, and a CF 2 group. Are pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, Isobutyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-he, Sanji Over dimethacrylate, a perfluorooctyl methacrylate, trifluoroethyl Mete chestnut rate, polyfunctional (meth) polymers derived from a precursor such as an acrylic acid ester such as urethane acrylate. In addition, it may be two kinds of copolymers, a mixture of two or more kinds of resins, or a modified body.
疎水性有機樹脂マトリックス成分を用いると、前記した金属酸化物粒子が凝集することなく分散し、ハードコート膜の表面に金属酸化物粒子が露出することがなく、耐アルカリ性に優れたハードコート膜が得られる。さらに、ハードコート膜の表面は平滑で、撥水性を有しているために耐水性に優れ、指紋付着性のないハードコート膜が得られる。なお、本発明で撥水性とは、透明被膜上に水を滴下し、３０分間放置した後、拭き取り、目視観察で水滴跡の有無、程度を意味する。 When the hydrophobic organic resin matrix component is used, the above-described metal oxide particles are dispersed without agglomeration, the metal oxide particles are not exposed on the surface of the hard coat film, and a hard coat film excellent in alkali resistance is obtained. can get. Furthermore, since the surface of the hard coat film is smooth and has water repellency, a hard coat film having excellent water resistance and no fingerprint adhesion can be obtained. In the present invention, the term “water repellency” refers to the presence or absence and degree of water droplet traces obtained by dropping water on the transparent film, leaving it for 30 minutes, wiping, and visually observing.
本発明ではさらに、疎水性有機樹脂マトリックスとともに、親水性有機樹脂マトリックス成分が含まれていることが好ましい。
親水性有機樹脂マトリックス成分として、具体的には、水酸基（ＯＨ基）、アミノ基、カルボキシル基、スルホ基等の親水性官能基を有する(メタ)アクリル酸エステル樹脂が挙げられ、例えば、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（メタ）アクリレート、ペンタエリスリトールテトラアクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサアクリレート等の他、ジエチルアミノメチルメタクリレート、ジメチルアミノメチルメタクリレート、ジメチルアミノエチルメタクリレート、ジエチルアミノエチルメタクリレート、２−ヒドロキシエチルメタクレート、２−ヒドロキシプロピルメタクレート、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、２−ヒドロキシブチルメタクレート、２−ヒドロキシ３フェノキシプロピルアクリレート、２−ヒドロキシ−３−アクリロイロキシプロピルアクリレート、メトキシトリエチレングリコールジメタクリレート、ブトキシジエチレングリコールメタクリレート、トリエチレングリコールジアクリレート、１．６−ヘキサンジオールジアクリレート、１，６-ヘキサンジオールジグリシジルエーテルアクリレート、ネオペンチルグリコールジグリシジルエーテルアクリレート、ジエチレングリコールジグリシジルエーテルジアクリレート、ジプロピレングリコールジグリシジルエーテルジアクリレート、２−メタクリロイロキシエチルコハク酸、２−アクロイロキシエチルコハク酸、２−アクロイロキシエチルフタル酸、２−メタクリロイロキシエチルヘキサヒドロフタル酸、２−アクロイロキシエチル−２−ヒドロキシエチルフタル酸、２−メタクリロイロキシエチルアシッドホスフェート、２−メタクリロイロキシエチルアシッドホスフェート、２−アクロイロキシエチルアシッドフォスフェート、２ヒドロキシ−３−フェノキシプロピルアクリレート、ビスフェノールＡジグリシジルエーテルメタクリル酸付加物、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などの多官能(メタ)アクリル酸エステルおよびこれらの混合物等の前駆体から誘導される重合体である。なお、２種以上の共重合体や変性体であってもよい。親水性有機樹脂マトリックス成分を用いると、前記した金属酸化物粒子が親水性有機樹脂マトリックスに高分散し、親水性有機樹脂マトリックスが前記疎水性マトリックスの下層に偏在し、疎水性マトリックスに分散した金属酸化物粒子が減少、さらには無くなるのでハードコート膜の表面に金属酸化物粒子が露出することがなく、耐アルカリ性に優れたハードコート膜が得られる。
In the present invention, it is preferable that a hydrophilic organic resin matrix component is contained together with the hydrophobic organic resin matrix.
Specific examples of the hydrophilic organic resin matrix component include (meth) acrylic acid ester resins having a hydrophilic functional group such as a hydroxyl group (OH group), an amino group, a carboxyl group, and a sulfo group. For example, pentaerythritol In addition to triacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, etc., diethylaminomethyl methacrylate, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylamino Ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypro Acrylate, 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, methoxytriethylene glycol dimethacrylate, butoxydiethylene glycol methacrylate, triethylene glycol diacrylate, 1.6 -Hexanediol diacrylate, 1,6-hexanediol diglycidyl ether acrylate, neopentyl glycol diglycidyl ether acrylate, diethylene glycol diglycidyl ether diacrylate, dipropylene glycol diglycidyl ether diacrylate, 2-methacryloyloxyethyl succinic acid, 2-acryloylethylsuccinic acid, 2-acryloylethylphthalic acid, 2-methyl Acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, 2-methacryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate Derived from precursors such as polyfunctional (meth) acrylates such as 2-hydroxy-3-phenoxypropyl acrylate, bisphenol A diglycidyl ether methacrylic acid adduct, bisphenol A diglycidyl ether acrylic acid adduct and mixtures thereof. It is a polymer. Two or more types of copolymers or modified products may be used. When a hydrophilic organic resin matrix component is used, the metal oxide particles described above are highly dispersed in the hydrophilic organic resin matrix, the hydrophilic organic resin matrix is unevenly distributed in the lower layer of the hydrophobic matrix, and the metal is dispersed in the hydrophobic matrix. Since the oxide particles are reduced and further eliminated, the metal oxide particles are not exposed on the surface of the hard coat film, and a hard coat film excellent in alkali resistance can be obtained.
疎水性有機樹脂マトリックス成分に加えて親水性有機樹脂マトリックス成分を含む場合、親水性有機樹脂マトリックス成分の固形分としての含有量（ＷMA）と疎水性有機樹脂マトリックス成分の固形分としての含有量（ＷMB）との比（ＷMB）／（ＷMA）が０．０１〜２、さらには０．０５〜１の範囲にあることが好ましい。前記（ＷMB）／（ＷMA）が小さいと、疎水性マトリックス成分が少ないために金属酸化物粒子が表面に露出したり、表面が異物で擦り合わされた場合に容易に露出することがあり、このため耐アルカリ性が不充分となることがある。 When the hydrophilic organic resin matrix component is included in addition to the hydrophobic organic resin matrix component, the content of the hydrophilic organic resin matrix component as a solid content (W MA ) and the content of the hydrophobic organic resin matrix component as a solid content (W MB) and the ratio of (W MB) / (W MA ) 0.01 to 2, more preferably in the range of 0.05 to 1. When the (W MB ) / (W MA ) is small, the metal oxide particles may be exposed on the surface because the hydrophobic matrix component is small, or may be easily exposed when the surface is rubbed with a foreign substance. For this reason, alkali resistance may become insufficient.
前記（ＷMB）／（ＷMA）が多すぎると、金属酸化物粒子の含有量によっても異なるが、親水性マトリックス成分が少なく、金属酸化物粒子が上部に偏在する疎水性マトリックス成分中に多く存在するようになり、金属酸化物粒子が表面に露出することがあり、このため耐アルカリ性が不充分となることがある。 If the amount of (W MB ) / (W MA ) is too large, it depends on the content of the metal oxide particles, but there are few hydrophilic matrix components and many in the hydrophobic matrix components in which the metal oxide particles are unevenly distributed at the top. The metal oxide particles may be exposed on the surface, which may result in insufficient alkali resistance.
ハードコート膜の厚さは、目的に応じて適宜選択される。通常厚さは、０.１〜３０μ
ｍ、さらには０.２〜２０μｍ、特に０.２〜１０μｍの範囲にあることが好ましい。ハードコート膜の厚さが前記範囲の下限未満の場合は、ハードコート膜が薄いためにハードコート膜表面に加わる応力を充分吸収することがでないために、ハードコート機能が不充分となる。ハードコート膜の厚さが前記範囲の上限を越えると、膜の厚さが均一になるように塗布したり、均一に乾燥することが困難となり、さらに収縮が大きくなるのでカーリング（ハードコート膜付基材が湾曲）が生じることがある。また、膜厚が厚すぎて透明性が不充分となることがある。
The thickness of the hard coat film is appropriately selected according to the purpose. Usually the thickness is 0.1-30μ
m, more preferably 0.2 to 20 μm, particularly preferably 0.2 to 10 μm. When the thickness of the hard coat film is less than the lower limit of the above range, since the hard coat film is thin, the stress applied to the hard coat film surface cannot be sufficiently absorbed, and the hard coat function is insufficient. When the thickness of the hard coat film exceeds the upper limit of the above range, it becomes difficult to apply the film so that the film thickness becomes uniform or to dry uniformly, and further shrinkage increases, so curling (with hard coat film) The substrate may be curved). Also, the film thickness may be too thick and the transparency may be insufficient.
このようなハードコート膜の屈折率は、透明性が要求される用途であれば、基材の屈折率との差が０．３以下、さらには０．２以下であることが好ましい。この屈折率差であれば干渉縞を生じることもない。
接着剤層
本発明に係るハードコート膜付基材は、基材のハードコート膜が形成されていない面上に接着剤層が設けられていてもよい。
If the refractive index of such a hard coat film is an application that requires transparency, the difference from the refractive index of the substrate is preferably 0.3 or less, and more preferably 0.2 or less. This difference in refractive index does not cause interference fringes.
Adhesive Layer The base material with a hard coat film according to the present invention may be provided with an adhesive layer on the surface of the base material on which the hard coat film is not formed.
接着剤層の接着剤としては透明性の良好なものであれば特に制限はなく従来公知の接着剤を用いることができる。例えば、アクリル系、ゴム系、ポリビニルエーテル系、シリコーン系等の接着剤が挙げられる。接着剤層を設けるには、前記接着剤を、必要に応じて架橋剤を添加し、溶剤を用いて所望の濃度、粘度になるように調節後、ハードコート膜を設けた反対側に塗布し、ついで、加熱、乾燥等により溶剤を除去する。また、別の方法としては、接着剤層を有する剥離紙の接着剤層の面を貼り付けることによっても設けることができる。 The adhesive for the adhesive layer is not particularly limited as long as it has good transparency, and conventionally known adhesives can be used. For example, adhesives such as acrylic, rubber, polyvinyl ether, and silicone are listed. In order to provide an adhesive layer, the above-mentioned adhesive is added to the opposite side where a hard coat film is provided after adding a cross-linking agent as necessary, adjusting to a desired concentration and viscosity using a solvent. Then, the solvent is removed by heating, drying or the like. Moreover, as another method, it can provide also by sticking the surface of the adhesive bond layer of the release paper which has an adhesive bond layer.
このようなハードコート膜は、後述する本発明に係るハードコート膜形成用塗布液を塗布、乾燥、硬化することによって形成することができる。
［ハードコート膜形成用塗布液］
本発明に係るハードコート膜形成用塗布液は、有機樹脂マトリックス形成成分と表面処理金属酸化物粒子と分散媒とを含んでなり、有機樹脂マトリックス形成成分が疎水性有機樹脂マトリックス形成成分であり、表面処理金属酸化物粒子の表面電荷量（ＱP）が１５
〜６０μｅｑ／ｇの範囲にあることを特徴としている。
金属酸化物粒子
金属酸化物粒子としては前記した金属酸化物粒子が用いられる。
ハードコート膜形成用塗布液中の金属酸化物粒子の濃度は、ハードコート膜中の金属酸化物粒子の含有量が前記したように５〜８０重量％、好ましくは１０〜６０重量％となるように用いるが、固形分として０．１〜３６重量％、さらには０．５〜３２重量％の範囲にあることが好ましい。
マトリックス形成成分
マトリックス形成成分としては、前記した疎水性有機樹脂マトリックス成分を形成しうる成分が用いられる。さらに、前記した親水性有機樹脂マトリックス成分を形成しうる成分が含まれていることが好ましい。これらのマトリックス形成成分は、上記熱可塑性樹脂の場合は、上記したマトリックス成分をそのまま使用することが可能であり、熱硬化性樹脂の場合、マトリックス成分を誘導する前駆体のモノマー、プレポリマーなどが使用される。
Such a hard coat film can be formed by applying, drying and curing a coating liquid for forming a hard coat film according to the present invention which will be described later.
[Coating liquid for forming hard coat film]
The coating liquid for forming a hard coat film according to the present invention comprises an organic resin matrix-forming component, surface-treated metal oxide particles, and a dispersion medium, and the organic resin matrix-forming component is a hydrophobic organic resin matrix-forming component, The surface charge amount (Q P ) of the surface-treated metal oxide particles is 15
It is characterized by being in the range of ˜60 μeq / g.
Metal oxide particles The metal oxide particles described above are used as the metal oxide particles.
The concentration of the metal oxide particles in the coating liquid for forming the hard coat film is such that the content of the metal oxide particles in the hard coat film is 5 to 80% by weight, preferably 10 to 60% by weight as described above. However, the solid content is preferably in the range of 0.1 to 36% by weight, more preferably 0.5 to 32% by weight.
Matrix-forming component As the matrix-forming component, a component capable of forming the above-described hydrophobic organic resin matrix component is used. Furthermore, it is preferable that the component which can form the above-mentioned hydrophilic organic resin matrix component is contained. In the case of the above thermoplastic resin, these matrix forming components can be used as they are, and in the case of a thermosetting resin, there are precursor monomers, prepolymers, etc. for deriving the matrix component. used.
疎水性有機樹脂マトリックス形成成分に加えて親水性有機樹脂マトリックス形成成分を含む場合、親水性有機樹脂マトリックス形成成分の固形分としての濃度（ＣMA）と疎水性有機樹脂マトリックス形成成分の固形分としての濃度（ＣME）との比（ＣME）／（ＣMA）が０．０１〜２、さらには０．０５〜１の範囲にあることが好ましい。前記（ＣMB）／（ＣMA）が少ないと得られるハードコート膜中の疎水性マトリックス成分が少ないために金属酸化物粒子が表面に露出することがあり、このため耐アルカリ性が不充分となることがある。前記（ＣMA）／（ＣMB）が多すぎると、金属酸化物粒子の含有量によっても異なるが、親水性マトリックス形成成分が少なく、得られるハードコート膜中で金属酸化物粒子が上部に偏在する疎水性マトリックス成分中に多く存在するようになり、金属酸化物粒子が表面に露出することがあり、このため耐アルカリ性が不充分となることがある。 When a hydrophilic organic resin matrix-forming component is included in addition to the hydrophobic organic resin matrix-forming component, the solid content of the hydrophilic organic resin matrix-forming component (C MA ) and the solid content of the hydrophobic organic resin matrix-forming component The ratio (C ME ) / (C MA ) to the concentration (C ME ) is preferably in the range of 0.01 to 2, and more preferably 0.05 to 1. When the amount of (C MB ) / (C MA ) is small, the metal matrix particles may be exposed on the surface due to the small amount of the hydrophobic matrix component in the obtained hard coat film, which results in insufficient alkali resistance. Sometimes. If the amount of (C MA ) / (C MB ) is too large, it depends on the content of the metal oxide particles, but there are few hydrophilic matrix forming components, and the metal oxide particles are unevenly distributed in the upper part in the obtained hard coat film. In the hydrophobic matrix component, the metal oxide particles may be exposed on the surface, and the alkali resistance may be insufficient.
ハードコート膜形成用塗布液中の有機樹脂マトリックス形成成分の濃度は、樹脂を固形分として１〜４０重量％、さらには２〜３０重量％の範囲にあることが好ましい。有機樹脂マトリックス形成成分が少ないと、一回の塗布では所定の膜厚が得られないことがあり、塗布、乾燥を繰り返すと密着性等が不充分となり、経済性や作業効率などの点でも不十分である。有機樹脂マトリックス形成成分の濃度が多すぎると、得られるハードコート膜の厚さが不均一になる傾向がある。
分散媒
分散媒としては水分散媒であってもアルコールなどの有機溶媒であってもよく、適宜選択して用いることができる。
The concentration of the organic resin matrix-forming component in the hard coat film-forming coating solution is preferably in the range of 1 to 40% by weight, more preferably 2 to 30% by weight, based on the resin. If the organic resin matrix forming component is small, a predetermined film thickness may not be obtained by a single application, and if application and drying are repeated, adhesion and the like become insufficient, and this is also not economical and efficient. It is enough. If the concentration of the organic resin matrix-forming component is too high, the resulting hard coat film tends to be uneven in thickness.
The dispersion medium dispersion medium may be an aqueous dispersion medium or an organic solvent such as alcohol, and can be appropriately selected and used.
分散媒としては前記有機樹脂マトリックス形成成分、必要に応じて用いる重合開始剤を溶解あるいは分散できるとともに表面処理された金属酸化物微粒子を均一に分散することができる、従来公知の分散媒を用いることができる。 As the dispersion medium, a conventionally known dispersion medium that can dissolve or disperse the organic resin matrix-forming component and, if necessary, the polymerization initiator and uniformly disperse the surface-treated metal oxide fine particles is used. Can do.
本発明では沸点の異なる２種以上の分散媒を混合して用いることが好ましい。このとき、沸点の最も高い分散媒は疎水性の分散媒であることが好ましい。沸点の最も高い分散媒が疎水性の分散媒であると、疎水性のマトリックス形成成分がハードコート膜の上層に偏在し、金属酸化物粒子を多く含む親水性マトリックス形成性分が下層に偏在することになり、このため金属酸化物粒子がハードコート膜の表面に露出しにくくなり耐アルカリ性に優れたハードコート膜を得ることができる。 In the present invention, it is preferable to use a mixture of two or more dispersion media having different boiling points. At this time, the dispersion medium having the highest boiling point is preferably a hydrophobic dispersion medium. If the dispersion medium having the highest boiling point is a hydrophobic dispersion medium, the hydrophobic matrix-forming component is unevenly distributed in the upper layer of the hard coat film, and the hydrophilic matrix-forming component containing a large amount of metal oxide particles is unevenly distributed in the lower layer. Therefore, the metal oxide particles are hardly exposed on the surface of the hard coat film, and a hard coat film having excellent alkali resistance can be obtained.
本発明では、５０〜１００℃に沸点有する分散媒(A)と１００超〜２００℃に沸点を有
する分散媒(B)とを組合わせて使用する。
具体的には、分散媒(A)として、水；メタノール、エタノール、プロパノール、2-プロ
パノール（ＩＰＡ）等などのアルコール類を含む親水性溶媒、酢酸メチル、酢酸エチル、酢酸イソプルピルなどのエステル類、アセトン、メチルエチルケトンなどのケトン類、ト
ルエン等の疎水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。分散媒(B)としては、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；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；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などのケトン類、等の疎水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。
In the present invention, a dispersion medium (A) having a boiling point at 50 to 100 ° C. and a dispersion medium (B) having a boiling point at more than 100 to 200 ° C. are used in combination.
Specifically, as the dispersion medium (A), water; hydrophilic solvents including alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), esters such as methyl acetate, ethyl acetate, isopropyl acetate, Examples include ketones such as acetone and methyl ethyl ketone, and hydrophobic solvents such as toluene. These may be used singly or in combination of two or more. Examples of the dispersion medium (B) include butanol, diacetone alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol; glycols such as ethylene glycol and hexylene glycol; diethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl. Hydrophilic solvents including ethers such as ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and ethyl ether of propylene glycol, propyl acetate, isobutyl acetate, Butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutylacetate , Cyclohexyl acetate, esters such as acetate also ethylene glycol; methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone and diisobutyl ketone, and the hydrophobic solvent and the like. These may be used singly or in combination of two or more.
このとき、混合分散媒中の分散媒(A)の割合が５０〜９０重量％の範囲にあり、分散媒(B)の割合が１０〜５０重量％の範囲にあることが好ましい。
混合分散媒中の分散媒(A)の割合がこれ以上多くすると、塗膜の乾燥が速すぎてハード
コート膜が緻密にならないことがあり、硬度や耐擦傷性、耐アルカリ性が不充分となることがある。混合分散媒中の分散媒(A)の割合を少なくしすぎると、逆に分散媒(B)が多くなり、塗膜の乾燥が遅くなり、分散媒が残留してハードコート膜は充分に硬化しない場合があり、硬度や耐擦傷性が不充分となることがある。
At this time, the ratio of the dispersion medium (A) in the mixed dispersion medium is preferably in the range of 50 to 90% by weight, and the ratio of the dispersion medium (B) is preferably in the range of 10 to 50% by weight.
If the ratio of the dispersion medium (A) in the mixed dispersion medium is increased more than this, the coating film is dried too fast and the hard coat film may not become dense, resulting in insufficient hardness, scratch resistance, and alkali resistance. Sometimes. If the ratio of the dispersion medium (A) in the mixed dispersion medium is too small, the dispersion medium (B) increases on the contrary, drying of the coating film becomes slow, the dispersion medium remains and the hard coat film is sufficiently cured. In some cases, the hardness and scratch resistance may be insufficient.
混合分散媒中の分散媒(B)のさらに好ましい割合は２０〜４０重量％の範囲の範囲であ
る。
透明被膜形成用塗料中の分散媒の割合は概ね５０〜９９重量％、さらには６０〜９８重量％の範囲にあることが好ましい。また、混合溶媒を用いる際の疎水性分散媒／親水性分散媒の混合比は概ね０．１〜０．５の範囲にあることが好ましい。
A more desirable ratio of the dispersion medium (B) in the mixed dispersion medium is in the range of 20 to 40% by weight.
The ratio of the dispersion medium in the coating for forming a transparent film is preferably in the range of about 50 to 99% by weight, more preferably 60 to 98% by weight. Moreover, it is preferable that the mixing ratio of the hydrophobic dispersion medium / hydrophilic dispersion medium when using the mixed solvent is generally in the range of 0.1 to 0.5.
また、本発明の塗布液には、マトリックス形成成分を溶解するとともに、容易に揮発しうる溶剤が含まれていてもよく、マトリックス形成成分が熱硬化性樹脂の場合は、必要に応じて硬化剤（重合開始剤）が配合されていてもよい。さらに、塗布液には分散性、安定性を高めるために界面活性剤等を添加することもできる。 In addition, the coating liquid of the present invention may contain a solvent that dissolves the matrix-forming component and easily volatilizes. If the matrix-forming component is a thermosetting resin, a curing agent is used as necessary (Polymerization initiator) may be blended. Further, a surfactant or the like can be added to the coating solution in order to improve dispersibility and stability.
このような塗布液をディップ法、スプレー法、スピナー法、ロールコート法等の周知の方法で前記した基材に塗布し、乾燥し、加熱処理、紫外線照射等によって硬化させることによってハードコート膜を形成することができる。
[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。
[実施例1]
金属酸化物粒子(1)分散液の調製
シリカゾル（触媒化成工業(株)製：カタロイドＳＩ−４５Ｐ、ＳiＯ2濃度４０重量％、平均粒子径４５ｎｍ、分散媒：水）の分散液を、限外濾過膜を用いて洗浄し、ついでメタノールにて溶媒置換するとともに固形分濃度３０重量％になるまで濃縮した。ついで、このゾル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３．６ｇ（信越シ
リコ−ン(株)製 ＫＢＭ−５０３ SiO2成分８１．９％）を混合し、５０℃で１５時間加熱撹拌して表面処理した金属酸化物粒子分散液を得た。
A hard coat film is formed by applying such a coating solution to the above-described substrate by a known method such as a dipping method, a spray method, a spinner method, a roll coating method, drying, and curing by heat treatment, ultraviolet irradiation, or the like. Can be formed.
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.
[Example 1]
Preparation of Dispersion of Metal Oxide Particles (1) Dispersion of silica sol (Catalyst Kasei Kogyo Co., Ltd .: Cataloid SI-45P, SiO 2 concentration 40 wt%, average particle diameter 45 nm, dispersion medium: water) After washing with a filtration membrane, the solvent was replaced with methanol and the solution was concentrated to a solid concentration of 30% by weight. Next, 3.6 g of γ-methacrylooxypropyltrimethoxysilane (KBM-503 SiO 2 component 81.9%, manufactured by Shin-Etsu Silicon Co., Ltd.) was mixed with 100 g of the sol, and the mixture was heated and stirred at 50 ° C. for 15 hours. Thus, a surface-treated metal oxide particle dispersion was obtained.
ついで、ロータリーエバポレーターにてイソプロピルアルコールに溶媒置換して濃度３
０重量％の金属酸化物粒子(1)分散液を得た。この金属酸化物粒子の表面電荷量を測定し
たところ２３．０μｅｑ／ｇであった。また、金属酸化物粒子(1)の平均粒子径および屈
折率を表１に示した。屈折率は標準屈折液としてCARGILL 製のSeriesＡ、ＡＡを用い、以下の方法で測定した。
粒子の屈折率の測定方法
（１）金属酸化物微粒子分散液をエバポレーターに採り、分散媒を蒸発させる。
（２）これを１２０℃で乾燥し、粉末とする。
（３）屈折率が既知の標準屈折液を２、３滴ガラス板上に滴下し、これに上記粉末を混合する。
（４）上記（３）の操作を種々の既知の標準屈折液で行い、混合液が透明になったときの標準屈折液の屈折率を微粒子の屈折率とする。
ハードコート膜形成用塗布液(1)の調製
このシリカ系酸化物微粒子分散液(1)１００ｇと疎水性マトリックス形成成分であるペ
ンタエリスリトールテトラアクリレート（共栄社化学(株)製：ライトアクリレートPE-4A
）２７ｇと疎水性マトリックス形成成分1,6-ヘキサンジオールジアクリレート（共栄社化学(株)製：ライトアクリレート1.6HX-A）３ｇに光開始剤（チバスプシャリティ(株)製イ
ルガキュア１８４）１．８ｇおよび溶媒イソプロパノ−ル１８．２ｇ、メチルイソブチルケトン５０ｇとを充分に混合してハードコート膜形成用塗布液(1)を調製した。
ハードコート膜付基材(1)の作製
ハードコート膜形成用塗布液(1)を、トリアセチルセルロース（TAC）フィルム（厚さ：８０μｍ、屈折率：１.５０、基材全光線透過率９２．０％、ヘーズ０．３％）にバーコ
ーター法（＃１０）で塗布し、７０℃で１２０秒間乾燥した後、高圧水銀灯で６００ｍＪ／ｃｍ2の紫外線を照射して硬化させてハードコート膜付基材(1)を作製した。このときのハードコート膜の膜厚は３μｍであった。
Next, the solvent was replaced with isopropyl alcohol on a rotary evaporator to obtain a concentration of 3
A dispersion of 0% by weight of metal oxide particles (1) was obtained. The surface charge amount of the metal oxide particles was measured and found to be 23.0 μeq / g. The average particle diameter and refractive index of the metal oxide particles (1) are shown in Table 1. The refractive index was measured by the following method using Series A and AA manufactured by CARGILL as the standard refractive liquid.
Method for Measuring Refractive Index of Particle (1) A metal oxide fine particle dispersion is taken in an evaporator and the dispersion medium is evaporated.
(2) This is dried at 120 ° C. to obtain a powder.
(3) A standard refraction liquid having a known refractive index is dropped on a glass plate of a few drops, and the above powder is mixed therewith.
(4) The operation of (3) is performed with various known standard refractive liquids, and the refractive index of the standard refractive liquid when the mixed liquid becomes transparent is used as the refractive index of the fine particles.
Preparation of coating liquid for hard coat film formation (1) 100 g of this silica-based oxide fine particle dispersion (1) and pentaerythritol tetraacrylate which is a hydrophobic matrix forming component (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate PE-4A
) 27 g and hydrophobic matrix-forming component 1,6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate 1.6HX-A) 3 g and photoinitiator (Cibapus Charity Co., Ltd. Irgacure 184) 1.8 g Then, 18.2 g of a solvent isopropanol and 50 g of methyl isobutyl ketone were sufficiently mixed to prepare a coating solution (1) for forming a hard coat film.
Preparation of base material with hard coat film (1) A coating liquid for hard coat film formation (1) was prepared from a triacetyl cellulose (TAC) film (thickness: 80 μm, refractive index: 1.50, base material total light transmittance 92). 0.0%, haze 0.3%) by a bar coater method (# 10), dried at 70 ° C. for 120 seconds, and then cured by irradiating with 600 mJ / cm 2 of ultraviolet light with a high-pressure mercury lamp. A base material (1) was prepared. The thickness of the hard coat film at this time was 3 μm.
得られたハードコート膜付基材(1)の全光線透過率およびヘーズをヘーズメーター（日
本電色(株)製：ＮＤＨ２０００）により測定し、また干渉縞の有無を観察し、結果を表１に示した。さらに、密着性、耐擦傷性および耐アルカリ性を評価し、結果を表１に示す。 表面観察
ハードコート膜付基材(1)に蛍光灯（三波長蛍光管）の光をあて、目視で干渉縞の有無
を観察し、結果を表1に示す。
密着性
ハードコート膜付基材(1)の表面にナイフで縦横１ｍｍの間隔で１１本の平行な傷を付
け１００個の升目を作り、これにセロハンテ−プを接着し、ついで、セロハンテ−プを剥離したときに被膜が剥離せず残存している升目の数を、以下の４段階に分類することにより密着性を評価した。結果を表１に示す。
残存升目の数１００個 ：◎
残存升目の数９０〜９９個 ：○
残存升目の数８５〜８９個 ：△
残存升目の数８４個以下 ：×
耐擦傷性の測定
＃００００スチールウールを用い、荷重５００ｇ／ｃｍ2で５０回摺動し、膜の表面を
目視観察し、以下の基準で評価し、結果を表に示した。
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 ：×
耐アルカリ性の評価（１）
ハードコート膜付基材(1)の透明被膜上に、２ＮのＮａＯＨ水溶液を滴下し、３分間放
置した後拭き取り、全光線透過率を測定し、結果を表１に示した。
耐アルカリ性の評価（２）
ハードコート膜付基材(1)の透明被膜上に、２ＮのＮａＯＨ水溶液を滴下し、３分間放
置した後拭き取り、上記と同様の耐擦傷性の測定を行い、同様の基準で評価し、結果を表１に示した。
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 ：×
[実施例２]
ハードコート膜形成用塗布液(2)の調製
実施例1で調製した金属酸化物粒子分散液(1)１００ｇと水酸基を有する親水性マトリックス形成成分であるネオペンチルグリコールジグリシジルエーテルアクリレート（新中村化学(株)：NKオリゴEA-5320）１５ｇ、と疎水性マトリックス形成成分であるペンタエリ
スリトールテトラアクリレート（共栄社化学(株)製：ライトアクリレートPE-4A）１５ｇ
に光開始剤（チバスプシャリティ(株)製イルガキュア１８４）１．８ｇおよび溶媒イソプロパノ−ル１８．２ｇ、メチルイソブチルケトン５０ｇとを充分に混合してハードコート膜形成用塗布液(2)を調製した。
ハードコート膜付基材(2)の作製
ハードコート膜形成用塗布液(2)を、トリアセチルセルロース（TAC）フィルム（厚さ：８０μｍ、屈折率：１.５０、基材全光線透過率９２．０％、ヘーズ０．３％）にバーコ
ーター法（＃１０）で塗布し、７０℃で１２０秒間乾燥した後、高圧水銀灯で６００ｍＪ／ｃｍ2の紫外線を照射して硬化させてハードコート膜付基材(2)を作製した。このときのハードコート膜の膜厚は３μｍであった。
Total light transmittance and haze of the obtained base material with a hard coat film (1) were measured with a haze meter (Nippon Denshoku Co., Ltd .: NDH2000), and the presence or absence of interference fringes was observed. It was shown to. Furthermore, adhesion, scratch resistance and alkali resistance were evaluated, and the results are shown in Table 1. The surface observation hard coat film-coated substrate (1) is irradiated with light from a fluorescent lamp (three-wavelength fluorescent tube) and visually observed for the presence or absence of interference fringes, and the results are shown in Table 1.
Adhesive hard coat film-coated substrate (1) The surface of the substrate (1) with a knife to make 11 parallel scratches at intervals of 1 mm in length and breadth to make 100 squares, cellophane tape is bonded to this, then cellophane tape The adhesiveness was evaluated by classifying the number of squares remaining when the film was peeled off without being peeled into the following four stages. The results are shown in Table 1.
Number of remaining squares: ◎
Number of remaining squares 90-99: ○
Number of remaining squares: 85 to 89: Δ
Number of remaining squares: 84 or less: ×
Measurement of scratch resistance Using # 0000 steel wool, sliding 50 times at a load of 500 g / cm 2 , visually observing the surface of the film, and evaluating according to the following criteria, the results are shown in the table.
Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×
Evaluation of alkali resistance (1)
A 2N NaOH aqueous solution was dropped on the transparent coating of the substrate with hard coat film (1), left standing for 3 minutes, wiped off, measured for total light transmittance, and the results are shown in Table 1.
Evaluation of alkali resistance (2)
A 2N NaOH aqueous solution was dropped on the transparent coating of the substrate with hard coat film (1), left to stand for 3 minutes, wiped off, measured for scratch resistance as described above, and evaluated according to the same criteria. Is shown in Table 1.
Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×
[Example 2]
Preparation of coating liquid (2) for forming a hard coat film 100 g of the metal oxide particle dispersion (1) prepared in Example 1 and neopentyl glycol diglycidyl ether acrylate, a hydrophilic matrix forming component having a hydroxyl group (Shin Nakamura Chemical) 15 g of NK Oligo EA-5320) and 15 g of pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate PE-4A) which is a hydrophobic matrix forming component
Then, 1.8 g of a photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd.), 18.2 g of a solvent isopropanol, and 50 g of methyl isobutyl ketone are sufficiently mixed to prepare a coating solution (2) for forming a hard coat film. did.
Preparation of base material with hard coat film (2) A coating liquid for forming a hard coat film (2) was prepared from a triacetyl cellulose (TAC) film (thickness: 80 μm, refractive index: 1.50, base material total light transmittance 92 0.0%, haze 0.3%) by a bar coater method (# 10), dried at 70 ° C. for 120 seconds, and then cured by irradiating with 600 mJ / cm 2 of ultraviolet light with a high-pressure mercury lamp. A base material (2) was prepared. The thickness of the hard coat film at this time was 3 μm.
得られたハードコート膜付基材(2)の全光線透過率およびヘーズ、干渉縞の有無、密着
性、耐擦傷性および耐アルカリ性を評価し、結果を表１に示す。
[実施例3]
ハードコート膜形成用塗布液(3)の調製
実施例1で調製した金属酸化物粒子分散液(1)１００ｇと水酸基を有する親水性マトリックス形成成分であるネオペンチルグリコールジグリシジルエーテルアクリレート（新中村化学(株)：NKオリゴEA-5320）２４ｇ、と疎水性マトリックス形成成分であるペンタエリ
スリトールテトラアクリレート（共栄社化学(株)製：ライトアクリレートPE-4A）６ｇに
光開始剤（チバスプシャリティ(株)製イルガキュア１８４）１．８ｇおよび溶媒イソプロパノ−ル１８．２ｇ、メチルイソブチルケトン５０ｇとを充分に混合してハードコート膜形成用塗布液(3)を調製した。
ハードコート膜付基材(3)の作製
ハードコート膜形成用塗布液(3)を、トリアセチルセルロース（TAC）フィルム（厚さ：８０μｍ、屈折率：１.５０、基材全光線透過率９２．０％、ヘーズ０．３％）にバーコ
ーター法（＃１０）で塗布し、７０℃で１２０秒間乾燥した後、高圧水銀灯で６００ｍＪ／ｃｍ2の紫外線を照射して硬化させてハードコート膜付基材(3)を作製した。このときのハードコート膜の膜厚は３μｍであった。
The obtained base material with a hard coat film (2) was evaluated for total light transmittance and haze, presence or absence of interference fringes, adhesion, scratch resistance and alkali resistance, and the results are shown in Table 1.
[Example 3]
Preparation of coating liquid for forming hard coat film (3) 100 g of the metal oxide particle dispersion (1) prepared in Example 1 and neopentyl glycol diglycidyl ether acrylate (Shin Nakamura Chemical Co., Ltd.) which is a hydrophilic matrix forming component having a hydroxyl group Co., Ltd .: NK Oligo EA-5320) 24g, and a hydrophobic matrix forming component pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate PE-4A) 6g photoinitiator (Ciba Spurality Co., Ltd.) 1.8 g of Irgacure 184), 18.2 g of solvent isopropanol, and 50 g of methyl isobutyl ketone were sufficiently mixed to prepare a coating solution (3) for forming a hard coat film.
Preparation of substrate (3) with hard coat film A coating liquid (3) for forming a hard coat film was prepared by using a triacetyl cellulose (TAC) film (thickness: 80 μm, refractive index: 1.50, substrate total light transmittance 92). 0.0%, haze 0.3%) by a bar coater method (# 10), dried at 70 ° C. for 120 seconds, and then cured by irradiating with 600 mJ / cm 2 of ultraviolet light with a high-pressure mercury lamp. A base material (3) was prepared. The thickness of the hard coat film at this time was 3 μm.
得られたハードコート膜付基材(3)の全光線透過率およびヘーズ、干渉縞の有無、密着
性、耐擦傷性および耐アルカリ性を評価し、結果を表１に示す。
[実施例4]
ハードコート膜形成用塗布液(4)の調製
実施例1で調製した金属酸化物粒子分散液(1)１００ｇと水酸基を有する親水性のマトリックス形成成分であるネオペンチルグリコールジグリシジルエーテルアクリレート（新中村化学(株)：NKオリゴEA-5320）６ｇ、と疎水性のマトリックス形成成分であるペンタエリスリトールテトラアクリレート（共栄社化学(株)製：ライトアクリレートPE-4A）２４ｇに光開始剤（チバスプシャリティ(株)製イルガキュア１８４）１．８ｇおよび溶媒イソプロパノ−ル１８．２ｇ、メチルイソブチルケトン５０ｇとを充分に混合してハードコート膜形成用塗布液(4)を調製した。
ハードコート膜付基材(4)の作製
ハードコート膜形成用塗布液(4)を、トリアセチルセルロース（TAC）フィルム（厚さ：８０μｍ、屈折率：１.５０、基材全光線透過率９２．０％、ヘーズ０．３％）にバーコ
ーター法（＃１０）で塗布し、７０℃で１２０秒間乾燥した後、高圧水銀灯で６００ｍＪ／ｃｍ2の紫外線を照射して硬化させてハードコート膜付基材(4)を作製した。このときのハードコート膜の膜厚は３μｍであった。
The obtained base material with hard coat film (3) was evaluated for total light transmittance and haze, presence or absence of interference fringes, adhesion, scratch resistance and alkali resistance, and the results are shown in Table 1.
[Example 4]
Preparation of Hard Coat Film Forming Coating Liquid (4) 100 g of the metal oxide particle dispersion (1) prepared in Example 1 and neopentyl glycol diglycidyl ether acrylate (Shin Nakamura) which is a hydrophilic matrix forming component having a hydroxyl group Chemical Co., Ltd .: NK Oligo EA-5320) and 6 g of pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate PE-4A), which is a hydrophobic matrix forming component, and photoinitiator (Ciba Specialty ( 1.8 g of Irgacure 184), 18.2 g of solvent isopropanol, and 50 g of methyl isobutyl ketone were sufficiently mixed to prepare a coating solution (4) for forming a hard coat film.
Preparation of base material with hard coat film (4) A coating liquid for forming a hard coat film (4) was prepared from a triacetyl cellulose (TAC) film (thickness: 80 μm, refractive index: 1.50, base material total light transmittance 92 0.0%, haze 0.3%) by a bar coater method (# 10), dried at 70 ° C. for 120 seconds, and then cured by irradiating with 600 mJ / cm 2 of ultraviolet light with a high-pressure mercury lamp. A base material (4) was prepared. The thickness of the hard coat film at this time was 3 μm.
得られたハードコート膜付基材(4)の全光線透過率およびヘーズ、干渉縞の有無、密着
性、耐擦傷性および耐アルカリ性を評価し、結果を表１に示す。
[実施例5]
ハードコート膜形成用塗布液(5)の調製
実施例1で調製した金属酸化物粒子分散液(1)８０ｇと水酸基を有する親水性のマトリックス形成成分である１，６-ヘキサンジオールジグリシジルエーテルアクリレート（新中
村化学(株)：NKオリゴEA-5521）１８ｇ、と疎水性のマトリックス形成成分であるペンタ
エリスリトールテトラアクリレート（共栄社化学(株)製：ライトアクリレートPE-4A）１
８ｇに光開始剤（チバスプシャリティ(株)製イルガキュア１８４）２．２ｇおよび溶媒イソプロパノ−ル３１．８ｇ、メチルイソブチルケトン５０ｇとを充分に混合してハードコート膜形成用塗布液(5)を調製した。
ハードコート膜付基材(5)の作製
ハードコート膜形成用塗布液(5)を、トリアセチルセルロース（TAC）フィルム（厚さ：８０μｍ、屈折率：１.５０、基材全光線透過率９２．０％、ヘーズ０．３％）にバーコ
ーター法（＃１０）で塗布し、７０℃で１２０秒間乾燥した後、高圧水銀灯で６００ｍＪ／ｃｍ2の紫外線を照射して硬化させてハードコート膜付基材(5)を作製した。このときのハードコート膜の膜厚は３μｍであった。
The obtained base material with hard coat film (4) was evaluated for total light transmittance and haze, presence or absence of interference fringes, adhesion, scratch resistance and alkali resistance, and the results are shown in Table 1.
[Example 5]
Preparation of coating liquid (5) for forming a hard coat film 80 g of the metal oxide particle dispersion (1) prepared in Example 1 and 1,6-hexanediol diglycidyl ether acrylate which is a hydrophilic matrix-forming component having a hydroxyl group (Shin Nakamura Chemical Co., Ltd .: NK Oligo EA-5521) 18 g, and pentaerythritol tetraacrylate (Kyoeisha Chemical Co., Ltd .: Light Acrylate PE-4A) which is a hydrophobic matrix forming component 1
8 g of photoinitiator (Irgacure 184, manufactured by Ciba Specialty Inc.), 31.8 g of solvent isopropanol, and 50 g of methyl isobutyl ketone were mixed thoroughly to prepare a coating solution (5) for forming a hard coat film. Prepared.
Preparation of base material with hard coat film (5) Coating liquid (5) for forming a hard coat film was prepared from a triacetyl cellulose (TAC) film (thickness: 80 μm, refractive index: 1.50, base material total light transmittance 92). 0.0%, haze 0.3%) by a bar coater method (# 10), dried at 70 ° C. for 120 seconds, and then cured by irradiating with 600 mJ / cm 2 of ultraviolet light with a high-pressure mercury lamp. A base material (5) was prepared. The thickness of the hard coat film at this time was 3 μm.
得られたハードコート膜付基材(5)の全光線透過率およびヘーズ、干渉縞の有無、密着
性、耐擦傷性および耐アルカリ性を評価し、結果を表１に示す。
[実施例6]
ハードコート膜形成用塗布液(6)の調製
実施例1で調製した金属酸化物粒子分散液(1)１２０ｇと水酸基を有する親水性のマトリックス形成成分である１，６-ヘキサンジオールジグリシジルエーテルアクリレート（新中村化学(株)：NKオリゴEA-5521）１２ｇ、と疎水性のマトリックス形成成分であるペンタエリスリトールテトラアクリレート（共栄社化学(株)製：ライトアクリレートPE-4A）１２ｇに光開始剤（チバスプシャリティ(株)製イルガキュア１８４）１．５ｇおよび溶媒イソプロパノ−ル４．５ｇ、メチルイソブチルケトン５０ｇとを充分に混合してハードコート膜形成用塗布液(6)を調製した。
ハードコート膜付基材(6)の作製
ハードコート膜形成用塗布液(6)を、トリアセチルセルロース（TAC）フィルム（厚さ：８０μｍ、屈折率：１.５０、基材全光線透過率９２．０％、ヘーズ０．３％）にバーコ
ーター法（＃１０）で塗布し、７０℃で１２０秒間乾燥した後、高圧水銀灯で６００ｍＪ／ｃｍ2の紫外線を照射して硬化させてハードコート膜付基材(6)を作製した。このときのハードコート膜の膜厚は３μｍであった。
The obtained base material with a hard coat film (5) was evaluated for total light transmittance and haze, presence or absence of interference fringes, adhesion, scratch resistance and alkali resistance, and the results are shown in Table 1.
[Example 6]
Preparation of coating liquid for forming hard coat film (6) 120 g of metal oxide particle dispersion (1) prepared in Example 1 and 1,6-hexanediol diglycidyl ether acrylate which is a hydrophilic matrix forming component having a hydroxyl group (Shin Nakamura Chemical Co., Ltd .: NK Oligo EA-5521) and 12 g of pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate PE-4A) as a hydrophobic matrix forming component A hard coat film-forming coating solution (6) was prepared by thoroughly mixing 1.5 g of Pirality Co., Ltd. Irgacure 184), 4.5 g of solvent isopropanol, and 50 g of methyl isobutyl ketone.
Preparation of base material with hard coat film (6) Coating liquid for hard coat film formation (6) was prepared from triacetyl cellulose (TAC) film (thickness: 80 μm, refractive index: 1.50, base material total light transmittance 92). 0.0%, haze 0.3%) by a bar coater method (# 10), dried at 70 ° C. for 120 seconds, and then cured by irradiating with 600 mJ / cm 2 of ultraviolet light with a high-pressure mercury lamp. A base material (6) was prepared. The thickness of the hard coat film at this time was 3 μm.
得られたハードコート膜付基材(6)の全光線透過率およびヘーズ、干渉縞の有無、密着
性、耐擦傷性および耐アルカリ性を評価し、結果を表１に示す。
[実施例7]
金属酸化物粒子(2)分散液の調製
シリカゾル（触媒化成工業(株)製：カタロイドＳＩ−４５Ｐ、ＳiＯ2濃度４０重量％、平均粒子径４５ｎｍ、分散媒：水）の分散液を、限外濾過膜を用いて洗浄し、ついでメタノールにて溶媒置換するとともに固形分濃度３０重量％になるまで濃縮した。ついで、このゾル１００ｇに正珪酸エチル１５．６ｇ（多摩化学(株)製 エチルシリケート２８ SiO2成分２８．８％）を混合し、５０℃で１５時間加熱撹拌して表面処理した金属酸化物粒子分散液を得た。
The obtained base material with hard coat film (6) was evaluated for total light transmittance and haze, presence or absence of interference fringes, adhesion, scratch resistance and alkali resistance, and the results are shown in Table 1.
[Example 7]
Preparation of dispersion of metal oxide particles (2) Dispersion of silica sol (catalyst chemical industry Co., Ltd .: Cataloid SI-45P, SiO 2 concentration 40% by weight, average particle diameter 45 nm, dispersion medium: water) After washing with a filtration membrane, the solvent was replaced with methanol and the solution was concentrated to a solid concentration of 30% by weight. Next, 15.6 g of normal ethyl silicate (ethyl silicate 28 SiO 2 component 28.8%, manufactured by Tama Chemical Co., Ltd.) was mixed with 100 g of this sol, and the surface was subjected to surface treatment by heating and stirring at 50 ° C. for 15 hours. A dispersion was obtained.
ついで、ロータリーエバポレーターにてイソプロピルアルコールに溶媒置換して濃度３０重量％の金属酸化物粒子(2)分散液を得た。この金属酸化物粒子(2)の表面電荷量を測定したところ３２．０μｅｑ／ｇであった。また、金属酸化物粒子(2)の平均粒子径および屈折率を表１に示した。
ハードコート膜形成用塗布液(7)の調製
金属酸化物粒子(1)分散液１００ｇと水酸基を有する親水性のマトリックス形成成分で
ある１，６-ヘキサンジオールジグリシジルエーテルアクリレート（新中村化学(株)：NK
オリゴEA-5521）１５ｇ、と疎水性のマトリックス形成成分であるジペンタエリスリトー
ルヘキサアクリレート（日本化薬(株)製：KAYARAD DPHA）１５ｇに光開始剤（チバスプシャリティ(株)製イルガキュア１８４）１．８ｇおよび溶媒イソプロパノ−ル１８．２ｇ、メチルイソブチルケトン５０ｇとを充分に混合してハードコート膜形成用塗布液(7)を調製した。
ハードコート膜付基材(7)の作製
ハードコート膜形成用塗布液(7)を、トリアセチルセルロース（TAC）フィルム（厚さ：８０μｍ、屈折率：１.５０、基材全光線透過率９２．０％、ヘーズ０．３％）にバーコ
ーター法（＃１０）で塗布し、７０℃で１２０秒間乾燥した後、高圧水銀灯で６００ｍＪ／ｃｍ2の紫外線を照射して硬化させてハードコート膜付基材(7)を作製した。このときのハードコート膜の膜厚は３μｍであった。
Subsequently, the solvent was replaced with isopropyl alcohol by a rotary evaporator to obtain a dispersion of metal oxide particles (2) having a concentration of 30% by weight. The surface charge amount of the metal oxide particles (2) was measured and found to be 32.0 μeq / g. The average particle diameter and refractive index of the metal oxide particles (2) are shown in Table 1.
Preparation of Hard Coat Film Forming Coating Liquid (7) 100 g of metal oxide particle (1) dispersion and 1,6-hexanediol diglycidyl ether acrylate (Shin Nakamura Chemical Co., Ltd.) which is a hydrophilic matrix forming component having a hydroxyl group ) ： NK
15 g of oligo EA-5521) and 15 g of dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA), which is a hydrophobic matrix forming component, and photoinitiator (Irgacure 184, manufactured by Ciba Specialty Corporation) 1 0.8 g, 18.2 g of solvent isopropanol, and 50 g of methyl isobutyl ketone were sufficiently mixed to prepare a coating solution (7) for forming a hard coat film.
Preparation of base material with hard coat film (7) A coating liquid for hard coat film formation (7) was prepared from a triacetyl cellulose (TAC) film (thickness: 80 μm, refractive index: 1.50, base material total light transmittance 92). 0.0%, haze 0.3%) by a bar coater method (# 10), dried at 70 ° C. for 120 seconds, and then cured by irradiating with 600 mJ / cm 2 of ultraviolet light with a high-pressure mercury lamp. A base material (7) was prepared. The thickness of the hard coat film at this time was 3 μm.
得られたハードコート膜付基材(7)の全光線透過率およびヘーズ、干渉縞の有無、密着
性、耐擦傷性および耐アルカリ性を評価し、結果を表１に示す。
[実施例8]
シリカ系酸化物微粒子(3)分散液の調製
シリカゾル（触媒化成工業(株)製：カタロイドＳＩ−４５Ｐ、ＳiＯ2濃度４０重量％、平均粒子径４５ｎｍ、分散媒：水）の分散液を限外濾過膜を用いて洗浄し、ついでメタノールにて溶媒置換するとともに固形分濃度３０重量％になるまで濃縮した。ついで、このゾル１００ｇにγ-アクリロオキシプロピルトリメトキシシラン５．５ｇ（信越化学（株）製：KBM−５１０３ ＳｉＯ2成分８１．２％）を混合し、５０℃で１５時間加熱撹拌して表面処理した金属酸化物粒子分散液を得た。
The obtained base material with a hard coat film (7) was evaluated for total light transmittance and haze, presence or absence of interference fringes, adhesion, scratch resistance and alkali resistance, and the results are shown in Table 1.
[Example 8]
Preparation of dispersion of silica-based oxide fine particles (3) Dispersion of silica sol (Catalyst Chemical Industries, Ltd .: Cataloid SI-45P, SiO 2 concentration 40% by weight, average particle size 45 nm, dispersion medium: water) is limited. After washing with a filtration membrane, the solvent was replaced with methanol and the solution was concentrated to a solid concentration of 30% by weight. Next, 5.5 g of γ-acrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103 SiO 2 component 81.2%) was mixed with 100 g of this sol, and heated and stirred at 50 ° C. for 15 hours. A surface-treated metal oxide particle dispersion was obtained.
ついで、ロータリーエバポレーターにてイソプロピルアルコールに溶媒置換して濃度３０重量％の金属酸化物粒子(3)分散液を得た。この金属酸化物粒子(3)の表面電荷量を測定したところ２０．０μｅｑ／ｇであった。また、金属酸化物粒子(3)の平均粒子径および屈折率を表１に示した。
ハードコート膜形成用塗布液(8)の調製
金属酸化物粒子分散液(3)１００ｇと水酸基を有する親水性のマトリックス形成成分で
ある１，６-ヘキサンジオールジグリシジルエーテルアクリレート（新中村化学(株)：NK
オリゴEA-5521）１５ｇ、と疎水性のマトリックス形成成分であるジペンタエリスリトー
ルヘキサアクリレート（日本化薬(株)製：KAYARAD DPHA）１５ｇに光開始剤（チバスプシャリティ(株)製イルガキュア１８４）１．８ｇおよび溶媒イソプロパノ−ル１８．２ｇ、メチルイソブチルケトン５０ｇとを充分に混合してハードコート膜形成用塗布液(8)を調製した。
ハードコート膜付基材(8)の作製
ハードコート膜形成用塗布液(8)を、トリアセチルセルロース（TAC）フィルム（厚さ：８０μｍ、屈折率：１.５０、基材全光線透過率９２．０％、ヘーズ０．３％）にバーコ
ーター法（＃１０）で塗布し、７０℃で１２０秒間乾燥した後、高圧水銀灯で６００ｍＪ／ｃｍ2の紫外線を照射して硬化させてハードコート膜付基材(8)を作製した。このときのハードコート膜の膜厚は３μｍであった。
Subsequently, the solvent was replaced with isopropyl alcohol by a rotary evaporator to obtain a metal oxide particle (3) dispersion having a concentration of 30% by weight. The surface charge amount of the metal oxide particles (3) was measured and found to be 20.0 μeq / g. The average particle diameter and refractive index of the metal oxide particles (3) are shown in Table 1.
Preparation of Hard Coat Film Forming Coating Liquid (8) 100 g of Metal Oxide Particle Dispersion (3) and 1,6-hexanediol diglycidyl ether acrylate (Shin Nakamura Chemical Co., Ltd.) which is a hydrophilic matrix forming component having a hydroxyl group ) ： NK
15 g of oligo EA-5521) and 15 g of dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA), which is a hydrophobic matrix forming component, and photoinitiator (Irgacure 184, manufactured by Ciba Specialty Corporation) 1 .8 g, 18.2 g of solvent isopropanol, and 50 g of methyl isobutyl ketone were sufficiently mixed to prepare a coating solution (8) for forming a hard coat film.
Preparation of substrate (8) with hard coat film A coating liquid (8) for forming a hard coat film was prepared by using a triacetyl cellulose (TAC) film (thickness: 80 μm, refractive index: 1.50, substrate total light transmittance 92). 0.0%, haze 0.3%) by a bar coater method (# 10), dried at 70 ° C. for 120 seconds, and then cured by irradiating with 600 mJ / cm 2 of ultraviolet light with a high-pressure mercury lamp. A base material (8) was prepared. The thickness of the hard coat film at this time was 3 μm.
得られたハードコート膜付基材(8)の全光線透過率およびヘーズ、干渉縞の有無、密着
性、耐擦傷性および耐アルカリ性を評価し、結果を表１に示す。
[実施例9]
金属酸化物粒子(4)分散液の調製
シリカ系中空微粒子分散ゾル（触媒化成工業(株)製：スルーリア１４２０、平均粒子径６０ｎｍ、濃度２０．５重量％、分散媒：イソプロパノ−ル、粒子屈折率１．３０）を用いた。このゾル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２．５ｇ
（信越シリコ−ン(株)製 ＫＢＭ−５０３ SiO2成分８１．９％）を混合し、超純水を１０ｇ添加し５０℃で５時間攪拌し表面処理した金属酸化物粒子分散液を得た（固形分２０．０％）。
The obtained base material with hard coat film (8) was evaluated for total light transmittance and haze, presence or absence of interference fringes, adhesion, scratch resistance and alkali resistance, and the results are shown in Table 1.
[Example 9]
Preparation of dispersion of metal oxide particles (4) Silica-based hollow fine particle dispersion sol (Catalyst Kasei Kogyo Co., Ltd .: Thruria 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion medium: isopropanol, particle refraction Rate 1.30) was used. To 100 g of this sol, 2.5 g of γ-methacryloxypropyltrimethoxysilane
(KBS-503 SiO 2 component 81.9% manufactured by Shin-Etsu Silicon Co., Ltd.) was mixed, 10 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 5 hours to obtain a surface-treated metal oxide particle dispersion. (Solid content 20.0%).
この金属酸化物粒子(4)の表面電荷量を測定したところ２１．０μｅｑ／ｇであった。
また、金属酸化物粒子(4)の平均粒子径および屈折率を表１に示した。
ハードコート膜形成用塗布液(9)の調製
金属酸化物粒子(4)分散液４４ｇと水酸基を有する親水性のマトリックス形成成分であ
るネオペンチルグリコールジグリシジルエーテルアクリレート（新中村化学(株)：NKオリゴEA-5320）２５．５ｇ、と疎水性のマトリックス形成成分であるペンタエリスリトール
テトラアクリレート（共栄社化学(株)製：ライトアクリレートPE-4A）２５．５ｇに光開
始剤（チバスプシャリティ(株)製イルガキュア１８４）３．１ｇおよび溶媒イソプロパノ−ル７７．４ｇ、メチルイソブチルケトン５０ｇとを充分に混合してハードコート膜形成用塗布液(9)を調製した。
ハードコート膜付基材(9)の作製
実施例１において、ハードコート膜形成用塗料(9)を用いた以外は同様にしてハードコ
ート膜付基材(9)を作製した。このときのハードコート膜の厚さは３μｍであった。
The surface charge amount of the metal oxide particles (4) was measured and found to be 21.0 μeq / g.
In addition, Table 1 shows the average particle diameter and refractive index of the metal oxide particles (4).
Preparation of coating liquid for forming hard coat film (9) 44 g of dispersion of metal oxide particles (4) and neopentyl glycol diglycidyl ether acrylate, a hydrophilic matrix-forming component having a hydroxyl group (Shin Nakamura Chemical Co., Ltd .: NK Oligo EA-5320) 25.5 g, and a hydrophobic matrix forming component pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate PE-4A) 25.5 g of photoinitiator (Ciba Specialty Co., Ltd.) Irgacure 184) 3.1 g, 77.4 g of solvent isopropanol, and 50 g of methyl isobutyl ketone were sufficiently mixed to prepare a coating solution (9) for forming a hard coat film.
Preparation of base material with hard coat film (9) A base material with hard coat film (9) was prepared in the same manner as in Example 1, except that the coating material for forming a hard coat film (9) was used. At this time, the thickness of the hard coat film was 3 μm.
得られたハードコート膜付基材(9)の全光線透過率およびヘーズ、干渉縞の有無、密着
性、耐擦傷性および耐アルカリ性を評価し、結果を表１に示す。
[実施例10]
金属酸化物粒子(5)分散液の調製
シリカゾル（触媒化成工業株式会社(株)製：カタロイドＳＩ−５５０、ＢＥＴ法により測定された平均粒子径：５ｎｍ、比表面積：５４５ｍ2／ｇ、ＳｉＯ２濃度：２０重量％
）１００ｇについて、ｐＨが２．８になるまで、強酸性陽イオン交換樹脂ＳＫ１ＢＨ(三
菱化学社製)０．４Ｌに空間速度３．１で通液を繰り返した。次に、このシリカゾルを強
塩基性イオン交換樹脂ＳＡＮＵＰＣ(三菱化学社製)０．４Ｌに空間速度３．１で通液させ、ｐＨを４．１とした後、ｐＨが８．５になるようにアルカリ性水溶液として５％水酸化ナトリウム水溶液を５ｇ添加した。
The obtained base material with hard coat film (9) was evaluated for total light transmittance and haze, presence or absence of interference fringes, adhesion, scratch resistance and alkali resistance, and the results are shown in Table 1.
[Example 10]
Preparation of dispersion of metal oxide particles (5) Silica sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Cataloid SI-550, average particle diameter measured by BET method: 5 nm, specific surface area: 545 m 2 / g, SiO 2 Concentration: 20% by weight
) About 100 g, the solution was repeatedly passed through 0.4 L of strongly acidic cation exchange resin SK1BH (manufactured by Mitsubishi Chemical Corporation) at a space velocity of 3.1 until the pH reached 2.8. Next, this silica sol is passed through 0.4 L of strongly basic ion exchange resin SANUPC (manufactured by Mitsubishi Chemical Corporation) at a space velocity of 3.1 to adjust the pH to 4.1, and then the pH becomes 8.5. 5 g of 5% sodium hydroxide aqueous solution was added as an alkaline aqueous solution.
ｐＨ調整したシリカゾルを１８０℃にて２時間加熱した。このシリカゾルをエバポレーターにてＳｉＯ２濃度２０重量％まで濃縮してシリカ粒子が鎖状に連結した金属酸化物粒子分散ゾルを調製した。 The pH-adjusted silica sol was heated at 180 ° C. for 2 hours. This silica sol was concentrated to an SiO 2 concentration of 20% by weight with an evaporator to prepare a metal oxide particle-dispersed sol in which silica particles were linked in a chain.
鎖状に連結した金属酸化物粒子の透過型電子顕微鏡写真（日立製作所製：Ｈ−８００）
の観察により、平均粒子径５ｎｍのシリカ粒子が平均１０個鎖状に連結していた。
ついで、この鎖状に連結した金属酸化物粒子分散ゾルを、限外濾過膜を用いて洗浄し、メタノールにて溶媒置換するとともに固形分濃度２０重量％になるまで濃縮した。このゾル１００ｇに正珪酸エチル６．９ｇ（多摩化学(株)製 エチルシリケート２８ SiO2成分２８．８％）を加え、５０℃で１５時間加熱撹拌して表面処理した金属酸化物粒子分散液を得た。
Transmission electron micrograph of metal oxide particles linked in a chain (Hitachi, Ltd .: H-800)
From the observation, silica particles having an average particle diameter of 5 nm were linked in an average of 10 chains.
Subsequently, the metal oxide particle-dispersed sol connected in the form of a chain was washed with an ultrafiltration membrane, replaced with a solvent with methanol, and concentrated to a solid content concentration of 20% by weight. To the sol 100 g, 6.9 g of ethyl orthosilicate (ethyl silicate 28 SiO 2 component 28.8%, manufactured by Tama Chemical Co., Ltd.) was added, and the surface-treated metal oxide particle dispersion was heated and stirred at 50 ° C. for 15 hours. Obtained.
ついで、ロータリーエバポレーターにてイソプロピルアルコールに溶媒置換して濃度３０重量％の金属酸化物粒子(5)分散液を得た。この金属酸化物粒子(5)の表面電荷量を測定したところ３５．０μｅｑ／ｇであった。
ハードコート膜形成用塗布液(10)の調製
金属酸化物粒子(5)分散液７０ｇと水酸基を有する親水性のマトリックス形成成分であ
る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（共栄社化学(株)製：NKオ
リゴEA-5521）４５ｇ、と疎水性のマトリックス形成成分であるペンタエリスリトールト
リアクリレートヘキサメチレンジイソシアネートウレタンポリマー（共栄社化学(株)製：UA-306H）１５ｇに光開始剤（チバスプシャリティ(株)製イルガキュア１８４）３ｇおよ
び溶媒イソプロパノ−ル７５ｇ、メチルイソブチルケトン５０ｇとを充分に混合してハードコート膜形成用塗布液(10)を調製した。
ハードコート膜付基材(10)の作製
実施例１において、ハードコート膜形成用塗料(10)を用いた以外は同様にしてハードコート膜付基材(10)を作製した。このときのハードコート膜の厚さは３μｍであった。
Subsequently, the solvent was replaced with isopropyl alcohol by a rotary evaporator to obtain a dispersion of metal oxide particles (5) having a concentration of 30% by weight. The surface charge amount of the metal oxide particles (5) was measured and found to be 35.0 μeq / g.
Preparation of coating liquid for hard coat film formation (10) 70 g of metal oxide particle (5) dispersion and 2 hydroxy-3 acryloyloxypropyl methacrylate (Kyoeisha Chemical Co., Ltd.) which is a hydrophilic matrix forming component having a hydroxyl group : 45 g of NK oligo EA-5521) and 15 g of pentaerythritol triacrylate hexamethylene diisocyanate urethane polymer (Kyoeisha Chemical Co., Ltd .: UA-306H) which is a hydrophobic matrix forming component ) Irgacure 184) 3 g, solvent isopropanol 75 g, and methyl isobutyl ketone 50 g were sufficiently mixed to prepare a hard coat film forming coating solution (10).
Preparation of substrate with hard coat film (10) A substrate with hard coat film (10) was prepared in the same manner as in Example 1 except that the paint (10) for forming a hard coat film was used. At this time, the thickness of the hard coat film was 3 μm.
得られたハードコート膜付基材(10)の全光線透過率およびヘーズ、干渉縞の有無、密着性、耐擦傷性および耐アルカリ性を評価し、結果を表１に示す。
[比較例1]
金属酸化物粒子(R1)分散液の調製
金属酸化物粒子として、シリカゾル（触媒化成工業（株）製：カタロイドＳＩ−４５Ｐ、ＳiＯ2濃度４０重量％、平均粒子径４５ｎｍ、分散媒：水）の分散液を、限外濾過膜を用いて洗浄し、ついでメタノールにて溶媒置換するとともに固形分濃度３０重量％になるまで濃縮し、濃度３０重量％の金属酸化物粒子(R1)分散液を得た。この金属酸化物粒子(R1)の表面電荷量を測定したところ６０．０μｅｑ／ｇであった。金属酸化物粒子(R1)の平均粒子径および屈折率を表１に示した。
ハードコート膜形成用塗布液(R1)の調製
実施例１において、金属酸化物粒子(R1)分散液１２０ｇを用いた以外は実施例1と同様
にしてハードコート膜形成用塗布液(R1)を調製した。
ハードコート膜付基材(R1)の作製
実施例１において、ハードコート膜形成用塗布液(R1)を用いた以外は同様にしてハードコート膜付基材(R1)を調製した。このときのハードコート膜の厚さは３μｍであった。
The obtained base material with a hard coat film (10) was evaluated for total light transmittance and haze, presence or absence of interference fringes, adhesion, scratch resistance and alkali resistance, and the results are shown in Table 1.
[Comparative Example 1]
Preparation of metal oxide particle (R1) dispersion As metal oxide particles, silica sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Cataloid SI-45P, SiO 2 concentration 40% by weight, average particle size 45 nm, dispersion medium: water) The dispersion is washed with an ultrafiltration membrane, and then the solvent is replaced with methanol and concentrated to a solid concentration of 30% by weight to obtain a metal oxide particle (R1) dispersion having a concentration of 30% by weight. It was. The surface charge amount of the metal oxide particles (R1) was measured and found to be 60.0 μeq / g. The average particle diameter and refractive index of the metal oxide particles (R1) are shown in Table 1.
In example 1 a hard coat film-forming coating liquid (R1), the metal oxide particles (R1) except for using the dispersion 120g in the same manner as in Example 1 for forming a hard coat film coating solution (R1) Prepared.
Preparation of base material with hard coat film (R1) A base material with hard coat film (R1) was prepared in the same manner as in Example 1 except that the coating liquid for forming a hard coat film (R1) was used. At this time, the thickness of the hard coat film was 3 μm.
得られたハードコート膜付基材(R1)の全光線透過率およびヘーズ、干渉縞の有無、密着性、耐擦傷性および耐アルカリ性を評価し、結果を表１に示す。
[比較例2]
金属酸化物粒子分散液(R2)の調製
シリカゾル（触媒化成工業（株）製：カタロイドＳＩ−４５Ｐ、ＳiＯ2濃度４０重量％、平均粒子径４５ｎｍ、分散媒：水）を限外濾過膜を用いて洗浄し、ついでメタノールにて溶媒置換するとともに固形分濃度３０重量％になるまで濃縮したもの１００ｇに有機ケイ素化合物としてパーフルオロオクチルエチルトリエトキシシラン（東レダウコーニング(株)製：AY43-158E、SiO2成分26.6％）を５．６ｇ加え、５０℃で１５時間加熱撹拌してフッ素系有機ケイ素化合物で表面処理した金属酸化物粒子分散ゾルを調製した。ついで、ロータリーエバポレーターにてイソプロピルアルコールに溶媒置換して濃度３０重量％の金属酸化物粒子(R2)分散液を得た。この金属酸化物粒子(R2)の表面電荷量を測定したところ７．０μｅｑ／ｇであった。金属酸化物粒子(R2)の平均粒子径および屈折率を表１に示した。
ハードコート膜形成用塗布液(R2)の調製
実施例１において、固形分濃度３０重量％の金属酸化物粒子(R2)分散液を用いた以外は同様にしてハードコート膜形成用塗布液(R2)を調製した。
ハードコート膜付基材(R2)の作製
実施例１において、ハードコート膜形成用塗布液(R2)を用いた以外は同様にしてハードコート膜付基材(R2)を調製した。このときのハードコート膜の厚さは３μｍであった。
得られたハードコート膜付基材(R2)の全光線透過率およびヘーズ、干渉縞の有無、密着性、耐擦傷性および耐アルカリ性を評価し、結果を表１に示す。
[比較例3]
金属酸化物粒子分散液(R3)の調製
五酸化アンチモン微粒子分散ゾル（触媒化成工業(株)製：ELCOM V−４５６０、平均粒
子径２０ｎｍ、濃度３０．５重量％、分散媒：イソプロパノ−ル、粒子屈折率１．６４）を用いた。このゾル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．
７６ｇ（信越シリコ−ン(株)製 ＫＢＭ−５０３ SiO2成分８１．９％）を混合し超純水を１０ｇ添加し５０℃で１５時間攪拌し表面処理した金属酸化物粒子(R3)分散液を得た（固形分２９．５％）。この金属酸化物粒子(R3)の表面電荷量を測定したところ９．８μｅｑ／ｇであった。金属酸化物粒子(R3)の平均粒子径および屈折率を表１に示した。
ハードコート膜形成用塗布液(R3)の調製
実施例1において、金属酸化物粒子(R3)分散を用いた以外は実施例1と同様にしてハードコート膜形成用塗布液(R3)を調製した。
ハードコート膜付基材(R3)の作製
実施例１において、ハードコート膜形成用塗布液(R3)を用いた以外は同様にしてハードコート膜付基材(R3)を調製した。このときのハードコート膜の厚さは３μｍであった。
The obtained base material with hard coat film (R1) was evaluated for total light transmittance and haze, presence or absence of interference fringes, adhesion, scratch resistance and alkali resistance, and the results are shown in Table 1.
[Comparative Example 2]
Preparation of Metal Oxide Particle Dispersion (R2) Silica sol (catalyst chemical industry Co., Ltd .: Cataloid SI-45P, SiO 2 concentration 40 wt%, average particle diameter 45 nm, dispersion medium: water) was used with an ultrafiltration membrane. After washing with solvent and then replacing with methanol and concentrating to a solid content concentration of 30% by weight, 100 g of perfluorooctylethyltriethoxysilane (manufactured by Toray Dow Corning Co., Ltd .: AY43-158E, 5.6 g of SiO 2 component 26.6%) was added, and the mixture was heated and stirred at 50 ° C. for 15 hours to prepare a metal oxide particle-dispersed sol surface-treated with a fluorine-based organosilicon compound. Subsequently, the solvent was replaced with isopropyl alcohol by a rotary evaporator to obtain a dispersion of metal oxide particles (R2) having a concentration of 30% by weight. The surface charge amount of the metal oxide particles (R2) was measured and found to be 7.0 μeq / g. The average particle diameter and refractive index of the metal oxide particles (R2) are shown in Table 1.
Preparation of Hard Coat Film Forming Coating Liquid (R2) A hard coat film forming coating liquid (R2) was prepared in the same manner as in Example 1 except that a metal oxide particle (R2) dispersion having a solid content of 30% by weight was used. ) Was prepared.
Preparation of substrate with hard coat film (R2) A substrate with hard coat film (R2) was prepared in the same manner as in Example 1, except that the coating liquid for forming a hard coat film (R2) was used. At this time, the thickness of the hard coat film was 3 μm.
The obtained base material with hard coat film (R2) was evaluated for total light transmittance and haze, presence or absence of interference fringes, adhesion, scratch resistance and alkali resistance, and the results are shown in Table 1.
[Comparative Example 3]
Preparation of metal oxide particle dispersion (R3) Antimony pentoxide fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: ELCOM V-4560, average particle diameter 20 nm, concentration 30.5% by weight, dispersion medium: isopropanol, A particle refractive index of 1.64) was used. 2. To 100 g of this sol, γ-methacrylooxypropyltrimethoxysilane;
76 g (KBM-503 manufactured by Shin-Etsu Silicon Co., Ltd., 81.9% of SiO 2 component) was added, 10 g of ultrapure water was added, and the mixture was stirred for 15 hours at 50 ° C. and surface-treated metal oxide particles (R3) dispersion (Solid content 29.5%) was obtained. The surface charge amount of the metal oxide particles (R3) was measured and found to be 9.8 μeq / g. The average particle diameter and refractive index of the metal oxide particles (R3) are shown in Table 1.
Preparation of hard coat film forming coating solution (R3) In Example 1, a hard coat film forming coating solution (R3) was prepared in the same manner as in Example 1 except that the metal oxide particle (R3) dispersion was used. .
Preparation of base material with hard coat film (R3) A base material with hard coat film (R3) was prepared in the same manner as in Example 1, except that the coating liquid for forming a hard coat film (R3) was used. At this time, the thickness of the hard coat film was 3 μm.
得られたハードコート膜付基材(R3)の全光線透過率およびヘーズ、干渉縞の有無、密着性、耐擦傷性および耐アルカリ性を評価し、結果を表１に示す。 The obtained base material with hard coat film (R3) was evaluated for total light transmittance and haze, presence or absence of interference fringes, adhesion, scratch resistance and alkali resistance, and the results are shown in Table 1.
Claims (11)
該ハードコート膜が有機樹脂マトリックス成分と、表面処理金属酸化物粒子とを含んでなり、前記有機樹脂マトリックス成分が疎水性有機樹脂マトリックス成分であり、前記表面処理金属酸化物粒子の表面電荷量（ＱP）が１５〜６０μｅｑ／ｇの範囲にあり、かつ
ハードコート膜表面に、金属酸化物粒子が露出していないことを特徴とするハードコート膜付基材。 Consisting of a base material and a hard coat film formed on one surface of the base material,
The hard coat film comprises an organic resin matrix component and surface-treated metal oxide particles, the organic resin matrix component is a hydrophobic organic resin matrix component, and the surface charge amount of the surface-treated metal oxide particles ( Q P ) is in the range of 15 to 60 μeq / g, and the metal oxide particles are not exposed on the surface of the hard coat film.
脂から選ばれる1種以上であり、前記親水性有機樹脂マトリックス成分が水酸基（ＯＨ基
）、アミノ基、カルボキシル基、スルホ基等の親水性官能基を有する(メタ)アクリル酸エステル樹脂から選ばれる1種以上であることを特徴とする請求項１〜３のいずれかに記載
のハードコート膜付基材。 The hydrophobic organic resin matrix component is one or more selected from polyfunctional (meth) acrylic acid ester resins having a hydrophobic functional group such as vinyl group, urethane group, epoxy group, (meth) acryloyl group, CF 2 group, etc. The hydrophilic organic resin matrix component is at least one selected from (meth) acrylic acid ester resins having a hydrophilic functional group such as a hydroxyl group (OH group), an amino group, a carboxyl group, and a sulfo group. The base material with a hard coat film according to any one of claims 1 to 3.
ハードコート膜形成用塗布液。 An organic resin matrix-forming component, surface-treated metal oxide particles, and a dispersion medium are included. The organic resin matrix-forming component is a hydrophobic organic resin matrix-forming component, and the surface charge amount of the metal oxide particles (Q P ) Is in the range of 15 to 60 μeq / g.
脂から選ばれる1種以上であり、前記親水性有機樹脂マトリックス成分が水酸基（ＯＨ基
）、アミノ基、カルボキシル基、スルホ基等の親水性官能基を有する(メタ)アクリル酸エステル樹脂から選ばれる１種以上であることを特徴とする請求項７または８に記載のハードコート膜形成用塗布液。 The hydrophobic organic resin matrix component is one or more selected from polyfunctional (meth) acrylic acid ester resins having a hydrophobic functional group such as vinyl group, urethane group, epoxy group, (meth) acryloyl group, CF 2 group, etc. And the hydrophilic organic resin matrix component is at least one selected from (meth) acrylic acid ester resins having a hydrophilic functional group such as a hydroxyl group (OH group), an amino group, a carboxyl group, and a sulfo group. The coating liquid for forming a hard coat film according to claim 7 or 8.
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| EP3504565A4 (en) * | 2016-09-21 | 2020-01-08 | Samsung Electronics Co., Ltd. | Optical member, polarization member, and display device employing polymer film |
| KR102429430B1 (en) * | 2016-09-21 | 2022-08-04 | 삼성전자주식회사 | Optical member, polarization member and display device employing polymer film |
| WO2022259847A1 (en) * | 2021-06-08 | 2022-12-15 | デクセリアルズ株式会社 | Optical laminate, polarizing plate, image display device, and method for manufacturing optical laminate |
| JP2022187987A (en) * | 2021-06-08 | 2022-12-20 | デクセリアルズ株式会社 | Optical laminate, polarizing plate, image display device, and method for manufacturing optical laminate |
| JP7377311B2 (en) | 2021-06-08 | 2023-11-09 | デクセリアルズ株式会社 | Optical laminate, polarizing plate, image display device, and method for producing optical laminate |
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