JPWO2014104312A1 - Water and / or organic solvent dispersion containing linked crystalline inorganic oxide fine particle group, method for producing the same, and coating solution for optical substrate containing linked crystalline inorganic oxide fine particle group - Google Patents
Water and / or organic solvent dispersion containing linked crystalline inorganic oxide fine particle group, method for producing the same, and coating solution for optical substrate containing linked crystalline inorganic oxide fine particle group Download PDFInfo
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- JPWO2014104312A1 JPWO2014104312A1 JP2014554601A JP2014554601A JPWO2014104312A1 JP WO2014104312 A1 JPWO2014104312 A1 JP WO2014104312A1 JP 2014554601 A JP2014554601 A JP 2014554601A JP 2014554601 A JP2014554601 A JP 2014554601A JP WO2014104312 A1 JPWO2014104312 A1 JP WO2014104312A1
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- Prior art keywords
- inorganic oxide
- oxide fine
- dispersion
- fine particles
- fine particle
- Prior art date
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- 239000010419 fine particle Substances 0.000 title claims abstract description 451
- 239000006185 dispersion Substances 0.000 title claims abstract description 318
- 229910052809 inorganic oxide Inorganic materials 0.000 title claims abstract description 286
- 238000000576 coating method Methods 0.000 title claims abstract description 136
- 239000011248 coating agent Substances 0.000 title claims abstract description 134
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000000758 substrate Substances 0.000 title claims abstract description 66
- 230000003287 optical effect Effects 0.000 title claims abstract description 46
- 239000003960 organic solvent Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 claims abstract description 71
- 239000002184 metal Substances 0.000 claims abstract description 69
- 239000002245 particle Substances 0.000 claims abstract description 61
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 61
- 239000010703 silicon Substances 0.000 claims abstract description 60
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 52
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002131 composite material Substances 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 14
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 239000010955 niobium Substances 0.000 claims abstract description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 101
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 95
- 239000007864 aqueous solution Substances 0.000 claims description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 53
- 239000000126 substance Substances 0.000 claims description 50
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 47
- 235000012239 silicon dioxide Nutrition 0.000 claims description 43
- 229920003023 plastic Polymers 0.000 claims description 29
- 239000004033 plastic Substances 0.000 claims description 29
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 17
- 239000002612 dispersion medium Substances 0.000 claims description 15
- 229920005992 thermoplastic resin Polymers 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000011859 microparticle Substances 0.000 claims 1
- 238000005299 abrasion Methods 0.000 abstract description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 360
- 239000010410 layer Substances 0.000 description 111
- 239000000243 solution Substances 0.000 description 71
- 238000002360 preparation method Methods 0.000 description 45
- 239000008199 coating composition Substances 0.000 description 42
- 239000007787 solid Substances 0.000 description 39
- -1 zirconium silicate compound Chemical class 0.000 description 28
- 239000007771 core particle Substances 0.000 description 26
- 229910010413 TiO 2 Inorganic materials 0.000 description 24
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 23
- 229910006404 SnO 2 Inorganic materials 0.000 description 23
- 238000012360 testing method Methods 0.000 description 22
- 239000011259 mixed solution Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 21
- 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 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 19
- 239000000377 silicon dioxide Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 239000003729 cation exchange resin Substances 0.000 description 18
- 239000002585 base Substances 0.000 description 17
- 239000004094 surface-active agent Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 229920001296 polysiloxane Polymers 0.000 description 15
- 150000002978 peroxides Chemical class 0.000 description 14
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- 229910000077 silane Inorganic materials 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- 239000007983 Tris buffer Substances 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 11
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000945 filler Substances 0.000 description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 11
- 229910001928 zirconium oxide Inorganic materials 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000000691 measurement method Methods 0.000 description 8
- 238000000108 ultra-filtration Methods 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 229920005862 polyol Polymers 0.000 description 7
- 235000019353 potassium silicate Nutrition 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 229920006311 Urethane elastomer Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
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- 229920001228 polyisocyanate Polymers 0.000 description 3
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- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
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- 238000010998 test method Methods 0.000 description 3
- 238000000733 zeta-potential measurement Methods 0.000 description 3
- 150000003755 zirconium compounds Chemical class 0.000 description 3
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 2
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
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- 101000983970 Conus catus Alpha-conotoxin CIB Proteins 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 2
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
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- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
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- GGROONUBGIWGGS-UHFFFAOYSA-N oxygen(2-);zirconium(4+);hydrate Chemical compound O.[O-2].[O-2].[Zr+4] GGROONUBGIWGGS-UHFFFAOYSA-N 0.000 description 2
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 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 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 150000003754 zirconium Chemical class 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- MZWXWSVCNSPBLH-UHFFFAOYSA-N 3-(3-aminopropyl-methoxy-methylsilyl)oxypropan-1-amine Chemical compound NCCC[Si](C)(OC)OCCCN MZWXWSVCNSPBLH-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- ZBSKZKPSSKTLNE-UHFFFAOYSA-N 4-methylpent-3-enoxysilane Chemical compound CC(=CCCO[SiH3])C ZBSKZKPSSKTLNE-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- WXEMMCVRSRPJNQ-UHFFFAOYSA-N O.O.O.O.O.O.O.O.O(Cl)Cl.[Zr].[Zr] Chemical compound O.O.O.O.O.O.O.O.O(Cl)Cl.[Zr].[Zr] WXEMMCVRSRPJNQ-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000003974 aralkylamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000002182 crystalline inorganic material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- DVYUOQXRGHUWKE-UHFFFAOYSA-N dimethyl(2-phenylethoxy)silane Chemical compound C[SiH](C)OCCC1=CC=CC=C1 DVYUOQXRGHUWKE-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002578 polythiourethane polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HJELPJZFDFLHEY-UHFFFAOYSA-N silicide(1-) Chemical compound [Si-] HJELPJZFDFLHEY-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical class C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-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
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DAVVOFDYOGMLNQ-UHFFFAOYSA-N trimethoxy-[1-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)C(C)OCC1CO1 DAVVOFDYOGMLNQ-UHFFFAOYSA-N 0.000 description 1
- ZNXDCSVNCSSUNB-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)CCOCC1CO1 ZNXDCSVNCSSUNB-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/001—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Paints Or Removers (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Silicon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
［課題］機械的強度（耐擦傷性、耐摩耗性）、外観適合性（曇り、干渉縞）、密着性、耐候性、耐光性、耐クラック性、光学特性（高屈折率）に優れた塗膜（ハードコート層膜およびプライマー層膜などの硬化膜）を形成するのに適した光学基材用塗布液の製造に有用な無機酸化物微粒子の分散液を提供すること。［解決手段］（１）チタニウム、ジルコニウム、ニオブ、セリウムおよび亜鉛からなる群から選ばれる少なくとも１種の金属元素Ｍ2とケイ素とを含む結晶性無機酸化物微粒子、（２）前記微粒子（１）を被覆する、ジルコニウム、アルミニウムおよびアンチモンからなる群から選ばれる少なくとも１種の金属元素Ｍ1とケイ素とを含む複合酸化物からなる被覆物質、および（３）該被覆物質と同一成分である複合酸化物からなり、隣接する、前記被覆物質（２）で被覆された前記微粒子（１）同士を連結する結合物質から構成された連結型結晶性無機酸化物微粒子群を含む水および／または有機溶媒の分散液。[Problem] Coating with excellent mechanical strength (scratch resistance, abrasion resistance), appearance compatibility (cloudiness, interference fringes), adhesion, weather resistance, light resistance, crack resistance, and optical properties (high refractive index) Disclosed is a dispersion of fine inorganic oxide particles useful for the production of a coating solution for an optical substrate suitable for forming a film (a cured film such as a hard coat layer film and a primer layer film). [Solutions] (1) Crystalline inorganic oxide fine particles containing at least one metal element M2 selected from the group consisting of titanium, zirconium, niobium, cerium and zinc, and silicon, (2) The fine particles (1) A coating material comprising a composite oxide containing at least one metal element M1 selected from the group consisting of zirconium, aluminum and antimony and silicon; and (3) a composite oxide which is the same component as the coating material. Dispersion of water and / or organic solvent containing connected crystalline inorganic oxide fine particle groups composed of a binding material that connects adjacent fine particles (1) coated with the coating material (2) .
Description
本発明は、連結型結晶性無機酸化物微粒子群を含有する水および／または有機溶媒分散液、その製造方法、ならびに前記連結型結晶性無機酸化物微粒子群を含む光学基材用塗布液に関する。 The present invention relates to a water and / or organic solvent dispersion containing linked crystalline inorganic oxide fine particles, a method for producing the same, and a coating liquid for an optical substrate containing the linked crystalline inorganic oxide fine particles.
ケイ素および金属元素を含む酸化物微粒子からなる充填材としては、一般に、(1)二酸化珪素と少なくとも他の金属酸化物（酸化ジルコニウム等）とを凝集させ、その酸化物の結晶化温度未満の温度で熱処理することにより製造した、二酸化珪素と他の金属酸化物とが独立した非晶質層を形成してなる充填材（特許文献１、特許文献２）や、(2) 約１００ｎｍ未満の平均粒子径を有する非重金属酸化物粒子（シリカ粒子等）と、重金属酸化物または約１００ｎｍ未満の平均粒子径を有する重金属酸化物粒子（酸化ジルコニウム粒子等）とを含む実質的にアモルファス状のクラスタを含む充填材（特許文献３）などがある。 As fillers composed of oxide fine particles containing silicon and metal elements, in general, (1) a temperature lower than the crystallization temperature of the oxide by agglomerating silicon dioxide and at least another metal oxide (zirconium oxide, etc.) A filler (Patent Document 1 and Patent Document 2) produced by heat treatment in which silicon dioxide and other metal oxides form an independent amorphous layer; and (2) an average of less than about 100 nm A substantially amorphous cluster comprising non-heavy metal oxide particles (such as silica particles) having a particle size and heavy metal oxides or heavy metal oxide particles (such as zirconium oxide particles) having an average particle size of less than about 100 nm. There is a filler (Patent Document 3) and the like.
しかし、これらの充填材は、シリカゾルとジルコニウム塩水溶液とを混合して、これをスプレイドライヤーなどを用いて乾燥した後、焼成することにより得られるため、屈折率などの性状が異なるシリカ微粒子と酸化ジルコニウム成分（微粒子）とが混在するものであった。結果として、得られる充填材には、屈折率などにおいてムラが生じる場合があった。さらに、これらの充填材では、粒子の細孔容積や粒子の強度を調整することができず、このために透明性を向上させることが難しくなり、更には重合性樹脂との密着性が求められる用途においてはその密着性が不十分であるため、強度や硬度が低下による摩耗に対する耐性などが不十分となることがあった。 However, these fillers are obtained by mixing silica sol and zirconium salt aqueous solution, drying it using a spray drier, etc., and firing it, so that it is oxidized with silica fine particles having different properties such as refractive index. A zirconium component (fine particles) was mixed. As a result, the resulting filler may have unevenness in refractive index and the like. Furthermore, with these fillers, the pore volume of the particles and the strength of the particles cannot be adjusted, which makes it difficult to improve transparency, and further requires adhesion to the polymerizable resin. In applications, the adhesiveness is insufficient, and thus the resistance to wear due to the decrease in strength and hardness may be insufficient.
そこで、本出願人は、シリカゾル、酸性珪酸液およびジルコニウム塩水溶液を混合して、この混合液をスプレイドライヤーなど用いて乾燥した後、焼成する充填材の製造方法（特許文献４）を開発している。これにより得られた充填材は、酸性珪酸液に由来するシリカ成分と酸性ジルコニウム成分とがよく混じり合った酸化物であるため、その性状は、シリカゾルに由来するシリカ微粒子に近づいた性状（例えば、屈折率など）のものになっている。しかし、シリカ微粒子が混在することには変わりないので、上記のような問題点が完全に解消されるものではなかった。 Therefore, the present applicant has developed a method for producing a filler (Patent Document 4) in which silica sol, acidic silicic acid solution and zirconium salt aqueous solution are mixed, the mixture is dried using a spray drier, and then fired. Yes. Since the filler thus obtained is an oxide in which the silica component derived from the acidic silicic acid solution and the acidic zirconium component are well mixed, the property is close to the silica fine particles derived from the silica sol (for example, Refractive index). However, since the silica fine particles are mixed, the above-mentioned problems have not been completely solved.
さらに、本発明者らは、従来の充填材に付随する上記のような問題を解決するため、ジルコニウムシリケート化合物からなる結晶性の無機酸化物微粒子を含む充填材を開発している（特許文献５）。また、本発明者らは、シリカ系微粒子の表面をジルコニウム、ケイ素および酸素からなる複合酸化物で被覆してなる鎖状非晶質シリカ系微粒子群およびその製造方法を開発している（特許文献６）。 Furthermore, the present inventors have developed a filler containing crystalline inorganic oxide fine particles made of a zirconium silicate compound in order to solve the above-mentioned problems associated with conventional fillers (Patent Document 5). ). In addition, the present inventors have developed a chain amorphous silica-based fine particle group in which the surface of silica-based fine particles is coated with a complex oxide composed of zirconium, silicon and oxygen, and a method for producing the same (Patent Document). 6).
特許文献５に記載された充填材は、強度や硬度および摩耗に対する耐久性等において優れた特性を有しているが、その使用用途によっては、有機珪素化合物、有機チタニウム化合物、有機ジルコニウム化合物等の有機金属化合物によって前記無機酸化物微粒子の表面を処理（または改質）することが必要となる。しかし、前記無機酸化物微粒子は、結晶性の表面性状を備えているため、その表面を前記有機金属化合物でむらなく処理することは必ずしも容易ではなかった。 The filler described in Patent Document 5 has excellent properties such as strength, hardness, and durability against wear, but depending on the intended use, an organic silicon compound, an organic titanium compound, an organic zirconium compound, etc. It is necessary to treat (or modify) the surface of the inorganic oxide fine particles with an organometallic compound. However, since the inorganic oxide fine particles have a crystalline surface property, it has not always been easy to uniformly treat the surface with the organometallic compound.
無機酸化物微粒子を塗膜などに配合する際には、得られる塗膜の強度を向上させることが求められており、さらに、特に眼鏡等の光学レンズのハードコート膜やプライマー膜などの用途においては様々な特性の向上が求められている。 When blending inorganic oxide fine particles in coatings, etc., it is required to improve the strength of the resulting coatings, and in particular, in applications such as hard coat films and primer films for optical lenses such as eyeglasses. Are required to improve various characteristics.
本発明では、このような背景に鑑みて、機械的強度（耐擦傷性、耐摩耗性）、外観適合性（曇り、干渉縞）、密着性、耐候性、耐光性、耐クラック性、光学特性（高屈折率）に優れた塗膜（ハードコート層膜およびプライマー層膜などの硬化膜）を形成するのに適した光学基材用塗布液の製造に有用な無機酸化物微粒子およびその分散液（水および／または有機溶剤分散液）を提供することを目的としている。 In the present invention, in view of such a background, mechanical strength (scratch resistance, abrasion resistance), appearance compatibility (cloudiness, interference fringes), adhesion, weather resistance, light resistance, crack resistance, optical characteristics. Inorganic oxide fine particles useful for the production of coating solutions for optical substrates suitable for forming coated films (hard coating layer films and cured films such as primer layer films) excellent in (high refractive index) and dispersions thereof The object is to provide (water and / or organic solvent dispersion).
さらに本発明は、これらの特性において優れた塗膜（ハードコート層膜およびプライマー層膜などの硬化膜）を形成するのに適した光学基材用塗布液、ならびにこれらの特性において優れた塗布膜（ハードコート層膜およびプライマー層膜などの硬化膜）および塗膜付基材（硬化膜付基材）を提供することを目的としている。 Furthermore, the present invention provides a coating solution for an optical substrate suitable for forming a coating film (hard film such as a hard coat layer film and a primer layer film) excellent in these characteristics, and a coating film excellent in these characteristics. It aims at providing (hardened film, such as a hard-coat layer film and a primer layer film), and a base material with a coating film (base material with a cured film).
本発明者らは、鋭意研究した結果、無機酸化物微粒子として、特定の連結型結晶性無機酸化物微粒子群を用いることにより上記課題を解決できることを見い出し、本発明を完成させた。 As a result of intensive studies, the present inventors have found that the above problems can be solved by using a specific group of linked crystalline inorganic oxide fine particles as inorganic oxide fine particles, and have completed the present invention.
本発明は、以下を要旨とするものである。 The gist of the present invention is as follows.
［１］
連結型結晶性無機酸化物微粒子群および分散媒を含む分散液であって、
該連結型結晶性無機酸化物微粒子群が
（１）チタニウム、ジルコニウム、ニオブ、セリウムおよび亜鉛からなる群から選ばれる少なくとも１種の金属元素Ｍ2とケイ素とを含む結晶性無機酸化物微粒子、
（２）前記微粒子（１）を被覆する、ジルコニウム、アルミニウムおよびアンチモンからなる群から選ばれる少なくとも１種の金属元素Ｍ1とケイ素とを含む複合酸化物からなる被覆物質、および
（３）該被覆物質と同一成分である複合酸化物からなり、隣接する、前記被覆物質（２）で被覆された前記微粒子（１）同士を連結する結合物質
から構成されており、
該分散媒が水および／または有機溶媒である
ことを特徴とする連結型結晶性無機酸化物微粒子群を含む分散液。[1]
A dispersion containing a linked crystalline inorganic oxide fine particle group and a dispersion medium,
The connected crystalline inorganic oxide fine particle group (1) a crystalline inorganic oxide fine particle containing at least one metal element M 2 and silicon selected from the group consisting of titanium, zirconium, niobium, cerium and zinc;
(2) A coating material comprising a composite oxide containing at least one metal element M 1 selected from the group consisting of zirconium, aluminum and antimony and covering silicon, and (3) the coating. It is composed of a complex oxide that is the same component as the substance, and is composed of a binding substance that connects adjacent fine particles (1) coated with the coating substance (2),
A dispersion comprising linked crystalline inorganic oxide fine particle groups, wherein the dispersion medium is water and / or an organic solvent.
［２］
前記無機酸化物微粒子（１）が、５〜１００ｎｍの平均粒子径を有することを特徴とする上記［１］に記載の連結型結晶性無機酸化物微粒子群を含む分散液。[2]
The dispersion containing the group of connected crystalline inorganic oxide fine particles according to [1], wherein the inorganic oxide fine particles (1) have an average particle diameter of 5 to 100 nm.
［３］
前記無機酸化物微粒子（１）を構成する金属元素Ｍ2として、さらにスズ、タングステン、アンチモンおよびインジウムからなる群から選ばれる少なくとも１種を含むことを特徴とする上記［１］または［２］に記載の連結型結晶性無機酸化物微粒子群を含む分散液。[3]
[1] or [2], wherein the metal element M 2 constituting the inorganic oxide fine particles (1) further includes at least one selected from the group consisting of tin, tungsten, antimony and indium. A dispersion containing the linked crystalline inorganic oxide fine particle group described.
［４］
前記無機酸化物微粒子（１）が、前記金属元素とケイ素とを含む複合酸化物微粒子（その表面がケイ素酸化物で被覆されていないもの）であることを特徴とする上記［１］〜［３］のいずれかに記載の連結型結晶性無機酸化物微粒子群を含む分散液。[4]
[1] to [3], wherein the inorganic oxide fine particles (1) are composite oxide fine particles containing the metal element and silicon (the surface of which is not coated with silicon oxide). ] A dispersion liquid comprising the linked crystalline inorganic oxide fine particle group according to any one of the above.
［５］
前記無機酸化物微粒子（１）が、前記金属元素の酸化物微粒子もしくは複合酸化物微粒子の表面をケイ素酸化物で被覆したもの、または前記金属元素とケイ素とを含む複合酸化物微粒子の表面をケイ素酸化物で被覆したものであることを特徴とする上記［１］〜［３］のいずれかに記載の連結型結晶性無機酸化物微粒子群を含む分散液。[5]
The inorganic oxide fine particles (1) are obtained by coating the surface of the oxide fine particles or composite oxide fine particles of the metal element with silicon oxide, or the surface of the composite oxide fine particles containing the metal element and silicon. A dispersion liquid comprising the linked crystalline inorganic oxide fine particle group according to any one of [1] to [3] above, which is coated with an oxide.
［６］
前記被覆物質（２）および前記結合物質（３）を構成する複合酸化物に含まれる前記金属元素成分をＭ1Ｏｘで表し、さらにケイ素成分をＳｉＯ2で表したとき、モル比（Ｍ1Ｏx／ＳｉＯ2）が５／９５〜９８／２の範囲にあることを特徴とする上記［１］〜［５］のいずれかに記載の連結型結晶性無機酸化物微粒子群を含む分散液。[6]
When the metal element component contained in the composite oxide constituting the coating material (2) and the binding material (3) is represented by M 1 Ox and the silicon component is represented by SiO 2 , the molar ratio (M 1 O x / SiO 2 ) is in the range of 5/95 to 98/2. The dispersion comprising the linked crystalline inorganic oxide fine particle group according to any one of [1] to [5] above.
［７］
前記結晶性無機酸化物微粒子（１）に含まれる金属元素Ｍ2およびケイ素の重量を、それぞれ、Ｍ2Ｏxの重量およびＳｉＯ2-(2)の重量に換算し、前記被覆物質（２）および前記結合物質（３）に含まれる金属元素Ｍ1およびケイ素の重量を、それぞれ、Ｍ1Ｏxの重量およびＳｉＯ2-(1)の重量に換算すると、重量比｛（Ｍ1Ｏx＋ＳｉＯ2-(1)）／（Ｍ2Ｏx＋ＳｉＯ2-(2)）｝が７／１００〜１５０／１００の範囲にあることを特徴とする上記［１］〜［６］のいずれかに記載の連結型結晶性無機酸化物微粒子群を含む分散液。[7]
The weight of the metal element M 2 and silicon contained in the crystalline inorganic oxide fine particles (1) is converted into the weight of M 2 O x and the weight of SiO 2- (2), respectively, and the coating substance (2) When the weights of the metal element M 1 and silicon contained in the binding substance (3) are converted into the weight of M 1 O x and the weight of SiO 2- (1), respectively, the weight ratio {(M 1 O x + SiO 2- (1)) / (M 2 O x + SiO 2- (2))} is in the range of 7/100 to 150/100, according to any one of [1] to [6] above A dispersion containing the above-mentioned linked crystalline inorganic oxide fine particle group.
［８］
前記連結型結晶性無機酸化物微粒子群が、走査型電子顕微鏡（ＳＥＭ）で観測した際に、帯状および／またはネットワーク状の形態として観測されることを特徴とする上記［１］〜［７］のいずれかに記載の連結型結晶性無機酸化物微粒子群を含む分散液。[8]
[1] to [7], wherein the connected crystalline inorganic oxide fine particle group is observed as a band-like and / or network-like form when observed with a scanning electron microscope (SEM). A dispersion containing the linked crystalline inorganic oxide fine particle group according to any one of the above.
［９］
前記分散媒が水であることを特徴とする上記［１］〜［８］のいずれかに記載の連結型結晶性無機酸化物微粒子群を含む分散液。[9]
The dispersion liquid comprising the linked crystalline inorganic oxide fine particle group according to any one of [1] to [8], wherein the dispersion medium is water.
［１０］
前記分散媒が有機溶媒または有機溶媒および水であることを特徴とする上記［１］〜［８］のいずれかに記載の連結型結晶性無機酸化物微粒子群を含む分散液。[10]
The dispersion liquid comprising the linked crystalline inorganic oxide fine particle group according to any one of [1] to [8], wherein the dispersion medium is an organic solvent or an organic solvent and water.
［１１］
前記有機溶媒がアルコール、エーテルおよびケトンからなる群から選ばれる少なくとも１種の有機化合物であることを特徴とする上記［１０］に記載の連結型結晶性無機酸化物微粒子群を含む分散液。[11]
The dispersion containing the linked crystalline inorganic oxide fine particle group according to [10], wherein the organic solvent is at least one organic compound selected from the group consisting of alcohol, ether and ketone.
［１２］
結晶性無機酸化物微粒子と、前記微粒子を被覆する被覆物質と、隣接する、前記被覆物質で被覆された前記微粒子同士とを連結する結合物質から構成された結晶性無機酸化物微粒子群を含む水分散液の製造方法であって、
（１）チタニウム、ジルコニウム、ニオブ、セリウムおよび亜鉛からなる群から選ばれる少なくとも１種の金属元素Ｍ2とケイ素とを含む結晶性無機酸化物微粒子（１）が１次元的または２次元的に連結した粒子を含有する水分散液を準備する工程、
（２）前記工程（１）で準備された水分散液に、ジルコニウム、アルミニウムおよびアンチモンからなる群から選ばれる少なくとも１種の金属元素Ｍ1の化合物を含むアルカリ性水溶液および珪酸を含む酸性水溶液を添加する工程、および
（３）前記工程（２）で得られた水分散液を水熱処理する工程
を含むことを特徴とする連結型結晶性無機酸化物微粒子群を含む水分散液の製造方法。[12]
Water containing a crystalline inorganic oxide fine particle group, a coating material that coats the fine particle, and a crystalline inorganic oxide fine particle group composed of a binding material that connects adjacent fine particles coated with the coating material A method for producing a dispersion, comprising:
(1) Crystalline inorganic oxide fine particles (1) containing at least one metal element M 2 selected from the group consisting of titanium, zirconium, niobium, cerium and zinc and silicon are connected one-dimensionally or two-dimensionally. Preparing an aqueous dispersion containing the prepared particles,
(2) To the aqueous dispersion prepared in the step (1), an aqueous alkaline solution containing a compound of at least one metal element M 1 selected from the group consisting of zirconium, aluminum and antimony and an acidic aqueous solution containing silicic acid are added. And (3) a method for producing an aqueous dispersion containing linked crystalline inorganic oxide fine particle groups, comprising the step of (3) hydrothermally treating the aqueous dispersion obtained in the step (2).
［１３］
前記工程（１）において、前記結晶性無機酸化物微粒子（１）が連結せずに分散した水分散液を準備し、前記水分散液のｐＨを２〜６に、および／または前記結晶性無機酸化物微粒子（１）と水との界面におけるゼータ電位（ただし、任意に水の量を調整し、水分散液中の前記結晶性無機酸化物微粒子（１）の含有量が０．１５重量％の状態で測定した場合のゼータ電位である。）を−３０〜−７０ｍＶに調整し、前記水分散液を２０〜４０℃の温度条件下に１〜５時間放置して、前記水分散液中に含まれる前記結晶性無機酸化物微粒子（１）を１次元的または２次元的に連結させ熟成させることを特徴とする上記［１２］に記載の連結型結晶性無機酸化物微粒子群を含む水分散液の製造方法。[13]
In the step (1), an aqueous dispersion in which the crystalline inorganic oxide fine particles (1) are dispersed without being connected is prepared, the pH of the aqueous dispersion is adjusted to 2 to 6, and / or the crystalline inorganic Zeta potential at the interface between the oxide fine particles (1) and water (however, the amount of water is arbitrarily adjusted so that the content of the crystalline inorganic oxide fine particles (1) in the aqueous dispersion is 0.15% by weight) Is adjusted to −30 to −70 mV, and the aqueous dispersion is allowed to stand at a temperature of 20 to 40 ° C. for 1 to 5 hours. The crystalline inorganic oxide fine particles (1) contained in the water are one-dimensionally or two-dimensionally coupled and aged, and water containing the linked crystalline inorganic oxide fine particle group according to [12] above A method for producing a dispersion.
［１４］
前記アルカリ性水溶液が、酸化物換算基準で０．５〜２０重量％の金属化合物の水溶液であることを特徴とする上記［１２］または［１３］に記載の連結型結晶性無機酸化物微粒子群を含む水分散液の製造方法。[14]
The group of connected crystalline inorganic oxide fine particles according to [12] or [13], wherein the alkaline aqueous solution is an aqueous solution of a metal compound of 0.5 to 20% by weight on an oxide conversion basis. A method for producing an aqueous dispersion containing the same.
［１５］
上記［９］に記載された分散液を、溶媒置換装置に供して該分散液中に含まれる水の一部または全てを有機溶媒で置換することを特徴とする連結型結晶性無機酸化物微粒子群を含む有機溶媒分散液の製造方法。[15]
Connected crystalline inorganic oxide fine particles, characterized in that the dispersion described in [9] above is subjected to a solvent replacement device to replace part or all of the water contained in the dispersion with an organic solvent. The manufacturing method of the organic-solvent dispersion liquid containing a group.
［１６］
上記［１０］に記載の連結型結晶性無機酸化物微粒子群を含む分散液からなる光学基材用塗布液。[16]
A coating solution for an optical substrate, comprising a dispersion containing the linked crystalline inorganic oxide fine particle group described in [10] above.
［１７］
さらに有機ケイ素化合物からなるバインダー成分を含有し、ハードコート層膜形成用塗布液であることを特徴とする上記［１６］に記載の光学基材用塗布液。[17]
The coating liquid for an optical substrate according to the above [16], further comprising a binder component composed of an organosilicon compound and being a coating liquid for forming a hard coat layer film.
［１８］
さらに熱硬化性樹脂または熱可塑性樹脂からなるバインダー成分を含有し、プライマー層膜形成用塗布液であることを特徴とする上記［１６］に記載の光学基材用塗布液。[18]
Furthermore, the coating liquid for optical substrates according to [16] above, which contains a binder component composed of a thermosetting resin or a thermoplastic resin and is a coating liquid for forming a primer layer film.
［１９］
前記光学基材が、プラスチックレンズであることを特徴とする上記［１６］〜［１８］のいずれかに記載の光学基材用塗布液。[19]
The optical substrate coating liquid according to any one of [16] to [18], wherein the optical substrate is a plastic lens.
本発明に係る連結型結晶性無機酸化物微粒子群またはその分散液（水および／または有機溶剤分散液）を用いると、機械的強度（耐擦傷性、耐摩耗性）、外観適合性（曇り、干渉縞）、密着性、耐候性、耐光性、耐クラック性、光学特性（高屈折率）などにおいて優れた塗膜（ハードコート層膜およびプライマー層膜などの硬化膜）を形成するのに適した光学基材用塗布液の製造することができる。 When the group of connected crystalline inorganic oxide fine particles according to the present invention or a dispersion thereof (water and / or organic solvent dispersion) is used, mechanical strength (scratch resistance, abrasion resistance), appearance suitability (cloudiness, Interference fringes), adhesiveness, weather resistance, light resistance, crack resistance, suitable for forming coating films (hard film such as hard coat layer and primer layer) excellent in optical properties (high refractive index) In addition, a coating liquid for an optical substrate can be produced.
また、本発明に係る光学基材用塗布液（ハードコート層膜形成用塗布液およびプライマー層膜形成用塗布液）を用いると、機械的強度（耐擦傷性、耐摩耗性）、外観適合性（曇り、干渉縞）、密着性、耐候性、耐光性、耐クラック性、光学特性（高屈折率）などにおいて優れた塗膜（ハードコート層膜およびプライマー層膜などの硬化膜）を形成することができる。 In addition, when the coating liquid for optical substrates (the coating liquid for forming a hard coat layer and the coating liquid for forming a primer layer film) according to the present invention is used, mechanical strength (scratch resistance, abrasion resistance) and appearance suitability (Coating, interference fringes), adhesion, weather resistance, light resistance, crack resistance, optical properties (high refractive index), etc. excellent coating film (hard coating layer film and cured film such as primer layer film) be able to.
さらに、本発明に係る塗膜（ハードコート層膜およびプライマー層膜などの硬化膜）および塗膜付基材（硬化膜付基材）は、これらの特性において優れている。 Furthermore, the coating film (cured film such as hard coat layer film and primer layer film) and the substrate with coating film (substrate with cured film) according to the present invention are excellent in these properties.
以下、本発明に係る連結型結晶性無機酸化物微粒子群、該微粒子群を含む分散液（水および／または有機溶媒分散液）、その製造方法、および前記連結型結晶性無機酸化物微粒子群を含む光学基材用塗布液について具体的に説明する。 Hereinafter, the linked crystalline inorganic oxide fine particle group according to the present invention, a dispersion containing the fine particle group (water and / or organic solvent dispersion), a production method thereof, and the linked crystalline inorganic oxide fine particle group The coating liquid for optical base materials to be included will be specifically described.
＜連結型結晶性無機酸化物微粒子群、および該微粒子群を含む分散液（水および／または有機溶媒分散液）＞
［連結型結晶性無機酸化物微粒子群］
本発明に係る連結型結晶性無機酸化物微粒子群の水および／または有機溶媒分散液は、
（１）チタニウム、ジルコニウム、ニオブ、セリウムおよび亜鉛からなる群から選ばれる少なくとも１種の金属元素Ｍ2とケイ素とを含む結晶性無機酸化物微粒子、
（２）前記微粒子（１）を被覆する、ジルコニウム、アルミニウムおよびアンチモンからなる群から選ばれる少なくとも１種の金属元素Ｍ1とケイ素とを含む複合酸化物からなる被覆物質、および
（３）該被覆物質と同一成分である複合酸化物からなり、隣接する、前記被覆物質（２）で被覆された前記微粒子（１）同士を連結する結合物質
から構成された連結型結晶性無機酸化物微粒子群を含んでいる。<Linked crystalline inorganic oxide fine particle group and dispersion containing the fine particle group (water and / or organic solvent dispersion)>
[Linked crystalline inorganic oxide fine particle group]
The water and / or organic solvent dispersion of the linked crystalline inorganic oxide fine particle group according to the present invention is:
(1) Crystalline inorganic oxide fine particles containing at least one metal element M 2 selected from the group consisting of titanium, zirconium, niobium, cerium and zinc, and silicon,
(2) A coating material comprising a composite oxide containing at least one metal element M 1 selected from the group consisting of zirconium, aluminum and antimony and covering silicon, and (3) the coating. A connected crystalline inorganic oxide fine particle group composed of a composite material composed of a composite oxide that is the same component as the material and composed of a binding material that connects adjacent fine particles (1) coated with the coating material (2). Contains.
結晶性無機酸化物微粒子（１）：
前記結晶性無機酸化物微粒子（１）（本明細書中では「無機酸化物微粒子（１）」、「微粒子（１）」などともいう。）は、金属元素Ｍ2として、さらにスズ、タングステン、アンチモンおよびインジウムからなる群から選ばれる少なくとも１種を含んでいてもよい。また、前記微粒子（１）には、その製造方法にもよるが、製造過程のアルカリ金属元素（ナトリウム、カリウム等）が少量残存していてもよい。 Crystalline inorganic oxide fine particles (1):
The crystalline inorganic oxide fine particles (1) (referred to herein as "inorganic oxide fine particles (1)", also referred to as "fine particles (1)".), As the metal element M 2, further tin, tungsten, It may contain at least one selected from the group consisting of antimony and indium. The fine particles (1) may contain a small amount of alkali metal elements (sodium, potassium, etc.) in the production process, depending on the production method.
前記微粒子（１）としては、前記金属元素とケイ素とを含む複合酸化物微粒子、前記金属元素の酸化物微粒子もしくは複合酸化物微粒子の表面をケイ素酸化物で被覆したもの、および前記金属元素とケイ素とを含む複合酸化物微粒子の表面をケイ素酸化物で被覆したものが挙げられる。これらの例としては、チタン、スズおよびケイ素の複合酸化物の微粒子、ジルコニウム酸化物の微粒子の表面をケイ素酸化物で被覆したものなどが挙げられる。 The fine particles (1) include composite oxide fine particles containing the metal element and silicon, oxide fine particles of the metal element or a surface of the composite oxide fine particles coated with silicon oxide, and the metal element and silicon. In which the surface of the composite oxide fine particles containing is coated with silicon oxide. Examples of these include fine particles of complex oxides of titanium, tin and silicon, and fine particles of zirconium oxide coated with silicon oxide.
前記複合酸化物微粒子の表面をケイ素酸化物で被覆する場合は、ケイ素酸化物の量は、前記複合酸化物微粒子の重量（１００重量％）に対して、０．５〜３０重量％の範囲であることが好ましい。 When the surface of the composite oxide fine particles is coated with silicon oxide, the amount of silicon oxide is in the range of 0.5 to 30% by weight with respect to the weight (100% by weight) of the composite oxide fine particles. Preferably there is.
前記微粒子（１）は、結晶性の微粒子である。前記微粒子（１）が結晶性であるとは、Ｘ線回折パターンより求めた前記微粒子（１）の結晶子径が３ｎｍを超えるものであることを意味する。結晶構造としては、金属元素の種類にもよるが、アナターゼ型、ルチル型、ブルッカイト型が挙げられる。前記微粒子（１）が結晶性であることにより、前記連結型結晶性無機酸化物微粒子群は高い屈折率を有する。 The fine particles (1) are crystalline fine particles. The fine particles (1) being crystalline means that the crystallite diameter of the fine particles (1) obtained from the X-ray diffraction pattern exceeds 3 nm. The crystal structure includes an anatase type, a rutile type, and a brookite type depending on the type of metal element. Since the fine particles (1) are crystalline, the linked crystalline inorganic oxide fine particle group has a high refractive index.
前記微粒子（１）の平均粒子径は、好ましくは５〜１００ｎｍであり、さらに好ましくは５〜５０ｎｍである。この平均粒子径の値は、走査型電子顕微鏡（ＳＥＭ）で観察された像に基づいて測定された、該無機酸化物微粒子（１）の長軸方向の長さの平均値であり、このＳＥＭによる観察の条件は、後述する実施例で採用された条件またはこれと同等の条件である。また、前記「長軸方向」とは、ＳＥＭ像における１つの微粒子（１）の内部で最も長い軸の方位をいう。平均粒子径が上記範囲よりも過度に小さいと、１次粒子同士が凝集しやすい傾向をもつため前記微粒子（１）の分散液が増粘しやすくなり、平均粒子径が上記範囲よりも過度に大きいと、前記微粒子（１）の分散液の透明性が低下する傾向がある。 The average particle diameter of the fine particles (1) is preferably 5 to 100 nm, and more preferably 5 to 50 nm. The value of the average particle diameter is an average value of the length in the major axis direction of the inorganic oxide fine particles (1) measured based on an image observed with a scanning electron microscope (SEM). The observation conditions are the conditions employed in the examples described later or conditions equivalent thereto. The “major axis direction” refers to the direction of the longest axis in one fine particle (1) in the SEM image. If the average particle size is excessively smaller than the above range, the primary particles tend to aggregate, so that the dispersion of the fine particles (1) tends to thicken, and the average particle size is excessively larger than the above range. If it is large, the transparency of the dispersion liquid of the fine particles (1) tends to decrease.
前記無機酸化物微粒子（１）の形状としては、球状、繊維状、針状、チューブ状、シート状等が挙げられる。 Examples of the shape of the inorganic oxide fine particles (1) include a spherical shape, a fiber shape, a needle shape, a tube shape, and a sheet shape.
以上のような前記無機酸化物微粒子としては、従来公知の湿式調製法または乾式調製法で得られる無機酸化物微粒子を用いることができ、たとえば、チタニウムを含む無機酸化物微粒子であれば、特開２００９−１５５４９６号公報に記載された無機酸化物微粒子、特開２０１０−１６８２６６号公報、特開２０１１−１３２４８４号公報、特開２０１１−１３６８５０号公報に記載された無機酸化物微粒子などが挙げられ、ジルコニウムを含む微粒子であれば、特開２０１２−０５６８１６号公報に記載されたコアシェル型無機酸化物微粒子、特開２０１１−０３７６５９号公報に記載された無機酸化物微粒子などを用いることができる。 As the inorganic oxide fine particles as described above, inorganic oxide fine particles obtained by a conventionally known wet preparation method or dry preparation method can be used. Inorganic oxide fine particles described in 2009-15596, and inorganic oxide fine particles described in JP 2010-168266 A, JP 2011-132484 A, and JP 2011-136850 A, and the like. As fine particles containing zirconium, core-shell type inorganic oxide fine particles described in JP 2012-056816 A, inorganic oxide fine particles described in JP 2011-037659 A, and the like can be used.
被覆物質（２）および連結物質（３）：
前記被覆物質（２）は、ジルコニウム、アルミニウムおよびアンチモンからなる群から選ばれる少なくとも１種の金属元素Ｍ1とケイ素とを含む複合酸化物からなり、前記微粒子（１）を被覆する。また、前記結合物質（３）は、前記被覆物質（２）と同一成分である複合酸化物からなり、隣接する、前記被覆物質（２）で被覆された前記微粒子（１）同士を連結する。 Coating material (2) and linking material (3):
The coating material (2) is made of a complex oxide containing at least one metal element M 1 selected from the group consisting of zirconium, aluminum, and antimony and silicon, and covers the fine particles (1). The binding substance (3) is composed of a complex oxide that is the same component as the coating substance (2), and connects the adjacent fine particles (1) coated with the coating substance (2).
前記被覆物質（２）および前記結合物質（３）を構成する複合酸化物には、後述する製法上の観点からは、金属元素（Ｍ1Ｏx）およびケイ素（ＳｉＯ2）が、モル比（Ｍ1Ｏx／ＳｉＯ2）で好ましくは５／９５〜９８／２、さらに好ましくは８／９２〜９６／４となる割合で含まれる。From the viewpoint of the manufacturing method to be described later, the complex oxide constituting the coating material (2) and the binding material (3) contains a metal element (M 1 O x ) and silicon (SiO 2 ) in a molar ratio ( M 1 O x / SiO 2 ), preferably 5/95 to 98/2, more preferably 8/92 to 96/4.
前記結晶性無機酸化物微粒子（１）に含まれる金属元素Ｍ2およびケイ素の重量を、それぞれ、その酸化物Ｍ2Ｏxの重量およびＳｉＯ2（以下の重量比の式では「ＳｉＯ2-(2)」と表す。）の重量に換算し、前記被覆物質（２）および前記結合物質（３）に含まれる金属元素Ｍ1およびケイ素の重量を、それぞれ、その酸化物Ｍ1Ｏxの重量およびＳｉＯ2（以下の重量比の式では「ＳｉＯ2-(1)」と表す。）の重量に換算すると、重量比｛（Ｍ1Ｏx＋ＳｉＯ2-(1)）／(Ｍ2Ｏx＋ＳｉＯ2-(2)）｝は、後述する製法上の観点からは、好ましくは７／１００〜１５０／１００、さらに好ましくは１０／１００〜１２０／１００の範囲にある。The weights of the metal element M 2 and silicon contained in the crystalline inorganic oxide fine particles (1) are respectively the weight of the oxide M 2 O x and SiO 2 (“SiO 2- ( 2) ”), and the weights of the metal element M 1 and silicon contained in the coating material (2) and the binding material (3) are the weight of the oxide M 1 O x , respectively. And SiO 2 (represented as “SiO 2- (1)” in the following weight ratio formula), the weight ratio {(M 1 O x + SiO 2- (1)) / (M 2 O x + SiO 2- (2))} is preferably in the range of 7/100 to 150/100, more preferably 10/100 to 120/100, from the viewpoint of the production method described later.
連結型結晶性無機酸化物微粒子群：
連結型結晶性無機酸化物微粒子群の平均粒子径は、好ましくは１０〜２００ｎｍであり、さらに好ましくは１５〜１５０ｎｍである。この平均粒子径の値は、走査型電子顕微鏡（ＳＥＭ）で観察された像に基づいて測定された、該連結型結晶性無機酸化物微粒子群の長軸方向の長さの平均値であり、このＳＥＭによる観察の条件は、後述する実施例で採用された条件またはこれと同等の条件である。また、前記「長軸方向」とは、ＳＥＭ像における１つの微粒子群の内部で最も長い軸の方位をいう。本発明に係る分散液をたとえば光学基材用塗布液（後述するハードコート層膜形成用塗布液、プライマー層膜形成用塗布液など）として用いる場合、前記平均粒子径が前記範囲よりも過度に小さいと、所望の機械的強度（耐擦傷性、耐摩耗性）が得られず、平均粒子径が前記範囲よりも過度に大きいと、塗膜の外観曇り不良が発生する。 Linked crystalline inorganic oxide fine particle group:
The average particle size of the connected crystalline inorganic oxide fine particle group is preferably 10 to 200 nm, more preferably 15 to 150 nm. The value of the average particle diameter is an average value of the length in the major axis direction of the linked crystalline inorganic oxide fine particle group measured based on an image observed with a scanning electron microscope (SEM), The observation conditions by SEM are the conditions adopted in the examples described later or conditions equivalent thereto. The “major axis direction” refers to the direction of the longest axis in one fine particle group in the SEM image. When the dispersion liquid according to the present invention is used as, for example, a coating liquid for an optical substrate (a coating liquid for forming a hard coat layer film, a coating liquid for forming a primer layer, which will be described later), the average particle diameter is excessively larger than the above range. If it is small, the desired mechanical strength (abrasion resistance, abrasion resistance) cannot be obtained, and if the average particle diameter is excessively larger than the above range, a poor appearance haze of the coating film occurs.
前記連結型結晶性無機酸化物微粒子群には、連結していない、被覆物質（２）で被覆された微粒子（１）が含まれていても良いが、その量は、たとえば５０重量％以下、好ましくは１０重量％以下である（微粒子群と、連結していない被覆物質（２）で被覆された微粒子（１）との合計量を１００重量％とする。）。 The linked crystalline inorganic oxide fine particle group may contain fine particles (1) coated with the coating substance (2) that are not linked, and the amount thereof is, for example, 50% by weight or less, The amount is preferably 10% by weight or less (the total amount of the fine particle group and the fine particles (1) coated with the unconnected coating substance (2) is 100% by weight).
本発明に係る分散液をたとえば光学基材用塗布液として用いる場合には、前記連結型結晶性無機酸化物微粒子群の屈折率は、好ましくは１．６〜２．６であり、さらに好ましくは１．７〜２．４である。屈折率が１．６よりも過度に小さいと、光学基材用塗布液を屈折率１．５６以上の基材に塗膜した時に外観干渉縞不良を起こし、屈折率が２．６よりも過度に大きいと、バインダー成分に対する前記連結型結晶性無機酸化物微粒子群の割合を小さくしなければならないために塗膜に所望の機械的強度（耐擦傷性、耐摩耗性）が得られ難い。 When the dispersion liquid according to the present invention is used as, for example, a coating liquid for an optical substrate, the refractive index of the linked crystalline inorganic oxide fine particle group is preferably 1.6 to 2.6, more preferably 1.7 to 2.4. When the refractive index is excessively smaller than 1.6, an interference fringe defect is caused when the coating liquid for optical substrate is coated on a substrate having a refractive index of 1.56 or more, and the refractive index is excessively larger than 2.6. On the other hand, since the ratio of the linked crystalline inorganic oxide fine particle group to the binder component must be reduced, it is difficult to obtain desired mechanical strength (abrasion resistance, abrasion resistance) in the coating film.
本発明に係る分散液をたとえば光学基材用塗布液として用いる場合には、前記連結型結晶性無機酸化物微粒子群のシェラー（Scherrer）の式を用いて算出されたＸ線回折結晶子径（結晶子径には、長軸、短軸があるが、ここでいう結晶子径は長軸である。）の結晶子径は、好ましくは５〜１００ｎｍであり、さらに好ましくは５〜５０ｎｍである。結晶子径が５ｎｍよりも過度に小さいと、結晶性が低下することで連結型結晶性無機酸化物微粒子群の屈折率が低下し、結晶子径が１００ｎｍよりも過度に大きいと、塗膜の透明性が低下する。 When the dispersion liquid according to the present invention is used as, for example, a coating liquid for an optical substrate, the X-ray diffraction crystallite diameter (Scherrer) calculated using the Scherrer formula of the linked crystalline inorganic oxide fine particle group ( The crystallite diameter has a major axis and a minor axis. The crystallite diameter here is the major axis.) The crystallite diameter is preferably 5 to 100 nm, more preferably 5 to 50 nm. . If the crystallite diameter is excessively smaller than 5 nm, the refractive index of the linked crystalline inorganic oxide fine particle group decreases due to a decrease in crystallinity, and if the crystallite diameter is excessively larger than 100 nm, Transparency decreases.
本発明に係る連結型結晶性無機酸化物微粒子群は、本発明に係る連結型結晶性無機酸化物微粒子群の分散液から分散媒を除去することにより製造（回収）することができる。 The connected crystalline inorganic oxide fine particle group according to the present invention can be produced (recovered) by removing the dispersion medium from the dispersion liquid of the connected crystalline inorganic oxide fine particle group according to the present invention.
［連結型結晶性無機酸化物微粒子群の分散液］
本発明に係る連結型結晶性無機酸化物微粒子群の分散液は、分散媒として水および／または有機溶媒を含んでいる。 [Dispersion of linked crystalline inorganic oxide fine particles]
The dispersion of the linked crystalline inorganic oxide fine particle group according to the present invention contains water and / or an organic solvent as a dispersion medium.
前記有機溶媒としては、メタノール、エタノール、ブタノール、プロパノール、イソプロピルアルコ-ル等のアルコール類、エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等のエーテル類、メチルエチルケトン、γ−ブチロラクトン等のケトン類から選ばれた有機化合物などが挙げられる。 Examples of the organic solvent include alcohols such as methanol, ethanol, butanol, propanol and isopropyl alcohol, ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether, methyl ethyl ketone, and γ-butyrolactone. Examples include organic compounds selected from ketones.
これらの中でも、本発明に係る有機溶媒分散液を光学基材用塗布液の調製に使用する場合であれば、メタノール等のアルコール類やプロピレングリコールモノメチルエーテル等のエーテル類から選ばれた有機化合物の少なくとも１種が好ましい。その理由は、塗布膜の乾燥速度が比較的速く、成膜し易いためである。 Among these, if the organic solvent dispersion according to the present invention is used for the preparation of a coating liquid for an optical substrate, an organic compound selected from alcohols such as methanol and ethers such as propylene glycol monomethyl ether. At least one is preferred. The reason is that the drying speed of the coating film is relatively fast and it is easy to form a film.
本発明に係る分散液が有機溶媒分散液である場合には、分散媒として、少量（たとえば、全分散媒１００重量％に対して０．５〜５重量％）の水が含まれていてもよい。 When the dispersion according to the present invention is an organic solvent dispersion, even if a small amount of water (for example, 0.5 to 5% by weight with respect to 100% by weight of the total dispersion medium) is contained as the dispersion medium. Good.
本発明に係る分散液中の前記連結型結晶性無機酸化物微粒子群の含有量は、前記分散液の用途や分散媒の種類等によっても異なるが、前記分散液中に、たとえば５〜５０重量％である。本発明に係る有機溶媒分散液を後述する光学基材用塗布液（ハードコート層膜形成用塗布液、プライマー層膜形成用塗布液など）として用いる場合であれば、前記連結型結晶性無機酸化物微粒子群の含有量は、好ましくは１０〜４０重量％である（分散液の全量を１００重量％とする。）。 The content of the linked crystalline inorganic oxide fine particle group in the dispersion according to the present invention varies depending on the use of the dispersion, the type of the dispersion medium, and the like. %. If the organic solvent dispersion according to the present invention is used as a coating liquid for an optical substrate (a coating liquid for forming a hard coat layer film, a coating liquid for forming a primer layer film, etc.) described later, the linked crystalline inorganic oxidation The content of the fine particle group is preferably 10 to 40% by weight (the total amount of the dispersion is 100% by weight).
＜連結型結晶性無機酸化物微粒子群を含む水分散液の製造方法＞
本発明に係る連結型結晶性無機酸化物微粒子群を含む水分散液は、好ましくは下記の工程（１）〜（３）を有する製造方法により製造される。
（１）前記結晶性無機酸化物微粒子が１次元的または２次元的に連結した粒子を含有する水分散液を準備する工程、
（２）前記工程（１）で準備された水分散液に、ジルコニウム、アルミニウムおよびアンチモンからなる群から選ばれる少なくとも１種の特定の金属元素Ｍ1の化合物を含むアルカリ性水溶液および珪酸を含む酸性水溶液を添加する工程、および
（３）前記工程（２）で得られた水分散液を水熱処理する工程。<Method for Producing Aqueous Dispersion Containing Linked Crystalline Inorganic Oxide Fine Particle Group>
The aqueous dispersion containing the linked crystalline inorganic oxide fine particle group according to the present invention is preferably produced by a production method having the following steps (1) to (3).
(1) preparing an aqueous dispersion containing particles in which the crystalline inorganic oxide fine particles are connected one-dimensionally or two-dimensionally;
(2) An alkaline aqueous solution containing at least one compound of a specific metal element M 1 selected from the group consisting of zirconium, aluminum and antimony and an acidic aqueous solution containing silicic acid in the aqueous dispersion prepared in the step (1). And (3) hydrothermally treating the aqueous dispersion obtained in the step (2).
工程（１）：
工程（１）では、前記結晶性無機酸化物微粒子（１）が１次元的または２次元的に連結した粒子を含有する水分散液を準備する。 Step (1):
In the step (1), an aqueous dispersion containing particles in which the crystalline inorganic oxide fine particles (1) are connected one-dimensionally or two-dimensionally is prepared.
前記結晶性無機酸化物微粒子（１）の詳細は上述のとおりである。 The details of the crystalline inorganic oxide fine particles (1) are as described above.
前記結晶性無機酸化物微粒子（１）が連結した粒子を含有する水分散液を調製するためには、たとえば、まず、前記結晶性無機酸化物微粒子（１）が連結せずに分散した水分散液（そのｐＨは、たとえば８〜１１程度である。）を準備する。この水分散液を準備するには、前記結晶性無機酸化物微粒子（１）を水に分散させて前記水分散液を調製してもよく、あるいは、前記結晶性無機酸化物微粒子（１）を水分散液の形態で製造してもよい。 In order to prepare an aqueous dispersion containing particles in which the crystalline inorganic oxide fine particles (1) are connected, for example, first, the aqueous dispersion in which the crystalline inorganic oxide fine particles (1) are dispersed without being connected. A liquid (its pH is, for example, about 8 to 11) is prepared. In order to prepare this aqueous dispersion, the crystalline inorganic oxide fine particles (1) may be dispersed in water to prepare the aqueous dispersion, or the crystalline inorganic oxide fine particles (1) may be prepared. It may be produced in the form of an aqueous dispersion.
この水分散液のｐＨを２〜６に調整することにより、近接する前記微粒子（１）同士は疑似的に連結する。このｐＨ調整は、たとえば前記水分散液を陽イオン交換樹脂と接触させることにより行うことができる。 By adjusting the pH of the aqueous dispersion to 2 to 6, the adjacent fine particles (1) are pseudo-coupled. This pH adjustment can be performed, for example, by bringing the aqueous dispersion into contact with a cation exchange resin.
また、このときの前記結晶性無機酸化物微粒子（１）と水との界面におけるゼータ電位（ただし、前記水分散液中の前記微粒子（１）の濃度が０．１５重量％であれば、該水分散液におけるゼータ電位であり、該濃度が０．１５重量％でない場合には、水の量を増減させて該濃度が０．１５重量％になるように調製された水分散液におけるゼータ電位である。）は、好ましくは−３０〜−７０ｍＶ、さらに好ましくは−４０〜−７０ｍＶである。−３０ｍＶよりも過度に小さいと、結晶性無機酸化物微粒子が三次元的に凝集しやすい傾向にあり、−７０ｍＶよりも過度に大きいと結晶性無機酸化物微粒子の斥力が強くなりやすい傾向にある。 Further, the zeta potential at the interface between the crystalline inorganic oxide fine particles (1) and water at this time (provided that the concentration of the fine particles (1) in the aqueous dispersion is 0.15 wt%, Zeta potential in an aqueous dispersion, and when the concentration is not 0.15% by weight, the zeta potential in an aqueous dispersion prepared by increasing or decreasing the amount of water to be 0.15% by weight Is preferably −30 to −70 mV, more preferably −40 to −70 mV. If it is excessively smaller than −30 mV, the crystalline inorganic oxide fine particles tend to aggregate three-dimensionally. If it is excessively larger than −70 mV, the repulsive force of the crystalline inorganic oxide fine particles tends to be strong. .
「粒子が疑似的に連結している」とは、静電的引力によって粒子同士が連結した状態であり、粒子同士が共有結合により連結した状態ではない。また、粒子が３次元的に連結した状態、いわゆる凝集状態ではなく、１次元的または２次元的に連結した状態である。 “The particles are quasi-coupled” is a state in which the particles are coupled by electrostatic attraction, and is not a state in which the particles are coupled by a covalent bond. Further, the particles are not three-dimensionally connected, that is, a so-called aggregated state, but one-dimensionally or two-dimensionally connected.
結晶性微粒子は、非晶質微粒子と比較して、表面ＯＨ基が少ないため、連結状構造をとらせる場合には、微粒子表面に表面処理剤により親水性基を付与することも考えられるが、結晶性微粒子の凝集を生じたりする可能性が高くなる恐れがあった。一方、本発明においては、前記結晶性無機酸化物微粒子（１）の水分散液のｐＨを調節することにより前記微粒子（１）を疑似的に連結するため、このような凝集を生じることがない。 Since the crystalline fine particles have fewer surface OH groups than the amorphous fine particles, it is considered that a hydrophilic group is imparted to the surface of the fine particles by a surface treatment agent when taking a connected structure. There is a possibility that the possibility of causing aggregation of the crystalline fine particles is increased. On the other hand, in the present invention, since the fine particles (1) are pseudo-connected by adjusting the pH of the aqueous dispersion of the crystalline inorganic oxide fine particles (1), such aggregation does not occur. .
工程（１）では、好ましくは、前記水分散液のｐＨを２〜６に、および／または前記結晶性無機酸化物微粒子（１）と水との界面におけるゼータ電位を−３０〜−７０ｍＶに調整し、前記水分散液を２０〜４０℃の温度条件下に０．５〜５時間（さらに好ましくは１〜２時間）放置する。こうすることによって、水分散液中の固形成分を熟成、すなわち、前記微粒子（１）同士の疑似的な連結をより強固にし、工程（２）で前記水分散液のｐＨを高めても疑似的な連結を維持することができる。この放置の際には、前記水分散液を撹拌することが好ましい。 In the step (1), preferably, the pH of the aqueous dispersion is adjusted to 2 to 6 and / or the zeta potential at the interface between the crystalline inorganic oxide fine particles (1) and water is adjusted to −30 to −70 mV. The aqueous dispersion is then allowed to stand for 0.5 to 5 hours (more preferably 1 to 2 hours) under a temperature condition of 20 to 40 ° C. By doing this, the solid component in the aqueous dispersion is aged, that is, the pseudo-connection between the fine particles (1) is further strengthened, and the pH of the aqueous dispersion is increased in the step (2). Connection can be maintained. In this case, the aqueous dispersion is preferably stirred.
工程（２）：
工程（２）では、前記工程（１）で得られた水分散液に、ジルコニウム、アルミニウムおよびアンチモンからなる群から選ばれる少なくとも１種の金属元素Ｍ1の化合物を含むアルカリ性水溶液および珪酸を含む酸性水溶液を添加する。 Step (2):
In the step (2), the aqueous dispersion obtained in the step (1) contains an alkaline aqueous solution containing a compound of at least one metal element M 1 selected from the group consisting of zirconium, aluminum and antimony, and an acid containing silicic acid. Add aqueous solution.
工程（２）では、まず、前記工程（１）で得られた水分散液のｐＨを７〜１１に調整する工程（以下「工程（２ａ）」ともいう。）を実施する。このｐＨ調整は、たとえば前記工程（１）で得られた水分散液にアルカリ金属の水酸化物（例：水酸化ナトリウム、水酸化カリウム）の水溶液を添加することにより行うことができる。 In the step (2), first, a step of adjusting the pH of the aqueous dispersion obtained in the step (1) to 7 to 11 (hereinafter also referred to as “step (2a)”) is performed. This pH adjustment can be performed, for example, by adding an aqueous solution of an alkali metal hydroxide (eg, sodium hydroxide, potassium hydroxide) to the aqueous dispersion obtained in the step (1).
次いで、工程（２ａ）によりｐＨを７〜１１に調整した水分散液を、７０〜９５℃に加熱したのち、この水分散液に特定の金属化合物のアルカリ性水溶液および珪酸を含む酸性水溶液を添加する。 Next, the aqueous dispersion whose pH is adjusted to 7 to 11 in the step (2a) is heated to 70 to 95 ° C., and then an aqueous alkaline solution of a specific metal compound and an acidic aqueous solution containing silicic acid are added to the aqueous dispersion. .
前記の特定の金属化合物のアルカリ性水溶液とは、ジルコニウム、アルミニウムおよびアンチモンからなる群から選ばれる少なくとも１種の金属元素の化合物を含むアルカリ水溶液である。 The alkaline aqueous solution of the specific metal compound is an alkaline aqueous solution containing a compound of at least one metal element selected from the group consisting of zirconium, aluminum, and antimony.
その具体例としては、特開２００８−１１５０６０号公報の［００２２］〜［００２９］に詳細が記載された、酸化ジルコニウム水和物を含む水溶液に、アルカリ金属の水酸化物および過酸化水素を添加して攪拌することにより、該酸化ジルコニウム水和物を解膠して溶解させた水溶液などが挙げられる。 As specific examples, an alkali metal hydroxide and hydrogen peroxide are added to an aqueous solution containing zirconium oxide hydrate described in detail in [0022] to [0029] of JP-A-2008-115060. Then, an aqueous solution in which the zirconium oxide hydrate is peptized and dissolved by stirring is exemplified.
前記アルカリ性水溶液は、前記金属元素をその酸化物換算基準で好ましくは０．３〜２０重量％含有する。 The alkaline aqueous solution preferably contains 0.3 to 20% by weight of the metal element on the oxide conversion standard.
前記の珪酸を含む酸性水溶液（以下「珪酸液」ともいう。）としては、アルカリ金属珪酸塩、有機塩基の珪酸塩等の珪酸塩水溶液を陽イオン交換樹脂で処理して脱アルカリしたものが挙げられる。また、これらの珪酸塩としては、珪酸ナトリウム（水ガラス）、珪酸カリウム等のアルカリ金属珪酸塩、第４級アンモニウムシリケート等の有機塩基の珪酸塩などが挙げられる。前記珪酸液としては、水ガラス（珪酸ナトリウム）を水で希釈した後、陽イオン交換樹脂で処理して脱アルカリしたものが好ましい。 Examples of the acidic aqueous solution containing silicic acid (hereinafter also referred to as “silicic acid solution”) include those obtained by treating a silicate aqueous solution such as an alkali metal silicate or an organic base silicate with a cation exchange resin and removing the alkali. It is done. Examples of these silicates include alkali metal silicates such as sodium silicate (water glass) and potassium silicate, and silicates of organic bases such as quaternary ammonium silicate. As the silicic acid solution, a solution obtained by diluting water glass (sodium silicate) with water and then treating it with a cation exchange resin is preferable.
この珪酸液の中でも、ｐＨが２〜４、好ましくは２〜３の範囲にあり、珪素成分の含有量がＳｉＯ2換算基準で０．５〜５重量％、好ましくは０．８〜４．８重量％の範囲にあるものが好ましい。前記ｐＨが２よりも過度に低いと、前記の処理に要する陽イオン交換樹脂の量と処理時間が必要以上に多くなって経済的ではなくなり、また前記ｐＨが４よりも過度に高いと、脱アルカリの度合いが低いため、珪酸液の安定性が悪くなる。さらに、前記含有量が０．５重量％よりも過度に少ないと、経済的に前記無機酸化物微粒子を得ることが難しくなり、また前記含有量が５重量％よりも過度に高いと、珪酸液の安定性が悪くなる。Among these silicic acid solutions, the pH is in the range of 2 to 4, preferably 2 to 3, and the silicon component content is 0.5 to 5% by weight, preferably 0.8 to 4.8, based on the SiO 2 conversion standard. Those in the weight percent range are preferred. When the pH is excessively lower than 2, the amount of the cation exchange resin required for the treatment and the treatment time are unnecessarily increased, which is not economical, and when the pH is excessively higher than 4, Since the degree of alkali is low, the stability of the silicic acid solution is deteriorated. Furthermore, if the content is excessively less than 0.5% by weight, it is difficult to economically obtain the inorganic oxide fine particles, and if the content is excessively higher than 5% by weight, a silicate solution The stability becomes worse.
前記アルカリ性水溶液および前記珪酸液は、前記アルカリ性水溶液中に含まれる金属元素成分をＭ1Ｏxで表し、前記珪酸液に含まれる珪素をＳｉＯ2で表したとき、モル比（Ｍ1Ｏx／ＳｉＯ2）が好ましくは５／９５〜９８／２、さらに好ましくは８／９２〜９６／４となる割合で、前記工程（２ａ）で得られた水分散液に、ゆっくりと添加される。前記モル比が５／９５よりも過度に小さいと、結晶性無機酸化物微粒子群を得ることが難しくなり、また前記モル比が９８／２よりも過度に大きいと、前記アルカリ性水溶液および前記珪酸液を前記工程（２ａ）で得られた水分散液に添加している間に、混合液が不安定となって前記結晶性無機酸化物微粒子（１）の凝集が起こってしまう。When the alkaline aqueous solution and the silicic acid solution represent the metal element component contained in the alkaline aqueous solution as M 1 O x and the silicon contained in the silicic acid solution as SiO 2 , the molar ratio (M 1 O x / SiO 2 ) is preferably slowly added to the aqueous dispersion obtained in the step (2a) at a ratio of 5/95 to 98/2, more preferably 8/92 to 96/4. When the molar ratio is excessively smaller than 5/95, it becomes difficult to obtain a crystalline inorganic oxide fine particle group. When the molar ratio is excessively larger than 98/2, the alkaline aqueous solution and the silicic acid liquid are used. While the solution is added to the aqueous dispersion obtained in the step (2a), the mixed solution becomes unstable and the crystalline inorganic oxide fine particles (1) are aggregated.
また、前記工程（２ａ）で得られた水分散液へのこれらの添加量は、前記結晶性無機酸化物微粒子（１）に含まれる金属元素Ｍ2およびケイ素の重量を、それぞれの酸化物（Ｍ2Ｏx、ＳｉＯ2（以下の重量比の式では「ＳｉＯ2-(2)」と表す。））の重量に換算し、前記アルカリ性水溶液に含まれる金属元素Ｍ1および前記珪酸液に含まれるケイ素の重量を、それぞれの酸化物（Ｍ1Ｏx、ＳｉＯ2（以下の重量比の式では「ＳｉＯ2-(1)」と表す。））の重量に換算すると、重量比｛（Ｍ1Ｏx＋ＳｉＯ2-(1)）／（Ｍ2Ｏx＋ＳｉＯ2-(2)）｝は、好ましくは７／１００〜１５０／１００、さらに好ましくは１０／１００〜１２０／１００となる量である。前記モル比が７／１００よりも過度に小さいと、結晶性無機酸化物微粒子群を得ることが難しくなり、また前記モル比が１５０／１００よりも過度に大きいと、前記アルカリ性水溶液および前記珪酸液を前記工程（２ａ）で得られた水分散液に添加している間に、混合液が不安定となって前記結晶性無機酸化物微粒子（１）の凝集が起こってしまう。In addition, these addition amounts to the aqueous dispersion obtained in the step (2a) are based on the weight of the metal element M 2 and silicon contained in the crystalline inorganic oxide fine particles (1), and the respective oxides ( Converted to the weight of M 2 O x and SiO 2 (represented as “SiO 2- (2)” in the following weight ratio formula)), it is contained in the metal element M 1 contained in the alkaline aqueous solution and the silicic acid solution. When the weight of silicon to be converted into the weight of each oxide (M 1 O x , SiO 2 (represented as “SiO 2- (1)” in the following weight ratio formula)), the weight ratio {(M 1 O x + SiO 2- (1)) / (M 2 O x + SiO 2- (2))} is preferably 7/100 to 150/100, more preferably 10/100 to 120/100. is there. When the molar ratio is excessively smaller than 7/100, it becomes difficult to obtain a crystalline inorganic oxide fine particle group. When the molar ratio is excessively larger than 150/100, the alkaline aqueous solution and the silicic acid liquid are used. While the solution is added to the aqueous dispersion obtained in the step (2a), the mixed solution becomes unstable and the crystalline inorganic oxide fine particles (1) are aggregated.
前記工程（２ａ）で得られた水分散液は、前記アルカリ性水溶液および前記珪酸液を添加する前に、７０〜９５℃、好ましくは８０〜９０℃の温度に加熱される。温度が前記範囲にあると、前記アルカリ性水溶液中の金属化合物（例：ジルコニウム化合物）と前記珪酸液中の珪酸との加水分解反応を進めることができる。一方、前記温度が過度に低いと、前記加水分解反応の進行が遅く、前記温度が過度に高いと、前記水分散液中の水の蒸発が進行してしまう。 The aqueous dispersion obtained in the step (2a) is heated to a temperature of 70 to 95 ° C., preferably 80 to 90 ° C. before adding the alkaline aqueous solution and the silicic acid solution. When the temperature is within the above range, the hydrolysis reaction between the metal compound (eg, zirconium compound) in the alkaline aqueous solution and the silicic acid in the silicic acid solution can proceed. On the other hand, when the temperature is excessively low, the hydrolysis reaction proceeds slowly, and when the temperature is excessively high, evaporation of water in the aqueous dispersion proceeds.
一方、前記工程（２ａ）で得られた水分散液に添加される前記アルカリ性水溶液および前記珪酸液は、加熱されたものであっても良く、室温のものであっても良い。 On the other hand, the alkaline aqueous solution and the silicic acid solution added to the aqueous dispersion obtained in the step (2a) may be heated or room temperature.
また、前記アルカリ性水溶液および前記珪酸液の添加は、これらの添加量や濃度によっても異なるが、好ましくは、同時に４〜２４時間かけてゆっくりと行われる。 The addition of the alkaline aqueous solution and the silicic acid solution is preferably performed slowly over 4 to 24 hours at the same time, although depending on the addition amount and concentration thereof.
工程（３）：
工程（３）では前記工程（２）で得られた水分散液を水熱処理する。 Step (3):
In step (3), the aqueous dispersion obtained in step (2) is hydrothermally treated.
前記水熱処理は、好ましくは耐圧・耐熱容器、さらに好ましくはステンレススチール製のオートクレーブの中で行われる。 The hydrothermal treatment is preferably carried out in a pressure-resistant and heat-resistant container, more preferably in a stainless steel autoclave.
また、前記水熱処理は、好ましくは１３０〜２５０℃、さらに好ましくは１５０〜２００℃の温度条件下で、好ましくは１０〜１００時間、さらに好ましくは１２〜４０時間かけて行われる。前記の条件下で水熱処理を行うと、前記工程（３）で前記水分散液に添加されるアルカリ水溶液中の特定の金属化合物（例：ジルコニウム化合物）と酸性水溶液中の珪酸との加水分解反応から得られる部分加水分解物および／または加水分解物の縮合反応を充分に進め、得られる縮合物によって前記結晶性無機酸化物微粒子を被覆しかつ連結することができる。 The hydrothermal treatment is preferably performed under a temperature condition of 130 to 250 ° C, more preferably 150 to 200 ° C, preferably 10 to 100 hours, more preferably 12 to 40 hours. When hydrothermal treatment is performed under the above conditions, hydrolysis reaction between a specific metal compound (eg, zirconium compound) in the alkaline aqueous solution added to the aqueous dispersion in the step (3) and silicic acid in the acidic aqueous solution The partial hydrolyzate and / or the condensation reaction of the hydrolyzate obtained from (1) can be sufficiently advanced, and the crystalline inorganic oxide fine particles can be coated and connected with the resulting condensate.
このように工程（１）〜（３）を経ることにより、チタニウム、ジルコニウム、ニオブ、セリウムおよび亜鉛からなる群から選ばれた少なくとも１種の金属元素とケイ素とを含む結晶性無機酸化物微粒子（１）、前記微粒子（１）を被覆する、ジルコニウム、アルミニウムおよびアンチモンからなる群から選ばれた少なくとも１種の金属元素とケイ素とを含む複合酸化物からなる被覆物質（２）、および前記被覆物質（２）と同一成分である複合酸化物からなり、隣接する、前記被覆物質（２）で被覆された前記結晶性無機酸化物微粒子（１）同士を連結する結合物質（３）から構成された連結型結晶性無機酸化物微粒子群を含む水分散液が得られる。 As described above, through the steps (1) to (3), crystalline inorganic oxide fine particles containing at least one metal element selected from the group consisting of titanium, zirconium, niobium, cerium and zinc and silicon ( 1) a coating material (2) made of a composite oxide containing at least one metal element selected from the group consisting of zirconium, aluminum and antimony and silicon, which covers the fine particles (1), and the coating material (2) composed of a composite oxide that is the same component as (2), and composed of a binding substance (3) that connects adjacent crystalline inorganic oxide fine particles (1) coated with the coating substance (2). An aqueous dispersion containing linked crystalline inorganic oxide fine particle groups is obtained.
また、本発明に係る分散液中に含まれる前記連結型結晶性無機酸化物微粒子群は、概ね図１の電子顕微鏡写真に示すような形状を有している。 In addition, the linked crystalline inorganic oxide fine particle group contained in the dispersion according to the present invention has a shape as shown in the electron micrograph of FIG.
＜連結型結晶性無機酸化物微粒子群を含む有機溶媒分散液の製造方法＞
本発明に係る連結型結晶性無機酸化物微粒子群を含む有機溶媒分散液は、本発明に係る連結型結晶性無機酸化物微粒子群を含む水分散液に含まれる分散媒である水を有機溶媒に置換することにより製造することができる。<Method for Producing Organic Solvent Dispersion Containing Linked Crystalline Inorganic Oxide Fine Particle Group>
The organic solvent dispersion containing the linked crystalline inorganic oxide fine particle group according to the present invention is obtained by using water as a dispersion medium contained in the aqueous dispersion containing the linked crystalline inorganic oxide fine particle group according to the present invention as an organic solvent. It can manufacture by substituting.
前記水分散液に含まれる連結型結晶性無機酸化物微粒子群は親水性の微粒子群であるため、有機溶媒分散液を製造する際には、前記微粒子群を予め疎水性にしておくことが望ましい。そのためには、表面処理剤を用いて該微粒子群の表面を従来公知の方法で処理しておくことが好ましい。 Since the linked crystalline inorganic oxide fine particle group contained in the aqueous dispersion is a hydrophilic fine particle group, it is desirable to make the fine particle group hydrophobic in advance when producing an organic solvent dispersion. . For this purpose, it is preferable to treat the surface of the fine particle group with a conventionally known method using a surface treating agent.
前記表面処理剤としては、有機ケイ素化合物やアミン系化合物などが挙げられる。 Examples of the surface treatment agent include organosilicon compounds and amine compounds.
ここで、前記有機ケイ素化合物としては、加水分解性基を有する従来公知のシランカップリング剤を用いることができ、具体例としては、
トリメチルエトキシシラン、ジメチルフェニルエトキシシラン、ジメチルビニルエトキシシラン等の一般式Ｒ3ＳｉＸ（式中、Ｒは、アルキル基、フェニル基、ビニル基、メタクリロキシ基、メルカプト基、アミノ基またはエポキシ基を有する有機基を表し、Ｘは、アルコキシ基、クロロ基等の加水分解性基を表す。）で表される単官能性シラン；
ジメチルジエトキシシラン、ジフェニルジエトキシシラン等の一般式Ｒ2ＳｉＸ2（式中、ＲおよびＸは上記の通りである。）で表される二官能性シラン；
メチルトリエトキシシラン、フェニルトリエトキシシラン等の一般式ＲＳｉＸ3（式中、ＲおよびＸは上記の通りである。）で表される三官能性シラン；
テトラメトキシシラン、テトラエトキシシラン等のテトラアルコキシシランなどの一般式ＳｉＸ4（式中、Ｘは上記の通りである。）で表される四官能性シラン
などが挙げられる。Here, as the organosilicon compound, a conventionally known silane coupling agent having a hydrolyzable group can be used. As a specific example,
General formula R 3 SiX such as trimethylethoxysilane, dimethylphenylethoxysilane, dimethylvinylethoxysilane (wherein R is an organic group having an alkyl group, phenyl group, vinyl group, methacryloxy group, mercapto group, amino group or epoxy group) A monofunctional silane represented by: X represents a hydrolyzable group such as an alkoxy group or a chloro group;
A bifunctional silane represented by a general formula R 2 SiX 2 (wherein R and X are as described above) such as dimethyldiethoxysilane and diphenyldiethoxysilane;
Trifunctional silanes represented by the general formula RSiX 3 (wherein R and X are as described above) such as methyltriethoxysilane and phenyltriethoxysilane;
Examples thereof include tetrafunctional silanes represented by a general formula SiX 4 (wherein X is as described above) such as tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane.
また、前記アミン系化合物としては、アンモニア；エチルアミン、トリエチルアミン、イソプロピルアミン、ｎ−プロピルアミン等のアルキルアミン、ベンジルアミン等のアラルキルアミン、ピペリジン等の脂環式アミン、モノエタノールアミン、トリエタノールアミン等のアルカノールアミン、テトラメチルアンモニウム塩、テトラメチルアンモニウムハイドロオキサイド等の第４級アンモニウム塩または第４級アンモニウムハイドロオキサイドなどが挙げられる。 Examples of the amine compound include ammonia; alkylamines such as ethylamine, triethylamine, isopropylamine and n-propylamine; aralkylamines such as benzylamine; alicyclic amines such as piperidine; monoethanolamine; And quaternary ammonium salts such as alkanolamine, tetramethylammonium salt, and tetramethylammonium hydroxide.
これらは、１種単独で用いてもよく２種以上を併用してもよい。 These may be used alone or in combination of two or more.
前記連結型結晶性無機酸化物微粒子群の表面処理は、たとえば表面処理剤として前記有機ケイ素化合物を用いる場合には、メタノールなどの有機溶媒に溶解した有機ケイ素化合物またはその部分加水分解物を前記水分散ゾル中に添加したのち、約４０〜６０℃の温度に加熱して約１〜２０時間、撹拌して、前記有機ケイ素化合物またはその部分加水分解物を加水分解させることによって行うことができる。
なお、この表面処理の操作が終了した段階では、前記有機ケイ素化合物の有する加水分解性基のすべてが、前記連結型結晶性無機酸化物微粒子群の表面に存在するＯＨ基と反応した状態となっていることが好ましいが、その一部が未反応のまま残存した状態であってもよい。For example, when the organosilicon compound is used as a surface treating agent, the surface treatment of the linked crystalline inorganic oxide fine particle group is performed by removing an organosilicon compound dissolved in an organic solvent such as methanol or a partially hydrolyzed product thereof. After being added to the dispersion sol, it can be carried out by heating to a temperature of about 40-60 ° C. and stirring for about 1-20 hours to hydrolyze the organosilicon compound or a partial hydrolyzate thereof.
At the stage where this surface treatment operation is completed, all of the hydrolyzable groups possessed by the organosilicon compound are in a state of reacting with OH groups present on the surface of the linked crystalline inorganic oxide fine particle group. However, it may be in a state in which a part thereof remains unreacted.
次いで、表面処理された連結型結晶性無機酸化物微粒子群を含む水分散液に含まれる水を有機溶媒に置換する。有機溶媒の詳細は前述のとおりである。 Next, the water contained in the aqueous dispersion containing the surface-treated linked crystalline inorganic oxide fine particle group is replaced with an organic solvent. The details of the organic solvent are as described above.
この置換操作では、溶媒置換装置として、従来公知の溶媒置換装置、たとえば限外濾過装置やロータリーエバポレーターなどを用いることができる。前記溶媒置換装置の操作条件は、使用する溶媒置換装置や前記有機溶媒の種類などによっても異なるが、たとえば限外濾過装置（旭化成（株）製ＳＩＰ−１０１３）を用いて行う場合には、限界濾過膜を備えた該装置内に、前記水分散ゾル（固形分濃度１〜３０重量％）と該ゾル中に含まれる水と置換すべき有機溶媒（たとえば、メタノール）を送入し、一般的な条件下（たとえば、ポンプ吐出圧１０〜２０ＭＰａ、溶媒置換後の水分含有量０．１〜５重量％など）で溶媒置換することが好ましい。 In this replacement operation, a conventionally known solvent replacement device such as an ultrafiltration device or a rotary evaporator can be used as the solvent replacement device. The operating conditions of the solvent displacement device vary depending on the solvent displacement device used, the type of the organic solvent, and the like. For example, when using an ultrafiltration device (SIP-1013 manufactured by Asahi Kasei Co., Ltd.) The water-dispersed sol (solid content concentration: 1 to 30% by weight) and an organic solvent (for example, methanol) to be replaced with water contained in the sol are fed into the apparatus equipped with a filtration membrane, It is preferable to perform solvent replacement under such conditions (for example, pump discharge pressure of 10 to 20 MPa, water content after solvent replacement of 0.1 to 5% by weight, etc.).
前記水分散液に含まれる連結型結晶性無機酸化物微粒子群の濃度が、所望する有機溶媒分散液の固形分濃度より遙かに低い場合には、該水分散液を限外濾過装置などを用いて濃縮して、該水分散液の固形分濃度を高めておいてから、前記の置換操作を行うことが好ましい。 When the concentration of the linked crystalline inorganic oxide fine particle group contained in the aqueous dispersion is much lower than the solid content concentration of the desired organic solvent dispersion, the aqueous dispersion is treated with an ultrafiltration device or the like. It is preferable to perform the above-described replacement operation after concentration using the solution to increase the solid concentration of the aqueous dispersion.
＜光学基材用塗布液、該塗布液を用いて形成した塗布膜および塗布膜付基材＞
［光学基材用塗布液］
本発明に係る連結型結晶性無機酸化物微粒子群の有機溶媒分散液は、たとえば、光学基材用塗布液、具体的には下記の２種の塗布液として使用することができる。<Optical substrate coating liquid, coating film formed using the coating liquid, and substrate with coating film>
[Coating liquid for optical substrate]
The organic solvent dispersion of the linked crystalline inorganic oxide fine particle group according to the present invention can be used, for example, as a coating liquid for an optical substrate, specifically, as the following two kinds of coating liquids.
ａ．ハードコート層膜形成用塗布液
ｂ．プライマー層膜形成用塗布液
ａ．ハードコート層膜形成用塗布液：
このハードコート層膜形成用塗布液は、本発明に係る連結型結晶性無機酸化物微粒子群の有機溶媒分散液からなり、さらに、バインダー成分としての有機ケイ素化合物（Ａ）（すなわち、ビヒクル成分）を含有する。a. Hard coat layer film forming coating solution b. Coating liquid for primer layer film formation
a. Hard coat layer coating solution:
This coating liquid for forming a hard coat layer film is composed of an organic solvent dispersion of linked crystalline inorganic oxide fine particles according to the present invention, and further, an organosilicon compound (A) as a binder component (that is, a vehicle component). Containing.
前記有機ケイ素化合物（Ａ）としては、下記一般式（Ｉ）で表される有機ケイ素化合物および／またはその加水分解物が挙げられる。 Examples of the organosilicon compound (A) include an organosilicon compound represented by the following general formula (I) and / or a hydrolyzate thereof.
Ｒ1 aＲ2 bＳｉ（ＯＲ3）4-(a+b) （Ｉ）
（式中、Ｒ1は炭素数１〜６のアルキル基、ビニル基を含有する炭素数８以下の有機基、エポキシ基を含有する炭素数８以下の有機基、メタクリロキシ基を含有する炭素数８以下の有機基、メルカプト基を含有する炭素数１〜５の有機基またはアミノ基を含有する炭素数１〜５の有機基であり、Ｒ2は炭素数３以下のアルキル基、アルキレン基、シクロアルキル基もしくはハロゲン化アルキル基またはアリル基であり、Ｒ3は炭素数３以下のアルキル基、アルキレン基またはシクロアルキル基である。また、ａは０または１の整数、ｂは０、１または２の整数である。）
前記一般式（Ｉ）で表される有機ケイ素化合物としては、アルコキシシラン化合物がその代表例として挙げられ、具体的には、テトラエトキシシラン、メチルトリメトキシシラン、ビニルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、トリメチルクロロシラン、α−グルシドキシメチルトリメトキシシラン、α−グリシドキシエチルトリメトキシシラン、β−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メチルジメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、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、β−（３，４−エポキシシクロヘキシル）−エチルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）−γ−アミノプロピルメチルジメトキキシラン、Ｎ−β（アミノエチル）−γ−アミノプロピルメチルジエトキキシランなどがある。これらの中でも、テトラエトキシシラン、メチ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メチルジエトキシシラン、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などを使用することが好ましい。これらの有機ケイ素化合物は、１種類単独で用いてもよく、２種類以上を併用してもよい。R 1 a R 2 b Si (OR 3 ) 4- (a + b) (I)
(In the formula, R 1 is an alkyl group having 1 to 6 carbon atoms, an organic group having 8 or less carbon atoms containing a vinyl group, an organic group having 8 or less carbon atoms containing an epoxy group, and 8 carbon atoms containing a methacryloxy group. The following organic group, an organic group having 1 to 5 carbon atoms containing a mercapto group or an organic group having 1 to 5 carbon atoms containing an amino group, R 2 is an alkyl group having 3 or less carbon atoms, an alkylene group, a cyclo group An alkyl group, a halogenated alkyl group, or an allyl group, R 3 is an alkyl group, alkylene group, or cycloalkyl group having 3 or less carbon atoms, a is an integer of 0 or 1, b is 0, 1, or 2 Is an integer.)
As the organosilicon compound represented by the general formula (I), an alkoxysilane compound is exemplified as a typical example, and specific examples thereof include tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, and γ-methacryloxy. Propyltrimethoxysilane, trimethylchlorosilane, α-glycidoxymethyltrimethoxysilane, α-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, β- (3 4-epoxycyclohexyl) Ethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropyl Examples include methyldietoxylan. Among these, tetraethoxysilane, methyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, etc. Is preferably used. These organosilicon compounds may be used alone or in combination of two or more.
前記ハードコート層膜形成用塗布液を調製する際に、前記有機ケイ素化合物（Ａ）は、好ましくは、無溶媒下またはアルコール等の極性有機溶媒中で、酸および水の存在下で部分加水分解または加水分解した後に、上述した連結型結晶性無機酸化物微粒子群の有機溶媒分散液（前記有機ケイ素化合物（Ａ）を含まない前記有機溶媒分散液）と混合される。前記有機ケイ素化合物（Ａ）は、前記有機溶媒分散液と混合した後に、部分加水分解または加水分解されてもよい。 In preparing the coating solution for forming the hard coat layer film, the organosilicon compound (A) is preferably partially hydrolyzed in the absence of a solvent or in a polar organic solvent such as alcohol in the presence of an acid and water. Or after hydrolyzing, it mixes with the organic solvent dispersion liquid (the said organic solvent dispersion liquid which does not contain the said organosilicon compound (A)) of the connection type | mold crystalline inorganic oxide fine particle group mentioned above. The organosilicon compound (A) may be partially hydrolyzed or hydrolyzed after mixing with the organic solvent dispersion.
前記ハードコート層膜形成用塗布液は、ハードコート層膜の染色性や、プラスチックレンズ基材等への密着性を向上させ、更にはクラックの発生を防止するために、上記の成分に加えて、未架橋エポキシ化合物を含有していてもよい。この未架橋エポキシ化合物としては、たとえば１，６−ヘキサンジオールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、グリセロールジグリシジルエーテル、グリセロールトリグリシジルエーテル等が挙げられる。これらの中でも１，６−ヘキサンジオールジグリシジルエーテル、グリセロールジグリシジルエーテル、グリセロールトリグリシジルエーテルなどを使用することが好ましい。また、これらの未架橋エポキシ化合物は、１種類単独で用いてもよく、２種類以上を併用してもよい。 In addition to the above components, the coating liquid for forming the hard coat layer film improves the dyeability of the hard coat layer film and the adhesion to the plastic lens substrate, and further prevents the occurrence of cracks. In addition, an uncrosslinked epoxy compound may be contained. Examples of the uncrosslinked epoxy compound include 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, and the like. Among these, it is preferable to use 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, or the like. Moreover, these uncrosslinked epoxy compounds may be used individually by 1 type, and may use 2 or more types together.
さらに、前記ハードコート層膜形成用塗布液は、ハードコート層膜形成用塗布液に通常含まれることのある上記以外の成分、たとえば界面活性剤、レベリング剤または紫外線吸収剤などを含んでいてもよい。 Further, the hard coat layer film-forming coating solution may contain components other than those usually mentioned above, such as surfactants, leveling agents or ultraviolet absorbers, which are usually included in the hard coat layer film-forming coating solution. Good.
前記ハードコート層膜形成用塗布液中の前記有機ケイ素化合物（Ａ）の量は、好ましくは、前記連結型結晶性無機酸化物微粒子群１００体積部に対し、２００〜１０００体積部である。 The amount of the organosilicon compound (A) in the hard coat layer film forming coating solution is preferably 200 to 1000 parts by volume with respect to 100 parts by volume of the linked crystalline inorganic oxide fine particle group.
ｂ．プライマー層膜形成用塗布液：
このプライマー層膜形成用塗布液は、本発明に係る連結型結晶性無機酸化物微粒子群の有機溶媒分散液からなり、さらに、バインダー成分としての熱硬化性樹脂または熱可塑性樹脂（Ｂ）（すなわち、樹脂成分）を含有する。 b. Coating liquid for primer layer film formation:
This primer layer film-forming coating solution is composed of an organic solvent dispersion of linked crystalline inorganic oxide fine particles according to the present invention, and further, a thermosetting resin or a thermoplastic resin (B) as a binder component (that is, , Resin component).
前記熱硬化性樹脂または熱可塑性樹脂（Ｂ）としては、熱硬化性樹脂であれば、ウレタン系樹脂、エポキシ系樹脂およびメラミン系樹脂などが挙げられ、これらの中でも、ウレタン系樹脂およびエポキシ系樹脂が好ましい。 Examples of the thermosetting resin or the thermoplastic resin (B) include a urethane resin, an epoxy resin, and a melamine resin as long as they are thermosetting resins. Among these, urethane resins and epoxy resins are used. Is preferred.
前記ウレタン系樹脂としては、たとえばヘキサメチレンジイソシアネート等のブロック型ポリイシシアネートとポリエステルポリオール、ポリエーテルポリオール等の活性水素含有化合物との反応物が挙げられ、また前記エポキシ樹脂としては、たとえばポリアルキレンエーテル変性エポキシ樹脂や分子鎖に柔軟性骨格（ソフトセグメント）を導入したエポキシ基含有化合物が挙げられ、前記メラミン系樹脂としては、たとえばエーテル化メチロールメラミンとポリエステルポリオール、ポリエーテルポリオールとの硬化物が挙げられる。これらの中でも、ブロック型イシシアネートとポリオールとの硬化物であるウレタン系樹脂が好ましい。また、これらの熱硬化性樹脂は、１種類単独で用いてもよく、２種類以上を併用してもよい。 Examples of the urethane resin include a reaction product of a block-type polyisocyanate such as hexamethylene diisocyanate and an active hydrogen-containing compound such as polyester polyol and polyether polyol, and examples of the epoxy resin include polyalkylene ether. Examples include modified epoxy resins and epoxy group-containing compounds in which a flexible skeleton (soft segment) is introduced into the molecular chain. Examples of the melamine resins include cured products of etherified methylol melamine, polyester polyol, and polyether polyol. It is done. Among these, a urethane resin that is a cured product of a block type isocyanate and a polyol is preferable. Moreover, these thermosetting resins may be used individually by 1 type, and may use 2 or more types together.
また、前記熱硬化性樹脂または熱可塑性樹脂（Ｂ）としては、熱可塑性樹脂であれば、としては、たとえばアクリル系樹脂、ウレタン系樹脂およびエステル系樹脂が挙げられ、これらの中でも、ウレタン系樹脂およびエステル系樹脂が好ましい。 Moreover, as said thermosetting resin or thermoplastic resin (B), if it is a thermoplastic resin, as this, an acrylic resin, a urethane-type resin, and ester-type resin will be mentioned, for example, Among these, urethane-type resin And ester resins are preferred.
前記アクリル系樹脂としては、たとえば（メタ）アクリル酸アルキスエステルモノマーから得られる水系エマルジョンや前記モノマーとスチレン、アクリロニトリル等とを共重合させたポリマーエマルジョンが挙げられ、また前記ウレタン系樹脂としては、たとえばポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオールなどのポリオール化合物とポリイシシアネートとを反応させてなる水系エマルジョンが挙げられ、前記エステル系樹脂としては、たとえばハードセグメントにポリエステル、ソフトセグメントにポリエーテルまたはポリエステルを用いたマルチブロック共重合体の水分散型エラストマーが挙げられる。これらの中でも、ポリエステルポリオールまたはポリエーテルポリオールとポリイシシアネートから得られる水分散型ウレタン系樹脂を使用することが好ましい。また、これらの熱可塑性樹脂は、１種類単独で用いてもよく、２種類以上を併用してもよい。 Examples of the acrylic resin include a water-based emulsion obtained from a (meth) acrylic acid alkyl ester monomer, and a polymer emulsion obtained by copolymerizing the monomer with styrene, acrylonitrile, and the urethane resin. For example, an aqueous emulsion formed by reacting a polyol compound such as polyester polyol, polyether polyol, polycarbonate polyol and polyisocyanate can be mentioned. Examples of the ester resin include polyester for a hard segment and polyether or polyester for a soft segment. A water-dispersed elastomer of a multi-block copolymer using Among these, it is preferable to use a water-dispersed urethane resin obtained from polyester polyol or polyether polyol and polyisocyanate. Moreover, these thermoplastic resins may be used individually by 1 type, and may use 2 or more types together.
さらに、前記プライマー層膜形成用塗布液は、プライマー層膜形成用塗布液に通常含まれることのある上記以外の成分、たとえば中和剤、界面活性剤または紫外線吸収剤などを含んでいてもよい。 Further, the primer layer film-forming coating solution may contain components other than those usually mentioned above, such as neutralizing agents, surfactants or ultraviolet absorbers, which are usually contained in the primer layer film-forming coating solution. .
前記プライマー層膜形成用塗布液中の前記熱硬化性樹脂または熱可塑性樹脂（Ｂ）の量は、好ましくは、前記連結型結晶性無機酸化物微粒子群１００体積部に対し、２００〜１０００体積部である。 The amount of the thermosetting resin or the thermoplastic resin (B) in the primer layer film forming coating solution is preferably 200 to 1000 parts by volume with respect to 100 parts by volume of the connected crystalline inorganic oxide fine particle group. It is.
［光学基材用塗膜（硬化膜）および塗膜付基材］
前記光学基材用塗布液を塗布するための光学基材としては、各種のプラスチック基材が挙げられ、これを光学レンズとして使用する場合には、たとえばポリスチレン樹脂、アリル樹脂（特に、芳香族系アリル樹脂）、ポリカーボネート樹脂、ポリチオウレタン樹脂、ポリチオエポキシ樹脂などで構成されたプラスチックレンズ基材が挙げられる。また、光学レンズ以外に用いられるプラスチック基材としては、たとえばＰＭＭＡ樹脂、ＡＢＳ樹脂、エポキシ樹脂、ポリサルフォン樹脂などで構成されたプラスチック基材が挙げられる。 [Coating film for optical substrate (cured film) and substrate with coating film]
Examples of the optical base material for applying the coating liquid for the optical base material include various plastic base materials. When this is used as an optical lens, for example, a polystyrene resin, an allyl resin (especially an aromatic resin). Allyl resin), polycarbonate resin, polythiourethane resin, polythioepoxy resin, and the like. Moreover, as a plastic base material used other than an optical lens, the plastic base material comprised by PMMA resin, ABS resin, an epoxy resin, polysulfone resin etc. is mentioned, for example.
また、昨今では、１．７以上、さらに詳しくは１．７１〜１．８１の比較的高い屈折率を有する光学基材（プラスチックレンズ基材など）が開発されているが、本発明に係る光学基材用塗布液は、これらの高屈折光学基材にも適用することができる。一方、本発明に係る光学基材用塗布液は、１．５０〜１．７０、さらに詳しくは１．５２〜１．６７の比較的低い屈折率を有する光学基材にも適用することができる。 Recently, optical substrates (such as plastic lens substrates) having a relatively high refractive index of 1.7 or higher, more specifically 1.71 to 1.81, have been developed. The coating solution for a substrate can be applied to these high refractive optical substrates. On the other hand, the coating liquid for an optical substrate according to the present invention can be applied to an optical substrate having a relatively low refractive index of 1.50 to 1.70, more specifically 1.52 to 1.67. .
前記プライマー層膜形成用塗布液は、従来公知の方法で前記光学基材上に直接、塗布される。一方、前記ハードコート層膜形成用塗布液は、従来公知の方法で前記光学基材上に直接、塗布されるか、あるいは前記プライマー層膜形成用塗布液から形成された塗膜（プライマー層膜）上に塗布される。 The primer layer film forming coating solution is directly applied onto the optical substrate by a conventionally known method. On the other hand, the coating liquid for forming the hard coat layer film is applied directly on the optical substrate by a conventionally known method, or a coating film (primer layer film) formed from the coating liquid for forming the primer layer film. ) Is applied on top.
このようにして光学基材上に形成された塗膜は、従来公知の方法で硬化させることにより、所望の光学基材用塗膜（硬化膜）、すなわちハードコート層膜やプライマー層膜が形成される。 The coating film thus formed on the optical substrate is cured by a conventionally known method to form a desired coating film for an optical substrate (cured film), that is, a hard coat layer film or a primer layer film. Is done.
以下、本発明を実施例に基づき具体的に説明する。しかし、本発明は、これらの実施例に記載された範囲に限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the scope described in these examples.
［測定方法および評価試験方法］
本発明の実施例その他で使用された測定方法および評価試験方法は以下の通りである。 [Measurement method and evaluation test method]
Measurement methods and evaluation test methods used in Examples and others of the present invention are as follows.
（無機酸化物微粒子等の測定）
（１）平均粒子径の測定方法
無機酸化物微粒子および連結型無機酸化物微粒子（以下、これらを区別せずに「無機酸化物微粒子等」ともいう。）の平均粒子径は、次のように測定した。まず、無機酸化物微粒子等を含む分散液（または混合液）を、水分散ゾルの場合は蒸留水で、メタノール分散ゾルの場合にはメタノールにて約１，０００倍希釈してコロジオン膜付き金属グリッド（応研商事（株））に塗布し２５０Ｗランプにて３０分間照射して溶媒を飛散し測定用サンプルを調製した。この測定用サンプルを用いて、高分解能走査型電子顕微鏡（ＳＥＭ）（（株）日立ハイテクノロジーズ製Ｓ−５５００）により、加速電圧３０ｋＶの条件下、倍率２５万倍でＳＥＭ写真を撮影し、この写真に撮影された任意の１００個以上の無機酸化物微粒子等の粒子径についてそれぞれ目視で観察し、それらの平均をとることにより平均粒子径を求めた。(Measurement of inorganic oxide fine particles, etc.)
(1) Measuring method of average particle diameter The average particle diameter of inorganic oxide fine particles and connected inorganic oxide fine particles (hereinafter also referred to as “inorganic oxide fine particles”, etc. without distinction) is as follows. It was measured. First, a dispersion (or mixed solution) containing inorganic oxide fine particles or the like is diluted 1,000 times with distilled water in the case of an aqueous dispersion sol or with methanol in the case of a methanol dispersion sol, and then a metal with a collodion film. The sample was applied to a grid (Oken Shoji Co., Ltd.) and irradiated with a 250 W lamp for 30 minutes to scatter the solvent to prepare a measurement sample. Using this measurement sample, a high-resolution scanning electron microscope (SEM) (S-5500, manufactured by Hitachi High-Technologies Corporation) was used to take a SEM photograph at a magnification of 250,000 times under the condition of an acceleration voltage of 30 kV. The particle sizes of 100 or more inorganic oxide fine particles or the like photographed in the photograph were each observed visually, and the average particle size was determined by taking the average of them.
（２）粒子の連結個数の測定方法
連結型無機酸化物微粒子群中の無機酸化物微粒子の連結個数は、無機酸化物微粒子等を含む分散液（または混合液）を乾燥させて無機酸化物微粒子等を準備し、高分解能走査型電子顕微鏡（ＳＥＭ）（（株）日立ハイテクノロジーズ製Ｓ−５５００）を用いて、加速電圧３０ｋＶの条件下、倍率２５万倍でＳＥＭ写真を撮影し、この写真に撮影された任意の１００個以上の連結型無機酸化物微粒子群について、無機酸化物微粒子の連結個数をそれぞれ目視で観察し、それらの平均的な値を求めた。(2) Measuring method of number of connected particles The number of connected inorganic oxide particles in the group of connected inorganic oxide particles is determined by drying a dispersion (or mixed solution) containing inorganic oxide particles, etc. Etc., and using a high-resolution scanning electron microscope (SEM) (S-5500 manufactured by Hitachi High-Technologies Corporation), SEM photographs were taken at a magnification of 250,000 times under the condition of an acceleration voltage of 30 kV. With respect to the group of 100 or more connected inorganic oxide fine particles photographed in 1), the number of connected inorganic oxide fine particles was visually observed, and the average value thereof was determined.
（３）比表面積の測定方法
無機酸化物微粒子等を含む分散液を乾燥させて得られた粉体を磁性ルツボ（Ｂ−２型）に約３０ｍｌ採取し、３００℃の温度で２時間乾燥後、デシケータに入れて室温まで冷却し、測定用サンプルを得た。次に、このサンプルを１ｇ取り、全自動表面積測定装置（湯浅アイオニクス社製、マルチソーブ１２型）を用いて、粒子の比表面積（ｍ2／ｇ）をＢＥＴ法にて測定した。(3) Specific surface area measurement method About 30 ml of powder obtained by drying a dispersion containing inorganic oxide fine particles and the like is collected in a magnetic crucible (type B-2) and dried at a temperature of 300 ° C. for 2 hours. Then, the sample was placed in a desiccator and cooled to room temperature to obtain a measurement sample. Next, 1 g of this sample was taken, and the specific surface area (m 2 / g) of the particles was measured by the BET method using a fully automatic surface area measuring device (manufactured by Yuasa Ionics Co., Ltd., Multisorb 12 type).
（４）無機酸化物微粒子等の組成分析方法
＜チタニウム、ケイ素、スズの含有量＞
固形分濃度１０重量％の無機酸化物微粒子等を含む水分散液（または混合液）３ｇを容量３０ｍｌの蓋付きジルコニアボールに採取し、乾燥（２００℃、２０分）させ、焼成（７００℃、５分）した後、Ｎａ2Ｏ2 ２ｇおよびＮａＯＨ １ｇを加えて１５分間溶融した。さらに、ＨＣｌ ５０ｍｌと水２００ｍｌを加えて溶解したのち、純水で５００ｍｌになるよう希釈して試料とした。得られた試料について、ＩＣＰ装置（島津製作所（株）製、ＩＣＰＳ−８１００、解析ソフトウェアＩＣＰＳ−８０００）を用いて、チタニウム、スズ、ケイ素の含有量を酸化物換算基準（ＴｉＯ2、ＳｎＯ2、ＳｉＯ2）で測定した。(4) Composition analysis method for inorganic oxide fine particles, etc. <Content of titanium, silicon, tin>
3 g of an aqueous dispersion (or mixed solution) containing inorganic oxide fine particles having a solid content concentration of 10% by weight was collected in a zirconia ball with a cap of 30 ml, dried (200 ° C., 20 minutes), and fired (700 ° C., 5 minutes), 2 g Na 2 O 2 and 1 g NaOH were added and melted for 15 minutes. Further, 50 ml of HCl and 200 ml of water were added and dissolved, and then diluted to 500 ml with pure water to prepare a sample. About the obtained sample, using an ICP apparatus (Shimadzu Corporation make, ICPS-8100, analysis software ICPS-8000), the content of titanium, tin, and silicon was converted into oxide conversion standards (TiO 2 , SnO 2 , Measured with SiO 2 ).
＜アルミニウム、ジルコニウム、ナトリウム、カリウムの含有量＞
固形分濃度１０重量％の無機酸化物微粒子等を含む水分散液（または混合液）９ｇを容量１００ｍｌの白金皿に採取し、サンドバス上で２００℃で２０分間加熱して乾燥させた後、バーナーで７００℃、５分間加熱して有機物を除去後、ＨＦ １０ｍｌおよびＨ2ＳＯ4 ５ｍｌを加えて白煙が出るまで加熱した。さらに、これを１００ｍｌとなるように純水で希釈した後、アルミニウムジルコニウムはＩＣＰ装置（（株）島津製作所製、ＩＣＰＳ−８１００、解析ソフトウェアＩＣＰＳ−８０００）を用いて酸化物換算基準（Ａｌ2Ｏ3，ＺｒＯ2）で測定し、ナトリウムおよびカリウムは原子吸光装置（（株）日立製作所製、Ｚ−５３００、ソフトウェアＺ−２０００）を用いて酸化物換算基準（Ｎａ2Ｏ、Ｋ2Ｏ）で測定した。<Contents of aluminum, zirconium, sodium and potassium>
After 9 g of an aqueous dispersion (or mixed solution) containing inorganic oxide fine particles having a solid content concentration of 10% by weight was collected in a platinum plate having a capacity of 100 ml and dried by heating at 200 ° C. for 20 minutes on a sand bath, After removing organic matter by heating at 700 ° C. for 5 minutes with a burner, 10 ml of HF and 5 ml of H 2 SO 4 were added and heated until white smoke was emitted. Furthermore, after diluting this with pure water so as to be 100 ml, the aluminum zirconium was converted into an oxide conversion standard (Al 2 O using an ICP device (manufactured by Shimadzu Corporation, ICPS-8100, analysis software ICPS-8000). 3 and ZrO 2 ), and sodium and potassium are measured in terms of oxide (Na 2 O, K 2 O) using an atomic absorption device (manufactured by Hitachi, Ltd., Z-5300, software Z-2000). It was measured.
（５）結晶性の測定方法
無機酸化物微粒子等の分散液（または混合液）を磁性ルツボ（Ｂ−２型）に約３０ｍｌ採取し、１１０℃で１２時間加熱して乾燥させた後、デシケータに入れて室温まで冷却した。次に、冷却物を乳鉢で１５分間粉砕した後、Ｘ線回折装置（理学電気（株）製、ＲＩＮＴ１４００）を用いて結晶形態を測定した。なお、本発明でいう結晶形態は、この測定結果から判定された形態（たとえば、ルチル型など）を示す。(5) Crystallinity measurement method About 30 ml of a dispersion (or mixed solution) of inorganic oxide fine particles or the like is collected in a magnetic crucible (type B-2), dried by heating at 110 ° C. for 12 hours, and then desiccator. And cooled to room temperature. Next, after cooling the cooled product in a mortar for 15 minutes, the crystal form was measured using an X-ray diffractometer (RINT1400, manufactured by Rigaku Corporation). In addition, the crystal | crystallization form said by this invention shows the form (for example, rutile type etc.) determined from this measurement result.
（６）ゼータ電位の測定方法
無機酸化物微粒子等の分散液に蒸留水を添加して、固形分濃度０．１５％に希釈した測定用サンプルを調製した。この測定用サンプルを用いて、ゼータ電位測定装置（Ｍａｌｖｅｒｎ Ｉｎｓｔｒｕｍｅｎｔｓ社製Ｚｅｔａ ｐｏｔｅｎｔｉａｌ ａｎａｌｙｚｅｒ，Ｚｅｔａｓｉｚｅｒ Ｎａｎｏ ＺおよびＭｕｌｔｉ ｐｕｒｐｏｓｅ Ｔｉｔｒａｔｏｒ，ＭＰＴ−２）を用いて、２５℃においてｐＨとゼータ電位を測定した。(6) Method for measuring zeta potential A sample for measurement was prepared by adding distilled water to a dispersion of inorganic oxide fine particles and the like to dilute to a solid content concentration of 0.15%. Using this measurement sample, pH and zeta potential were measured at 25 ° C. using a zeta potential measurement apparatus (Zeta potential analyzer, Zetasizer Nano Z and Multipurpose Titator, MPT-2 manufactured by Malvern Instruments).
（硬化塗膜の測定）
（７）膜硬度（Ｂａｙｅｒ値）の測定方法
磨耗試験機ＢＴＭ（米コルツ社製）およびヘーズ値測定装置（ＮＩＰＰＯＮ ＤＥＮＳＨＯＫＵ製ＮＤＨ２０００）を使用し、実施例または比較例の分散液を用いて作製したプラスチックレンズ基板（以下「被試験レンズ」ともいう。）と基準レンズとのヘーズ値の変化に基づいてＢａｙｅｒ値を算出した。基準レンズとしては、市販のプラスチックレンズ基材ＣＲ−３９基材（ジエチレングリコールビスアリルカーボネート、ＰＰＧ社製モノマー使用、基材の屈折率１．６０）を使用した。(Measurement of cured coating)
(7) Measurement Method of Film Hardness (Bayer Value) Abrasion tester BTM (manufactured by Colts, USA) and a haze value measuring device (NDH2000 manufactured by NIPPON DENSHOKU) were used to produce the dispersions of Examples or Comparative Examples. The Bayer value was calculated based on the change in haze value between the plastic lens substrate (hereinafter also referred to as “the lens under test”) and the reference lens. As a reference lens, a commercially available plastic lens base material CR-39 base material (diethylene glycol bisallyl carbonate, using monomer manufactured by PPG, base material refractive index 1.60) was used.
具体的には、まずそれぞれのレンズのヘーズ値を測定し、基準レンズの初期ヘーズ値をＤ(std0)、被試験レンズの初期ヘーズ値をＤ(test0)とした。それぞれのレンズを上記磨耗試験機のパンに設置し、その上に研磨材（専用砂）５００ｇを充填し、パンを６００回左右に振動させた。振動後のレンズのヘーズ値を測定し、基準レンズのヘーズ値をＤ(stdf)、被試験レンズのヘーズ値をＤ(testf)とした。Ｂａｙｅｒ試験値（Ｒ）を以下の数式から算出した。 Specifically, first, the haze value of each lens was measured, the initial haze value of the reference lens was D (std0), and the initial haze value of the lens under test was D (test0). Each lens was placed in the pan of the wear tester, and 500 g of abrasive material (exclusive sand) was filled thereon, and the pan was vibrated left and right 600 times. The haze value of the lens after vibration was measured, the haze value of the reference lens was D (stdf), and the haze value of the lens under test was D (testf). The Bayer test value (R) was calculated from the following formula.
Ｒ＝［Ｄ(stdf)−Ｄ(std0)］／［Ｄ(testf)−Ｄ(test0)］
（８）塗膜の外観（干渉縞）の評価方法
内壁が黒色である箱の中に蛍光灯「商品名：メロウ５Ｎ」（東芝ライテック（株）製、三波長型昼白色蛍光灯）を取り付け、蛍光灯の光を実施例または比較例の分散液を用いて作製されたプラスチックレンズ基板のハードコート層膜または反射防止層膜表面で反射させ、光の干渉による虹模様（干渉縞）の発生を目視にて確認し、以下の基準で評価した。R = [D (stdf) -D (std0)] / [D (testf) -D (test0)]
(8) Evaluation method of appearance of coating film (interference fringes) A fluorescent lamp "Product name: Mellow 5N" (manufactured by Toshiba Lighting & Technology Co., Ltd., three-wavelength daylight white fluorescent lamp) is mounted in a box whose inner wall is black. Fluorescent lamp light is reflected on the hard coat layer film or antireflection layer film surface of the plastic lens substrate manufactured using the dispersion liquid of the example or comparative example, and the rainbow pattern (interference fringes) is generated by the interference of light. Was visually confirmed and evaluated according to the following criteria.
Ｓ：干渉縞が殆ど無い
Ａ：干渉縞が目立たない
Ｂ：干渉縞が認められるが、許容範囲にある
Ｃ：干渉縞が目立つ
Ｄ：ぎらつきのある干渉縞がある。S: There is almost no interference fringe. A: The interference fringe is not conspicuous. B: Although the interference fringe is recognized, it is within an allowable range. C: The interference fringe is conspicuous. D: There is a glare interference fringe.
（９）塗膜の外観（曇り）の評価方法
内壁が黒色である箱の中に蛍光灯「商品名：メロウ５Ｎ」（東芝ライテック（株）製、三波長型昼白色蛍光灯）を取り付け、プラスチックレンズ基板を蛍光灯の直下に、ハードコート層膜側または反射防止層膜側を蛍光灯に向けて置き、これらの透明度（曇りの程度）をヘーズメーター（ＮＩＰＰＯＮ ＤＥＮＳＨＯＫＵ製ＮＤＨ２０００）にて確認し、以下の基準で評価した。(9) Evaluation method of appearance (cloudiness) of coating film A fluorescent lamp “trade name: Mellow 5N” (manufactured by Toshiba Lighting & Technology Co., Ltd., three-wavelength type daylight white fluorescent lamp) is attached in a box whose inner wall is black. Place the plastic lens substrate directly under the fluorescent lamp, with the hard coat layer film side or antireflection layer film side facing the fluorescent lamp, and check their transparency (degree of cloudiness) with a haze meter (NDH 2000 manufactured by NIPPON DENSHOKU). The evaluation was based on the following criteria.
Ａ：ヘーズ値が０．３％未満
Ｂ：ヘーズ値が０．３％以上〜１．０％未満
Ｃ：ヘーズ値が１．０％以上〜５．０％未満
Ｄ：ヘーズ値が５．０％以上
（１０）塗膜の耐擦傷性の評価方法
実施例または比較例で作製したプラスチックレンズ基板のハードコート層膜側または反射防止層膜側の表面を、ボンスタースチールウール♯００００（日本スチールウール（株）製）に１ｋｇの荷重をかけ、幅１ｃｍ、３ｃｍの距離を５０往復／１００秒の条件で擦った後、スチールウール摺動面積に対する傷自体の面積を目視にて判定し、以下の基準で評価した。A: Haze value is less than 0.3% B: Haze value is from 0.3% to less than 1.0% C: Haze value is from 1.0% to less than 5.0% D: Haze value is 5.0 % Or more (10) Method for evaluating scratch resistance of coating film The surface of the plastic lens substrate produced in Examples or Comparative Examples on the hard coat layer side or antireflection layer side is treated with Bonstar Steel Wool # 0000 (Nippon Steel Wool). (Made by Co., Ltd.) with a load of 1 kg, rubbing a distance of 1 cm in width and 3 cm under the condition of 50 reciprocations / 100 seconds, and then visually determining the area of the scratch against the steel wool sliding area. Evaluated by criteria.
Ａ：２％未満
Ｂ：２％以上〜３０％未満
Ｃ：３０％以上〜６０％未満
Ｄ：６０％以上
（１１）塗膜の密着性の評価方法
ハードコート層膜を有するプラスチックレンズ基板のハードコート層膜側または反射防止層膜側の表面に、ナイフにより１ｍｍ間隔で切れ目を入れ、１平方ｍｍのマス目を１００個形成し、セロハン製粘着テープを、これらのマス目に強く押し付けた後、プラスチックレンズ基板の面内方向に対して９０度方向へ急激に引っ張り、この操作を合計５回行い、剥離していないマス目の数を数え、以下の基準で評価した。A: Less than 2% B: 2% or more and less than 30% C: 30% or more and less than 60% D: 60% or more (11) Evaluation method for adhesion of coating film Hard plastic lens substrate having a hard coat layer film After cutting the surface of the coating layer film side or the antireflection layer film side with a knife at intervals of 1 mm to form 100 squares of 1 mm 2 and pressing the cellophane adhesive tape strongly on these squares The plastic lens substrate was pulled abruptly in the direction of 90 degrees with respect to the in-plane direction of the plastic lens substrate, and this operation was performed a total of 5 times. The number of squares that were not peeled was counted and evaluated according to the following criteria.
○：剥離していないマス目の数が９５個以上
×：剥離していないマス目の数が９５個未満。○: The number of cells not peeled is 95 or more. ×: The number of cells not peeled is less than 95.
（１２）塗膜の耐候的な密着性（耐候的密着性）の評価方法
ハードコート層膜を有するプラスチックレンズ基板をキセノンウエザーメーター（スガ試験機（株）製Ｘ−７５型）で曝露試験をした後、外観の確認および前記の密着性の評価と同様の評価を行い、以下の基準で評価した。なお、曝露時間は、反射防止膜を有している基板は２５０時間、反射防止膜を有していない基板は５０時間とした。(12) Evaluation method of weather resistance of coating film (weather resistance) An exposure test of a plastic lens substrate having a hard coat layer film with a xenon weather meter (X-75 type manufactured by Suga Test Instruments Co., Ltd.) After that, the same evaluation as the confirmation of the appearance and the evaluation of the adhesion was performed, and the following criteria were evaluated. The exposure time was 250 hours for a substrate having an antireflection film, and 50 hours for a substrate having no antireflection film.
○：剥離していないマス目の数が９５個以上
×：剥離していないマス目の数が９５個未満。○: The number of cells not peeled is 95 or more. ×: The number of cells not peeled is less than 95.
（１３）塗膜の耐光性の評価方法
退色試験用水銀ランプ（東芝（株）製Ｈ４００−Ｅ）により紫外線を５０時間照射し、試験前後のプラスチックレンズ基板の透過率測定（日本電子（株）製、Ｖ−５５０）を行い、以下の基準で評価した。なお、ランプとプラスチックレンズ基板との距離は、７０ｍｍとし、ランプの出力は、プラスチックレンズ基板の表面温度が４５±５℃となるように調整した。また、この試験は、反射防止層膜をハードコート層膜の表面に設けたプラスチックレンズ基板を対象として行った。(13) Method for evaluating light resistance of coating film Irradiation with ultraviolet light for 50 hours by mercury lamp for fading test (H400-E manufactured by Toshiba Corporation), and measuring transmittance of plastic lens substrate before and after the test (JEOL Ltd.) Manufactured, V-550) and evaluated according to the following criteria. The distance between the lamp and the plastic lens substrate was 70 mm, and the output of the lamp was adjusted so that the surface temperature of the plastic lens substrate was 45 ± 5 ° C. This test was conducted on a plastic lens substrate having an antireflection layer film provided on the surface of the hard coat layer film.
○：透過率変化が５％未満
△：透過率変化が５％以上〜１０％未満
×：透過率変化が１０％以上
（１４）耐クラック性の評価方法
試験片のレンズ凹凸面および周辺部に発生した微細クラックを目視観察し、以下の基準で評価した。○: Change in transmittance is less than 5% Δ: Change in transmittance is from 5% to less than 10% ×: Change in transmittance is 10% or more (14) Evaluation method for crack resistance The generated fine cracks were visually observed and evaluated according to the following criteria.
○：クラック本数が２本未満
×：クラック本数が２本以上
（１５）粒子の屈折率測定方法
連結型無機酸化物微粒子の屈折率は、塗膜屈折率からの算定法を採用して求めた。具体的には、特開２０１０−１６８２６６号公報の［０１０５］〜［０１１０］に記載した手順により塗膜を作成し、分光エリプソメーター（ソプラ社製、ＳＯＰＲＡ ＥＳＶＧ）を用い、屈折率を測定し算定した。○: Number of cracks is less than 2 ×: Number of cracks is 2 or more (15) Particle refractive index measurement method The refractive index of the linking type inorganic oxide fine particles was determined by adopting a calculation method from the coating film refractive index. . Specifically, a coating film was prepared according to the procedure described in [0105] to [0110] of JP 2010-168266 A, and the refractive index was measured using a spectroscopic ellipsometer (manufactured by Sopra, SOPRA ESVG). Calculated.
Ａ．微粒子分散液、塗料組成物等の調製
［実施例１］
＜工程（１）＞
（操作1.1）チタニウムを主成分とする複合酸化物微粒子（コア粒子）の調製
四塩化チタン（大阪チタニウムテクノロジーズ（株）製）をＴｉＯ2換算基準で７．７５重量％含む四塩化チタン水溶液９３．７ｋｇと、アンモニアを１５重量％含むアンモニア水（宇部興産（株）製）３６．３ｋｇとを混合し、ｐＨ９．５の白色スラリー液を調製した。次いで、このスラリーを濾過した後、純水で洗浄して、固形分含有量が１０重量％の含水チタン酸ケーキ７２．６ｋｇを得た。 A. Preparation of fine particle dispersion, coating composition, etc. [Example 1]
<Step (1)>
(Operation 1.1) Preparation of Composite Oxide Fine Particles (Core Particles) with Titanium as Main Component Titanium tetrachloride aqueous solution containing 7.75% by weight of titanium tetrachloride (Osaka Titanium Technologies Co., Ltd.) on a TiO 2 basis. 7 kg and 36.3 kg of ammonia water containing 15% by weight of ammonia (manufactured by Ube Industries, Ltd.) were mixed to prepare a white slurry liquid having a pH of 9.5. Next, this slurry was filtered and then washed with pure water to obtain 72.6 kg of a hydrous titanate cake having a solid content of 10% by weight.
次に、このケーキに、過酸化水素を３５重量％含む過酸化水素水（三菱瓦斯化学（株）製）８３．０ｋｇと純水４１１．４ｋｇとを加えた後、８０℃の温度で１時間、撹拌下で加熱し、さらに純水１５９．０ｋｇを加えて、過酸化チタン酸をＴｉＯ2換算基準で１重量％含む過酸化チタン酸水溶液を７２６．０ｋｇ得た。この過酸化チタン酸水溶液は、透明な黄褐色でｐＨは８．５であった。Next, 83.0 kg of hydrogen peroxide containing 35% by weight of hydrogen peroxide (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 411.4 kg of pure water are added to the cake, and then at a temperature of 80 ° C. for 1 hour. The mixture was heated under stirring, and 159.0 kg of pure water was further added to obtain 726.0 kg of an aqueous solution of titanic acid peroxide containing 1% by weight of titanic acid peroxide on a TiO 2 basis. This aqueous solution of titanic acid peroxide was transparent yellowish brown and had a pH of 8.5.
次いで、前記過酸化チタン酸水溶液７２．９ｋｇに、陽イオン交換樹脂（三菱化学（株）製）３．５ｋｇを混合して、さらにスズ酸カリウム（昭和化工（株）製）をＳｎＯ2換算基準で１重量％含むスズ酸カリウム水溶液９．１ｋｇを撹拌下で徐々に添加した。Subsequently, 3.5 kg of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was mixed with 72.9 kg of the aqueous solution of titanic acid titanate, and further potassium stannate (manufactured by Showa Kako Co., Ltd.) was converted to SnO 2 conversion standard. Then, 9.1 kg of an aqueous potassium stannate solution containing 1 wt% was gradually added with stirring.
次に、得られた混合物に、カリウムイオンなどを取り込んだ前記陽イオン交換樹脂を分離した後、平均粒子径が７ｎｍのシリカ微粒子を１５重量％含むシリカゾル（日揮触媒化成（株）製）０．８ｋｇおよび純水１８．０ｋｇを混合し、オートクレーブ（耐圧硝子工業（株）製、１２０Ｌ）中で１６５℃の温度で１８時間、加熱することにより、チタニウムを主成分とする複合酸化物微粒子（コア粒子）の水分散液を得た。 Next, after separating the cation exchange resin into which potassium ions and the like have been incorporated into the obtained mixture, silica sol containing 15% by weight of silica fine particles having an average particle diameter of 7 nm (manufactured by JGC Catalysts & Chemicals Co., Ltd.) 8 kg and 18.0 kg of pure water were mixed and heated in an autoclave (pressure-resistant glass industry, 120 L) at a temperature of 165 ° C. for 18 hours to obtain composite oxide fine particles (core) containing titanium as a main component. An aqueous dispersion of particles) was obtained.
得られた水分散液を室温まで冷却した後、限外濾過膜装置（旭化成（株）製、ＡＣＶ−３０１０）で濃縮して、固形分含有量が１０重量％の水分散液（チタニウムを主成分とするコア粒子を含む水分散液（１ａ））１０．０ｋｇを得た。 After cooling the obtained aqueous dispersion to room temperature, it was concentrated with an ultrafiltration membrane device (ACV-3010, manufactured by Asahi Kasei Co., Ltd.), and an aqueous dispersion having a solid content of 10% by weight (mainly titanium). 10.0 kg of an aqueous dispersion (1a) containing core particles as components was obtained.
この水分散液（１ａ）の中に含まれるコア粒子はルチル型の結晶構造を有し、このコア粒子に含まれる金属元素の含有量（酸化物換算値）を測定したところ、ＴｉＯ2が７５．２重量％、ＳｎＯ2が９．３重量％、ＳｉＯ2が１２．２重量％、Ｋ2Ｏが３．３重量％であった。またこのコア粒子の平均粒子径は１８ｎｍであった。The core particles contained in the aqueous dispersion (1a) have a rutile-type crystal structure, and when the content of metal elements (oxide equivalent value) contained in the core particles is measured, TiO 2 is 75. 0.2% by weight, SnO 2 was 9.3% by weight, SiO 2 was 12.2% by weight, and K 2 O was 3.3% by weight. The average particle size of the core particles was 18 nm.
（操作1.2）連結型無機酸化物微粒子群の水分散液（Ｐ−１）の調製
オキシ塩化ジルコニウム（太陽鉱工（株）製）をＺｒＯ2換算基準で２重量％含むオキシ塩化ジルコニウム水溶液２６．３ｋｇに、アンモニアを１５重量％含むアンモニア水を撹拌下で徐々に添加して、ｐＨ８．５のスラリー液を得た。次いで、このスラリーを濾過した後、純水で洗浄して、ジルコニウム成分をＺｒＯ2に換算基準で１０重量％含むケーキ５．２６ｋｇを得た。 (Operation 1.2) Preparation of aqueous dispersion (P-1) of linked inorganic oxide fine particle group Zirconium oxychloride aqueous solution containing 2% by weight of zirconium oxychloride (manufactured by Taiyo Mining Co., Ltd.) in terms of ZrO 2 Aqueous ammonia containing 15% by weight of ammonia was gradually added to 3 kg with stirring to obtain a slurry solution having a pH of 8.5. Next, this slurry was filtered and then washed with pure water to obtain 5.26 kg of a cake containing 10% by weight of a zirconium component in terms of ZrO 2 in terms of conversion.
次に、このケーキ２００ｇに純水１．８０ｋｇを加え、さらに水酸化カリウム（関東化学（株）製）を１０重量％含む水酸化カリウム水溶液１２０ｇを加えてアルカリ性にした後、過酸化水素を３５重量％含む過酸化水素水４００ｇを加えて、５０℃の温度に加熱してこのケーキを溶解した。さらに、純水１．４８ｋｇを加えて、過酸化ジルコン酸をＺｒＯ2換算基準で０．５重量％含む過酸化ジルコン酸水溶液（１）４．０ｋｇを得た。なお、この過酸化ジルコン酸水溶液のｐＨは、１２．２であった。Next, 1.80 kg of pure water was added to 200 g of this cake, and 120 g of an aqueous potassium hydroxide solution containing 10% by weight of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was added to make it alkaline. 400 g of hydrogen peroxide containing wt% was added and heated to a temperature of 50 ° C. to dissolve this cake. Further, 1.48 kg of pure water was added to obtain 4.0 kg of an aqueous zirconate peroxide solution (1) containing 0.5 wt% of zirconate peroxide in terms of ZrO 2 . The aqueous zirconate peroxide solution had a pH of 12.2.
また、市販の水ガラス（ＡＧＣエスアイテック（株）製）を純水にて希釈した後、陽イオン交換樹脂（三菱化学（株）製）を用いて脱アルカリして、珪酸をＳｉＯ2換算基準で２重量％含む珪酸水溶液（１）を得た。なお、この珪酸水溶液液のｐＨは、２．３であった。Moreover, after diluting a commercially available water glass (manufactured by AGC S-Tech Co., Ltd.) with pure water, it is dealkalized using a cation exchange resin (manufactured by Mitsubishi Chemical Corporation), and silicic acid is converted into a SiO 2 conversion standard. An aqueous silicic acid solution (1) containing 2% by weight was obtained. The pH of the aqueous silicic acid solution was 2.3.
次に、上記操作1.1で得られた、チタニウムを主成分とするコア粒子を含む水分散液（１ａ）３．０ｋｇに純水１２．０ｋｇを加えて固形分含有量を２重量％としたものを、陽イオン交換樹脂（三菱化学（株）製）を用いて脱アルカリしてそのｐＨを２．８に調整し、次いで前記陽イオン交換樹脂を分離し、室温で１時間撹拌して、粒子同士が連結した無機酸化物微粒子の分散液（１ｂ）を得た。なお、この分散液の中の無機酸化物微粒子が連結していることは、この分散液を抜き取り、これをＳＥＭ観察することにより確認した。 Next, 12.0 kg of pure water was added to 3.0 kg of the aqueous dispersion (1a) containing core particles mainly composed of titanium obtained in the above operation 1.1, so that the solid content was 2% by weight. The cation exchange resin (manufactured by Mitsubishi Chemical Co., Ltd.) is used to adjust the pH to 2.8, and then the cation exchange resin is separated and stirred at room temperature for 1 hour to obtain particles. A dispersion (1b) of inorganic oxide fine particles in which they were connected was obtained. In addition, it was confirmed by extracting this dispersion liquid and observing this by SEM that the inorganic oxide fine particles in this dispersion liquid were connected.
さらに、この無機酸化物微粒子を含む分散液の、前述の測定方法でゼータ電位測定を行った際のｐＨは３．８、ゼータ電位は−５０ｍＶであった。
＜工程（２）＞
次に、この無機酸化物微粒子分散液（１ｂ）に水酸化カリウム水溶液を加えて、分散液のｐＨを１０．０に調整して、この分散液を９０℃の温度に加熱した後、これに前記過酸化ジルコン酸水溶液（１）１２．０ｋｇおよび珪酸水溶液（１）３．０ｋｇを同時に徐々に添加し、添加終了後、さらに９０℃の温度に保ちながら攪拌下で１時間熟成を行い、混合液（１ｃ）を得た。ここで、過酸化ジルコン酸水溶液（１）中に含まれるジルコン酸をＺｒＯ2で表し、珪酸水溶液（１）中に含まれる珪酸をＳｉＯ2で表したとき（以下の重量比の式では「ＳｉＯ2-(1)」と表す。）、これらのモル比（ＺｒＯ2／ＳｉＯ2）は３３／６７であった。また、混合液（１ｃ）中の無機酸化物微粒子に含まれる金属の重量を酸化物（ＴｉＯ2、ＳｎＯ2、ＳｉＯ2（以下の重量比の式では「ＳｉＯ2-(2)」と表す。））の重量に換算すると、重量比（（ＺｒＯ2＋ＳｉＯ2-(1)）／（ＴｉＯ2＋ＳｎＯ2＋ＳｉＯ2-(2)））は４０／１００であった。Further, the dispersion containing the inorganic oxide fine particles had a pH of 3.8 and a zeta potential of −50 mV when the zeta potential was measured by the measurement method described above.
<Step (2)>
Next, an aqueous potassium hydroxide solution is added to the inorganic oxide fine particle dispersion (1b) to adjust the pH of the dispersion to 10.0, and the dispersion is heated to a temperature of 90 ° C. 12.0 kg of the aqueous zirconate peroxide solution (1) and 3.0 kg of the silicic acid aqueous solution (1) were gradually added at the same time. After the addition was completed, the mixture was aged with stirring for 1 hour while maintaining the temperature at 90 ° C. A liquid (1c) was obtained. Here, when the zirconic acid contained in the zirconium peroxide aqueous solution (1) is represented by ZrO 2 and the silicic acid contained in the silicic acid aqueous solution (1) is represented by SiO 2 (in the following weight ratio formula, “SiO 2- (1) ”), and the molar ratio (ZrO 2 / SiO 2 ) was 33/67. In addition, the weight of the metal contained in the inorganic oxide fine particles in the mixed liquid (1c) is represented by oxide (TiO 2 , SnO 2 , SiO 2 (“SiO 2- (2)” in the following weight ratio formula). )), The weight ratio ((ZrO 2 + SiO 2- (1)) / (TiO 2 + SnO 2 + SiO 2- (2))) was 40/100.
＜工程（３）＞
次いで、この混合液（１ｃ）をオートクレーブ（耐圧硝子工業（株）製、５０Ｌ）に入れて、１６０℃の温度で１８時間、加熱処理を行なったのち、室温まで冷却して、限外濾過膜装置（旭化成（株）製、ＳＩＰ−１０１３）を用いて固形分含有量１０重量％に濃縮することにより、チタニウムを主成分とするコア粒子の表面を、ジルコニウムおよびケイ素を含む複合酸化物からなるシェルで被覆してなる無機酸化物微粒子（１）の透明乳白色水分散液（以下、「Ｐ−１」ともいう。）を調製した。<Step (3)>
Next, this mixed liquid (1c) is put in an autoclave (manufactured by Pressure Glass Industrial Co., Ltd., 50 L), heat-treated at a temperature of 160 ° C. for 18 hours, cooled to room temperature, and then subjected to an ultrafiltration membrane. The surface of the core particles mainly composed of titanium is composed of a complex oxide containing zirconium and silicon by concentrating to a solid content of 10% by weight using a device (Asahi Kasei Co., Ltd., SIP-1013). A transparent milky white aqueous dispersion (hereinafter also referred to as “P-1”) of inorganic oxide fine particles (1) coated with a shell was prepared.
この無機酸化物微粒子（１）は４〜５個連結して連結型微粒子群を構成しており、連結型微粒子群の比表面積は２６６ｍ2／ｇであった。以下、上記水分散液（Ｐ−１）を「連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−１）」ともいう。4 to 5 inorganic oxide fine particles (1) were connected to form a connected fine particle group, and the specific surface area of the connected fine particle group was 266 m 2 / g. Hereinafter, the aqueous dispersion (P-1) is also referred to as “aqueous dispersion (P-1) of linked crystalline inorganic oxide fine particle group”.
この連結型微粒子群のＸ線回折では結晶性ピークが検出され、結晶構造はルチル型であった。 A crystallinity peak was detected by X-ray diffraction of this connected fine particle group, and the crystal structure was a rutile type.
この連結型微粒子群に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＴｉＯ2が５２．１重量％、ＳｎＯ2が６．５重量％、ＳｉＯ2が２５．０重量％、ＺｒＯ2が１４．８重量％、Ｋ2Ｏが１．６重量％であった。ここで、この連結型微粒子群に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は０．２８９であった。When the proportion of metal components contained in the connected fine particle group (as oxide value) was measured, TiO 2 was 52.1 wt%, SnO 2 was 6.5 wt%, SiO 2 was 25.0 wt%, ZrO 2 was 14.8% by weight and K 2 O was 1.6% by weight. Here, the molar ratio (ZrO 2 / SiO 2 ) was 0.289 when zirconium contained in this connected fine particle group was expressed as ZrO 2 and silicon was expressed as SiO 2 .
（操作1.3）連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−１）の調製
上記操作1.2で得られた連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−１）１４７０ｇに陽イオン交換樹脂を混合して脱イオン処理した後、前記イオン交換樹脂を分離して得られた分散液に、表面処理剤としてのテトラエトキシシラン（多摩化学工業（株）製）を溶解させたメタノール溶液を撹拌下で添加した後、５０℃の温度で６時間、加熱した。 (Operation 1.3) Preparation of Methanol Dispersion (MP-1) of Linked Crystalline Inorganic Oxide Fine Particle Group 1470 g of Aqueous Dispersion (P-1) of Linked Crystalline Inorganic Oxide Fine Particle Group Obtained in Operation 1.2 above After mixing the cation exchange resin and deionizing, tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd.) as a surface treatment agent is dissolved in the dispersion obtained by separating the ion exchange resin. The methanol solution was added with stirring and then heated at a temperature of 50 ° C. for 6 hours.
次に、得られた混合液を室温まで冷却してから、限外濾過膜（旭化成（株）製濾過膜、ＳＩＰ−１０１３）を用いて分散媒を水からメタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）に置換した。 Next, after cooling the obtained liquid mixture to room temperature, the dispersion medium was changed from water to methanol (manufactured by Hayashi Junyaku Co., Ltd.) using an ultrafiltration membrane (filter membrane manufactured by Asahi Kasei Co., Ltd., SIP-1013). , Methyl alcohol concentration: 99.9% by weight).
得られた無機酸化物微粒子のメタノール分散液（以下「ＭＰ−１」という）の水分含有量は約０．５重量％、固形分濃度は３０重量％であった。 The resulting aqueous dispersion of inorganic oxide fine particles in methanol (hereinafter referred to as “MP-1”) had a water content of about 0.5 wt% and a solid content concentration of 30 wt%.
この無機酸化物微粒子の平均粒子径は１８ｎｍであり、この微粒子は４〜５個連結して連結型微粒子群を構成しており、連結型微粒子群の比表面積は３０６ｍ2／ｇであった。以下、上記分散液（ＭＰ−１）を「連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−１）」ともいう。The average particle diameter of the inorganic oxide fine particles was 18 nm, and 4 to 5 fine particles were connected to form a connected fine particle group, and the specific surface area of the connected fine particle group was 306 m 2 / g. Hereinafter, the dispersion (MP-1) is also referred to as “methanol dispersion (MP-1) of linked crystalline inorganic oxide fine particle group”.
このメタノール分散液（ＭＰ−１）中の連結型微粒子群に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＴｉＯ2が４７．９重量％、ＳｎＯ2が５．５重量％、ＳｉＯ2が３２．０重量％、ＺｒＯ2が１３．１重量％、Ｋ2Ｏが１．６重量％であった。ここで、この連結型微粒子群に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は０．２００であった。When the ratio of metal components contained in the linked fine particle group in this methanol dispersion (MP-1) (as oxide) was measured, 47.9% by weight of TiO 2 and 5.5% by weight of SnO 2 were measured. SiO 2 was 32.0% by weight, ZrO 2 was 13.1% by weight, and K 2 O was 1.6% by weight. Here, the molar ratio (ZrO 2 / SiO 2 ) when zirconium contained in the group of connected fine particles was expressed as ZrO 2 and silicon was expressed as SiO 2 was 0.200.
（操作1.4）ハードコート層膜形成用塗料組成物（Ｈ１）の調製
γ−グリシドキシプロピルトリメトキシシラン（東レ・ダウコーニング（株）製Ｚ−６０４０）１８０．４ｇおよびメタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）３１．９ｇの混合液中に、混合液を攪拌しながら０．０１Ｎの塩酸水溶液６１．５ｇを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行い、加水分解液を得た。 (Operation 1.4) Preparation of Hard Coat Layer Film Forming Coating Composition (H1 ) 180.4 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Hayashi Junyaku ( Co., Ltd., methyl alcohol concentration: 99.9% by weight) 61.5 g of 0.01N hydrochloric acid aqueous solution was added dropwise to 31.9 g of the mixture while stirring the mixture. Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.
次いで、この加水分解液に、メタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）２７８．５ｇおよび上記操作1.3で調製した固形分濃度３０重量％の連結型無機酸化物微粒子群のメタノール分散液（ＭＰ−１）３９８．８ｇ、プロピレングリコールモノメチルエーテル（ダウケミカル製）４０．６ｇ、トリス（２，４−ペンタンジオナト）アルミニウム（III）（東京化成工業（株）製）７．２ｇおよびレベリング剤としてのシリコーン系界面活性剤（東レ・ダウコーニング（株）製、Ｌ−７６０４）１．１ｇを加え、室温で一昼夜攪拌して、ハードコート層膜形成用塗料組成物（Ｈ１）を調製した。 Subsequently, to this hydrolyzed solution, 278.5 g of methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a linked inorganic oxide having a solid content concentration of 30 wt% prepared in the above-mentioned operation 1.3 Fine particle group methanol dispersion (MP-1) 398.8 g, propylene glycol monomethyl ether (Dow Chemical) 40.6 g, tris (2,4-pentanedionato) aluminum (III) (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 7.2 g and 1.1 g of a silicone surfactant as a leveling agent (manufactured by Toray Dow Corning Co., Ltd., L-7604) were added and stirred at room temperature for a whole day and night to form a coating composition for forming a hard coat layer film (H1) was prepared.
（操作1.5）ハードコート層膜形成用塗料組成物（Ｈ２）の調製
γ−グリシドキシプロピルトリメトキシシラン（東レ・ダウコーニング（株）製Ｚ−６０４０）１６１．９ｇおよびメタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）２８．７ｇの混合液中に、混合液を攪拌しながら０．０１Ｎの塩酸水溶液５５．２ｇを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行い、加水分解液を得た。 (Operation 1.5) Preparation of Hard Coat Layer Film Forming Coating Composition (H2 ) 161.9 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Hayashi Junyaku ( 55.2 g of a 0.01N hydrochloric acid aqueous solution was added dropwise to 28.7 g of a mixed solution, manufactured by Co., Ltd. and methyl alcohol concentration: 99.9% by weight. Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.
次いで、この加水分解液に、メタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）２４５．７ｇおよび上記操作1.3で調製した固形分濃度３０重量％の連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−１）４６０．３ｇ、プロピレングリコールモノメチルエーテル（ダウケミカル製）４０．６ｇ、トリス（２，４−ペンタンジオナト）アルミニウム（III）（東京化成工業（株）製）６．５ｇおよびレベリング剤としてのシリコーン系界面活性剤（東レ・ダウコーニング（株）製、Ｌ−７６０４）１．１ｇを加え、室温で一昼夜攪拌して、ハードコート層膜形成用塗料組成物（Ｈ２）を調製した。 Subsequently, 245.7 g of methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) was added to this hydrolyzed solution, and a linked crystalline inorganic inorganic material having a solid content concentration of 30 wt% prepared in the above operation 1.3. 460.3 g of methanol dispersion (MP-1) of oxide fine particle group, 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentanedionato) aluminum (III) (Tokyo Chemical Industry Co., Ltd.) )) 6.5 g and 1.1 g of silicone surfactant as a leveling agent (Toray Dow Corning Co., Ltd., L-7604) were added, and the mixture was stirred overnight at room temperature to form a coating film for forming a hard coat layer. Composition (H2) was prepared.
（操作1.6）プライマー層膜形成用塗料組成物（Ｙ１）の調製
市販の熱可塑性樹脂であるポリウレタンのエマルジョン「スーパーフレックス１５０」（第一工業製薬製、水分散型ウレタンエラストマー固形分含有量３０％）２０５．３ｇに、上記操作1.3で調製した連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−１）１６４．２ｇおよびイオン交換水９６．９ｇを加えて１時間攪拌し、次いで、メタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）５３１．１ｇ、およびレベリング剤としてのシリコーン系界面活性剤（東レ・ダウコーニング（株）製、Ｌ−７６０４）０．３ｇを加えて室温で一昼夜攪拌して、プライマー層膜形成用塗料組成物（Ｙ１）を調製した。 (Operation 1.6) Preparation of primer layer film-forming coating composition (Y1) Polyurethane emulsion “Superflex 150”, which is a commercially available thermoplastic resin (Daiichi Kogyo Seiyaku Co., Ltd., water-dispersed urethane elastomer solid content: 30% ) To 205.3 g, 164.2 g of a methanol dispersion (MP-1) of the linked crystalline inorganic oxide fine particle group prepared in the above operation 1.3 and 96.9 g of ion-exchanged water were added and stirred for 1 hour. 531.1 g of methanol (manufactured by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight), and silicone surfactant as a leveling agent (manufactured by Toray Dow Corning Co., Ltd., L-7604) 3 g was added and stirred at room temperature for a whole day and night to prepare a primer layer film-forming coating composition (Y1).
（操作1.7）プライマー層膜形成用塗料組成物（Ｙ２）の調製
市販の熱可塑性樹脂であるポリウレタンのエマルジョン「スーパーフレックス１５０」（第一工業製薬製、水分散型ウレタンエラストマー固形分含有量３０％）１６０．７ｇに、上記操作1.3で調製した連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−１）２０８．９ｇおよびイオン交換水９６．９ｇを加えて１時間攪拌し、次いで、メタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）５３１．１ｇ、およびレベリング剤としてのシリコーン系界面活性剤（東レ・ダウコーニング（株）製、Ｌ−７６０４）０．３ｇを加えて室温で一昼夜攪拌して、プライマー層膜形成用塗料組成物（Ｙ２）を調製した。 (Operation 1.7) Preparation of primer layer film-forming coating composition (Y2) Polyurethane emulsion “Superflex 150”, a commercially available thermoplastic resin (Daiichi Kogyo Seiyaku Co., Ltd., water-dispersed urethane elastomer solid content: 30% ) To 160.7 g, 208.9 g of a methanol dispersion (MP-1) of the linked crystalline inorganic oxide fine particle group prepared in the above operation 1.3 and 96.9 g of ion-exchanged water were added and stirred for 1 hour, 531.1 g of methanol (manufactured by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight), and silicone surfactant as a leveling agent (manufactured by Toray Dow Corning Co., Ltd., L-7604) 3 g was added and stirred at room temperature for a whole day and night to prepare a primer layer film-forming coating composition (Y2).
［実施例２］
（操作2.2）連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−２）の調製
実施例１の操作1.2において、無機酸化物微粒子分散液（１ｂ）に添加する過酸化ジルコン酸水溶液の量を１２．０ｋｇから４．６ｋｇに変更し、珪酸水溶液の量を３．０ｋｇから４．９ｋｇに変更したこと以外は上記操作1.2と同様の操作を行うことにより、チタニウムを主成分とするコア粒子の表面を、ジルコニウムとケイ素を含む複合酸化物からなるシェルで被覆してなる無機酸化物微粒子（２）の透明乳白色水分散液（以下、「Ｐ−２」という）を調製した。なお、この調製の過程で、操作1.2と同様に、粒子同士が疑似的に連結した無機酸化物微粒子分散液が得られた。[Example 2]
(Operation 2.2) Preparation of Aqueous Dispersion (P-2) of Linked Crystalline Inorganic Oxide Fine Particle Group In operation 1.2 of Example 1, the aqueous solution of zirconate peroxide added to inorganic oxide fine particle dispersion (1b) By changing the amount from 12.0 kg to 4.6 kg and changing the amount of the silicic acid aqueous solution from 3.0 kg to 4.9 kg, the same operation as in the above operation 1.2 is performed. A transparent milky white aqueous dispersion (hereinafter referred to as “P-2”) of inorganic oxide fine particles (2) formed by coating the surfaces of the particles with a shell made of a complex oxide containing zirconium and silicon was prepared. In the course of this preparation, an inorganic oxide fine particle dispersion in which particles were pseudo-connected was obtained in the same manner as in Operation 1.2.
ここで、過酸化ジルコン酸水溶液中に含まれるＺｒと珪酸水溶液中に含まれるＳｉとのモル比（Ｚｒ／Ｓｉ）は１０／９０であった。 Here, the molar ratio (Zr / Si) between Zr contained in the aqueous zirconate peroxide solution and Si contained in the aqueous silicic acid solution was 10/90.
この無機酸化物微粒子（２）は４〜５個連結して連結型微粒子群を構成しており、この連結型微粒子群の比表面積は２７２ｍ2／ｇであった。以下、上記水分散液（Ｐ−２）を「連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−２）」ともいう。4 to 5 inorganic oxide fine particles (2) are connected to form a connected fine particle group, and the specific surface area of the connected fine particle group is 272 m 2 / g. Hereinafter, the aqueous dispersion (P-2) is also referred to as “aqueous dispersion (P-2) of linked crystalline inorganic oxide fine particle group”.
この連結型微粒子群のＸ線回折では結晶性ピークが検出され、結晶構造はルチル型であった。 A crystallinity peak was detected by X-ray diffraction of this connected fine particle group, and the crystal structure was a rutile type.
この連結型微粒子群に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＴｉＯ2が５２．４重量％、ＳｎＯ2が６．４重量％、ＳｉＯ2が３４．０重量％、ＺｒＯ2が５．７重量％、Ｋ2Ｏが１．５重量％であった。ここで、この連結型微粒子群に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は０．０８２であった。When the ratio of metal components contained in the connected fine particle group (oxide equivalent value) was measured, TiO 2 was 52.4 wt%, SnO 2 was 6.4 wt%, SiO 2 was 34.0 wt%, ZrO 2 was 5.7% by weight and K 2 O was 1.5% by weight. Here, the molar ratio (ZrO 2 / SiO 2 ) was 0.082 when zirconium contained in the group of connected fine particles was expressed as ZrO 2 and silicon was expressed as SiO 2 .
（操作2.3）連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−２）の調製
実施例１の操作1.3において、上記操作1.2で調製した連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−１）１４７０ｇに替えて上記操作2.2で調製した連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−２）１４７０ｇを用いたこと以外は上記操作1.3と同様の操作を行うことにより、無機酸化物微粒子のメタノール分散液（以下「ＭＰ−２」という）を調製した。 (Operation 2.3) Preparation of Methanol Dispersion (MP-2) of Linked Crystalline Inorganic Oxide Fine Particle Group In Operation 1.3 of Example 1, water dispersion of the linked crystalline inorganic oxide fine particle group prepared in Operation 1.2 above The same operation as in the above operation 1.3 is performed except that 1470 g of the aqueous dispersion (P-2) of the linked crystalline inorganic oxide fine particle group prepared in the above operation 2.2 is used instead of the liquid (P-1) 1470 g. Thus, a methanol dispersion of inorganic oxide fine particles (hereinafter referred to as “MP-2”) was prepared.
このメタノール分散液（ＭＰ−２）の水分含有量は約０．５重量％、固形分濃度は３０重量％であった。 The methanol dispersion (MP-2) had a water content of about 0.5% by weight and a solid content concentration of 30% by weight.
この無機酸化物微粒子は４〜５個連結して連結型微粒子群を構成しており、連結型微粒子群の比表面積は３１０ｍ2／ｇであった。以下、上記分散液（ＭＰ−２）を「連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−２）」ともいう。Four to five inorganic oxide fine particles are connected to form a connected fine particle group, and the specific surface area of the connected fine particle group is 310 m 2 / g. Hereinafter, the dispersion (MP-2) is also referred to as “methanol dispersion (MP-2) of linked crystalline inorganic oxide fine particle group”.
このメタノール分散液（ＭＰ−２）中の連結型微粒子群に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＴｉＯ2４６．６が重量％、ＳｎＯ2５．８が重量％、ＳｉＯ2が４１．１重量％、ＺｒＯ2が５．０重量％、Ｋ2Ｏが１．５重量％であった。ここで、この連結型微粒子群に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は０．０５９であった。When the proportion of metal components (oxide equivalent value) contained in the linked fine particle group in this methanol dispersion (MP-2) was measured, TiO 2 46.6 was wt% and SnO 2 5.8 was wt%. SiO 2 was 41.1% by weight, ZrO 2 was 5.0% by weight, and K 2 O was 1.5% by weight. Here, the molar ratio (ZrO 2 / SiO 2 ) when zirconium contained in the group of connected fine particles was expressed as ZrO 2 and silicon was expressed as SiO 2 was 0.059.
（操作2.4）ハードコート層膜形成用塗料組成物（Ｈ３）の調製
γ−グリシドキシプロピルトリメトキシシラン（東レ・ダウコーニング（株）製Ｚ−６０４０）１７３．８ｇおよびメタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）３０．８ｇの混合液中に、混合液を攪拌しながら０．０１Ｎの塩酸水溶液５９．２ｇを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行い、加水分解液を得た。 (Operation 2.4) Preparation of Hard Coat Layer Film Forming Coating Composition (H3 ) 173.8 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Hayashi Junyaku ( Co., Ltd., methyl alcohol concentration: 99.9% by weight) Into a mixed solution of 30.8 g, 59.2 g of 0.01N hydrochloric acid aqueous solution was dropped while stirring the mixed solution. Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.
次いで、この加水分解液に、メタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）２６６．８ｇおよび上記操作2.3で調製した固形分濃度３０重量％の連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−２）４２０．８ｇ、プロピレングリコールモノメチルエーテル（ダウケミカル製）４０．６ｇ、トリス（２，４−ペンタンジオナト）アルミニウム（III）（東京化成工業（株）製）７．０ｇおよびレベリング剤としてのシリコーン系界面活性剤（東レ・ダウコーニング（株）製、Ｌ−７６０４）１．１ｇを加え、室温で一昼夜攪拌して、ハードコート層膜形成用塗料組成物（Ｈ３）を調製した。 Subsequently, 266.8 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) was added to this hydrolyzate and a solid crystalline concentration of 30 wt% solid content prepared in the above operation 2.3 was added. 420.8 g of methanol dispersion (MP-2) of oxide fine particle group, 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentanedionato) aluminum (III) (Tokyo Chemical Industry Co., Ltd.) )) 7.0 g of silicone surfactant as a leveling agent (L-7604, manufactured by Toray Dow Corning Co., Ltd.) was added, and the mixture was stirred overnight at room temperature to form a coating film for forming a hard coat layer. A composition (H3) was prepared.
［実施例３］
（操作3.2）連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−３）の調製
実施例１の操作1.2において、無機酸化物微粒子分散液（１ｂ）に添加する過酸化ジルコン酸水溶液の量を１２．０ｋｇから２３．４ｋｇに変更し、珪酸水溶液の量を３．０ｋｇから０．１５ｋｇに変更したこと以外は上記操作1.2と同様の操作を行い、チタニウムを主成分とするコア粒子の表面を、ジルコニウムとケイ素を含む複合酸化物からなるシェルで被覆してなる無機酸化物微粒子（３）の透明乳白色水分散液（以下、「Ｐ−３」という）を調製した。なお、この調製の過程で、操作1.2と同様に、粒子同士が疑似的に連結した無機酸化物微粒子分散液が得られた。[Example 3]
(Operation 3.2) Preparation of Aqueous Dispersion (P-3) of Linked Crystalline Inorganic Oxide Fine Particle Group In operation 1.2 of Example 1, the aqueous solution of zirconate peroxide added to inorganic oxide fine particle dispersion (1b) The same procedure as in the above procedure 1.2 was performed except that the amount was changed from 12.0 kg to 23.4 kg and the amount of the silicic acid aqueous solution was changed from 3.0 kg to 0.15 kg. A transparent milky white aqueous dispersion (hereinafter referred to as “P-3”) of inorganic oxide fine particles (3) obtained by coating the surface with a shell made of a complex oxide containing zirconium and silicon was prepared. In the course of this preparation, an inorganic oxide fine particle dispersion in which particles were pseudo-connected was obtained in the same manner as in Operation 1.2.
ここで、過酸化ジルコン酸水溶液中に含まれるジルコン酸をＺｒＯ2で表し、珪酸水溶液中に含まれる珪酸をＳｉＯ2で表したとき、モル比（ＺｒＯ2／ＳｉＯ2）は９５／５であった。Here, when the zirconic acid contained in the aqueous zirconium peroxide solution is represented by ZrO 2 and the silicic acid contained in the silicic acid aqueous solution is represented by SiO 2 , the molar ratio (ZrO 2 / SiO 2 ) was 95/5. It was.
この無機酸化物微粒子（３）は５〜１０個連結して連結型微粒子群を構成しており、連結型微粒子群の比表面積は２５８ｍ2／ｇであった。以下、上記水分散液（Ｐ−３）を「連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−３）」ともいう。5 to 10 inorganic oxide fine particles (3) were connected to form a connected fine particle group, and the specific surface area of the connected fine particle group was 258 m 2 / g. Hereinafter, the aqueous dispersion (P-3) is also referred to as “aqueous dispersion (P-3) of linked crystalline inorganic oxide fine particle group”.
この連結型微粒子群のＸ線回折では結晶性ピークが検出され、結晶構造はルチル型であった。 A crystallinity peak was detected by X-ray diffraction of this connected fine particle group, and the crystal structure was a rutile type.
この連結型微粒子群に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＴｉＯ2が６５．９重量％、ＳｎＯ2が８．２重量％、ＳｉＯ2が１１．４重量％、ＺｒＯ2が１２．９重量％、Ｋ2Ｏが１．６重量％であった。ここで、この連結型微粒子群に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は０．５５２であった。When the ratio of metal components contained in the connected fine particle group (oxide equivalent value) was measured, TiO 2 was 65.9 wt%, SnO 2 was 8.2 wt%, SiO 2 was 11.4 wt%, ZrO 2 was 12.9% by weight and K 2 O was 1.6% by weight. Here, the molar ratio (ZrO 2 / SiO 2 ) was 0.552 when zirconium contained in this connected fine particle group was expressed as ZrO 2 and silicon was expressed as SiO 2 .
（操作3.3）連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−３）の調製
実施例１の操作1.3において、上記操作1.2で調製した連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−１）１４７０ｇに替えて上記操作3.2で調製した連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−３）１４７０ｇを用いたこと以外は上記操作1.3と同様の操作を行うことにより、無機酸化物微粒子のメタノール分散液（以下「ＭＰ−３」という）を調製した。 (Operation 3.3) Preparation of Methanol Dispersion (MP-3) of Linked Crystalline Inorganic Oxide Fine Particle Group In Operation 1.3 of Example 1, water dispersion of the linked crystalline inorganic oxide fine particle group prepared in Operation 1.2 above The same operation as in the above operation 1.3 is performed except that 1470 g of the aqueous dispersion (P-3) of the linked crystalline inorganic oxide fine particle group prepared in the above operation 3.2 is used instead of the liquid (P-1) 1470 g. Thus, a methanol dispersion of inorganic oxide fine particles (hereinafter referred to as “MP-3”) was prepared.
このメタノール分散液（ＭＰ−３）の水分含有量は約０．５重量％、固形分濃度は３０重量％であった。 This methanol dispersion (MP-3) had a water content of about 0.5% by weight and a solid content concentration of 30% by weight.
この無機酸化物微粒子は５〜１０個連結して連結型微粒子群を構成しており、連結型微粒子群の比表面積は２９６ｍ2／ｇであった。以下、上記分散液（ＭＰ−３）を「連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−３）」ともいう。5 to 10 inorganic oxide fine particles are connected to form a connected fine particle group, and the specific surface area of the connected fine particle group is 296 m 2 / g. Hereinafter, the dispersion (MP-3) is also referred to as “methanol dispersion (MP-3) of linked crystalline inorganic oxide fine particle group”.
このメタノール分散液（ＭＰ−３）中の連結型微粒子群に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＴｉＯ2が６０．７重量％、ＳｎＯ2が７．５重量％、ＳｉＯ2が１８．２重量％、ＺｒＯ2が１２．０重量％、Ｋ2Ｏが１．６重量％であった。ここで、この連結型微粒子群に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は０．３２２であった。When the ratio of metal components contained in the linked fine particle group in this methanol dispersion (MP-3) (as oxide value) was measured, TiO 2 was 60.7 wt% and SnO 2 was 7.5 wt%. SiO 2 was 18.2% by weight, ZrO 2 was 12.0% by weight, and K 2 O was 1.6% by weight. Here, the molar ratio (ZrO 2 / SiO 2 ) was 0.322 when zirconium contained in this connected fine particle group was represented as ZrO 2 and silicon was represented as SiO 2 .
（操作3.4）ハードコート層膜形成用塗料組成物（Ｈ４）の調製
γ−グリシドキシプロピルトリメトキシシラン（東レ・ダウコーニング（株）製Ｚ−６０４０）１８３．８ｇおよびメタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）３２．６ｇの混合液中に、混合液を攪拌しながら０．０１Ｎの塩酸水溶液６２．７ｇを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行い、加水分解液を得た。 (Operation 3.4) Preparation of Hard Coat Layer Film Forming Coating Composition (H4 ) 183.8 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Hayashi Junyaku ( 62.7 g of a 0.01N hydrochloric acid aqueous solution was added dropwise to 32.6 g of a mixed solution (made by Co., Ltd., methyl alcohol concentration: 99.9 wt%) while stirring the mixed solution. Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.
次いで、この加水分解液に、メタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）２８４．７ｇおよび上記操作3.3で調製した固形分濃度３０重量％の連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−３）３８７．２ｇ、プロピレングリコールモノメチルエーテル（ダウケミカル製）４０．６ｇ、トリス（２，４−ペンタンジオナト）アルミニウム（III）（東京化成工業（株）製）７．４ｇおよびレベリング剤としてのシリコーン系界面活性剤（東レ・ダウコーニング（株）製、Ｌ−７６０４）１．１ｇを加え、室温で一昼夜攪拌して、ハードコート層膜形成用塗料組成物（Ｈ４）を調製した。 Next, to this hydrolyzed solution, 284.7 g of methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid crystalline concentration of 30 wt% prepared in the above operation 3.3 were used. 387.2 g of methanol dispersion (MP-3) of oxide fine particle group, 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentanedionato) aluminum (III) (Tokyo Chemical Industry Co., Ltd.) )) 7.4 g and 1.1 g of a silicone surfactant as a leveling agent (manufactured by Toray Dow Corning Co., Ltd., L-7604) were added and stirred at room temperature for a whole day and night to form a paint for forming a hard coat layer film A composition (H4) was prepared.
［実施例４］
（操作4.2）連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−４）の調製
実施例１の操作1.2において、無機酸化物微粒子分散液（１ｂ）に添加する過酸化ジルコン酸水溶液の量を１２．０ｋｇから３．０ｋｇに変更し、珪酸水溶液の量を３．０ｋｇから０．７５ｋｇに変更したこと以外は上記操作1.2と同様の操作を行うことにより、チタニウムを主成分とするコア粒子の表面を、ジルコニウムとケイ素を含む複合酸化物からなるシェルで被覆してなる無機酸化物微粒子（４）の透明乳白色水分散液（以下、「Ｐ−４」という）を調製した。なお、この調製の過程で、操作1.2と同様に、粒子同士が疑似的に連結した無機酸化物微粒子分散液が得られた。[Example 4]
(Operation 4.2) Preparation of Aqueous Dispersion (P-4) of Linked Crystalline Inorganic Oxide Fine Particle Group In operation 1.2 of Example 1, the aqueous solution of zirconate peroxide added to inorganic oxide fine particle dispersion (1b) By changing the amount from 12.0 kg to 3.0 kg and changing the amount of the silicic acid aqueous solution from 3.0 kg to 0.75 kg, the same operation as in the above operation 1.2 is performed. A transparent milky white aqueous dispersion (hereinafter referred to as “P-4”) of inorganic oxide fine particles (4) obtained by coating the surfaces of the particles with a shell made of a complex oxide containing zirconium and silicon was prepared. In the course of this preparation, an inorganic oxide fine particle dispersion in which particles were pseudo-connected was obtained in the same manner as in Operation 1.2.
ここで、過酸化ジルコン酸水溶液中に含まれるジルコン酸をＺｒＯ2で表し、珪酸水溶液中に含まれる珪酸をＳｉＯ2で表したとき（以下の重量比の式では「ＳｉＯ2-(1)」と表す。）、モル比（ＺｒＯ2／ＳｉＯ2）は３３／６７であった。また、水分散液（Ｐ−４）中の無機酸化物微粒子に含まれる金属の重量を酸化物（ＴｉＯ2、ＳｎＯ2、ＳｉＯ2（以下の重量比の式では「ＳｉＯ2-(2)」と表す。））の重量に換算すると、重量比（（ＺｒＯ2＋ＳｉＯ2-(1)）／（ＴｉＯ2＋ＳｎＯ2＋ＳｉＯ2-(2)））は１０／１００であった。Here, it represents a zirconate contained in peroxide zirconate solution in ZrO 2, in the formula when expressed silicate contained in the silicate solution with SiO 2 (following weight ratio "SiO 2 - (1)" The molar ratio (ZrO 2 / SiO 2 ) was 33/67. Further, the weight of the metal contained in the inorganic oxide fine particles in the aqueous dispersion (P-4) is expressed as oxide (TiO 2 , SnO 2 , SiO 2 (“SiO 2- (2)” in the following weight ratio formula). The weight ratio ((ZrO 2 + SiO 2- (1)) / (TiO 2 + SnO 2 + SiO 2- (2))) was 10/100.
この無機酸化物微粒子（４）は３〜４個連結して連結型微粒子群を構成しており、この連結型微粒子群の比表面積は２５９ｍ2／ｇであった。以下、上記水分散液（Ｐ−４）を「連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−４）」ともいう。Three to four inorganic oxide fine particles (4) are connected to form a connected fine particle group, and the specific surface area of the connected fine particle group is 259 m 2 / g. Hereinafter, the aqueous dispersion (P-4) is also referred to as “aqueous dispersion (P-4) of linked crystalline inorganic oxide fine particle group”.
この連結型微粒子群のＸ線回折では結晶性ピークが検出され、結晶構造はルチル型であった。 A crystallinity peak was detected by X-ray diffraction of this connected fine particle group, and the crystal structure was a rutile type.
また、この連結型微粒子群に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＴｉＯ2が７３．３重量％、ＳｎＯ2が９．２重量％、ＳｉＯ2が１３．１重量％、ＺｒＯ2が２．９重量％、Ｋ2Ｏが１．５重量％であった。ここで、この連結型微粒子群に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は０．１０８であった。Further, when the ratio of metal components contained in the connected fine particle group (oxide equivalent value) was measured, TiO 2 was 73.3% by weight, SnO 2 was 9.2% by weight, and SiO 2 was 13.1% by weight. %, ZrO 2 was 2.9% by weight, and K 2 O was 1.5% by weight. Here, the molar ratio (ZrO 2 / SiO 2 ) was 0.108 when zirconium contained in this connected fine particle group was represented as ZrO 2 and silicon was represented as SiO 2 .
（操作4.3）連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−４）の調製
実施例１の操作1.3において、上記操作1.2で調製した連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−１）１４７０ｇに替えて上記操作4.2で調製した連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−４）１４７０ｇを用いたこと以外は上記操作1.3と同様の操作を行うことにより、無機酸化物微粒子のメタノール分散液（以下「ＭＰ−４」という）を調製した。 (Operation 4.3) Preparation of Methanol Dispersion (MP-4) of Linked Crystalline Inorganic Oxide Fine Particle Group In Operation 1.3 of Example 1, water dispersion of the linked crystalline inorganic oxide fine particle group prepared in Operation 1.2 above. The same operation as in the above operation 1.3 is performed except that 1470 g of the aqueous dispersion (P-4) of the linked crystalline inorganic oxide fine particle group prepared in the above operation 4.2 is used instead of the liquid (P-1) 1470 g. Thus, a methanol dispersion of inorganic oxide fine particles (hereinafter referred to as “MP-4”) was prepared.
このメタノール分散液（ＭＰ−４）の水分含有量は約０．５重量％、固形分濃度は３０重量％であった。 This methanol dispersion (MP-4) had a water content of about 0.5% by weight and a solid content concentration of 30% by weight.
この無機酸化物微粒子は３〜４個連結して連結型微粒子群を構成しており、連結型微粒子群の比表面積は２９９ｍ2／ｇであった。以下、上記分散液（ＭＰ−４）を「連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−４）」ともいう。Three to four inorganic oxide fine particles were connected to form a connected fine particle group, and the specific surface area of the connected fine particle group was 299 m 2 / g. Hereinafter, the dispersion (MP-4) is also referred to as “methanol dispersion (MP-4) of linked crystalline inorganic oxide fine particle group”.
このメタノール分散液（ＭＰ−４）中の連結型微粒子群に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＴｉＯ2が６８．２重量％、ＳｎＯ2が８．５重量％、ＳｉＯ2が２０．０重量％、ＺｒＯ2が１．８重量％、Ｋ2Ｏが１．５重量％であった。ここで、この連結型微粒子群に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は０．０４４であった。When the ratio of metal components contained in the linked fine particle group in this methanol dispersion (MP-4) (as oxide value) was measured, TiO 2 was 68.2% by weight and SnO 2 was 8.5% by weight. SiO 2 was 20.0% by weight, ZrO 2 was 1.8% by weight, and K 2 O was 1.5% by weight. Here, the molar ratio (ZrO 2 / SiO 2 ) when zirconium contained in the group of connected fine particles was expressed as ZrO 2 and silicon was expressed as SiO 2 was 0.044.
（操作4.4）ハードコート層膜形成用塗料組成物（Ｈ５）の調製
γ−グリシドキシプロピルトリメトキシシラン（東レ・ダウコーニング（株）製Ｚ−６０４０）１９９．３ｇおよびメタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）３５．３ｇの混合液中に、混合液を攪拌しながら０．０１Ｎの塩酸水溶液６７．９ｇを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行い、加水分解液を得た。 (Operation 4.4) Preparation of coating composition (H5) for forming a hard coat layer film 199.3 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Hayashi Junyaku ( 67.9 g of a 0.01N hydrochloric acid aqueous solution was added dropwise to 35.3 g of a mixed solution (manufactured by Co., Ltd., methyl alcohol concentration: 99.9 wt%) while stirring the mixed solution. Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.
次いで、この加水分解液に、メタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）３１２．１ｇおよび上記操作4.3で調製した固形分濃度３０重量％の連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−４）３３５．７ｇ、プロピレングリコールモノメチルエーテル（ダウケミカル製）４０．６ｇ、トリス（２，４−ペンタンジオナト）アルミニウム（III）（東京化成工業（株）製）８．０ｇおよびレベリング剤としてのシリコーン系界面活性剤（東レ・ダウコーニング（株）製、Ｌ−７６０４）１．１ｇを加え、室温で一昼夜攪拌して、ハードコート層膜形成用塗料組成物（Ｈ５）を調製した。 Subsequently, to this hydrolyzed solution, 312.1 g of methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) and a linked crystalline inorganic material having a solid content concentration of 30% by weight prepared in the above operation 4.3. 335.7 g of methanol dispersion (MP-4) of oxide fine particle group, 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentanedionato) aluminum (III) (Tokyo Chemical Industry Co., Ltd.) )) 8.0 g and 1.1 g of a silicone surfactant as a leveling agent (manufactured by Toray Dow Corning Co., Ltd., L-7604), stirred at room temperature for a whole day and night, and a paint for forming a hard coat layer film A composition (H5) was prepared.
［実施例５］
（操作5.2）連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−５）の調製
実施例１の操作1.2において、無機酸化物微粒子分散液（１ｂ）に添加する過酸化ジルコン酸水溶液の量を１２．０ｋｇから３０．０ｋｇに変更し、珪酸水溶液の量を３．０ｋｇから７．５ｋｇに変更したこと以外は上記操作1.2と同様の操作を行い、チタニウムを主成分とするコア粒子の表面を、ジルコニウムとケイ素を含む複合酸化物からなるシェルで被覆してなる無機酸化物微粒子（５）の透明乳白色水分散液（以下、「Ｐ−５」という）を調製した。なお、この調製の過程で、操作1.2と同様に、粒子同士が疑似的に連結した無機酸化物微粒子分散液が得られた。[Example 5]
(Operation 5.2) Preparation of Aqueous Dispersion (P-5) of Linked Crystalline Inorganic Oxide Fine Particle Group In operation 1.2 of Example 1, the aqueous solution of zirconate peroxide added to the inorganic oxide fine particle dispersion (1b) was prepared. The same procedure as in the above procedure 1.2 was performed except that the amount was changed from 12.0 kg to 30.0 kg and the amount of the silicic acid aqueous solution was changed from 3.0 kg to 7.5 kg. A transparent milky white aqueous dispersion (hereinafter referred to as “P-5”) of inorganic oxide fine particles (5) formed by coating the surface with a shell made of a complex oxide containing zirconium and silicon was prepared. In the course of this preparation, an inorganic oxide fine particle dispersion in which particles were pseudo-connected was obtained in the same manner as in Operation 1.2.
ここで、過酸化ジルコン酸水溶液中に含まれるジルコン酸をＺｒＯ2で表し、珪酸水溶液中に含まれる珪酸をＳｉＯ2で表したとき（以下の重量比の式では「ＳｉＯ2-(1)」と表す。）、モル比（ＺｒＯ2／ＳｉＯ2）は３３／６７であった。また、水分散液（Ｐ−５）中の無機酸化物微粒子に含まれる金属の重量を酸化物（ＴｉＯ2、ＳｎＯ2、ＳｉＯ2（以下の重量比の式では「ＳｉＯ2-(2)」と表す。））の重量に換算すると、重量比（（ＺｒＯ2＋ＳｉＯ2-(1)）／（ＴｉＯ2＋ＳｎＯ2＋ＳｉＯ2-(2)））は１００／１００であった。Here, it represents a zirconate contained in peroxide zirconate solution in ZrO 2, in the formula when expressed silicate contained in the silicate solution with SiO 2 (following weight ratio "SiO 2 - (1)" The molar ratio (ZrO 2 / SiO 2 ) was 33/67. In addition, the weight of the metal contained in the inorganic oxide fine particles in the aqueous dispersion (P-5) is expressed as oxide (TiO 2 , SnO 2 , SiO 2 (“SiO 2- (2)” in the following weight ratio formula). The weight ratio ((ZrO 2 + SiO 2- (1)) / (TiO 2 + SnO 2 + SiO 2- (2))) was 100/100.
この無機酸化物微粒子（５）は５〜１０個連結して連結型微粒子群を構成しており、この連結型微粒子群の比表面積は２７１ｍ2／ｇであった。以下、上記水分散液（Ｐ−５）を「連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−５）」ともいう。5 to 10 inorganic oxide fine particles (5) were connected to form a connected fine particle group, and the specific surface area of the connected fine particle group was 271 m 2 / g. Hereinafter, the aqueous dispersion (P-5) is also referred to as “aqueous dispersion (P-5) of linked crystalline inorganic oxide fine particle group”.
この連結型微粒子群のＸ線回折では結晶性ピークが検出され、結晶構造はルチル型であった。 A crystallinity peak was detected by X-ray diffraction of this connected fine particle group, and the crystal structure was a rutile type.
この連結型微粒子群に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＴｉＯ2が３３．０重量％、ＳｎＯ2が４．１重量％、ＳｉＯ2が３５．７重量％、ＺｒＯ2が２５．５重量％、Ｋ2Ｏが１．７重量％であった。ここで、この連結型微粒子群に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は０．３４６であった。When the proportion of metal components contained in the connected fine particle group (as oxide value) was measured, TiO 2 was 33.0 wt%, SnO 2 was 4.1 wt%, SiO 2 was 35.7 wt%, ZrO 2 was 25.5% by weight and K 2 O was 1.7% by weight. Here, the molar ratio (ZrO 2 / SiO 2 ) was 0.346 when the zirconium contained in this group of connected fine particles was expressed as ZrO 2 and silicon was expressed as SiO 2 .
（操作5.3）連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−５）の調製
実施例１の操作1.3において、上記操作1.2で調製した連結型結晶性無機酸化物微粒子群の水分散（Ｐ−１）１４７０ｇに替えて上記操作5.2で調製した連結型結晶性無機酸化物微粒子群の水分散（Ｐ−５）１４７０ｇを用いたこと以外は上記操作1.3と同様の操作を行い、無機酸化物微粒子のメタノール分散液（以下「ＭＰ−５」という）を調製した。 (Operation 5.3) Preparation of Methanol Dispersion (MP-5) of Linked Crystalline Inorganic Oxide Fine Particle Group In Operation 1.3 of Example 1, water dispersion of the linked crystalline inorganic oxide fine particle group prepared in the above Operation 1.2 (P-1) The same operation as in the above operation 1.3 was performed except that 1470 g of the aqueous dispersion (P-5) of the linked crystalline inorganic oxide fine particle group prepared in the above operation 5.2 was used instead of 1470 g. A methanol dispersion of oxide fine particles (hereinafter referred to as “MP-5”) was prepared.
このメタノール分散液（ＭＰ−５）の水分含有量は約０．５重量％、固形分濃度は３０重量％であった。 This methanol dispersion (MP-5) had a water content of about 0.5% by weight and a solid content concentration of 30% by weight.
この無機酸化物微粒子は５〜１０個連結して連結型微粒子群を構成しており、連結型微粒子群の比表面積は３０９ｍ2／ｇであった。以下、上記分散液（ＭＰ−５）を「連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−５）」ともいう。5 to 10 inorganic oxide fine particles are connected to form a connected fine particle group, and the specific surface area of the connected fine particle group is 309 m 2 / g. Hereinafter, the dispersion (MP-5) is also referred to as “methanol dispersion (MP-5) of linked crystalline inorganic oxide fine particle group”.
このメタノール分散液（ＭＰ−５）中の連結型微粒子群に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＴｉＯ2が２９．４重量％、ＳｎＯ2が３．７重量％、ＳｉＯ2が４２．６重量％、ＺｒＯ2が２２．６重量％、Ｋ2Ｏが１．７重量％であった。ここで、この連結型微粒子群に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は０．９１９であった。When the proportion of metal components contained in the linked fine particle group in this methanol dispersion (MP-5) (as oxide) was measured, TiO 2 was 29.4 wt% and SnO 2 was 3.7 wt%. SiO 2 was 42.6% by weight, ZrO 2 was 22.6% by weight, and K 2 O was 1.7% by weight. Here, the molar ratio (ZrO 2 / SiO 2 ) was 0.919 when zirconium contained in the group of connected fine particles was expressed as ZrO 2 and silicon was expressed as SiO 2 .
（操作5.4）ハードコート層膜形成用塗料組成物（Ｈ６）の調製
γ−グリシドキシプロピルトリメトキシシラン（東レ・ダウコーニング（株）製Ｚ−６０４０）１３６．３ｇおよびメタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）２４．１ｇの混合液中に、混合液を攪拌しながら０．０１Ｎの塩酸水溶液４６．５ｇを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行い、加水分解液を得た。 (Operation 5.4) Preparation of Hard Coat Layer Film Forming Coating Composition (H6 ) 136.3 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Hayashi Junyaku ( Co., Ltd., methyl alcohol concentration: 99.9% by weight) Into a mixture of 24.1 g, 46.5 g of 0.01N hydrochloric acid aqueous solution was added dropwise while stirring the mixture. Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.
次いで、この加水分解液に、メタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）２００．３ｇおよび上記操作5.3で調製した固形分濃度３０重量％の連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−５）５４５．５ｇ、さらにプロピレングリコールモノメチルエーテル（ダウケミカル製）４０．６ｇ、トリス（２，４−ペンタンジオナト）アルミニウム（III）（東京化成工業（株）製）５．５ｇおよびレベリング剤としてのシリコーン系界面活性剤（東レ・ダウコーニング（株）製、Ｌ−７６０４）１．１ｇを加え、室温で一昼夜攪拌して、ハードコート層膜形成用塗料組成物（Ｈ６）を調製した。 Next, to this hydrolyzed solution, 200.3 g of methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) and a linked crystalline inorganic having a solid content concentration of 30% by weight prepared in the above operation 5.3 545.5 g of methanol dispersion (MP-5) of fine oxide particles, 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentandionato) aluminum (III) (Tokyo Chemical Industry ( 5.5 g) and 1.1 g of a silicone surfactant as a leveling agent (manufactured by Toray Dow Corning Co., Ltd., L-7604) were added, and the mixture was stirred overnight at room temperature to form a hard coat layer film. A coating composition (H6) was prepared.
［実施例６］
＜工程（１）＞
（操作6.1.1）ジルコニウムを主成分とする複合酸化物微粒子（コア粒子）の調製
純水５２．１３ｋｇにオキシ塩化ジルコニウム８水和物（太陽鉱工（株）製、ＺｒＯＣｌ2・８Ｈ2Ｏ）１．４０ｋｇを溶解し、これに濃度１０重量％のＫＯＨ水溶液４９．１３ｋｇを添加してジルコニウム水酸化物ヒドロゲル（ＺｒＯ2濃度１重量％）を調製した。次いで、得られたジルコニウム水酸化物ヒドロゲルを、限外濾過膜法により電導度が０．５ｍＳ／ｃｍ以下になるまで洗浄した。[Example 6]
<Step (1)>
(Operation 6.1.1) Preparation of Composite Oxide Fine Particles (Core Particles) Mainly Containing Zirconium Zirconium Oxychloride Octahydrate (ZrOCl 2 · 8H 2 O, manufactured by Taiyo Mining Co., Ltd.) was added to 52.13 kg of pure water. ) 1.40 kg was dissolved, and 49.13 kg of a 10 wt% KOH aqueous solution was added thereto to prepare a zirconium hydroxide hydrogel (ZrO 2 concentration 1 wt%). Next, the obtained zirconium hydroxide hydrogel was washed by an ultrafiltration membrane method until the conductivity reached 0.5 mS / cm or less.
上記操作により得られたＺｒＯ2としての濃度が１重量％のジルコニウム水酸化物ヒドロゲル１０２．７５ｋｇに、濃度１０重量％のＫＯＨ水溶液２０．２４ｋｇを加えて十分攪拌した後、濃度３５重量％の過酸化水素水溶液０．５６ｋｇを加えた。このとき、溶液は激しく発泡して透明になり、ｐＨは１１．４であった。After adding 10.24 kg of a 10 wt% KOH aqueous solution to 102.75 kg of the zirconium hydroxide hydrogel having a concentration of 1 wt% as ZrO 2 obtained by the above operation, the mixture was sufficiently stirred, and then an excess of 35 wt% of the concentration was added. 0.56 kg of aqueous hydrogen oxide solution was added. At this time, the solution foamed vigorously and became transparent, and the pH was 11.4.
次いで、この溶液に濃度２８．８重量％のアンモニア水溶液５．６３ｋｇを加えて充分攪拌して、ジルコニウム酸化物微粒子（コア粒子）の前駆体スラリーを得た。このとき、前記スラリーは薄黄色になり、ｐＨは１３．４であった。 Next, 5.63 kg of an aqueous ammonia solution having a concentration of 28.8% by weight was added to this solution and sufficiently stirred to obtain a precursor slurry of zirconium oxide fine particles (core particles). At this time, the slurry was light yellow and the pH was 13.4.
この前駆体スラリーの１／３をオートクレーブ（耐圧硝子工業（株）製、１００Ｌ）に充填し、１５０℃で１１時間水熱処理を行った後、遠心沈降法によりジルコニウム酸化物微粒子を分離し、これを充分に洗浄したのちイオン交換水に分散させて、ジルコニウム酸化物微粒子（コア粒子）の水分散液１０．１０ｋｇを得た。この水分散液のジルコニウムの含有量はＺｒＯ2換算基準で１０重量％であった。1/3 of this precursor slurry was filled in an autoclave (100 L, manufactured by Pressure Glass Industrial Co., Ltd.), hydrothermally treated at 150 ° C. for 11 hours, and then the zirconium oxide fine particles were separated by centrifugal sedimentation. Was sufficiently washed and then dispersed in ion-exchanged water to obtain 10.10 kg of an aqueous dispersion of zirconium oxide fine particles (core particles). The content of zirconium in this aqueous dispersion was 10% by weight in terms of ZrO 2 .
次いで、前記コア粒子の水分散液１０．１０ｋｇをスプレードライヤー（ＮＩＲＯ社製ＮＩＲＯ ＡＴＯＭＩＺＥＲ）に供して噴霧乾燥した。これにより、ジルコニウム酸化物微粒子（コア粒子）の乾燥粉体０．９０ｋｇを得た。得られた乾燥粉体に含まれるコア粒子の平均粒子径は約２μｍであった。 Next, 10.10 kg of the aqueous dispersion of the core particles was spray-dried using a spray dryer (NIRO ATOMIZER manufactured by NIRO). As a result, 0.90 kg of dry powder of zirconium oxide fine particles (core particles) was obtained. The average particle diameter of the core particles contained in the obtained dry powder was about 2 μm.
次に、この乾燥粉体０．９０ｋｇを、空気雰囲気下、５００℃の温度にて２時間焼成して、ジルコニウム酸化物微粒子（コア粒子）の焼成粉体０．８４ｋｇを得た。 Next, 0.90 kg of this dry powder was calcined in an air atmosphere at a temperature of 500 ° C. for 2 hours to obtain 0.84 kg of calcined powder of zirconium oxide fine particles (core particles).
この焼成粉体０．８４ｋｇを純水０．７４ｋｇに分散させ、これに、濃度２８．６％の酒石酸水溶液０．５５ｋｇ、濃度５０重量％のＫＯＨ水溶液０．２３ｋｇを加えて充分攪拌した。次いで、粒子径０．１ｍｍのアルミナビーズ（大明化学工業（株）製 高純度アルミナビーズ）を加え、これを湿式粉砕機（カンペハピオ（株）製バッチ式卓上サンドミル）に供して１８０分間、前記焼成粉体の粉砕及び分散処理を行った。その後、アルミナビーズを、目開き４４μｍのステンレス製フィルターを用いて分離・除去したのち、さらに純水６．６５ｋｇを添加して撹拌を行い、ジルコニウム酸化物微粒子（コア粒子）の水分散液８．８４ｋｇを得た。この水分散液の固形分含有量は１１重量％であった。 0.84 kg of the calcined powder was dispersed in 0.74 kg of pure water, and 0.55 kg of a 28.6% aqueous tartaric acid solution and 0.23 kg of a 50% aqueous KOH aqueous solution were added thereto and sufficiently stirred. Subsequently, alumina beads having a particle diameter of 0.1 mm (high-purity alumina beads manufactured by Daimei Chemical Industry Co., Ltd.) are added, and this is subjected to a wet crusher (batch type tabletop sand mill manufactured by Campehapio Co., Ltd.) for 180 minutes. The powder was pulverized and dispersed. Thereafter, the alumina beads are separated and removed using a stainless steel filter having an opening of 44 μm, and 6.65 kg of pure water is further added and stirred to obtain an aqueous dispersion of zirconium oxide fine particles (core particles). 84 kg was obtained. The solid content of this aqueous dispersion was 11% by weight.
次いで、この水分散液を、限外濾過膜を用いてイオン交換水で洗浄し、さらに陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）０．４３ｋｇを加えて脱イオン処理をした後、遠心分離機（日立工機（株）製ＣＲ−２１Ｇ）に供して１２，０００ｒｐｍの速度で１時間処理して粗大粒子を除去し、ＺｒＯ2換算基準の固形分濃度が１０重量％のジルコニウム酸化物微粒子（コア粒子）の水分散液９．５０ｋｇを得た。Next, this aqueous dispersion was washed with ion-exchanged water using an ultrafiltration membrane, and further subjected to deionization treatment by adding 0.43 kg of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC), Zirconium oxide was applied to a centrifuge (CR-21G manufactured by Hitachi Koki Co., Ltd.) to remove coarse particles by treating at a speed of 12,000 rpm for 1 hour, and the solid content concentration in terms of ZrO 2 was 10% by weight. 9.50 kg of an aqueous dispersion of product fine particles (core particles) was obtained.
前記水分散液に含まれるコア粒子の平均粒子径は２０ｎｍ、比表面積は９２ｍ2/ｇであった。さらに、このコア粒子に含まれる金属成分の含有量は、各金属成分の酸化物換算基準で、ＺｒＯ2が９８．５重量％、Ｋ2Ｏが１．５重量％であった。The average particle diameter of the core particles contained in the aqueous dispersion was 20 nm, and the specific surface area was 92 m 2 / g. Furthermore, the content of the metal component contained in the core particles was 98.5% by weight for ZrO 2 and 1.5% by weight for K 2 O on the basis of oxide conversion of each metal component.
（操作6.1.2）シリカ被覆コア粒子の調製
市販の水ガラス（ＡＧＣエスアイテック（株）製、ＪＩＳ３号水硝子、ＳｉＯ2濃度２４質量％）を純水にて希釈した後、陽イオン交換樹脂（三菱化学（株）製）を用いて脱アルカリして、珪酸をＳｉＯ2換算基準で４．５重量％含む、ｐＨが２．３の珪酸水溶液を得た。 (Operation 6.1.2) Preparation of silica-coated core particles A commercially available water glass (manufactured by AGC S-Tech Co., Ltd., JIS No. 3 water glass, SiO 2 concentration 24 mass%) was diluted with pure water, and then a cation exchange resin. (Mitsubishi Chemical Co., Ltd.) was used for dealkalization to obtain a silicic acid aqueous solution having a pH of 2.3 containing 4.5% by weight of silicic acid on a SiO 2 conversion basis.
操作6.1.2で得られたジルコニウム酸化物微粒子（コア粒子）の水分散液３．０ｋｇを、陽イオン交換樹脂（三菱化学（株）製）０．３ｋｇを用いて脱アルカリした後、樹脂分離して水分散ゾルを得た。次いで、この水分散ゾルに前記珪酸液１６８１．１ｇを攪拌しながら徐々に添加し、さらに添加終了後、３５℃の温度に保ちながら攪拌下で１時間熟成することにより、シリカで被覆されたコア微粒子の水分散液を得た。なお、この水分散液の固形分含有量は６．９重量％であった。 3.0 kg of the aqueous dispersion of zirconium oxide fine particles (core particles) obtained in operation 6.1.2 was dealkalized using 0.3 kg of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation), followed by resin separation. Thus, an aqueous dispersion sol was obtained. Next, 1681.1 g of the silicic acid solution is gradually added to this water-dispersed sol while stirring, and after completion of addition, the core is coated with silica by aging for 1 hour while stirring at a temperature of 35 ° C. An aqueous dispersion of fine particles was obtained. The aqueous dispersion had a solid content of 6.9% by weight.
（操作6.2）連結型無機酸化物微粒子群の水分散液（Ｐ−６）の調製
実施例１の操作1.2において、操作1.1で調製したチタニウムを主成分とするコア粒子の水分散液（１ａ）３．０ｋｇに替えて上記操作6.1.2で調製したジルコニウムを主成分とするコア粒子の水分散液３．０ｋｇを用いた以外は実施例１の操作1.2と同様の操作を行うことにより、ジルコニウムを主成分とするコア粒子の表面を、ジルコニウムとケイ素を含む複合酸化物からなるシェルで被覆してなる無機酸化物微粒子（６）の透明乳白色水分散液（以下、「Ｐ−６」という）を調製した。なお、この調製の過程で、操作1.2と同様に、粒子同士が疑似的に連結した無機酸化物微粒子分散液が得られた。さらに、この無機酸化物微粒子を含む分散液は、ゼータ電位測定において、ｐＨは３．８、ゼータ電位は−４５ｍＶであった。 (Operation 6.2) Preparation of aqueous dispersion (P-6) of linked inorganic oxide fine particle group In Operation 1.2 of Example 1, core particle aqueous dispersion (1a) prepared in Operation 1.1 in Operation 1.1 By replacing the 3.0 kg with the same operation as the operation 1.2 in Example 1 except that 3.0 kg of the aqueous dispersion of core particles mainly composed of zirconium prepared in the above operation 6.1.2 was used. A transparent milky white aqueous dispersion (hereinafter referred to as “P-6”) of inorganic oxide fine particles (6) obtained by coating the surface of core particles mainly composed of silicon with a shell made of a complex oxide containing zirconium and silicon. Was prepared. In the course of this preparation, an inorganic oxide fine particle dispersion in which particles were pseudo-connected was obtained in the same manner as in Operation 1.2. Furthermore, the dispersion containing the inorganic oxide fine particles had a pH of 3.8 and a zeta potential of −45 mV in the zeta potential measurement.
この無機酸化物微粒子（６）は４〜５個連結して連結型微粒子群を構成しており、この連結型微粒子群の比表面積は２０４ｍ2／ｇであった。以下、上記水分散液（Ｐ−６）を「連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−６）」ともいう。Four to five inorganic oxide fine particles (6) are connected to form a connected fine particle group, and the specific surface area of the connected fine particle group is 204 m 2 / g. Hereinafter, the aqueous dispersion (P-6) is also referred to as “aqueous dispersion of linked crystalline inorganic oxide fine particles (P-6)”.
この連結型無機酸化物微粒子群のＸ線回折では結晶性ピークが検出され、結晶構造は単斜晶系と立方晶系とからなる結晶型であった。 Crystallinity peaks were detected by X-ray diffraction of this group of connected inorganic oxide fine particles, and the crystal structure was a crystal type composed of a monoclinic system and a cubic system.
この連結型無機酸化物微粒子群に含まれる金属成分を測定したところ、ＳｉＯ2が７７．９重量％、ＺｒＯ2が２０．６重量％、Ｋ2Ｏが１．５重量％であった。ここで、この連結型微粒子群に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は１．８４４であった。Was measured metal component contained in the linked fine inorganic oxide particle group, SiO 2 is 77.9 wt%, ZrO 2 is 20.6 wt%, K 2 O of 1.5 wt%. Here, the molar ratio (ZrO 2 / SiO 2 ) when zirconium contained in the group of connected fine particles was expressed as ZrO 2 and silicon was expressed as SiO 2 was 1.844.
（操作6.3）連結型無機酸化物微粒子群のメタノール分散液（ＭＰ−６）の調製
実施例１の操作1.3において、上記操作1.2で調製した連結型無機酸化物微粒子群の水分散（Ｐ−１）１４７０ｇに替えて上記操作6.2で調製した連結型無機酸化物微粒子群の水分散（Ｐ−６）１４７０ｇを用いたこと以外は上記操作1.3と同様の操作を行うことにより、無機酸化物微粒子のメタノール分散液（以下「ＭＰ−６」という）を調製した。 (Operation 6.3) Preparation of Linked Inorganic Oxide Fine Particle Group Methanol Dispersion (MP-6) In Operation 1.3 of Example 1, the aqueous dispersion of the linked inorganic oxide fine particle group prepared in the above Operation 1.2 (P-1 ) In the same manner as in the above operation 1.3 except that 1470 g of the aqueous dispersion (P-6) of the linked inorganic oxide fine particle group prepared in the above operation 6.2 was used instead of 1470 g, A methanol dispersion (hereinafter referred to as “MP-6”) was prepared.
このメタノール分散液（ＭＰ−６）の水分含有量は約０．５重量％、固形分濃度は３０重量％であった。 This methanol dispersion (MP-6) had a water content of about 0.5% by weight and a solid content concentration of 30% by weight.
この無機酸化物微粒子の平均粒子径は２０ｎｍであり、この無機酸化物微粒子は４〜５個連結して連結型微粒子群を構成しており、連結型微粒子群の比表面積は２５４ｍ2／ｇであった。以下、上記分散液（ＭＰ−６）を「連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−６）」ともいう。The average particle diameter of the inorganic oxide fine particles is 20 nm, and 4 to 5 inorganic oxide fine particles are connected to form a connected fine particle group. The specific surface area of the connected fine particle group is 254 m 2 / g. there were. Hereinafter, the dispersion liquid (MP-6) is also referred to as “methanol dispersion liquid of linked crystalline inorganic oxide fine particle group (MP-6)”.
このメタノール分散液（ＭＰ−６）中の連結型微粒子群に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＳｉＯ2が７０．９重量％、ＺｒＯ2が２７．６重量％、Ｋ2Ｏが１．５重量％であった。ここで、この連結型微粒子群に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は１．２５３であった。When the proportion of metal components contained in the linked fine particle group in this methanol dispersion (MP-6) (as oxide value) was measured, SiO 2 was 70.9 wt% and ZrO 2 was 27.6 wt%. , K 2 O was 1.5% by weight. Here, the molar ratio (ZrO 2 / SiO 2 ) when zirconium contained in the group of connected fine particles was expressed as ZrO 2 and silicon was expressed as SiO 2 was 1.253.
ハードコート層膜形成用塗料組成物（Ｈ７）の調製
γ−グリシドキシプロピルトリメトキシシラン（東レ・ダウコーニング（株）製Ｚ−６０４０）１４３．９ｇおよびメタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）２５．５ｇの混合液中に、攪拌しながら０．０１Ｎの塩酸水溶液４９．０ｇを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行い、加水分解液を得た。 Preparation of Hard Coat Layer Film Forming Coating Composition (H7 ) 143.9 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (manufactured by Hayashi Junyaku Co., Ltd.) (Methyl alcohol concentration: 99.9% by weight) 49.0 g of a 0.01N hydrochloric acid aqueous solution was added dropwise to 25.5 g of a mixed solution with stirring. Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.
次いで、この加水分解液に、メタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）２１３．７ｇおよび上記操作6.3で調製した固形分濃度３０重量％の連結型結晶性無機酸化物微粒子群のメタノール分散液（ＭＰ−６）５２０．４ｇ、プロピレングリコールモノメチルエーテル（ダウケミカル製）４０．６ｇ、トリス（２，４-ペンタンジオナト）アルミニウム（III）（東京化成工業（株）製）５．８ｇおよびレベリング剤としてシリコーン系界面活性剤（東レ・ダウコーニング（株）製、Ｌ−７６０４）１．１ｇを加え、室温で一昼夜攪拌して、ハードコート層膜形成用塗料組成物（Ｈ７）を調製した。 Subsequently, to this hydrolyzed solution, 213.7 g of methanol (manufactured by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) and a linked crystalline inorganic having a solid content concentration of 30% by weight prepared in the above operation 6.3 520.4 g of methanol dispersion (MP-6) of oxide fine particle group, 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentanedionato) aluminum (III) (Tokyo Chemical Industry Co., Ltd.) )) 5.8 g and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added and stirred at room temperature for a whole day and night to form a coating composition for forming a hard coat layer film A product (H7) was prepared.
［比較例１］
（操作C1.2）非連結型結晶性無機酸化物微粒子の水分散液（Ｃ−１）の調製
実施例１の操作1.2において、無機酸化物微粒子の分散液（１ｂ）に過酸化ジルコン酸水溶液（１）および珪酸水溶液（１）を添加することに替えてチタニウムを主成分とするコア粒子を含む水分散液（１ａ）に過酸化ジルコン酸水溶液（１）６．０ｋｇおよび珪酸水溶液（１）４．５ｋｇを添加したこと（すなわち、「水分散液（１ａ）に純水を加えたものを陽イオン交換樹脂を用いて脱アルカリして、ｐＨを２．８に、かつ前述の測定方法でゼータ電位測定を行った際のｐＨは３．８、ゼータ電位は−５０ｍＶに調整し、次いで前記陽イオン交換樹脂を分離して、室温で１時間撹拌して、粒子同士を疑似的に連結させる」操作を実施しなかったこと）以外は上記操作1.2と同様の操作を行い、チタニウムを主成分とするコア粒子の表面を、ジルコニウムとケイ素を含む複合酸化物からなるシェルで被覆してなる無機酸化物微粒子（Ｃ１）の透明乳白色水分散液（以下、「Ｃ−１」という）を調製した。[Comparative Example 1]
(Operation C1.2) Preparation of Non-Linked Crystalline Inorganic Oxide Fine Particle Water Dispersion (C-1) In Operation 1.2 of Example 1, an aqueous solution of zirconate peroxide was added to the inorganic oxide fine particle dispersion (1b). In place of adding (1) and aqueous silicic acid solution (1), 6.0 kg of aqueous zirconate peroxide solution (1) and aqueous silicic acid solution (1) are added to an aqueous dispersion (1a) containing core particles mainly composed of titanium. 4.5 kg is added (ie, “water dispersion (1a) added with pure water is dealkalized using a cation exchange resin to a pH of 2.8, and the above measurement method is used. The pH at the time of zeta potential measurement was adjusted to 3.8, the zeta potential was adjusted to −50 mV, and then the cation exchange resin was separated and stirred at room temperature for 1 hour to quasi-couple the particles. ”Operation other than that) A transparent milky white aqueous dispersion of inorganic oxide fine particles (C1) formed by coating the surface of core particles mainly composed of titanium with a shell made of a composite oxide containing zirconium and silicon by the same operation as in 1.2 Hereinafter, “C-1”) was prepared.
ここで、過酸化ジルコン酸水溶液中に含まれるジルコン酸をＺｒＯ2で表し、珪酸水溶液中に含まれる珪酸をＳｉＯ2で表したとき（以下の重量比の式では「ＳｉＯ2-(1)」と表す。）、モル比（ＺｒＯ2／ＳｉＯ2）は１４／８６であった。また、水分散液（Ｃ−１）中の無機酸化物微粒子に含まれる金属の重量を酸化物（ＴｉＯ2、ＳｎＯ2、ＳｉＯ2（以下の重量比の式では「ＳｉＯ2-(2)」と表す。））の重量に換算すると、重量比（（ＺｒＯ2＋ＳｉＯ2-(1)）／（ＴｉＯ2＋ＳｎＯ2＋ＳｉＯ2-(2)））は４０／１００であった。Here, it represents a zirconate contained in peroxide zirconate solution in ZrO 2, in the formula when expressed silicate contained in the silicate solution with SiO 2 (following weight ratio "SiO 2 - (1)" The molar ratio (ZrO 2 / SiO 2 ) was 14/86. Further, the weight of the metal contained in the inorganic oxide fine particles in the aqueous dispersion (C-1) is changed to oxide (TiO 2 , SnO 2 , SiO 2 (“SiO 2- (2)” in the following weight ratio formula). The weight ratio ((ZrO 2 + SiO 2- (1)) / (TiO 2 + SnO 2 + SiO 2- (2))) was 40/100.
この無機酸化物微粒子（Ｃ１）は互いに連結しておらず、この微粒子の比表面積は２０８ｍ2／ｇであった。以下、上記水分散液（Ｃ−１）を「非連結型結晶性無機酸化物微粒子の水分散液（Ｃ−１）」ともいう。The inorganic oxide fine particles (C1) were not connected to each other, and the specific surface area of the fine particles was 208 m 2 / g. Hereinafter, the aqueous dispersion (C-1) is also referred to as “aqueous dispersion (C-1) of non-linked crystalline inorganic oxide fine particles”.
この無機酸化物微粒子（Ｃ１）のＸ線回折では結晶性ピークが検出され、結晶構造はルチル型であった。 In the X-ray diffraction of the inorganic oxide fine particles (C1), a crystalline peak was detected, and the crystal structure was a rutile type.
この無機酸化物微粒子（Ｃ１）に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＴｉＯ2が５２．２重量％、ＳｎＯ2が６．５重量％、ＳｉＯ2が２４．９重量％、ＺｒＯ2が１４．８重量％、Ｋ2Ｏが１．６重量％であった。ここで、この無機酸化物微粒子に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は０．２９０であった。When the ratio of the metal component contained in the inorganic oxide fine particles (C1) (oxide conversion value) was measured, TiO 2 was 52.2% by weight, SnO 2 was 6.5% by weight, and SiO 2 was 24.9. % By weight, 14.8% by weight of ZrO 2 and 1.6% by weight of K 2 O. Here, the molar ratio (ZrO 2 / SiO 2 ) when zirconium contained in the inorganic oxide fine particles was expressed as ZrO 2 and silicon was expressed as SiO 2 was 0.290.
（操作C1.3）非連結型結晶性無機酸化物微粒子のメタノール分散液（ＭＣ−１）の調製
実施例１の操作1.3において、上記操作1.2で調製した連結型結晶性無機酸化物微粒子の水分散（Ｐ−１）１４７０ｇに替えて上記操作C1.2で調製した非連結型結晶性無機酸化物微粒子の水分散（Ｃ−１）１４７０ｇを用いたこと以外は上記操作1.3と同様の操作を行うことにより、無機酸化物微粒子のメタノール分散液（以下「ＭＣ−１」という）を調製した。 (Operation C1.3) Preparation of Methanol Dispersion (MC-1) of Unconnected Crystalline Inorganic Oxide Fine Particles In operation 1.3 of Example 1, the water of the connected crystalline inorganic oxide fine particles prepared in operation 1.2 above. The same operation as in the above operation 1.3 was performed except that 1470 g of the dispersion (C-1) of the unconnected crystalline inorganic oxide fine particles prepared in the above operation C1.2 was used instead of the dispersion (P-1) 1470 g. By performing, a methanol dispersion of inorganic oxide fine particles (hereinafter referred to as “MC-1”) was prepared.
このメタノール分散液（ＭＣ−１）の水分含有量は約０．５重量％、固形分濃度は３０重量％であった。 The methanol dispersion (MC-1) had a water content of about 0.5% by weight and a solid content concentration of 30% by weight.
この無機酸化物微粒子は連結しておらず、この微粒子の比表面積は２２４ｍ2／ｇであった。以下、上記分散液（Ｃ−１）を「非連結型結晶性無機酸化物微粒子のメタノール分散液（ＭＣ−１）」ともいう。The inorganic oxide fine particles were not connected, and the specific surface area of the fine particles was 224 m 2 / g. Hereinafter, the dispersion (C-1) is also referred to as “methanol dispersion (MC-1) of unconnected crystalline inorganic oxide fine particles”.
このメタノール分散液（ＭＣ−１）中の無機酸化物微粒子に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＴｉＯ2が４７．８重量％、ＳｎＯ2が５．５重量％、ＳｉＯ2が３２．０重量％、ＺｒＯ2が１３．２重量％、Ｋ2Ｏが１．６重量％であった。ここで、この無機酸化物微粒子に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は０．２０１であった。When the ratio of the metal component contained in the inorganic oxide fine particles in the methanol dispersion (MC-1) (as oxide) was measured, 47.8% by weight of TiO 2 and 5.5% by weight of SnO 2 were obtained. SiO 2 was 32.0% by weight, ZrO 2 was 13.2% by weight, and K 2 O was 1.6% by weight. Here, when the zirconium contained in the inorganic oxide fine particles was expressed as ZrO 2 and silicon was expressed as SiO 2 , the molar ratio (ZrO 2 / SiO 2 ) was 0.201.
（操作C1.4）ハードコート層膜形成用塗料組成物（Ｒ１）の調製
γ−グリシドキシプロピルトリメトキシシラン（東レ・ダウコーニング（株）製Ｚ−６０４０）１８０．４ｇおよびメタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）３１．９ｇの混合液中に、混合液を攪拌しながら０．０１Ｎの塩酸水溶液６１．５ｇを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行い、加水分解液を得た。 (Operation C1.4) Preparation of coating composition (R1) for forming a hard coat layer film 180.4 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Jun Hayashi) 61.5 g of 0.01N aqueous hydrochloric acid solution was added dropwise to 31.9 g of a liquid mixture made by Yakuhin Co., Ltd. (methyl alcohol concentration: 99.9% by weight) while stirring the liquid mixture. Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.
次いで、この加水分解液に、メタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）２７８．５ｇおよび上記操作C1.3で調製した固形分濃度３０重量％の非連結型結晶性無機酸化物微粒子のメタノール分散液（ＭＣ−１）３９８．８ｇ、さらにプロピレングリコールモノメチルエーテル（ダウケミカル製）４０．６ｇ、トリス（２，４−ペンタンジオナト）アルミニウム（III）（東京化成工業（株）製）７．２ｇおよびレベリング剤としてのシリコーン系界面活性剤（東レ・ダウコーニング（株）製、Ｌ−７６０４）１．１ｇを加え、室温で一昼夜攪拌して、ハードコート層膜形成用塗料組成物（Ｒ１）を調製した。 Subsequently, to this hydrolyzed solution, 278.5 g of methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a non-linked type having a solid content concentration of 30 wt% prepared in the above operation C1.3 398.8 g of methanol dispersion (MC-1) of crystalline inorganic oxide fine particles, 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentanedionato) aluminum (III) (Tokyo Kasei) Industrial Co., Ltd. (7.2 g) and a silicone surfactant as a leveling agent (Toray Dow Corning Co., Ltd., L-7604) (1.1 g) were added and stirred at room temperature all day and night to form a hard coat layer film A forming coating composition (R1) was prepared.
（操作C1.5）ハードコート層膜形成用塗料組成物（Ｒ２）の調製
γ−グリシドキシプロピルトリメトキシシラン（東レ・ダウコーニング（株）製Ｚ−６０４０）１６１．９ｇおよびメタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）２８．７ｇの混合液中に、混合液を攪拌しながら０．０１Ｎの塩酸水溶液５５．２ｇを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行い、加水分解液を得た。 (Operation C1.5) Preparation of Hard Coat Layer Film-Forming Coating Composition (R2 ) 161.9 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Jun Hayashi 55.2 g of 0.01N hydrochloric acid aqueous solution was added dropwise to 28.7 g of a mixed solution (manufactured by Yakuhin Co., Ltd., methyl alcohol concentration: 99.9 wt%) while stirring the mixed solution. Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.
次いで、この加水分解液に、メタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）２４５．７ｇおよび上記操作C1.3で調製した固形分濃度３０重量％の非連結型結晶性無機酸化物微粒子のメタノール分散液（ＭＣ−１）４６０．３ｇ、プロピレングリコールモノメチルエーテル（ダウケミカル製）４０．６ｇ、トリス（２，４−ペンタンジオナト）アルミニウム（III）（東京化成工業（株）製）６．５ｇおよびレベリング剤としてのシリコーン系界面活性剤（東レ・ダウコーニング（株）製、Ｌ−７６０４）１．１ｇを加え、室温で一昼夜攪拌して、ハードコート層膜形成用塗料組成物（Ｒ２）を調製した。 Next, this hydrolyzed solution was mixed with 245.7 g of methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid content concentration of 30 wt% prepared in the above operation C1.3. 460.3 g of methanol dispersion (MC-1) of crystalline inorganic oxide fine particles, 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentanedionato) aluminum (III) (Tokyo Chemical Industry) 6.5 g and 1.1 g of a silicone surfactant as a leveling agent (manufactured by Toray Dow Corning Co., Ltd., L-7604) were added and stirred at room temperature all day and night to form a hard coat layer film A coating composition (R2) was prepared.
（操作C1.6）プライマー層膜形成用塗料組成物（Ｓ１）の調製
市販の熱可塑性樹脂であるポリウレタンエマルジョン「スーパーフレックス１５０」（第一工業製薬製、水分散型ウレタンエラストマー固形分含有量３０％）２０５．３ｇに、上記操作C1.3で調製した非連結型結晶性無機酸化物微粒子のメタノール分散液（ＭＣ−１）１６４．２ｇおよびイオン交換水９６．９ｇを加えて１時間攪拌し、次いで、メタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）５３１．１ｇ、およびレベリング剤としてのシリコーン系界面活性剤（東レ・ダウコーニング（株）製、Ｌ−７６０４）０．３ｇを加えて室温で一昼夜攪拌して、プライマー層膜形成用塗料組成物（Ｓ１）を調製した。 (Operation C1.6) Preparation of primer layer film-forming coating composition (S1) Polyurethane emulsion “ Superflex 150” which is a commercially available thermoplastic resin (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., water-dispersed urethane elastomer solid content 30) %) 205.3 g of methanol dispersion (MC-1) 164.2 g of non-linked crystalline inorganic oxide fine particles prepared in the above operation C1.3 and 96.9 g of ion-exchanged water were added and stirred for 1 hour. Next, 531.1 g of methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) and a silicone surfactant as a leveling agent (manufactured by Toray Dow Corning Co., Ltd., L-7604) ) 0.3 g was added and stirred at room temperature for a whole day and night to prepare a primer layer film-forming coating composition (S1).
（操作C1.7）プライマー層膜形成用塗料組成物（Ｓ２）の調製
市販の熱可塑性樹脂であるポリウレタンエマルジョン「スーパーフレックス１５０」（第一工業製薬製、水分散型ウレタンエラストマー固形分含有量３０％）１６０．７ｇに、上記操作C1.3で調製した非連結型結晶性無機酸化物微粒子のメタノール分散液（ＭＣ−１）２０８．９ｇおよびイオン交換水９６．９ｇを加えて、１時間攪拌し、次いで、メタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）５３１．１ｇ、およびレベリング剤としてのシリコーン系界面活性剤（東レ・ダウコーニング（株）製、Ｌ−７６０４）０．３ｇを加えて室温で一昼夜攪拌して、プライマー層膜形成用塗料組成物（Ｓ２）を調製した。 (Operation C1.7) Preparation of primer layer film-forming coating composition (S2) Polyurethane emulsion “ Superflex 150” which is a commercially available thermoplastic resin (Daiichi Kogyo Seiyaku Co., Ltd., water-dispersed urethane elastomer solid content 30) %) 160.7 g of methanol dispersion (MC-1) 208.9 g of unlinked crystalline inorganic oxide fine particles prepared in the above operation C1.3 and 96.9 g of ion-exchanged water were added and stirred for 1 hour. Next, 531.1 g of methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) and a silicone surfactant as a leveling agent (manufactured by Toray Dow Corning Co., Ltd., L- 7604) 0.3 g was added and stirred at room temperature for a whole day and night to prepare a primer layer film-forming coating composition (S2).
［比較例２］
（操作C2.2）連結型シリカ微粒子群の水分散液（Ｃ−２）の調製
シリカゾル（日揮触媒化成（株）製：ＳＩ−５５０、ＳｉＯ2濃度２０重量％）２．０ｋｇにイオン交換水６．０ｋｇを加え、次いで陽イオン交換樹脂（三菱化学（株）製：ＳＫ−１ＢＨ）４００ｇを添加し、１時間撹拌して脱アルカリ処理した。得られた脱アルカリ処理物に、陽イオン交換樹脂を分離してから陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）４００ｇを添加し、これらを１時間撹拌して脱アニオン処理して陰イオン交換樹脂を分離し、次いでオートクレーブ（耐圧硝子工業（株）製、１０Ｌ）に入れて、２００℃の温度で４時間、加熱処理を行なった後、室温まで冷却した。次いで、得られた処理物に再び陽イオン交換樹脂（三菱化学（株）製：ＳＫ−１ＢＨ）４００ｇを添加し、これらを１時間撹拌して脱アルカリ処理して陽イオン交換樹脂を分離することにより、ＳｉＯ2濃度５重量％のシリカ粒子の分散液（Ｃ−２）を調製した。[Comparative Example 2]
(Operation C2.2) Preparation of Aqueous Dispersion (C-2) of Linked Silica Fine Particles Group Ion-exchanged water was added to 2.0 kg of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SI-550, SiO 2 concentration 20 wt%). 6.0 kg was added, and then 400 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) was added, and the mixture was stirred for 1 hour for dealkalization. After separating the cation exchange resin, 400 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) is added to the dealkalized product thus obtained, and these are stirred for 1 hour and subjected to deanion treatment. The ion exchange resin was separated, then placed in an autoclave (manufactured by Pressure Glass Industrial Co., Ltd., 10 L), subjected to heat treatment at a temperature of 200 ° C. for 4 hours, and then cooled to room temperature. Next, 400 g of cation exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SK-1BH) is added again to the treated product, and these are stirred for 1 hour to dealkalize and separate the cation exchange resin. Thus, a dispersion (C-2) of silica particles having a SiO 2 concentration of 5% by weight was prepared.
このＳｉＯ2微粒子のＸ線回折では結晶性ピークが検出されず、ＳｉＯ2微粒子は非晶質であった。In the X-ray diffraction of the SiO 2 fine particles, no crystalline peak was detected, and the SiO 2 fine particles were amorphous.
このＳｉＯ2微粒子に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＳｉＯ2が９９．９８重量％、Ｎａ2Ｏが０．０２重量％であった。When the ratio of metal components contained in the SiO 2 fine particles (as oxide) was measured, it was 99.98 wt% for SiO 2 and 0.02 wt% for Na 2 O.
このＳｉＯ2微粒子の平均粒子径は１５ｎｍであり、この粒状微粒子は３〜４個連結して連結型微粒子群を構成しており、連結型微粒子群の比表面積は１７０ｍ2／ｇであった。以下、上記水分散液（Ｃ−２）を「連結型シリカ微粒子群の水分散液（Ｃ−２）」ともいう。The average particle diameter of the SiO 2 fine particles was 15 nm. Three to four granular fine particles were connected to form a connected fine particle group, and the specific surface area of the connected fine particle group was 170 m 2 / g. Hereinafter, the aqueous dispersion (C-2) is also referred to as “aqueous dispersion (C-2) of linked silica fine particles”.
（操作C2.3）連結型シリカ微粒子のメタノール分散液（ＭＣ−２）の調製
実施例１の操作1.3において、上記操作1.2で調製した連結型結晶性無機酸化物微粒子の水分散（Ｐ−１）１４７０ｇに替えて上記操作C2.2で調製した連結型シリカ微粒子群の水分散（Ｃ−２）２．９４ｋｇを用いたこと以外は上記操作1.3と同様の操作を行うことにより、シリカ微粒子のメタノール分散液（以下「ＭＣ−２」という）を調製した。 (Operation C2.3) Preparation of Methanol Dispersion of Linked Silica Fine Particles (MC-2) In Operation 1.3 of Example 1, the aqueous dispersion of linked crystalline inorganic oxide particles prepared in Operation 1.2 above (P-1 ) By performing the same operation as in the above operation 1.3 except that 2.94 kg of the aqueous dispersion (C-2) of the linked silica fine particle group prepared in the above operation C2.2 was used instead of 1470 g, A methanol dispersion (hereinafter referred to as “MC-2”) was prepared.
このメタノール分散液（ＭＣ−２）の水分含有量は約０．５重量％、固形分濃度は３０重量％であった。 This methanol dispersion (MC-2) had a water content of about 0.5% by weight and a solid content concentration of 30% by weight.
このシリカ微粒子の平均粒子径は１５ｎｍであり、この微粒子は３〜４個連結して連結型微粒子群を構成しており、連結型微粒子群の比表面積は１７３ｍ2／ｇであった。以下、上記分散液（ＭＣ−２）を「連結型シリカ微粒子群のメタノール分散液（ＭＣ−２）」ともいう。The silica fine particles had an average particle diameter of 15 nm, and 3 to 4 fine particles were connected to form a connected fine particle group. The specific surface area of the connected fine particle group was 173 m 2 / g. Hereinafter, the dispersion (MC-2) is also referred to as “methanol dispersion (MC-2) of linked silica fine particles”.
このメタノール分散液（ＭＣ−２）中のシリカ微粒子に含まれる金属成分を測定したところ、ＳｉＯ2１００．０重量％であった。When the metal component contained in the silica fine particles in this methanol dispersion (MC-2) was measured, it was 100.0% by weight of SiO 2 .
（操作C2.4）ハードコート層膜形成用塗料組成物（Ｒ３）の調製
γ−グリシドキシプロピルトリメトキシシラン（東レ・ダウコーニング（株）製Ｚ−６０４０）１９８．１ｇおよびメタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）３５．１ｇの混合液中に、混合液を攪拌しながら０．０１Ｎの塩酸水溶液６７．５ｇを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行い、加水分解液を得た。 (Operation C2.4) Preparation of coating composition (R3) for forming a hard coat layer film 198.1 g of γ-glycidoxypropyltrimethoxysilane (Z-6040, manufactured by Toray Dow Corning Co., Ltd.) and methanol (Jun Hayashi) 67.5 g of 0.01N aqueous hydrochloric acid solution was added dropwise to 35.1 g of a mixed solution (manufactured by Yakuhin Co., Ltd., methyl alcohol concentration: 99.9 wt%) while stirring the mixed solution. Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.
次いで、この加水分解液に、メタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）３１０．０ｇおよび上記操作C2.3で調製した固形分濃度３０重量％の連結型シリカ微粒子群のメタノール分散液（ＭＣ−２）３３９．５ｇ、さらにプロピレングリコールモノメチルエーテル（ダウケミカル製）４０．６ｇ、トリス（２，４−ペンタンジオナト）アルミニウム（III）（東京化成工業（株）製）７．９ｇおよびレベリング剤としてのシリコーン系界面活性剤（東レ・ダウコーニング（株）製、Ｌ−７６０４）１．１ｇを加え、室温で一昼夜攪拌して、ハードコート層膜形成用塗料組成物（Ｒ３）を調製した。 Next, to this hydrolyzed solution, 310.0 g of methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a linked silica having a solid content concentration of 30 wt% prepared in the above operation C2.3 339.5 g of a fine particle group methanol dispersion (MC-2), 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentandionato) aluminum (III) (Tokyo Chemical Industry Co., Ltd.) 7.9 g) and 1.1 g of a silicone-based surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent, and stirred at room temperature all day and night to form a coating composition for forming a hard coat layer film A product (R3) was prepared.
［比較例３］
（操作C3.2）連結型無機酸化物微粒子群の水分散液（Ｃ−３）の調製
実施例１の操作1.1から操作1.2にかけて工程（１）を実施せず、操作1.2の工程（２）、（３）において、無機酸化物微粒子分散液（１ｂ）に替えてシリカゾル（日揮触媒化成（株）製 ＳＩ−３０、平均粒子径１２ｎｍ、ＳｉＯ2濃度３０重量％）１．０ｋｇを用いたこと以外は上記操作1.2と同様の操作を行うことにより、シリカのコア粒子の表面を、ジルコニウムおよびケイ素を含む複合酸化物からなるシェルで被覆してなるコアシェル微粒子（Ｃ３）の透明乳白色水分散液（以下、「Ｃ−３」という）を調製した。[Comparative Example 3]
(Operation C3.2) Preparation of Aqueous Dispersion (C-3) of Linked Inorganic Oxide Fine Particle Group Step (1) is not carried out from Operation 1.1 to Operation 1.2 in Example 1 but in Operation 1.2. In (3), instead of the inorganic oxide fine particle dispersion (1b), 1.0 kg of silica sol (SI-30 manufactured by JGC Catalysts & Chemicals Co., Ltd., average particle diameter 12 nm, SiO 2 concentration 30% by weight) was used. A transparent milky white aqueous dispersion of core-shell fine particles (C3) formed by coating the surface of the silica core particles with a shell made of a complex oxide containing zirconium and silicon by performing the same operation as in the above operation 1.2 except for Hereinafter, “C-3”) was prepared.
この無機酸化物粒状微粒子（Ｃ３）は４〜５個連結して連結型微粒子群を構成しており、連結型微粒子群の比表面積は２５４ｍ2／ｇであった。以下、上記分散液（Ｃ−３）を「連結型無機酸化物微粒子群の水分散液（Ｃ−３）」ともいう。Four to five inorganic oxide particulates (C3) are connected to form a connected fine particle group, and the specific surface area of the connected fine particle group is 254 m 2 / g. Hereinafter, the dispersion (C-3) is also referred to as “aqueous dispersion (C-3) of linked inorganic oxide fine particle group”.
この連結型微粒子群のＸ線回折では結晶性ピークが検出されず、無機酸化物微粒子（Ｃ３）は非晶質であった。 X-ray diffraction of this coupled fine particle group did not detect a crystalline peak, and the inorganic oxide fine particles (C3) were amorphous.
この連結型微粒子群に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＳｉＯ2が８４．７重量％、ＺｒＯ2が１４．３重量％、Ｋ2Ｏが１．０重量％であった。ここで、この無機酸化物微粒子に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は０．０８２であった。When the proportion of metal components contained in the group of connected fine particles (converted oxide value) was measured, SiO 2 was 84.7% by weight, ZrO 2 was 14.3% by weight, and K 2 O was 1.0% by weight. Met. Here, the molar ratio (ZrO 2 / SiO 2 ) when zirconium contained in the inorganic oxide fine particles was expressed as ZrO 2 and silicon was expressed as SiO 2 was 0.082.
（操作C3.3）連結型無機酸化物微粒子群のメタノール分散液（ＭＣ−３）の調製
実施例１の操作1.3において、上記操作1.2で調製した連結型結晶性無機酸化物微粒子群の水分散液（Ｐ−１）１４７０ｇに替えて上記操作C3.2で調製した連結型無機酸化物微粒子群の水分散液（Ｃ−３）１４７０ｇを用いたこと以外は上記操作1.3と同様の操作を行うことにより、無機酸化物微粒子のメタノール分散液（以下「ＭＣ−３」という）を調製した。 (Operation C3.3) Preparation of Methanol Dispersion (MC-3) of Linked Inorganic Oxide Fine Particle Group In Operation 1.3 of Example 1, water dispersion of the linked crystalline inorganic oxide fine particle group prepared in Operation 1.2 above. The same operation as in the above operation 1.3 is performed except that 1470 g of the aqueous dispersion (C-3) of the linked inorganic oxide fine particle group prepared in the above operation C3.2 is used instead of the liquid (P-1) 1470 g. Thus, a methanol dispersion of inorganic oxide fine particles (hereinafter referred to as “MC-3”) was prepared.
このメタノール分散液（ＭＣ−３）の水分含有量は約０．５重量％、固形分濃度は３０重量％であった。 This methanol dispersion (MC-3) had a water content of about 0.5% by weight and a solid content concentration of 30% by weight.
この無機酸化物微粒子の平均粒子径は１２ｎｍであり、この微粒子は４〜５個連結して連結型微粒子群を構成しており、連結型微粒子群の比表面積は２５４ｍ2／ｇであった。以下、上記分散液（ＭＰ−２）を「連結型無機酸化物微粒子群のメタノール分散液（ＭＰ−２）」ともいう。The average particle diameter of the inorganic oxide fine particles was 12 nm, and 4 to 5 fine particles were connected to form a connected fine particle group, and the specific surface area of the connected fine particle group was 254 m 2 / g. Hereinafter, the dispersion (MP-2) is also referred to as “methanol dispersion (MP-2) of linked inorganic oxide fine particle group”.
このメタノール分散液（ＭＰ−２）中の連結型微粒子群に含まれる金属成分の割合（酸化物換算値）を測定したところ、ＳｉＯ2が９１．１重量％、ＺｒＯ2が８．１重量％、Ｋ2Ｏが０．８重量％であった。ここで、この連結型微粒子群に含まれるジルコニウムをＺｒＯ2と表し、ケイ素をＳｉＯ2と表したときのモル比（ＺｒＯ2／ＳｉＯ2）は０．０４３であった。When the ratio of metal components contained in the linked fine particle group in this methanol dispersion (MP-2) (as oxide value) was measured, SiO 2 was 91.1 wt% and ZrO 2 was 8.1 wt%. , K 2 O was 0.8% by weight. Here, the molar ratio (ZrO 2 / SiO 2 ) when zirconium contained in the group of connected fine particles was expressed as ZrO 2 and silicon was expressed as SiO 2 was 0.043.
（操作C3.4）ハードコート層膜形成用塗料組成物（Ｒ４）の調製
γ−グリシドキシプロピルトリメトキシシラン（東レ・ダウコーニング（株）製Ｚ−６０４０）１９８．１ｇおよびメタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）３５．１ｇの混合液中に、混合液を攪拌しながら０．０１Ｎの塩酸水溶液６７．５ｇを滴下した。更に、この混合液を室温で一昼夜攪拌して、シラン化合物の加水分解を行い、加水分解液を得た。 (Operation C3.4) Preparation of Hard Coat Layer Film Forming Coating Composition (R4) 198.1 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Jun Hayashi) 67.5 g of 0.01N aqueous hydrochloric acid solution was added dropwise to 35.1 g of a mixed solution (manufactured by Yakuhin Co., Ltd., methyl alcohol concentration: 99.9 wt%) while stirring the mixed solution. Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.
次いで、この加水分解液に、メタノール（林純薬（株）製、メチルアルコール濃度：９９．９重量％）３１０．０ｇおよび上記操作C3.3で調製した固形分濃度３０重量％の連結型シリカ微粒子のメタノール分散液（ＭＣ−３）３３９．５ｇ、プロピレングリコールモノメチルエーテル（ダウケミカル製）４０．６ｇ、トリス（２，４−ペンタンジオナト）アルミニウム（III）（東京化成工業（株）製）７．９ｇおよびレベリング剤としてのシリコーン系界面活性剤（東レ・ダウコーニング（株）製、Ｌ−７６０４）１．１ｇを加え、室温で一昼夜攪拌して、ハードコート層膜形成用塗料組成物（Ｒ４）を調製した。 Next, to this hydrolyzed solution, 310.0 g of methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a linked silica having a solid content concentration of 30 wt% prepared in the above operation C3.3 339.5 g of fine particle methanol dispersion (MC-3), 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentanedionato) aluminum (III) (manufactured by Tokyo Chemical Industry Co., Ltd.) 7.9 g and 1.1 g of a silicone surfactant as a leveling agent (manufactured by Toray Dow Corning Co., Ltd., L-7604) were added and stirred at room temperature for a whole day and night to form a coating composition for forming a hard coat layer film ( R4) was prepared.
実施例１〜５および比較例１〜３で調製した各無機酸化物微粒子および各分散液の性状を表１〜５に示す。 Properties of each inorganic oxide fine particle and each dispersion prepared in Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Tables 1 to 5.
Ｂ．試験用プラスチックレンズ基板（試験片）の作製および評価
＜プラスチックレンズ基板（試験片）の作製＞
（１）プラスチックレンズ基材の前処理
市販のプラスチックレンズ基材「モノマー名：ＭＲ−８」（三井化学（株）製、基材の屈折率１．６０）および「モノマー名：ＭＲ−７」（三井化学（株）製、基材の屈折率１．６７）を、４０℃に保った１０重量％濃度のＫＯＨ水溶液に２分間浸漬してエッチング処理を行った。更に、これらを取り出して水洗したのち、十分に乾燥させた。 B. Production and evaluation of plastic lens substrate (test piece) for test < Production of plastic lens substrate (test piece)>
(1) Pretreatment of plastic lens substrate Commercially available plastic lens substrate “monomer name: MR-8” (manufactured by Mitsui Chemicals, Inc., refractive index of substrate 1.60) and “monomer name: MR-7” Etching was carried out by immersing (with Mitsui Chemicals, Inc., base material refractive index 1.67) in a 10 wt% KOH aqueous solution kept at 40 ° C. for 2 minutes. Further, these were taken out, washed with water, and then sufficiently dried.
（２）プライマー層膜の形成
前処理を行ったプラスチックレンズ基材にプライマー層膜形成用塗料組成物をそれぞれ塗布して塗膜を形成した。なお、この塗料組成物の塗布は、ディッピング法を用いて行った。(2) Formation of primer layer film A primer layer film-forming coating composition was applied to each pre-treated plastic lens substrate to form a coating film. In addition, application | coating of this coating composition was performed using the dipping method.
次に、前記塗膜を１００℃で１０分間、加熱処理して、塗膜（プライマー層）の予備乾燥を行った。 Next, the said coating film was heat-processed for 10 minutes at 100 degreeC, and the preliminary drying of the coating film (primer layer) was performed.
このようにして形成された前記プライマー層の予備硬化後の膜厚は、概ね０．５〜１．０μｍであった。 The film thickness of the primer layer thus formed after preliminary curing was approximately 0.5 to 1.0 μm.
（３）ハードコート層膜の形成
前記前処理を行ったプラスチックレンズ基材、またはプライマー層膜を形成したプラスチックレンズ基材の表面に、ハードコート層膜形成用の塗料組成物を塗布して塗膜を形成した。なお、この塗料組成物の塗布は、ディッピング法を用いて行った。(3) Formation of hard coat layer film A coating composition for forming a hard coat layer film is applied to the surface of the plastic lens substrate that has been subjected to the pretreatment or the plastic lens substrate on which the primer layer film has been formed. A film was formed. In addition, application | coating of this coating composition was performed using the dipping method.
次に、前記塗膜を９０℃で１０分間、乾燥させた後、１１０℃で２時間、加熱処理して、塗膜（ハードコート層）の硬化を行った。この際、前記プライマー層の本硬化も同時に行った。 Next, after drying the said coating film for 10 minutes at 90 degreeC, it heat-processed for 2 hours at 110 degreeC, and hardened | cured the coating film (hard-coat layer). At this time, the main curing of the primer layer was also performed at the same time.
このようにして形成された前記ハードコート層膜の硬化後の膜厚は、概ね３．０〜３．５μｍであった。 The thickness of the hard coat layer film thus formed after curing was approximately 3.0 to 3.5 μm.
（４）反射防止膜層の形成
前記ハードコート層膜の表面に、以下に示す構成の無機酸化物成分を真空蒸着法によって蒸着させた。ここでは、ハードコート層側から大気側に向かって、ＳｉＯ2：０．０６λ、ＺｒＯ2：０．１５λ、ＳｉＯ2：０．０４λ、ＺｒＯ2：０．２５λ、ＳｉＯ2：０．２５λの順序で積層された反射防止層膜の層をそれぞれ形成した。また、設計波長λは、５２０ｎｍとした。(4) Formation of antireflection film layer An inorganic oxide component having the following constitution was deposited on the surface of the hard coat layer film by a vacuum deposition method. Here, the order of SiO 2 : 0.06λ, ZrO 2 : 0.15λ, SiO 2 : 0.04λ, ZrO 2 : 0.25λ, and SiO 2 : 0.25λ from the hard coat layer side toward the atmosphere side. Each of the layers of the antireflection layer film laminated in (1) was formed. The design wavelength λ was 520 nm.
＜プラスチックレンズ基板（試験片）の評価＞
実施例１〜５、比較例１〜３で得られたハードコート層膜形成用の塗料組成物Ｈ１、Ｈ２、Ｈ３、Ｈ４、Ｈ５、Ｈ６、Ｈ７、Ｒ１、Ｒ２、Ｒ３、Ｒ４と、プライマー層膜形成用塗料組成物Ｙ１、Ｙ２、Ｓ１、Ｓ２を用いて、表６に示す組み合わせで前処理を行ったプラスチックレンズ基材上にプライマー層膜およびハードコート層膜を形成して試験片１〜１３を作製した。<Evaluation of plastic lens substrate (test piece)>
Coating compositions H1, H2, H3, H4, H5, H6, H7, R1, R2, R3, R4 and primer layers for hard coat layer film formation obtained in Examples 1 to 5 and Comparative Examples 1 to 3 Using the coating composition for film formation Y1, Y2, S1, and S2, a primer layer film and a hard coat layer film were formed on a plastic lens substrate that had been pretreated with the combinations shown in Table 6, and test pieces 1 to 13 was produced.
なお、プライマー層膜形成用塗料組成物Ｙ１とハードコート層膜形成用塗料組成物Ｈ１を塗布し反射防止層膜を形成した試験片９の基材、および、プライマー層膜形成用塗料組成物Ｓ１とハードコート層膜形成用塗料組成物Ｒ１を塗布し反射防止層膜を形成した試験片１１を作成した。 The primer layer film-forming coating composition Y1 and the hard coat layer film-forming coating composition H1 were applied to form a base material for the test piece 9 and the primer layer film-forming coating composition S1. Then, a test piece 11 was prepared by applying the coating composition R1 for forming a hard coat layer film and forming an antireflection layer film.
さらに、プライマー層膜形成用塗料組成物Ｙ２とハードコート層膜形成用塗料組成物Ｈ２を塗布し反射防止層膜を形成した試験片１２の基材、および、プライマー層膜形成用塗料組成物Ｓ２とハードコート層膜形成用塗料組成物Ｒ２を塗布し反射防止層膜を形成した試験片１３を作成した。ここで、試験片１２〜１３の基材としては「モノマー名：ＭＲ−７」（三井化学（株）製、基材の屈折率１．６７）を用い、それ以外の試験片の基材には「モノマー名：ＭＲ−８」（三井化学（株）製、基材の屈折率１．６０）を用いた。 Furthermore, the base material of the test piece 12 which applied the coating composition Y2 for forming the primer layer film and the coating composition H2 for forming the hard coat layer film to form the antireflection layer film, and the coating composition S2 for forming the primer layer film Then, a test piece 13 in which an antireflection layer film was formed by applying the coating composition R2 for forming a hard coat layer film was prepared. Here, “monomer name: MR-7” (manufactured by Mitsui Chemicals, Inc., refractive index 1.67 of the base material) is used as the base material of the test pieces 12 to 13, and the other test piece base materials are used. Used was “monomer name: MR-8” (manufactured by Mitsui Chemicals, Inc., refractive index of substrate 1.60).
このようにして得られた試験片１〜１３について、上記の評価試験法を用いて、外観（干渉縞）、外観（曇り）、耐擦傷性、膜硬度、密着性、耐候性、耐光性、屈折率を試験して評価した。その結果を表７に示す。 About the test pieces 1-13 obtained in this way, using the above-described evaluation test method, appearance (interference fringes), appearance (cloudiness), scratch resistance, film hardness, adhesion, weather resistance, light resistance, The refractive index was tested and evaluated. The results are shown in Table 7.
この結果から明らかなように、実施例で作成した塗料組成物を塗布して得られた試験片では耐擦傷性および膜硬度が非常に高いとともに、曇りがなく透明度が高いことがわかった。また、外観干渉縞も良好で、さらに密着性、耐候的密着性および耐光性が高いことがわかった。 As is clear from this result, it was found that the test piece obtained by applying the coating composition prepared in the example had very high scratch resistance and film hardness, and had no cloudiness and high transparency. Further, it was found that the appearance interference fringes were good, and the adhesion, weather resistance and light resistance were high.
本発明に係る連結型結晶性無機酸化物微粒子群およびその分散液は、該微粒子群を構成するチタニウムやジルコニウムなどの無機酸化物微粒子の屈折率が高いことから、光学材料用途に利用でき、その他にも、ハードコード材料、接着材料、封止材料、高反射性材料、紫外光吸収材料などの様々な用途に使用することができる。 The linked crystalline inorganic oxide fine particle group and the dispersion thereof according to the present invention can be used for optical material applications because the refractive index of the inorganic oxide fine particles such as titanium and zirconium constituting the fine particle group is high. In addition, it can be used for various applications such as hard cord materials, adhesive materials, sealing materials, highly reflective materials, and ultraviolet light absorbing materials.
Claims (19)
該連結型結晶性無機酸化物微粒子群が
（１）チタニウム、ジルコニウム、ニオブ、セリウムおよび亜鉛からなる群から選ばれる少なくとも１種の金属元素Ｍ2とケイ素とを含む結晶性無機酸化物微粒子、
（２）前記微粒子（１）を被覆する、ジルコニウム、アルミニウムおよびアンチモンからなる群から選ばれる少なくとも１種の金属元素Ｍ1とケイ素とを含む複合酸化物からなる被覆物質、および
（３）該被覆物質と同一成分である複合酸化物からなり、隣接する、前記被覆物質（２）で被覆された前記微粒子（１）同士を連結する結合物質
から構成されており、
該分散媒が水および／または有機溶媒である
ことを特徴とする連結型結晶性無機酸化物微粒子群を含む分散液。A dispersion containing a linked crystalline inorganic oxide fine particle group and a dispersion medium,
The connected crystalline inorganic oxide fine particle group (1) a crystalline inorganic oxide fine particle containing at least one metal element M 2 and silicon selected from the group consisting of titanium, zirconium, niobium, cerium and zinc;
(2) A coating material comprising a composite oxide containing at least one metal element M 1 selected from the group consisting of zirconium, aluminum and antimony and covering silicon, and (3) the coating. It is composed of a complex oxide that is the same component as the substance, and is composed of a binding substance that connects adjacent fine particles (1) coated with the coating substance (2),
A dispersion comprising linked crystalline inorganic oxide fine particle groups, wherein the dispersion medium is water and / or an organic solvent.
（１）チタニウム、ジルコニウム、ニオブ、セリウムおよび亜鉛からなる群から選ばれる少なくとも１種の金属元素Ｍ2とケイ素とを含む結晶性無機酸化物微粒子（１）が１次元的または２次元的に連結した粒子を含有する水分散液を準備する工程、
（２）前記工程（１）で準備された水分散液に、ジルコニウム、アルミニウムおよびアンチモンからなる群から選ばれる少なくとも１種の金属元素Ｍ1の化合物を含むアルカリ性水溶液および珪酸を含む酸性水溶液を添加する工程、および
（３）前記工程（２）で得られた水分散液を水熱処理する工程
を含むことを特徴とする連結型結晶性無機酸化物微粒子群を含む水分散液の製造方法。Water containing a crystalline inorganic oxide fine particle group, a coating material that coats the fine particle, and an adjacent binding material that connects the fine particles coated with the coating material to each other. A method for producing a dispersion, comprising:
(1) Crystalline inorganic oxide fine particles (1) containing at least one metal element M 2 selected from the group consisting of titanium, zirconium, niobium, cerium and zinc and silicon are connected one-dimensionally or two-dimensionally. Preparing an aqueous dispersion containing the prepared particles,
(2) To the aqueous dispersion prepared in the step (1), an aqueous alkaline solution containing a compound of at least one metal element M 1 selected from the group consisting of zirconium, aluminum and antimony and an acidic aqueous solution containing silicic acid are added. And (3) a method for producing an aqueous dispersion containing linked crystalline inorganic oxide fine particle groups, comprising the step of (3) hydrothermally treating the aqueous dispersion obtained in the step (2).
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008115060A (en) * | 2006-11-07 | 2008-05-22 | Catalysts & Chem Ind Co Ltd | Method for producing water dispersion containing chain silica-based fine particle group, water dispersion of chain silica-based fine particle group, and organic solvent dispersion thereof |
| WO2010071010A1 (en) * | 2008-12-18 | 2010-06-24 | 日揮触媒化成株式会社 | Chain-shaped silica-based hollow fine particles and process for producing same, coating fluid for transparent coating film formation containing the fine particles, and substrate with transparent coating film |
| JP2011093754A (en) * | 2009-10-30 | 2011-05-12 | Jgc Catalysts & Chemicals Ltd | Antimony pentoxide based complex oxide fine particle, coating liquid for forming transparency coating film containing the fine particle, and base material with transparency coating film |
| WO2011102467A1 (en) * | 2010-02-19 | 2011-08-25 | 国立大学法人東京大学 | Method for producing crystalline metal oxide structure |
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| JP6278902B2 (en) | 2018-02-14 |
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