JP2008037995A - Highly dispersed solid-liquid dispersion and coating liquid compounded with the same - Google Patents
Highly dispersed solid-liquid dispersion and coating liquid compounded with the same Download PDFInfo
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- JP2008037995A JP2008037995A JP2006213120A JP2006213120A JP2008037995A JP 2008037995 A JP2008037995 A JP 2008037995A JP 2006213120 A JP2006213120 A JP 2006213120A JP 2006213120 A JP2006213120 A JP 2006213120A JP 2008037995 A JP2008037995 A JP 2008037995A
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- 239000006185 dispersion Substances 0.000 title claims abstract description 139
- 239000007788 liquid Substances 0.000 title claims abstract description 132
- 238000000576 coating method Methods 0.000 title claims description 31
- 239000011248 coating agent Substances 0.000 title claims description 30
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 154
- 239000000843 powder Substances 0.000 claims abstract description 87
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 43
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 31
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003960 organic solvent Substances 0.000 claims abstract description 29
- 239000011164 primary particle Substances 0.000 claims abstract description 29
- 239000011787 zinc oxide Substances 0.000 claims abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 90
- 238000004381 surface treatment Methods 0.000 claims description 65
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 60
- 229910052731 fluorine Inorganic materials 0.000 claims description 24
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 18
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 18
- 229910001887 tin oxide Inorganic materials 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 9
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 229910052809 inorganic oxide Inorganic materials 0.000 claims 1
- 239000002270 dispersing agent Substances 0.000 abstract description 9
- 239000010419 fine particle Substances 0.000 description 49
- 239000007787 solid Substances 0.000 description 21
- 239000011324 bead Substances 0.000 description 18
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 18
- 229910052845 zircon Inorganic materials 0.000 description 18
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 18
- 239000002245 particle Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002156 mixing Methods 0.000 description 10
- 241001561902 Chaetodon citrinellus Species 0.000 description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 235000010746 mayonnaise Nutrition 0.000 description 9
- 239000008268 mayonnaise Substances 0.000 description 9
- 229910000077 silane Inorganic materials 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 239000007822 coupling agent Substances 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 perfluorooctylmethyl Chemical group 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WGGNJZRNHUJNEM-UHFFFAOYSA-N 2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N1 WGGNJZRNHUJNEM-UHFFFAOYSA-N 0.000 description 1
- HJIMAFKWSKZMBK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HJIMAFKWSKZMBK-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- HCBWKLFYOBHREQ-UHFFFAOYSA-N C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(C(C(C(C(F)(F)[Si](C(C(F)(F)F)(F)F)(Cl)Cl)(F)F)(F)F)(F)F)(F)F Chemical compound C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(C(C(C(C(F)(F)[Si](C(C(F)(F)F)(F)F)(Cl)Cl)(F)F)(F)F)(F)F)(F)F HCBWKLFYOBHREQ-UHFFFAOYSA-N 0.000 description 1
- MBIPLTWQROCVBC-UHFFFAOYSA-N FC(C(F)(F)F)([Si](Cl)(Cl)Cl)C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F Chemical compound FC(C(F)(F)F)([Si](Cl)(Cl)Cl)C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F MBIPLTWQROCVBC-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- YZCQLQBGROVEIY-UHFFFAOYSA-N [O--].[O--].[SiH4].[Zr+4] Chemical compound [O--].[O--].[SiH4].[Zr+4] YZCQLQBGROVEIY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- DJROWNUOVBJKIM-UHFFFAOYSA-N dimethoxy-methyl-(2,2,2-trifluoroethyl)silane Chemical compound CO[Si](C)(OC)CC(F)(F)F DJROWNUOVBJKIM-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 235000019441 ethanol Nutrition 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
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 238000005259 measurement Methods 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
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- GODUNKOEQVIXQA-UHFFFAOYSA-N trichloro(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-nonadecafluorononyl)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[Si](Cl)(Cl)Cl GODUNKOEQVIXQA-UHFFFAOYSA-N 0.000 description 1
- WEUBQNJHVBMUMD-UHFFFAOYSA-N trichloro(3,3,3-trifluoropropyl)silane Chemical compound FC(F)(F)CC[Si](Cl)(Cl)Cl WEUBQNJHVBMUMD-UHFFFAOYSA-N 0.000 description 1
- MLXDKRSDUJLNAB-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F MLXDKRSDUJLNAB-UHFFFAOYSA-N 0.000 description 1
- LLGVQQLZYJJDBZ-UHFFFAOYSA-N trimethoxy(2,2,2-trifluoroethyl)silane Chemical compound CO[Si](OC)(OC)CC(F)(F)F LLGVQQLZYJJDBZ-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
本発明は、高分散の固液分散体およびそれを配合したコーティング液に関する。 The present invention relates to a highly dispersed solid-liquid dispersion and a coating liquid containing the same.
例えば、微粒子二酸化チタンは、一次粒子径を１００ｎｍ以下の超微細状にすることによって、可視光線部における光透過性を大きくし、かつ紫外部での光遮蔽性を大きくすることができるという特徴ある性質を有している。 For example, fine particle titanium dioxide has a feature that it can increase the light transmittance in the visible light region and increase the light shielding property in the ultraviolet region by making the primary particle diameter into an ultrafine shape of 100 nm or less. It has properties.
しかしながら、この微粒子二酸化チタンも、他の無機粉体と同様に、一次粒子径が小さくなればなるほど、それに応じて粒子同士の凝集力が強くなり、そのため、有機溶剤に対して充分に分散させることができず、充分な分散状態を得ようとすれば、強力な分散が必要になる。そこで、例えば、サンドグラインダーミルなど、強力な分散装置を用いて分散させることが行われることになるが、たとえ、そのような強力な分散装置を用いたとしても、機械的手段によるだけでは、ある程度までしか分散させることができず、その分散には、自ずと限界がある。 However, as with other inorganic powders, the fine particle titanium dioxide also has a higher cohesive force between the particles as the primary particle diameter becomes smaller. Therefore, it should be sufficiently dispersed in the organic solvent. However, if a sufficient dispersion state is to be obtained, strong dispersion is required. Therefore, for example, dispersion using a powerful dispersing device such as a sand grinder mill is performed, but even if such a powerful dispersing device is used, it is only to some extent by mechanical means. Can only be dispersed, and the dispersion is naturally limited.
そこで、微粒子二酸化チタンなどの無機粉体の有機溶剤への分散性を向上させるため、界面活性剤などの分散剤を添加することが行われている（例えば、特許文献１、特許文献２）。 Therefore, in order to improve the dispersibility of inorganic powder such as fine particle titanium dioxide in an organic solvent, a dispersant such as a surfactant is added (for example, Patent Document 1 and Patent Document 2).
しかしながら、分散剤を添加して固液分散体を調製することは、それだけ不純物を固液分散体中に存在させることになり、その結果、上記固液分散体の溶剤成分を除いた後で分散剤由来の固形分が無機粉体近傍に存在することになる。 However, the preparation of a solid-liquid dispersion by adding a dispersant results in the presence of impurities in the solid-liquid dispersion, and as a result, the dispersion after removing the solvent component of the solid-liquid dispersion. The solid content derived from the agent is present in the vicinity of the inorganic powder.
そのため、上記固液分散体を例えば樹脂と混合し、その樹脂組成物を用いて成形体を作製する場合、それら分散剤由来の固形分が成形体の硬化を阻害させたり、特性を低下させるなどの問題を生じさせる原因になる。 Therefore, when the solid-liquid dispersion is mixed with, for example, a resin, and a molded body is produced using the resin composition, the solid content derived from the dispersant inhibits the curing of the molded body or deteriorates the characteristics. Cause problems.
本発明は、上記のような従来技術の問題点を解決し、無機粉体の有機溶剤への分散性を高め、分散剤を用いることなく、高分散の固液分散体を提供することを目的とする。 The object of the present invention is to solve the above-mentioned problems of the prior art, to improve the dispersibility of inorganic powder in an organic solvent, and to provide a highly dispersed solid-liquid dispersion without using a dispersant. And
本発明者は、無機粉体を特定複数種のシランカップリング剤で表面処理することによって、無機粉体の有機溶剤に対する分散性を大きく向上させることができることを見出し、それに基づいて、本発明を完成するにいたった。 The present inventor has found that the dispersibility of an inorganic powder in an organic solvent can be greatly improved by surface-treating the inorganic powder with a specific plurality of types of silane coupling agents. It came to completion.
すなわち、本発明は、分子中にフッ素原子を有するシランカップリング剤と分子中にケイ素−窒素結合を有するシランカップリング剤との２種類のシランカップリング剤で表面処理した無機粉体と、有機溶剤とで構成したことを特徴とする高分散の固液分散体に関するものである。 That is, the present invention relates to an inorganic powder surface-treated with two types of silane coupling agents: a silane coupling agent having a fluorine atom in the molecule and a silane coupling agent having a silicon-nitrogen bond in the molecule; The present invention relates to a highly dispersed solid-liquid dispersion characterized by comprising a solvent.
本発明の固液分散体は、上記特定のシランカップリング剤で表面処理した無機粉体が有機溶剤中に高度に分散しているが、そのような高分散状態は、分散剤の添加を要することなく、達成できる。従って、本発明の固液分散体によれば、前記したような残存分散剤による悪影響を及ぼすことがない。 In the solid-liquid dispersion of the present invention, the inorganic powder surface-treated with the specific silane coupling agent is highly dispersed in the organic solvent. Such a highly dispersed state requires the addition of a dispersant. Can be achieved without. Therefore, according to the solid-liquid dispersion of the present invention, there is no adverse effect due to the residual dispersant as described above.
例えば、無機粉体として、平均一次粒子径が５〜２００ｎｍの微粒子二酸化チタン、微粒子酸化亜鉛などのような紫外部の光線を遮蔽し可視光線部の光線を透過させる微細粉体を用いて本発明の固液分散体を構成し、それを、例えば、透明な樹脂に配合し、その樹脂組成物を用いて塗膜を作製すれば、透明で、かつ残存した分散剤による悪影響を受けない高品質の紫外線遮蔽フィルムを容易に製造することができる。 For example, the present invention uses a fine powder that blocks ultraviolet light and transmits visible light, such as fine particle titanium dioxide and fine particle zinc oxide having an average primary particle diameter of 5 to 200 nm as the inorganic powder. If a solid-liquid dispersion is composed, for example, it is blended with a transparent resin, and a coating film is produced using the resin composition, it is transparent and high quality that is not adversely affected by the remaining dispersant. The ultraviolet shielding film can be easily produced.
また、無機粉体として微粒子二酸化チタンを用いた場合は、その微粒子二酸化チタンの有する屈折率の高さを生かして、高屈折率の膜を容易に製造することができる。 Further, when fine particle titanium dioxide is used as the inorganic powder, a film having a high refractive index can be easily manufactured by taking advantage of the high refractive index of the fine particle titanium dioxide.
本発明の固液分散体は、前記のように、特定複数種のシランカップリング剤で表面処理した無機粉体と、それを分散する分散媒としての有機溶剤とで構成される。 As described above, the solid-liquid dispersion of the present invention is composed of an inorganic powder surface-treated with a specific plurality of types of silane coupling agents and an organic solvent as a dispersion medium for dispersing the inorganic powder.
上記無機粉体としては、一次粒子に分散できるものであれば特に限定されることはないが、本発明は紫外線遮蔽能を有し、かつ可視光線に対して透明性を示す塗膜や、高屈折率を有する塗膜の作製に適用したときに、特にその効果を顕著に発現することから、平均一次粒子径が５〜２００ｎｍの範囲内にある微粒子状の二酸化チタン、酸化亜鉛、酸化スズ、酸化セリウム、酸化ケイ素、酸化ジルコニウム、アンチモンドープ酸化スズ、スズドープ酸化インジウムなどの酸化物が好ましく、特に微粒子二酸化チタンや微粒子酸化亜鉛などが、本発明の固液分散体を塗膜の作製に適用したときに、特に塗膜を高透明性で、かつ高屈折率のものにすることができることから好ましい。 The inorganic powder is not particularly limited as long as it can be dispersed in the primary particles, but the present invention has a coating film that has ultraviolet shielding ability and transparency to visible light, When applied to the production of a coating film having a refractive index, the effect is particularly prominent, so that fine particles of titanium dioxide, zinc oxide, tin oxide having an average primary particle diameter in the range of 5 to 200 nm, Oxides such as cerium oxide, silicon oxide, zirconium oxide, antimony-doped tin oxide, and tin-doped indium oxide are preferable. Particularly, fine particle titanium dioxide, fine particle zinc oxide, and the like were applied to the production of the coating film by using the solid-liquid dispersion of the present invention. Sometimes, it is particularly preferable because the coating film can be made highly transparent and have a high refractive index.
また、上記無機粉体は、その粒子形状に関して、特に限定されることはなく、例えば、球状、楕円状、針状、板状などのいずれであってもよい。 The inorganic powder is not particularly limited with respect to the particle shape, and may be any of spherical, elliptical, needle-like, plate-like, and the like.
上記無機粉体は、そのまま用いてもよいし、また、シランカップリング剤による表面処理に先立ち、その表面を異種金属の酸化物や水酸化物で被覆したり、あるいは異種金属を粒子内に固溶させたものであってもよい。 The inorganic powder may be used as it is, or the surface may be coated with a dissimilar metal oxide or hydroxide before the surface treatment with the silane coupling agent, or the dissimilar metal may be solidified in the particles. It may be dissolved.
例えば、無機粉体が二酸化チタン、酸化亜鉛、酸化セリウムなどの場合、その粒子表面を、ケイ素、ジルコニウム、アルミニウムなどの異種金属の酸化物や水酸化物で被覆したり、粒子中にアンチモンやスズなどの異種金属を部分的に固溶させたものを用いてもよい。 For example, when the inorganic powder is titanium dioxide, zinc oxide, cerium oxide or the like, the particle surface is coated with an oxide or hydroxide of a different metal such as silicon, zirconium, or aluminum, or antimony or tin is contained in the particles. A material obtained by partially dissolving a dissimilar metal such as may be used.
本発明においては、上記無機粉体の粒子表面を表面処理するシランカップリング剤として、分子中にフッ素原子を有するシランカップリング剤と分子中にケイ素−窒素結合を有するシランカップリング剤との２種類のシランカップリング剤を用いる。 In the present invention, as the silane coupling agent for surface-treating the particle surface of the inorganic powder, a silane coupling agent having a fluorine atom in the molecule and a silane coupling agent having a silicon-nitrogen bond in the molecule. Use different types of silane coupling agents.
上記分子中にフッ素原子を有するシランカップリング剤としては、例えば、パーフルオロオクチルエチルトリエトキシシラン〔示性式：ｎ−Ｃ８Ｆ１７（ＣＨ２）２Ｓｉ（ＯＣ２Ｈ５）３〕、トリフルオロプロピルトリメトキシシラン〔示性式：ＣＦ３（ＣＨ２）３Ｓｉ（ＯＣＨ３）３〕、トリフルオロプロピルトリクロルシラン〔示性式：ＣＦ３Ｃ２Ｈ４ＳｉＣｌ３〕、パーフルオロオクチルメチルノナエトキシシラン〔示性式：ｎ−Ｃ８Ｆ１７（ＣＨ２）Ｓｉ（ＯＣ２Ｈ５）９〕、パーフルオロヘキシルエチルトリクロルシラン〔示性式：ＣＦ３（ＣＦ２）５（ＣＨ２）２ＳｉＣｌ３〕、パーフルオロオクチルメチルトリクロルシラン〔示性式：ＣＦ３（ＣＦ２）７（ＣＨ２）ＳｉＣｌ３〕、パーフルオロオクチルエチルトリメトキシシラン〔示性式：ＣＦ３（ＣＦ２）７（ＣＨ２）２Ｓｉ（ＯＣＨ３）３〕、パーフルオロオクチルエチルメチルジクロルシラン〔示性式：ＣＦ３（ＣＦ２）７（ＣＨ２）２Ｓｉ（ＣＨ３）Ｃｌ２〕、トリフルオロエチルトリメトキシシラン〔示性式：ＣＦ３（ＣＨ２）２Ｓｉ（ＯＣＨ３）２〕、トリフルオロエチルメチルジメトキシシラン〔示性式：ＣＦ３（ＣＨ２）３Ｓｉ（ＣＨ３）（ＯＣＨ３）２〕などが挙げられ、特にトリフルオロプロピルトリメトキシシランが分散性付与効果が優れていることから好ましい。 As the silane coupling agent having a fluorine atom in the molecule, for example, perfluorooctylethyltriethoxysilane [representative formula: nC 8 F 17 (CH 2 ) 2 Si (OC 2 H 5 ) 3 ], Trifluoropropyltrimethoxysilane [representative formula: CF 3 (CH 2 ) 3 Si (OCH 3 ) 3 ], trifluoropropyltrichlorosilane [representative formula: CF 3 C 2 H 4 SiCl 3 ], perfluorooctylmethyl Nonaethoxysilane [representative formula: nC 8 F 17 (CH 2 ) Si (OC 2 H 5 ) 9 ], perfluorohexylethyltrichlorosilane [representative formula: CF 3 (CF 2 ) 5 (CH 2 ) 2 SiCl 3], perfluorooctyl methyltrichlorosilane [rational formula: CF 3 (CF 2) 7 (CH 2) SiCl 3 , Perfluorooctyl ethyl trimethoxysilane [rational formula: CF 3 (CF 2) 7 (CH 2) 2 Si (OCH 3) 3 ], perfluoro octyl ethyl methyldichlorosilane [rational formula: CF 3 (CF 2 ) 7 (CH 2 ) 2 Si (CH 3 ) Cl 2 ], trifluoroethyltrimethoxysilane [representative formula: CF 3 (CH 2 ) 2 Si (OCH 3 ) 2 ], trifluoroethylmethyldimethoxysilane [ Illustrative formula: CF 3 (CH 2 ) 3 Si (CH 3 ) (OCH 3 ) 2 ] and the like, and trifluoropropyltrimethoxysilane is particularly preferred because of its excellent dispersibility-imparting effect.
また、分子中にケイ素−窒素結合を有するカップリング剤としては、ケイ素−窒素結合を２個有するジシラザン系化合物、ケイ素−窒素結合を３個有するトリシラザン系化合物、ケイ素−窒素結合を４個有するテトラシラザン系化合物のいずれも用いることができ、そのような分子中にケイ素−窒素結合を有するシランカップリング剤としては、例えば、ヘキサメチルジシラザン〔示性式：（ＣＨ３）３ＳｉＮＨＳｉ（ＣＨ３）３〕、１，１，３，３，５，５−ヘキサメチルシクロトリシラザン〔分子式：Ｓｉ３Ｃ６Ｈ２１Ｎ３〕、１，１，３，３，５，５，７，７−オクタメチルシクロテトラシラザン〔分子式：Ｓｉ４Ｃ８Ｈ２８Ｎ４〕、などが挙げられ、特にヘキサメチルジシラザンが分散性付与効果が優れていることから好ましい。 The coupling agent having a silicon-nitrogen bond in the molecule includes a disilazane compound having two silicon-nitrogen bonds, a trisilazane compound having three silicon-nitrogen bonds, and a tetra having four silicon-nitrogen bonds. Any of the silazane compounds can be used, and examples of the silane coupling agent having a silicon-nitrogen bond in the molecule include hexamethyldisilazane [descriptive formula: (CH 3 ) 3 SiNHSi (CH 3 3 ], 1,1,3,3,5,5-hexamethylcyclotrisilazane [molecular formula: Si 3 C 6 H 21 N 3 ], 1,1,3,3,5,5,7,7- octamethylcyclotetrasilazane [molecular formula: Si 4 C 8 H 28 N 4 ], and the like, it is particularly hexamethyldisilazane is superior in dispersibility-imparting effect Et al preferred.
このような２種類のシランカップリング剤による表面処理が、無機粉体の有機溶剤に対する分散性を優れたものにする理由については、現在のところ、必ずしも明確ではないが、分子中にフッ素原子を有するシランカップリング剤中のフッ素原子や、フッ素原子中にケイ素−窒素結合を有するシランカップリング剤中のケイ素−窒素結合による電荷偏在が、分散媒としての有機溶剤中における分散粒子の電荷バランスに何らかの好ましい相乗効果をもたらし、その結果として優れた一次粒子分散性を発現しているものと考えられる。 The reason why such surface treatment with two kinds of silane coupling agents makes the inorganic powder excellent in dispersibility in organic solvents is not necessarily clear at present, but fluorine atoms are present in the molecule. Dispersion of electric charge due to fluorine atoms in the silane coupling agent and silicon-nitrogen bonds in the silane coupling agent having a silicon-nitrogen bond in the fluorine atom contributes to the charge balance of the dispersed particles in the organic solvent as the dispersion medium. It is considered that some favorable synergistic effect is brought about, and as a result, excellent primary particle dispersibility is expressed.
例えば、分子中にフッ素原子を有するシランカップリング剤や、分子中にケイ素−窒素結合を有するシランカップリング剤を、それぞれ単独で用いた場合は、いずれも、充分な分散性の向上が得られず、また、それらのいずれかとビニルシラン系のシランカップリング剤やメタクリロキシシラン系のシランカップリング剤とを併用した場合も充分な分散性の向上が得られない。 For example, when a silane coupling agent having a fluorine atom in the molecule or a silane coupling agent having a silicon-nitrogen bond in the molecule is used alone, sufficient improvement in dispersibility can be obtained. In addition, when any of them is used in combination with a vinylsilane-based silane coupling agent or a methacryloxysilane-based silane coupling agent, a sufficient improvement in dispersibility cannot be obtained.
上記分子中にフッ素原子を有するシランカップリング剤と分子中にケイ素−窒素結合を有するシランカップリング剤との比率としては、質量比で７０：３０〜３０：７０が好ましく、６０：４０〜４０：６０がより好ましく、５５：４５〜４５：５５がさらに好ましく、とりわけ５０：５０（つまり、１：１）が好ましい。すなわち、分子中にフッ素原子を有するシランカップリング剤が上記比率より少ない場合は、分散性付与効果が低下して、無機粉体が凝集しやすく、得られる固液分散体が層分離を起こしやすくなり、また、分子中にフッ素原子を有するシランカップリング剤が上記比率より多い場合も、得られる固液分散体が層分離を起こしやすくなって、いずれの場合も充分な分散性の向上が得られなくなるおそれがある。 The ratio of the silane coupling agent having a fluorine atom in the molecule and the silane coupling agent having a silicon-nitrogen bond in the molecule is preferably 70:30 to 30:70, and 60:40 to 40 by mass ratio. : 60 is more preferable, 55:45 to 45:55 is more preferable, and 50:50 (that is, 1: 1) is particularly preferable. That is, when the number of silane coupling agents having fluorine atoms in the molecule is less than the above ratio, the dispersibility-imparting effect is reduced, the inorganic powder tends to aggregate, and the resulting solid-liquid dispersion tends to cause layer separation. In addition, even when the number of silane coupling agents having fluorine atoms in the molecule is larger than the above ratio, the obtained solid-liquid dispersion tends to cause layer separation, and in any case, sufficient improvement in dispersibility can be obtained. There is a risk of being lost.
無機粉体に対するシランカップリング剤の表面処理量としては、分子中にフッ素原子を有するシランカップリング剤と分子中にケイ素−窒素結合を有するシランカップリング剤とを合わせたシランカップリング剤全体の量として、無機粉体に対して１〜５０質量％（つまり、無機粉体１００質量部に対してシランカップリング剤が１〜５０質量部）が好ましく、５〜４０質量％がより好ましく、１０〜３０質量％がさらに好ましい。なお、無機粉体をシランカップリング剤で表面処理した場合、シランカップリング剤は無機粉体の粒子表面を被覆することになるので、上記無機粉体に対するシランカップリング剤の表面処理量は無機粉体に対するシランカップリング剤の被覆量に相当する。ただし、上記被覆は、必ずしも、無機粉体の粒子表面をシランカップリング剤で完全に覆っていることは要求されず、有機溶剤への分散性が充分に向上していさせすれば、部分的に無機粉体の粒子表面が露出していてもよい。 As the surface treatment amount of the silane coupling agent with respect to the inorganic powder, the total amount of the silane coupling agent in which the silane coupling agent having a fluorine atom in the molecule and the silane coupling agent having a silicon-nitrogen bond in the molecule are combined. The amount is preferably 1 to 50% by mass with respect to the inorganic powder (that is, 1 to 50 parts by mass of the silane coupling agent with respect to 100 parts by mass of the inorganic powder), more preferably 5 to 40% by mass. More preferably, it is -30 mass%. When the inorganic powder is surface-treated with a silane coupling agent, the silane coupling agent coats the particle surface of the inorganic powder, so the surface treatment amount of the silane coupling agent relative to the inorganic powder is inorganic. This corresponds to the coating amount of the silane coupling agent on the powder. However, the coating is not necessarily required to completely cover the particle surface of the inorganic powder with the silane coupling agent, and if the dispersibility in the organic solvent is sufficiently improved, the coating is partially The particle surface of the inorganic powder may be exposed.
無機粉体に対するシランカップリング剤の表面処理量が、上記より少ない場合は、無機粉体の有機溶剤への分散性を充分に向上させることができず、逆に多すぎる場合は、処理に利用されなかったシランカップリング剤が不純物として無機粉体近傍に残留し、樹脂に配合した後の強度低下や密着性の低下を引き起すなど、分散剤を添加した場合と同様の問題を生じさせる原因になる。 If the surface treatment amount of the silane coupling agent with respect to the inorganic powder is less than the above, the dispersibility of the inorganic powder in the organic solvent cannot be improved sufficiently. Causes of the same problems as when adding a dispersant, such as the silane coupling agent that was not retained remains in the vicinity of the inorganic powder as an impurity, causing reduction in strength and adhesion after blending with the resin become.
上記２種類のシランカップリング剤の無機粉体への処理順序としては、あらかじめシランカップリング剤同士を混合して同時に処理してもよいし、どちらか一方のシランカップリング剤を先に処理した後、他方のシランカップリング剤を後から処理してもよい。このように、分子中にフッ素原子を有するシランカップリング剤と分子中にケイ素−窒素結合を有するシランカップリング剤とを二段階に分けて処理しても、それらの処理量や両者の比率の関係で、二層処理の状態（つまり、先に処理したシランカップリング剤の上に後から処理したシランカップリング剤が被覆するような状態）にはならず、両者が混在した状態で無機粉体の粒子表面を被覆するようになり、分子中にフッ素原子を有するシランカップリング剤と分子中にケイ素−窒素結合を有するシランカップリング剤との併用による相乗効果が奏されるようになる。 As processing order to the inorganic powder of the above-mentioned two kinds of silane coupling agents, the silane coupling agents may be mixed in advance and processed at the same time, or one of the silane coupling agents is processed first. Later, the other silane coupling agent may be treated later. Thus, even if the silane coupling agent having a fluorine atom in the molecule and the silane coupling agent having a silicon-nitrogen bond in the molecule are treated in two stages, the treatment amount and the ratio of both In relation to this, the inorganic powder is not in a state of two-layer treatment (that is, a state in which a silane coupling agent treated later is coated on a silane coupling agent that has been treated earlier). The particle surface of the body is coated, and a synergistic effect is achieved by the combined use of a silane coupling agent having a fluorine atom in the molecule and a silane coupling agent having a silicon-nitrogen bond in the molecule.
無機粉体をシランカップリング剤で表面処理する方法としては、大きく分けて乾式法と湿式法とがあるが、本発明ではいずれの方法も採用することができる。 Methods for surface-treating inorganic powder with a silane coupling agent are broadly classified into a dry method and a wet method, and any method can be employed in the present invention.
乾式法では、例えば、ヘンシェルミキサーなどの高速攪拌機や、あるいは、ジェットミルなどの気流式粉砕機を用い、無機粉体を攪拌、粉砕しながら、シランカップリング剤または事前にシランカップリング剤を有機溶剤と混合して調製しておいた液体を添加していく方法を採用することができる。 In the dry method, for example, a high-speed stirrer such as a Henschel mixer or an airflow-type grinder such as a jet mill is used to stir and pulverize the inorganic powder while the silane coupling agent or the silane coupling agent is preliminarily organically mixed. A method of adding a liquid prepared by mixing with a solvent can be employed.
湿式法では、例えば、あらかじめシランカップリング剤を有機溶剤と混合した液体を調製しておき、また、無機粉体を溶剤と混合したスラリーを別途調製し、それらを攪拌機で充分に混合した後、さらに横型連続式サンドグラインダーミルなどの攪拌、粉砕が可能な装置を用いて処理を行なう方法を採用することができる。 In the wet method, for example, a liquid in which a silane coupling agent is mixed with an organic solvent in advance is prepared, and a slurry in which an inorganic powder is mixed with a solvent is separately prepared. After sufficiently mixing them with a stirrer, Furthermore, the method of processing using the apparatus which can stir and grind | pulverize, such as a horizontal type continuous sand grinder mill, is employable.
上記表面処理終了後のスラリーは、ニーダーに投入して減圧加熱を行なうなど、溶剤成分を除去し、さらに１２０〜１５０℃の温度でキュアリングを行うことによって、目的とする表面処理無機粉体を得ることができる。 The slurry after the surface treatment is put into a kneader and heated under reduced pressure to remove the solvent component and further cure at a temperature of 120 to 150 ° C. to obtain the desired surface-treated inorganic powder. Obtainable.
なお、本発明において、無機粉体の表面処理時に用いる溶剤は、上記の通り、有機溶剤であるが、これは、有機溶剤であれば、シランカップリング剤の表面処理反応を大きく阻害するおそれがないからである。このような有機溶剤としては、特に限定されることはないものの、例えば、トルエン、酢酸ブチル、プロピルアルコール、ブチルアルコール、メチルエチルケトン、キシレンなどが好適に用いられる。これらの有機溶剤のうち多くのものは、本発明の固液分散体の調製にあたって分散媒として使用可能であるが、その場合、トルエンは単独での使用は適切でなく、イソプロピルアルコールなどの極性溶媒と混合して用いることが好ましい。 In the present invention, the solvent used in the surface treatment of the inorganic powder is an organic solvent as described above. However, if this is an organic solvent, the surface treatment reaction of the silane coupling agent may be greatly inhibited. Because there is no. Such an organic solvent is not particularly limited, but for example, toluene, butyl acetate, propyl alcohol, butyl alcohol, methyl ethyl ketone, xylene and the like are preferably used. Many of these organic solvents can be used as a dispersion medium in the preparation of the solid-liquid dispersion of the present invention. In that case, toluene is not suitable for use alone, and a polar solvent such as isopropyl alcohol. It is preferable to use a mixture.
本発明の固液分散体は、上記のように特定の２種類のシランカップリング剤で表面処理した無機粉体を有機溶剤中に分散させることによって得られる。 The solid-liquid dispersion of the present invention is obtained by dispersing an inorganic powder surface-treated with two specific types of silane coupling agents as described above in an organic solvent.
この有機溶剤としては、例えば、酢酸ブチル、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、イソブチルアルコール、メチルエチルケトン、さらには、トルエンやキシレンなどの無極性溶媒とエチルアルコールやイソプロピルアルコールなどの極性溶媒との混合溶媒などを用いることができ、特にメチルエチルケトン、イソプロピルアルコール、トルエンとイソプロピルアルコールとの混合溶媒などが好ましい。 Examples of the organic solvent include butyl acetate, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, methyl ethyl ketone, and nonpolar solvents such as toluene and xylene and polar solvents such as ethyl alcohol and isopropyl alcohol. In particular, methyl ethyl ketone, isopropyl alcohol, a mixed solvent of toluene and isopropyl alcohol, and the like are preferable.
表面処理した無機粉体の有機溶剤への分散にあたっては、あらかじめ上記表面処理した無機粉体と有機溶剤とを予備混合した後、サンドミル、ボールミルなどの湿式粉砕機能を有する混合装置を用いて分散を行うと、無機粉体同士の凝集を避けやすいので好ましい。 In dispersing the surface-treated inorganic powder in the organic solvent, the surface-treated inorganic powder and the organic solvent are premixed in advance, and then dispersed using a mixing device having a wet grinding function such as a sand mill or a ball mill. This is preferable because aggregation of inorganic powders can be easily avoided.
固液分散体の調製にあたって、表面処理した無機粉体と有機溶剤との配合比率としては、固液分散体中に表面処理した無機粉体、すなわち、固液分散体を蒸発乾固した後の固形分の質量が、１０〜７０質量％になるようにすることが好ましく、１５〜５０質量％になるようにすることがより好ましく、２０〜４０質量％になるようにすることがさらに好ましい。表面処理した無機粉体が、上記より多くなると、固液分散体の分散性が低下し、充分な分散ができなくなるおそれがあり、逆に上記より少なくなってしまうと、無機粉体固有の特性を充分に発揮させることができなくなるおそれがある。 In the preparation of the solid-liquid dispersion, the blending ratio of the surface-treated inorganic powder and the organic solvent is the inorganic powder surface-treated in the solid-liquid dispersion, that is, after the solid-liquid dispersion is evaporated to dryness. The solid content is preferably 10 to 70% by mass, more preferably 15 to 50% by mass, and still more preferably 20 to 40% by mass. If the amount of the surface-treated inorganic powder is larger than the above, the dispersibility of the solid-liquid dispersion may be reduced, and sufficient dispersion may not be achieved. May not be able to be fully exhibited.
このようにして得られた本発明の固液分散体は、表面処理した無機粉体の濃度が０．０２５質量％になるまで希釈した場合の透明度がヘーズ値（ＨＡＺＥ値）で３０％以下という高い透明性を有している。 The solid-liquid dispersion of the present invention thus obtained has a transparency value of 30% or less in terms of haze value (HAZE value) when diluted until the concentration of the surface-treated inorganic powder becomes 0.025% by mass. High transparency.
この「ヘーズ値」とは、曇値ともいう曇り程度の指標であり、この値が小さいほど、透明度が高いことを示している。このヘーズ値の測定は、ＪＩＳ Ｋ ７１０５に記載の方法に基づいて行われる。そして、その測定結果は拡散光透過率（Ｔｄ）／全光線透過率（Ｔｔ）×１００で示す１００分率で表されることが多く、本発明においても、それを採用し、ヘーズ（％）で表示する。 The “haze value” is an index of a haze level, also called a haze value, and the smaller this value, the higher the transparency. The haze value is measured based on the method described in JIS K 7105. The measurement result is often expressed as a 100-minute fraction expressed by diffuse light transmittance (Td) / total light transmittance (Tt) × 100. In the present invention, it is adopted and the haze (%) is adopted. Is displayed.
本発明において、無機粉体として平均一次粒子径が５〜２００ｎｍ程度の微粒子無機粉体を用いると、それらの微粒子無機粉体をシランカップリング剤で表面処理し、固液分散体を調製したときにも、それら微粒子無機粉体の有する紫外線遮蔽能や可視光線部での透明性、高い屈折率を生かすことができる。そして、そのような平均一次粒子径が５〜２００ｎｍの微粒子無機粉体としては、微粒子二酸化チタン、微粒子酸化亜鉛などが好ましく、特に微粒子二酸化チタンはそれらの中でも高い紫外線遮蔽能や高い透明性、高い屈折率を有することから好ましい。 In the present invention, when a fine inorganic powder having an average primary particle size of about 5 to 200 nm is used as the inorganic powder, the fine inorganic powder is surface-treated with a silane coupling agent to prepare a solid-liquid dispersion. In addition, it is possible to make use of the ultraviolet shielding ability, transparency in the visible light region, and high refractive index of these fine particle inorganic powders. And as such fine particle inorganic powder with an average primary particle diameter of 5 to 200 nm, fine particle titanium dioxide, fine particle zinc oxide and the like are preferable, and particularly fine particle titanium dioxide has high ultraviolet shielding ability, high transparency, and high among them. It is preferable because it has a refractive index.
本発明において、上記微粒子無機粉体に関し、その平均一次粒子径が５〜２００ｎｍのものを好ましいとしているのは、平均一次粒子径が５ｎｍより小さいものは、無機粉体粒子の凝集力が強くなって、無機粉体を均一に分散させることができず、平均一次粒子径が２００ｎｍより大きくなると、透明性が低下し、また、無機粉体が分散体中で沈降して、分散安定性が低下するおそれがあるという理由によるものであり、特に平均一次粒子径が１０〜１００ｎｍの微粒子状のものが好ましい。なお、本発明において、上記無機粉体の平均一次粒子径は、無機粉体を透明型電子顕微鏡で撮影し（撮影個数は１，０００個以上）、撮影された個々の粒子の定方向径（粒子の面積を２分する水平線の長さ）をプロットし、それらを平均することによって求めたものである。 In the present invention, regarding the fine particle inorganic powder, those having an average primary particle size of 5 to 200 nm are preferred. Those having an average primary particle size of less than 5 nm have a stronger cohesive force of the inorganic powder particles. When the average primary particle size is larger than 200 nm, the inorganic powder cannot be uniformly dispersed, and the transparency is lowered, and the inorganic powder is precipitated in the dispersion and the dispersion stability is lowered. In particular, fine particles having an average primary particle diameter of 10 to 100 nm are preferable. In the present invention, the average primary particle diameter of the inorganic powder is determined by photographing the inorganic powder with a transparent electron microscope (captured number is 1,000 or more), and the unidirectional diameter of each photographed particle ( The length of the horizontal line that divides the particle area into two) is plotted, and the results are averaged.
本発明の固液分散体を用いてコーティング液を調製するにあたり、樹脂としては、特に制約されることはないが、例えば、アクリル樹脂、アルキド樹脂、メラミン樹脂、ポリエステル樹脂、塩ビ−酢ビ樹脂、エポキシ樹脂、ウレタン樹脂、フェノール樹脂、アミノ樹脂、フッ素樹脂、ポリビニルアルコール樹脂、エチレン−酢酸ビニル共重合体、アクリル−スチレン共重合体などを好適に用いることができる。 In preparing the coating liquid using the solid-liquid dispersion of the present invention, the resin is not particularly limited. For example, an acrylic resin, an alkyd resin, a melamine resin, a polyester resin, a vinyl chloride-vinyl acetate resin, Epoxy resins, urethane resins, phenol resins, amino resins, fluororesins, polyvinyl alcohol resins, ethylene-vinyl acetate copolymers, acrylic-styrene copolymers, and the like can be suitably used.
コーティング液の調製にあたって、それらの樹脂成分に対する固液分散体の配合量は、特に制約されることはないものの、固液分散体中の表面処理無機粉体（本発明において、この「表面処理無機粉体」とは、前記の分子中にフッ素原子を有するシランカップリング剤と分子中にケイ素−窒素結合を有するシランカップリング剤との２種類のシランカップリング剤で表面処理した無機粉体をいう）が、樹脂成分１００質量部に対して１０〜８００質量部、特に１０〜４００質量部になるようにすることが好ましい。 In the preparation of the coating liquid, the amount of the solid-liquid dispersion with respect to these resin components is not particularly limited, but the surface-treated inorganic powder in the solid-liquid dispersion (in the present invention, this “surface-treated inorganic “Powder” means an inorganic powder surface-treated with two types of silane coupling agents, a silane coupling agent having a fluorine atom in the molecule and a silane coupling agent having a silicon-nitrogen bond in the molecule. Is preferably 10 to 800 parts by weight, particularly 10 to 400 parts by weight, based on 100 parts by weight of the resin component.
なお、上記コーティング液の調製にあたっては、固液分散体と樹脂以外に、必要に応じて、有機溶剤を用いてもよいし、さらに、それら以外に、安定剤、硬化剤、重合開始剤などの添加剤を適宜コーティング液に添加してもよい。 In the preparation of the coating liquid, in addition to the solid-liquid dispersion and the resin, if necessary, an organic solvent may be used, and besides these, a stabilizer, a curing agent, a polymerization initiator, etc. You may add an additive to a coating liquid suitably.
コーティング液を調製する方法としては、例えば、固液分散体と樹脂とを直接混合する方法や、樹脂をあらかじめ溶剤に溶解し、得られた樹脂溶液と固液分散体とを混合する方法などが採用することができる。その際の混合装置としては、羽根型攪拌機、ディスパー、ホモミキサー、ディソルバー、インペラーミルなどを用いることができる。 Examples of the method for preparing the coating liquid include a method of directly mixing the solid-liquid dispersion and the resin, and a method of dissolving the resin in a solvent in advance and mixing the obtained resin solution and the solid-liquid dispersion. Can be adopted. As a mixing device at that time, a blade-type stirrer, a disper, a homomixer, a dissolver, an impeller mill, or the like can be used.
上記コーティング液を用いて塗膜を作製するにあたっては、例えば、アクリル板、塩化ビニル樹脂板、フィルム、ガラス板などの基材に対して、上記コーティング液をバーコート、スプレーコートなどの塗装機により塗布したり、スピンコート、ディップコートなどにより塗工する方法などを採用することができ、それによって、紫外線遮蔽能と高い透明性、高屈折率などを併せ持った塗膜を作製することができる。 In preparing a coating film using the coating liquid, for example, the coating liquid is applied to a base material such as an acrylic plate, a vinyl chloride resin plate, a film, or a glass plate by a coating machine such as a bar coat or a spray coat. A coating method such as coating or spin coating, dip coating, or the like can be employed, whereby a coating film having both ultraviolet shielding ability, high transparency, and high refractive index can be produced.
つぎに、実施例を挙げて本発明をさらに詳細に説明する。ただし、本発明はそれらの実施例に制限されるものではない。なお、以下において、液や分散体の濃度を示す％は、特にその単位を付記しないかぎり、質量％である。 Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In the following, “%” indicating the concentration of the liquid or dispersion is “% by mass” unless otherwise indicated.
実施例１
この実施例１では、無機粉体として平均一次粒子径が１５ｎｍの微粒子二酸化チタンを用い、分子中にフッ素原子を有するシランカップリング剤としてトリフルオロプロピルトリメトキシシラン〔信越化学工業社製シランカップリング剤ＫＢＭ−７１０３（商品名）〕を用い、分子中にケイ素−窒素結合を有するシランカップリング剤としてヘキサメチルジシラザン〔トーレダウコーニング社製シランカップリング剤Ｚ−６０７９（商品名）〕を用い、以下に示すように、シランカップリング剤による表面処理および固液分散体の調製を行った。
Example 1
In this Example 1, fine titanium dioxide having an average primary particle diameter of 15 nm was used as the inorganic powder, and trifluoropropyltrimethoxysilane [silane coupling made by Shin-Etsu Chemical Co., Ltd.] as the silane coupling agent having fluorine atoms in the molecule. Agent KBM-7103 (trade name)] and hexamethyldisilazane [silane coupling agent Z-6079 (trade name) manufactured by Tore Dow Corning Co., Ltd.] as the silane coupling agent having a silicon-nitrogen bond in the molecule. As shown below, surface treatment with a silane coupling agent and preparation of a solid-liquid dispersion were performed.
まず、比表面積が８０ｍ２／ｇで、平均一次粒子径が１５ｎｍの微粒子二酸化チタン粉末（テイカ社製ＭＴ−１００ＨＤ）３００ｇをヘンシェルミキサーに入れ、約１００℃で、回転速度１５００ｒｐｍで攪拌しながら、上記トリフルオロプロピルトリメトキシシランとトルエンとの質量比1：１の混合液４５ｇと、上記ヘキサメチルジシラザンとトルエンとの質量比１：１の混合液４５ｇとを、エアースプレーを用いて霧化しつつ、上記微粒子二酸化チタンに吹き付け、微粒子二酸化チタンのシランカップリング剤による表面処理を行った。さらに、上記処理混合物を回転速度１５００ｒｐｍで１５分間攪拌した後、１２０℃で３時間乾燥することによって、シランカップリング剤による微粒子二酸化チタンの表面で処理を終了した。上記のシランカップリング剤による表面処理により、微粒子二酸化チタンの粒子表面はシランカップリング剤により被覆されていた。この際のシランカップリング剤の表面処理量（シランカップリング剤の被覆量）は、微粒子二酸化チタンに対し１５質量％（つまり、微粒子二酸化チタン１００質量部に対してシランカップリング剤の表面処理量は１５質量部）であった。 First, 300 g of fine particle titanium dioxide powder (MT-100HD manufactured by Teica) having a specific surface area of 80 m 2 / g and an average primary particle size of 15 nm was put in a Henschel mixer, and stirred at about 100 ° C. at a rotation speed of 1500 rpm. 45 g of a mixture of trifluoropropyltrimethoxysilane and toluene in a mass ratio of 1: 1 and 45 g of a mixture of hexamethyldisilazane and toluene in a mass ratio of 1: 1 are atomized using an air spray. Then, the fine particle titanium dioxide was sprayed onto the fine particle titanium dioxide to carry out a surface treatment with the fine particle titanium dioxide with a silane coupling agent. Further, the treatment mixture was stirred at a rotation speed of 1500 rpm for 15 minutes, and then dried at 120 ° C. for 3 hours, whereby the treatment was completed on the surface of the particulate titanium dioxide with the silane coupling agent. By the surface treatment with the silane coupling agent, the particle surface of the fine particle titanium dioxide was coated with the silane coupling agent. In this case, the surface treatment amount of the silane coupling agent (the coating amount of the silane coupling agent) is 15% by mass with respect to the fine particle titanium dioxide (that is, the surface treatment amount of the silane coupling agent with respect to 100 parts by mass of the fine particle titanium dioxide). Was 15 parts by mass).
このシランカップリング剤の表面処理量は、表面処理後の微粒子二酸化チタンを５５０℃で３時間熱処理し、その強熱残分を蛍光Ｘ線にて定量分析し、Ｓｉ量から分子量換算で求めたものである。 The surface treatment amount of the silane coupling agent was obtained by heat-treating the finely divided titanium dioxide after the surface treatment at 550 ° C. for 3 hours, quantitatively analyzing the ignition residue with fluorescent X-ray, and obtaining the molecular weight conversion from the Si amount. Is.
上記シランカップリング剤による表面処理後の微粒子二酸化チタン粉末２０ｇ、トルエンとイソプロピルアルコールとの質量比１：１の混合溶剤６０ｇおよび直径０．５ｍｍのジルコンビーズ２５０ｇを、２００ｍｌのマヨネーズ瓶に仕込み、ペイントコンディショナー（レッドデビル社製＃５１１０型）にて２４０分間分散処理を行った後、ジルコンビーズを取り除いて固液分散体を得た。この固液分散体の固形分濃度は２５質量％であった。この固液分散体の固形分濃度は、固液分散体を５５０℃で３時間加熱し、その強熱残存物から求めたものである。 A 200 ml mayonnaise bottle was charged with 20 g of finely divided titanium dioxide powder after surface treatment with the silane coupling agent, 60 g of a mixed solvent of toluene and isopropyl alcohol having a mass ratio of 1: 1 and 250 g of zircon beads having a diameter of 0.5 mm. After performing dispersion treatment for 240 minutes with a conditioner (Red Devil # 5110 type), the zircon beads were removed to obtain a solid-liquid dispersion. The solid concentration of this solid-liquid dispersion was 25% by mass. The solid content concentration of the solid-liquid dispersion is obtained from the residue obtained by heating the solid-liquid dispersion at 550 ° C. for 3 hours.
実施例２
この実施例２では、無機粉体として平均一次粒子径が１５ｎｍの微粒子酸化亜鉛を用い、シランカップリング剤は実施例１と同様のものを用い、以下に示すように、微粒子酸化亜鉛へのシランカップリング剤による表面処理および固液分散体の調製を行った。
Example 2
In Example 2, fine zinc oxide having an average primary particle diameter of 15 nm is used as the inorganic powder, and the silane coupling agent is the same as in Example 1. As shown below, silane to fine zinc oxide is used. Surface treatment with a coupling agent and preparation of a solid-liquid dispersion were performed.
比表面積が５０ｍ２／ｇで、平均一次粒子径が１５ｎｍの微粒子酸化亜鉛（テイカ社製ＭＺ−５００）３００ｇをヘンシェルミキサーに入れ、約１００℃で、回転速度１５００ｒｐｍで攪拌しながら、トリフルオロプロピルトリメトキシシラン（前記の信越化学工業社製シランカップリング剤ＫＢＭ−７１０３で、分子中にフッ素原子を有するシランカップリング剤）とトルエンとの質量比１：１の混合液３０ｇと、ヘキサメチルジシラザン（前記のトーレダウコーニング社製シランカップリング剤Ｚ−６０７９で、分子中にケイ素−窒素結合を有するシランカップリング剤）とトルエンとの質量比１：１の混合液３０ｇとをエアースプレーを用いて霧化しつつ、微粒子酸化亜鉛に吹き付けて、微粒子酸化亜鉛の表面処理を行った。さらに、処理混合物を回転速度１５００ｒｐｍで１５分間攪拌した後、１２０℃で３時間乾燥することによって、シランカップリング剤による微粒子酸化亜鉛の表面処理を終了した。このシランカップリング剤の表面処理量を実施例１と同様に求めたところ、シランカップリング剤の表面処理量は微粒子酸化亜鉛に対して１０質量％であった。 300 g of finely divided zinc oxide (Mika-MZ-500, manufactured by Teica) having a specific surface area of 50 m 2 / g and an average primary particle diameter of 15 nm was placed in a Henschel mixer and stirred at about 100 ° C. at a rotation speed of 1500 rpm. 30 g of a mixed solution of trimethoxysilane (silane coupling agent KBM-7103 made by Shin-Etsu Chemical Co., Ltd., silane coupling agent having a fluorine atom in the molecule) and toluene in a mass ratio of 1: 1, hexamethyldi An air spray was applied to 30 g of a mixed solution of silazane (a silane coupling agent Z-6079 manufactured by Toray Dow Corning Co., which has a silicon-nitrogen bond in the molecule) and toluene in a mass ratio of 1: 1. While being atomized, the fine particle zinc oxide was sprayed onto the fine particle zinc oxide for surface treatment. Further, the treatment mixture was stirred at a rotation speed of 1500 rpm for 15 minutes and then dried at 120 ° C. for 3 hours, thereby completing the surface treatment of the fine zinc oxide with the silane coupling agent. When the surface treatment amount of the silane coupling agent was determined in the same manner as in Example 1, the surface treatment amount of the silane coupling agent was 10% by mass with respect to the fine zinc oxide.
上記シランカップリング剤による表面処理後の微粒子酸化亜鉛粉末２０ｇ、トルエンとイソプロピルアルコールとの質量比１：１の混合溶剤６０ｇおよび直径０．５ｍｍのジルコンビーズ２５０ｇを、８０ｍｌのマヨネーズ瓶に仕込み、ペイントコンディショナー（レッドデビル社製＃５１１０型）にて２４０分間分散処理を行った後、ジルコンビーズを取り除いて固液分散体を得た。この固液分散体の固形分濃度は２５質量％であった。この固液分散体の固形分濃度は、固液分散体を５５０℃で３時間加熱し、その強熱残存物から求めたものである。 20 g of fine zinc oxide powder after surface treatment with the silane coupling agent, 60 g of a mixed solvent of toluene and isopropyl alcohol in a mass ratio of 1: 1, and 250 g of zircon beads having a diameter of 0.5 mm are charged into an 80 ml mayonnaise bottle and painted. After performing dispersion treatment for 240 minutes with a conditioner (Red Devil # 5110 type), the zircon beads were removed to obtain a solid-liquid dispersion. The solid concentration of this solid-liquid dispersion was 25% by mass. The solid content concentration of the solid-liquid dispersion is obtained from the residue obtained by heating the solid-liquid dispersion at 550 ° C. for 3 hours.
実施例３
この実施例３では、無機粉体として平均一次粒子径が７ｎｍの微粒子酸化スズを用い、シランカップリング剤は実施例１と同様のものを用い、以下に示すように、微粒子酸化スズへのシランカップリング剤による表面処理および固液分散体の調製を行なった。
Example 3
In Example 3, fine particle tin oxide having an average primary particle diameter of 7 nm was used as the inorganic powder, and the silane coupling agent was the same as in Example 1. As shown below, silane into fine particle tin oxide was used. Surface treatment with a coupling agent and preparation of a solid-liquid dispersion were performed.
比表面積が５０ｍ２／ｇで平均一次粒子径が７ｎｍの微粒子酸化スズ３００ｇをヘンシェルミキサーに入れ、約１００℃で回転速度１５００ｒｐｍで攪拌しながら、トリフルオロプロピルトリメトキシシラン（前記の信越化学工業社製シランカップリング剤ＫＢＭ−７１０３で、分子中にフッ素原子を有するシランカップリング剤）とトルエンとの質量比１：１の混合液３０ｇと、ヘキサメチルジシラザン（前記のトーレダウコーニング社製シランカップリング剤Ｚ−６０７９で、分子中にケイ素−窒素結合を有するシランカップリング剤）とトルエンとの質量比１：１の混合液３０ｇとをエアースプレーを用いて霧化しつつ、微粒子酸化スズの表面処理を行った。さらに、処理混合物を回転速度１５００ｒｐｍで１５分間攪拌した後、１２０℃で３時間乾燥処理することによって、シランカップリング剤による微粒子酸化スズの表面処理を終了した。このシランカップリング剤の表面処理量を実施例１と同様に求めたところ、シランカップリング剤の表面処理量は微粒子酸化スズに対して１５質量％であった。 300 g of fine-particle tin oxide having a specific surface area of 50 m 2 / g and an average primary particle diameter of 7 nm was placed in a Henschel mixer and stirred at about 100 ° C. at a rotation speed of 1500 rpm. The trifluoropropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) Silane coupling agent KBM-7103, a silane coupling agent having a fluorine atom in the molecule) and toluene in a mass ratio of 1: 1 and 30 g of hexamethyldisilazane (the above-mentioned Toray Dow Corning silane) While atomizing with a coupling agent Z-6079 a silane coupling agent having a silicon-nitrogen bond in the molecule) and toluene in a mass ratio of 1: 1 with an air spray, fine tin oxide Surface treatment was performed. Further, the treatment mixture was stirred at a rotation speed of 1500 rpm for 15 minutes, and then dried at 120 ° C. for 3 hours, thereby completing the surface treatment of fine-particle tin oxide with a silane coupling agent. When the surface treatment amount of the silane coupling agent was determined in the same manner as in Example 1, the surface treatment amount of the silane coupling agent was 15% by mass with respect to the fine particle tin oxide.
上記シランカップリング剤による表面処理後の微粒子酸化スズ粉末２０ｇ、トルエンとイソプロピルアルコールとの質量比１：１の混合溶剤６０ｇおよび直径０．５ｍｍのジルコンビーズ２５０ｇを、２００ｍｌのマヨネーズ瓶に仕込み、ペイントコンディショナー（レッドデビル社製＃５１１０型）にて２４０分間分散処理を行なった後、ジルコンビーズを取り除いて固液分散体を得た。この固液分散体の固形分濃度は２５質量％であった。この固液分散体の固形分濃度は、固液分散体を５５０℃で３時間加熱し、その強熱残存物から求めたものである。 A 200 ml mayonnaise bottle was charged with 20 g of finely divided tin oxide powder after surface treatment with the silane coupling agent, 60 g of a mixed solvent of 1: 1 mass ratio of toluene and isopropyl alcohol, and 250 g of zircon beads having a diameter of 0.5 mm. After performing dispersion treatment for 240 minutes with a conditioner (Red Devil # 5110 type), zircon beads were removed to obtain a solid-liquid dispersion. The solid concentration of this solid-liquid dispersion was 25% by mass. The solid content concentration of the solid-liquid dispersion is obtained from the residue obtained by heating the solid-liquid dispersion at 550 ° C. for 3 hours.
実施例４
この実施例４では、無機粉体として平均一次粒子径が２０ｎｍのアンチモンドープ酸化スズを用い、シランカップリング剤は実施例１と同様のものを用い、以下に示すように、微粒子アンチモンドープ酸化スズへのシランカップリング剤による表面処理および固液分散体の調製を行なった。
Example 4
In this Example 4, antimony-doped tin oxide having an average primary particle size of 20 nm was used as the inorganic powder, and the silane coupling agent was the same as in Example 1. As shown below, fine-particle antimony-doped tin oxide was used. Surface treatment with a silane coupling agent and preparation of a solid-liquid dispersion were performed.
比表面積が７７ｍ２／ｇで平均一次粒子径が２０ｎｍのアンチモンドープ酸化スズ〔三菱マテリアル社製Ｔ−１（商品名）〕３００ｇをヘンシェルミキサーに入れ、約１００℃で、回転速度１５００ｒｐｍで攪拌しながら、トリフルオロプロピルトリメトキシシラン（前記の信越化学工業社製シランカップリング剤ＫＢＭ−７１０３で、分子中にフッ素原子を有するシランカップリング剤）とトルエンとの質量比１：１の混合液３０ｇと、ヘキサメチルジシラザン（前記のトーレダウコーニング社製シランカップリング剤Ｚ−６０７９で、分子中にケイ素−窒素結合を有するシランカップリング剤）とトルエンとの質量比１：１の混合液３０ｇとを、エアースプレーを用いて霧化しつつ、アンチモンドープ酸化スズの表面処理を行なった。さらに、処理混合物を回転速度１５００ｒｐｍで１５分間攪拌した後、１２０℃で３時間乾燥処理することによって、シランカップリング剤によるアンチモンドープ酸化スズの表面処理を終了した。このシランカップリング剤の表面処理量を実施例１と同様に求めたところ、シランカップリング剤の表面処理量はアンチモンドープ酸化スズに対して１５質量％であった。 300 g of antimony-doped tin oxide [T-1 (trade name) manufactured by Mitsubishi Materials Corporation] having a specific surface area of 77 m 2 / g and an average primary particle size of 20 nm was placed in a Henschel mixer and stirred at about 100 ° C. at a rotation speed of 1500 rpm. However, 30 g of a mixed solution of trifluoropropyltrimethoxysilane (the above silane coupling agent KBM-7103 manufactured by Shin-Etsu Chemical Co., Ltd., a silane coupling agent having a fluorine atom in the molecule) and toluene in a mass ratio of 1: 1. And hexamethyldisilazane (the above-mentioned Toray Dow Corning silane coupling agent Z-6079, a silane coupling agent having a silicon-nitrogen bond in the molecule) and toluene in a mass ratio of 1: 1 mixture 30 g The surface treatment of antimony-doped tin oxide was performed while atomizing using an air spray. Further, the treatment mixture was stirred at a rotation speed of 1500 rpm for 15 minutes, and then dried at 120 ° C. for 3 hours, thereby completing the surface treatment of antimony-doped tin oxide with a silane coupling agent. When the surface treatment amount of the silane coupling agent was determined in the same manner as in Example 1, the surface treatment amount of the silane coupling agent was 15% by mass with respect to antimony-doped tin oxide.
上記シランカップリング剤による表面処理後のアンチモンドープ酸化スズ粉末２０ｇ、トルエンとイソプロピルアルコールとの質量比１：１の混合溶剤６０ｇおよび直径０．５ｍｍのジルコンビーズ２５０ｇを、２００ｍｌのマヨネーズ瓶に仕込み、ペイントコンディショナー（レッドデビル社製＃５１１０型）にて２４０分間分散処理を行なった後、ジルコンビーズを取り除いて固液分散体を得た。この固液分散体の固形分濃度は２５質量％であった。この固液分散体の固形分濃度は、固液分散体を５５０℃で３時間加熱し、その強熱残存物から求めたものである。 20 g of antimony-doped tin oxide powder after surface treatment with the silane coupling agent, 60 g of a mixed solvent of 1: 1 mass ratio of toluene and isopropyl alcohol, and 250 g of zircon beads having a diameter of 0.5 mm are charged into a 200 ml mayonnaise bottle, After a dispersion treatment for 240 minutes with a paint conditioner (# 5110 type manufactured by Red Devil), the zircon beads were removed to obtain a solid-liquid dispersion. The solid concentration of this solid-liquid dispersion was 25% by mass. The solid content concentration of the solid-liquid dispersion is obtained from the residue obtained by heating the solid-liquid dispersion at 550 ° C. for 3 hours.
実施例５
この実施例５では、無機粉体として平均一次粒子径が１５ｎｍの酸化ジルコニウムを用い、シランカップリング剤は実施例１と同様のものを用い、以下に示すように、酸化ジルコニウムへのシランカップリング剤による表面処理および固液分散体の調製を行なった。
Example 5
In this Example 5, zirconium oxide having an average primary particle diameter of 15 nm was used as the inorganic powder, and the silane coupling agent was the same as in Example 1. As shown below, silane coupling to zirconium oxide was performed. Surface treatment with an agent and preparation of a solid-liquid dispersion were performed.
比表面積が８０ｍ２／ｇで平均一次粒子径が１５ｎｍの酸化ジルコニウム３００ｇをヘンシェルミキサーに入れ、約１００℃で、回転速度１５００ｒｐｍで攪拌しながら、トリフルオロプロピルトリメトキシシラン（前記の信越化学工業社製シランカップリング剤ＫＢＭ−７１０３で、分子中にフッ素原子を有するシランカップリング剤）とトルエンとの質量比１：１の混合液４５ｇと、ヘキサメチルジシラザン（前記のトーレダウコーニング社製シランカップリング剤Ｚ−６０７９で、分子中ケイ素−窒素結合を有するシランカップリング剤）とトルエンとの重量比１：１の混合液４５ｇとを、エアースプレーを用いて霧化しつつ、上記酸化ジルコニウムに吹き付け、酸化ジルコニウムのシランカップリング剤による表面処理を行なった。さらに、上記処理混合物を回転速度１５００ｒｐｍで１５分間攪拌した後、１２０℃で３時間乾燥することによって、シランカップリング剤による酸化ジルコニウムの表面処理を終了した。このシランカップリング剤の表面処理量を実施例１と同様に求めたところ、シランカップリング剤の表面処理量は酸化ジルコニウムに対して１５質量％であった。 300 g of zirconium oxide having a specific surface area of 80 m 2 / g and an average primary particle diameter of 15 nm was placed in a Henschel mixer and stirred at about 100 ° C. at a rotation speed of 1500 rpm while the above-mentioned Shin-Etsu Chemical Co., Ltd. Silane coupling agent KBM-7103, silane coupling agent having a fluorine atom in the molecule) and 45 g of a 1: 1 mixture of toluene and hexamethyldisilazane (the above-mentioned Toray Dow Corning silane) A silane coupling agent having a silicon-nitrogen bond in the molecule with coupling agent Z-6079) and 45 g of a 1: 1 mixed solution of toluene are atomized using an air spray to the above zirconium oxide. Sprayed and surface treated with zirconium oxide silane coupling agent Furthermore, after the said processing mixture was stirred for 15 minutes at the rotational speed of 1500 rpm, the surface treatment of the zirconium oxide by a silane coupling agent was completed by drying at 120 degreeC for 3 hours. When the surface treatment amount of the silane coupling agent was determined in the same manner as in Example 1, the surface treatment amount of the silane coupling agent was 15% by mass with respect to zirconium oxide.
上記シランカップリング剤による表面処理後の酸化ジルコニウム２０ｇ、トルエンとイソプロピルアルコールとの質量比１：１の混合溶剤６０ｇおよび直径０．５ｍｍのジルコンビーズ２５０ｇを、２００ｍｌのマヨネーズ瓶に仕込み、ペイントコンディショナー（レッドデビル社製＃５１１０型）にて２４０分間分散処理を行なった後、ジルコンビーズを取り除いて固液分散体を得た。この固液分散体の固形分濃度は２５質量％であった。この固液分散体の固形分濃度は、固液分散体を５５０℃で３時間加熱し、その強熱残存物から求めたものである。 20 g of zirconium oxide after the surface treatment with the silane coupling agent, 60 g of a mixed solvent of 1: 1 mass ratio of toluene and isopropyl alcohol, and 250 g of zircon beads having a diameter of 0.5 mm were charged into a 200 ml mayonnaise bottle, and a paint conditioner ( The dispersion process was performed for 240 minutes using a Red Devil # 5110 model), and then the zircon beads were removed to obtain a solid-liquid dispersion. The solid concentration of this solid-liquid dispersion was 25% by mass. The solid content concentration of the solid-liquid dispersion is obtained from the residue obtained by heating the solid-liquid dispersion at 550 ° C. for 3 hours.
実施例６
この実施例６では、無機粉体として平均一次粒子径が２５ｎｍの酸化ケイ素を用い、シランカップリング剤は実施例１と同様のものを用い、以下に示すように、酸化ケイ素へのシランカップリング剤による表面処理および固液分散体の調製を行なった。
Example 6
In this Example 6, silicon oxide having an average primary particle diameter of 25 nm was used as the inorganic powder, and the silane coupling agent was the same as in Example 1. As shown below, silane coupling to silicon oxide was performed. Surface treatment with an agent and preparation of a solid-liquid dispersion were performed.
比表面積が１４０ｍ２／ｇで平均一次粒子径が２５ｎｍの酸化ケイ素３００ｇをヘンシェルミキサーに入れ、約１００℃で、回転速度１５００ｒｐｍで攪拌しながら、トリフルオロプロピルトリメトキシシラン（前記の信越化学工業社製シランカップリング剤ＫＢＭ−７１０３で、分子中にフッ素原子を有するシランカップリング剤）とトルエンとの質量比１：１の混合液９０ｇと、ヘキサメチルジシラザン（前記のトーレダウコーニング社製シランカップリング剤Ｚ−６０７９で、分子中にケイ素−窒素結合を有するシランカップリング剤）とトルエンとの質量比１：１の混合液９０ｇとを、エアースプレーを用いて霧化しつつ、上記酸化ケイ素に吹き付け、酸化ケイ素のシランカップリング剤による表面処理を行なった。さらに、上記処理混合物を回転速度１５００ｒｐｍで１５分間攪拌した後、１２０℃で３時間乾燥することによって、シランカップリング剤による酸化ケイ素の表面処理を終了した。このシランカップリング剤の表面処理量を実施例１と同様に求めたところ、シランカップリング剤の表面処理量は酸化ケイ素に対して３０質量％であった。 300 g of silicon oxide having a specific surface area of 140 m 2 / g and an average primary particle size of 25 nm was placed in a Henschel mixer and stirred at about 100 ° C. at a rotation speed of 1500 rpm. 90 g of a silane coupling agent KBM-7103, a silane coupling agent having a fluorine atom in the molecule) and toluene in a mass ratio of 1: 1, and hexamethyldisilazane (the above-mentioned Toray Dow Corning silane) The above silicon oxide was atomized with a coupling agent Z-6079 by atomizing 90 g of a mixed solution of silane coupling agent having a silicon-nitrogen bond in the molecule) and toluene in a mass ratio of 1: 1. And surface treatment with a silane coupling agent of silicon oxide was performed. Furthermore, the treatment mixture was stirred at a rotation speed of 1500 rpm for 15 minutes, and then dried at 120 ° C. for 3 hours, thereby completing the surface treatment of silicon oxide with a silane coupling agent. When the surface treatment amount of this silane coupling agent was calculated | required similarly to Example 1, the surface treatment amount of the silane coupling agent was 30 mass% with respect to the silicon oxide.
上記シランカップリング剤による表面処理後の酸化ケイ素１０ｇ、トルエンとイソプロピルアルコールとの質量比１：１の混合溶剤７０ｇおよび直径０．５ｍｍのジルコンビーズ２５０ｇを、２００ｍｌのマヨネーズ瓶に仕込み、ペイントコンディショナー（レッドデビル社製＃５１１０型）にて２４０分間分散処理を行なった後、ジルコンビーズを取り除いて固液分散体を得た。この固液分散体の固形分濃度は１２．５質量％であった。この固液分散体の固形分濃度は、固液分散体を５５０℃で３時間加熱し、その強熱残存物から求めたものである。 10 g of silicon oxide after the surface treatment with the silane coupling agent, 70 g of a mixed solvent of 1: 1 mass ratio of toluene and isopropyl alcohol, and 250 g of zircon beads having a diameter of 0.5 mm are charged into a 200 ml mayonnaise bottle, and paint conditioner ( The dispersion process was performed for 240 minutes using a Red Devil # 5110 model), and then the zircon beads were removed to obtain a solid-liquid dispersion. The solid concentration of this solid-liquid dispersion was 12.5% by mass. The solid content concentration of the solid-liquid dispersion is obtained from the residue obtained by heating the solid-liquid dispersion at 550 ° C. for 3 hours.
実施例７
この実施例７では、無機粉体として平均一次粒子径が２５ｎｍの酸化セリウムを用い、
シランカップリング剤は実施例１と同様のものを用い、以下に示すように、酸化セリウムへのシランカップリング剤による表面処理および固液分散体の調製を行なった。
Example 7
In Example 7, cerium oxide having an average primary particle size of 25 nm was used as the inorganic powder.
The same silane coupling agent as in Example 1 was used. As shown below, cerium oxide was surface-treated with a silane coupling agent and a solid-liquid dispersion was prepared.
比表面積が１７１ｍ２／ｇで平均一次粒子径が１０ｎｍの酸化セリウム３００ｇをヘンシェルミキサーに入れ、約１００℃で、回転速度１５００ｒｐｍで攪拌しながら、トリフルオロプロピルトリメトキシシラン（前記の信越化学工業社製シランカップリング剤ＫＢＭ−７１０３で、分子中にフッ素原子を有するシランカップリング剤）とトルエンとの質量比１：１の混合液９０ｇと、ヘキサメチルジシラザン（前記のトーレダウコーニング社製シランカップリング剤Ｚ−６０７９で、分子中にケイ素−窒素結合を有するシランカップリング剤）とトルエンとの質量比１：１の混合液９０ｇとを、エアースプレーを用いて霧化しつつ、上記酸化セリウムに吹き付け、酸化セリウムのシランカップリング剤による表面処理を行なった。さらに、上記処理混合物を回転速度１５００ｒｐｍで１５分間攪拌した後、１２０℃で３時間乾燥することによって、シランカップリング剤による酸化セリウムの表面処理を終了した。このシランカップリング剤の表面処理量を実施例１と同様に求めたところ、シランカップリング剤の表面処理量は酸化セリウムに対して３０質量％であった。 300 g of cerium oxide having a specific surface area of 171 m 2 / g and an average primary particle diameter of 10 nm was placed in a Henschel mixer and stirred at about 100 ° C. at a rotational speed of 1500 rpm. 90 g of a silane coupling agent KBM-7103, a silane coupling agent having a fluorine atom in the molecule) and toluene in a mass ratio of 1: 1, and hexamethyldisilazane (the above-mentioned Toray Dow Corning silane) The above cerium oxide was prepared by atomizing 90 g of a mixed solution of a 1: 1 mass ratio of a silane coupling agent having a silicon-nitrogen bond in the molecule and toluene with a coupling agent Z-6079 using an air spray. And surface treatment with a cerium oxide silane coupling agent. Further, the treatment mixture was stirred for 15 minutes at a rotational speed of 1500 rpm, and then dried at 120 ° C. for 3 hours, thereby completing the surface treatment of cerium oxide with a silane coupling agent. When the surface treatment amount of this silane coupling agent was calculated | required similarly to Example 1, the surface treatment amount of the silane coupling agent was 30 mass% with respect to cerium oxide.
上記シランカップリング剤による表面処理後の酸化セリウム２０ｇ、トルエンとイソプロピルアルコールとの質量比１：１の混合溶剤６０ｇおよび直径０．５ｍｍのジルコンビーズ２５０ｇを、２００ｍｌのマヨネーズ瓶に仕込み、ペイントコンディショナー（レッドデビル社製＃５１１０型）にて２４０分間分散処理を行なった後、ジルコンビーズを取り除いて固液分散体を得た。この固液分散体の固形分濃度は２５質量％であった。この固液分散体の固形分濃度は、固液分散体を５５０℃で３時間加熱し、その強熱残存物から求めたものである。 20 g of cerium oxide after the surface treatment with the silane coupling agent, 60 g of a mixed solvent of 1: 1 mass ratio of toluene and isopropyl alcohol, and 250 g of zircon beads having a diameter of 0.5 mm were charged into a 200 ml mayonnaise bottle, and a paint conditioner ( The dispersion process was performed for 240 minutes using a Red Devil # 5110 model), and then the zircon beads were removed to obtain a solid-liquid dispersion. The solid concentration of this solid-liquid dispersion was 25% by mass. The solid content concentration of the solid-liquid dispersion is obtained from the residue obtained by heating the solid-liquid dispersion at 550 ° C. for 3 hours.
実施例８
この実施例８では、固液分散体の調製にあたって使用する有機溶剤をトルエンとイソプロピルアルコールとの混合溶剤からメチルエチルケトンに変更した以外は、実施例１と同様にシランカップリング剤による表面処理および固液分散体の調製を行った。
Example 8
In Example 8, surface treatment with a silane coupling agent and solid-liquid were performed in the same manner as in Example 1 except that the organic solvent used in the preparation of the solid-liquid dispersion was changed from a mixed solvent of toluene and isopropyl alcohol to methyl ethyl ketone. A dispersion was prepared.
すなわち、実施例１と同様にシランカップリング剤による表面処理を行った微粒子二酸化チタン粉末２０ｇ、メチルエチルケトン６０ｇおよび直径０．５ｍｍのジルコンビーズ２５０ｇを、２００ｍｌのマヨネーズ瓶に仕込み、ペイントコンディショナー（レッドデビル社製＃５１１０型）にて２４０分間分散処理を行なった後、ジルコンビーズを取り除いて固液分散体を得た。この固液分散体の固形分濃度は２５質量％であった。この固液分散体の固形分濃度は、固液分散体を５５０℃で３時間加熱し、その強熱残存物から求めたものである。 That is, 20 g of fine particle titanium dioxide powder subjected to surface treatment with a silane coupling agent as in Example 1, 60 g of methyl ethyl ketone and 250 g of zircon beads having a diameter of 0.5 mm were charged into a 200 ml mayonnaise bottle, and paint conditioner (Red Devil) (# 5110 type) for 240 minutes, the zircon beads were removed to obtain a solid-liquid dispersion. The solid concentration of this solid-liquid dispersion was 25% by mass. The solid content concentration of the solid-liquid dispersion is obtained from the residue obtained by heating the solid-liquid dispersion at 550 ° C. for 3 hours.
実施例９
この実施例９では、固液分散体の調製にあたって使用する有機溶剤をトルエンとイソプロピルアルコールとの混合溶剤からイソプロピルアルコールに変更した以外は、実施例１と同様に、シランカップリング剤による表面処理および固液分散体の調製を行った。
Example 9
In Example 9, the surface treatment with a silane coupling agent was performed in the same manner as in Example 1 except that the organic solvent used in the preparation of the solid-liquid dispersion was changed from a mixed solvent of toluene and isopropyl alcohol to isopropyl alcohol. A solid-liquid dispersion was prepared.
すなわち、実施例１と同様にシランカップリング剤による表面処理を行った微粒子二酸化チタン粉末２０ｇ、イソプロピルアルコール６０ｇおよび直径０．５ｍｍのジルコンビーズ２５０ｇを、２００ｍｌのマヨネーズ瓶に仕込み、ペイントコンディショナー（レッドデビル社製＃５１１０型）にて２４０分間分散処理を行なった後、ジルコンビーズを取り除いて固液分散体を得た。この固液分散体の固形分濃度は２５質量％であった。この固液分散体の固形分濃度は、固液分散体を５５０℃で３時間加熱し、その強熱残存物から求めたものである。 That is, 20 g of fine particle titanium dioxide powder, 60 g of isopropyl alcohol and 250 g of zircon beads having a diameter of 0.5 mm, which had been surface-treated with a silane coupling agent in the same manner as in Example 1, were charged into a 200 ml mayonnaise bottle, and paint conditioner (Red Devil) The dispersion was performed for 240 minutes using a # 5110 model), and then the zircon beads were removed to obtain a solid-liquid dispersion. The solid concentration of this solid-liquid dispersion was 25% by mass. The solid content concentration of the solid-liquid dispersion is obtained from the residue obtained by heating the solid-liquid dispersion at 550 ° C. for 3 hours.
比較例１
実施例１と同様の微粒子二酸化チタンをシランカップリング剤による表面処理をすることなくそのまま用い、固液分散体の調製を試みた。しかしながら、ペースト状になり、分散体は得られなかった。従って、以後の評価は行わなかった。
Comparative Example 1
The same fine particle titanium dioxide as that of Example 1 was used as it was without surface treatment with a silane coupling agent, and an attempt was made to prepare a solid-liquid dispersion. However, it became a paste and no dispersion was obtained. Therefore, subsequent evaluation was not performed.
比較例２
実施例１と同様の微粒子二酸化チタンを、実施例１と同様の分子中にフッ素原子を有するシランカップリング剤のみで表面処理し、この表面処理微粒子二酸化チタンを用いた以外は、実施例１と同様に固液分散体の調製を行った。しかしながら、この比較例２では、分子中にケイ素−窒素結合を有するシランカップリング剤での表面処理をしていないため、調製されたものは、２層に分離し、安定な固液分散体は得られなかった。
Comparative Example 2
The same fine particle titanium dioxide as in Example 1 was surface-treated only with a silane coupling agent having a fluorine atom in the same molecule as in Example 1, and this surface-treated fine particle titanium dioxide was used. Similarly, a solid-liquid dispersion was prepared. However, in Comparative Example 2, since the surface treatment with a silane coupling agent having a silicon-nitrogen bond in the molecule was not performed, the prepared product was separated into two layers, and the stable solid-liquid dispersion was It was not obtained.
比較例３
実施例１と同様の微粒子二酸化チタンを、実施例１と同様の分子中にケイ素−窒素結合を有するシランカップリング剤のみで表面処理し、この表面処理微粒子二酸化チタンを用いた以外は、実施例１と同様に固液分散体の調製を行った。しかしながら、この比較例３では、分子中にフッ素原子を有するシランカップリング剤での表面処理をしていないため、調製されたものは、２層に分離し、安定な固液分散体は得られなかった。
Comparative Example 3
Except that the same fine particle titanium dioxide as in Example 1 was surface-treated only with a silane coupling agent having a silicon-nitrogen bond in the same molecule as in Example 1, and this surface-treated fine particle titanium dioxide was used. In the same manner as in Example 1, a solid-liquid dispersion was prepared. However, in Comparative Example 3, since the surface treatment was not performed with a silane coupling agent having a fluorine atom in the molecule, the prepared product was separated into two layers, and a stable solid-liquid dispersion was obtained. There wasn't.
比較例４
分子中にフッ素原子を有するシランカップリング剤に代えてビニルシラン系シランカップリング剤であるビニルトリメトキシシラン〔示性式：（Ｃ２Ｈ５Ｏ）３ＳｉＣＨ＝ＣＨ２〕を用いた以外は、実施例１と同様に微粒子二酸化チタンの表面処理を行い、得られた表面処理微粒子二酸化チタンを用いた以外は、実施例１と同様に固液分散体の調製を行った。しかしながら、上記表面処理後の微粒子二酸化チタンが溶剤中で激しく凝集してペースト状になり、安定した固液分散体は得られなかった。
Comparative Example 4
Except for using vinyltrimethoxysilane [representative formula: (C 2 H 5 O) 3 SiCH═CH 2 ], which is a vinylsilane-based silane coupling agent, instead of the silane coupling agent having a fluorine atom in the molecule, A solid-liquid dispersion was prepared in the same manner as in Example 1 except that the surface treatment of fine particle titanium dioxide was performed in the same manner as in Example 1 and the obtained surface-treated fine particle titanium dioxide was used. However, the finely divided titanium dioxide after the surface treatment aggregated vigorously in a solvent to form a paste, and a stable solid-liquid dispersion could not be obtained.
つまり、この比較例４では、実施例１と同様の微粒子二酸化チタンを用い、分子中にフッ素原子を有するシランカップリング剤に代えてビニルシラン系シランカップリング剤を用いた以外、実施例１と同様に表面処理および固液分散体の調製をしているが、上記のように、表面処理後の微粒子二酸化チタンの激しい凝集が生じて、高分散の固液分散体は得られなかった。 That is, Comparative Example 4 is the same as Example 1 except that the same fine particle titanium dioxide as in Example 1 is used, and a vinylsilane-based silane coupling agent is used instead of the silane coupling agent having a fluorine atom in the molecule. The surface treatment and the preparation of the solid-liquid dispersion were carried out, but as described above, the finely divided titanium dioxide after the surface treatment was agglomerated and a highly dispersed solid-liquid dispersion could not be obtained.
比較例５
分子中にフッ素原子を有するシランカップリング剤に代えてメタクリロキシシラン系シランカップリング剤であるγーメタクリロキシプロピルトリメトキシシラン〔示性式：（ＣＨ３Ｏ）３ＳｉＣ３Ｈ６ＯＣ（Ｏ）Ｃ（ＣＨ３）＝ＣＨ２〕を用いた以外は、実施例１と同様に微粒子二酸化チタンの表面処理を行い、得られた表面処理微粒子二酸化チタンを用いた以外は、実施例１と同様に固液分散体の調製を試みた。しかしながら、上記表面処理後の微粒子二酸化チタンが激しく凝集してペースト状になり、安定した固液分散体は得られなかった。
Comparative Example 5
Instead of a silane coupling agent having a fluorine atom in the molecule, γ-methacryloxypropyltrimethoxysilane which is a methacryloxysilane-based silane coupling agent [representative formula: (CH 3 O) 3 SiC 3 H 6 OC (O ) Except for using C (CH 3 ) ═CH 2 ], the surface treatment of fine particle titanium dioxide was performed in the same manner as in Example 1, and the same as in Example 1 except that the obtained surface-treated fine particle titanium dioxide was used. An attempt was made to prepare a solid-liquid dispersion. However, the fine particle titanium dioxide after the surface treatment was agglomerated into a paste and a stable solid-liquid dispersion could not be obtained.
つまり、この比較例５では、実施例１と同様の微粒子二酸化チタンを用い、分子中にフッ素原子を有するシランカップリング剤に代えてメタクリロキシシラン系シランカップリング剤を用いた以外は、実施例１と同様に表面処理および固液分散体の調製をしているが、上記のように、表面処理後の微粒子二酸化チタンの激しい凝集が生じて、高分散の固液分散体は得られなかった。 That is, in Comparative Example 5, the same fine particle titanium dioxide as in Example 1 was used, except that a methacryloxysilane-based silane coupling agent was used instead of the silane coupling agent having a fluorine atom in the molecule. The surface treatment and the solid-liquid dispersion were prepared in the same manner as in No. 1, but as described above, intense aggregation of the fine-particle titanium dioxide after the surface treatment occurred, and a highly dispersed solid-liquid dispersion could not be obtained. .
固液分散体の透明度の測定：
実施例１〜９および比較例２〜５で調製した固液分散体をトルエンとイソプロピルアルコールとの質量比１：１の混合溶剤で希釈して固液分散体中の表面処理無機粉体の濃度を０．０２５％にした。
Measuring the transparency of solid-liquid dispersions:
The solid-liquid dispersions prepared in Examples 1 to 9 and Comparative Examples 2 to 5 were diluted with a 1: 1 mixed solvent of toluene and isopropyl alcohol, and the concentration of the surface-treated inorganic powder in the solid-liquid dispersion Of 0.025%.
得られた固液分散体の透明度を直読ヘーズコンピューター（スガ試験機社製ＨＤＭ−２ＤＰ型）を用いて測定した。その結果を表１に示す。上記固液分散体の透明度はヘーズ（％）で表され、このヘーズ（％）値が小さいほど透明性が高いことを示している。そして、この透明性でもって、分散性を評価し、透明性が高いものほど分散性が高いと評価する。 The transparency of the obtained solid-liquid dispersion was measured using a direct reading haze computer (HDM-2DP type manufactured by Suga Test Instruments Co., Ltd.). The results are shown in Table 1. The transparency of the solid-liquid dispersion is expressed in haze (%), and the smaller the haze (%) value, the higher the transparency. And with this transparency, dispersibility is evaluated, and the higher the transparency, the higher the dispersibility.
表１に示すように、実施例１〜９は、比較例２〜５に比べて、透明度を示すヘーズ（％）値が小さかった。この結果から、実施例１〜９の固液分散体は、比較例２〜５の固液分散体に比べて、分散度が高いことがわかる。 As shown in Table 1, the haze (%) value which shows transparency was small in Examples 1-9 compared with Comparative Examples 2-5. From this result, it can be seen that the solid-liquid dispersions of Examples 1 to 9 have a higher degree of dispersion than the solid-liquid dispersions of Comparative Examples 2 to 5.
コーティング液の調製とその評価：
実施例１の固液分散体と、紫外線硬化型ウレタンアクリレート樹脂〔荒川化学社製ビームセット５７７（商品名）〕と、重合開始剤〔チバガイギー社製イルガキュア（ＩＲＧＡＣＵＲＥ：登録商標）１８４／８１９＝１／１（質量比）〕とを混合、攪拌してコーティング液を調製した。
Preparation and evaluation of coating solutions:
The solid-liquid dispersion of Example 1, an ultraviolet curable urethane acrylate resin [Arakawa Chemical Co., Ltd. Beam Set 577 (trade name)], and a polymerization initiator [Ciba Geigy Co., Ltd. IRGACURE: 184/819 = 1] / 1 (mass ratio)] was mixed and stirred to prepare a coating solution.
重合開始剤の配合量は、紫外線硬化型ウレタンアクリレート樹脂に対して３％（紫外線硬化型ウレタンアクリレート樹脂１００質量部に対して重合開始剤３質量部）であり、紫外線硬化型ウレタンアクリレート樹脂と固液分散体の配合割合は表２に記載のように変動させた。ただし、固液分散体の量は表面処理した微粒子二酸化チタンに換算した量で示しており、表２では、これを「固液分散体中の顔料分」として表示する。 The blending amount of the polymerization initiator is 3% with respect to the UV curable urethane acrylate resin (3 parts by mass of the polymerization initiator with respect to 100 parts by mass of the UV curable urethane acrylate resin). The blending ratio of the liquid dispersion was varied as shown in Table 2. However, the amount of the solid-liquid dispersion is shown in terms of the amount converted to the surface-treated fine particle titanium dioxide, and in Table 2, this is indicated as “pigment content in the solid-liquid dispersion”.
得られたコーティング液をそれぞれ別々にＰＥＴ（ポリエチレンテレフタレート）フィルムに平均乾燥膜厚が３μｍになるようにバーコーターＮｏ．６で塗布し、自然乾燥後、紫外線源としての高圧水銀ランプ（３００ｍＪ／ｃｍ２）を用いて紫外線を照射することにより塗膜を作製した。 Each of the obtained coating solutions was separately applied to a PET (polyethylene terephthalate) film so that the average dry film thickness was 3 μm. The coating film was produced by irradiating with ultraviolet rays using a high-pressure mercury lamp (300 mJ / cm 2 ) as an ultraviolet ray source.
得られた各塗膜のヘーズ値を上記の直読ヘーズコンピューターを用いて測定し、さらに鉛筆硬度をＪＩＳ Ｋ ５４００に従って評価した。その結果を表２に樹脂に対する顔料分の比率（すなわち、紫外線硬化型ウレタンアクリレート樹脂１００質量部に対する表面処理した微粒子二酸化チタンの質量部）と共に示す。 The haze value of each coating film obtained was measured using the direct reading haze computer, and the pencil hardness was evaluated according to JIS K 5400. The results are shown in Table 2 together with the ratio of the pigment to the resin (that is, the mass part of the surface-treated fine particle titanium dioxide with respect to 100 parts by mass of the UV curable urethane acrylate resin).
表２に示すように、実施例１の固液分散体を用いた場合、ブランク（すなわち、実施例１の固液分散体を用いずに、紫外線硬化型ウレタンアクリレート樹脂のみの場合）に比べて、ヘーズ（％）値の増加はそれほど大きくなく、また、鉛筆硬度の低下もそれほど大きくなく、充分な実用性を有していた。 As shown in Table 2, when the solid-liquid dispersion of Example 1 was used, compared with the blank (that is, without using the solid-liquid dispersion of Example 1 and only the ultraviolet curable urethane acrylate resin). The increase in the haze value (%) was not so great, and the decrease in pencil hardness was not so great, and it had sufficient practicality.
以上説明したように、本発明の固液分散体は、それ自身の分散度が高く、つまり、上記特定２種類のシランカップリング剤で表面処理した無機粉体の有機溶剤への分散度が高く、また、有機溶剤系の樹脂や樹脂溶液と容易に混合でき、紫外線遮蔽能、透明性、屈折率が高く、かつ適度な硬度を有する塗膜を作製することができる。その結果、本発明の固液分散体は、コスト的に有利に、ＦＰＤ（フラットパネルディスプレー）のＡＲ（反射防止：Ａｎｔｉ Ｒｅｆｌｅｃｔｉｏｎ）層の高屈折率層、ＨＣ（ハードコート）層の屈折率調整剤およびその他、光学部材の屈折率調整材料として提供することができる。 As described above, the solid-liquid dispersion of the present invention has a high degree of dispersion itself, that is, the degree of dispersion of the inorganic powder surface-treated with the above two specific types of silane coupling agents in an organic solvent is high. Moreover, it can be easily mixed with an organic solvent-based resin or a resin solution, and a coating film having an ultraviolet shielding ability, transparency, a high refractive index, and an appropriate hardness can be produced. As a result, the solid-liquid dispersion of the present invention is advantageous in terms of cost because of the high refractive index layer of the AR (anti-reflection) layer and the refractive index adjustment of the HC (hard coat) layer of the FPD (flat panel display). It can be provided as a refractive index adjusting material for an agent and other optical members.
Claims (9)
A coating comprising 10 to 800 parts by mass of the solid-liquid dispersion according to any one of claims 1 to 8 in terms of a surface-treated inorganic powder with respect to 100 parts by mass of the resin component of the coating liquid. liquid.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010209186A (en) * | 2009-03-09 | 2010-09-24 | Sumitomo Osaka Cement Co Ltd | Optical material, dispersion of inorganic fine particle, process for producing optical material, and light-emitting element |
| JP2011137097A (en) * | 2009-12-28 | 2011-07-14 | Jgc Catalysts & Chemicals Ltd | Coating liquid for transparent film formation, substrate with transparent film, and method for producing hydrophobic metal oxide particle |
| JP2012051762A (en) * | 2010-09-01 | 2012-03-15 | Nano Cube Japan Co Ltd | Method for producing tin oxide ultrafine particle |
| JP2013204029A (en) * | 2012-03-29 | 2013-10-07 | Admatechs Co Ltd | Optical resin composition |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1025427A (en) * | 1996-07-12 | 1998-01-27 | Mitsui Eng & Shipbuild Co Ltd | Hydrophobic material for surface having gas holding capability |
| JP2000044226A (en) * | 1998-05-18 | 2000-02-15 | Shin Etsu Chem Co Ltd | Silane-surface-treated siliceous fine particles, their production and organic resin composition containing same |
| JP2008001781A (en) * | 2006-06-21 | 2008-01-10 | Koito Mfg Co Ltd | Composition for preventing adhesion of snow and ice and its use, and liquid spraying device |
-
2006
- 2006-08-04 JP JP2006213120A patent/JP4895366B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1025427A (en) * | 1996-07-12 | 1998-01-27 | Mitsui Eng & Shipbuild Co Ltd | Hydrophobic material for surface having gas holding capability |
| JP2000044226A (en) * | 1998-05-18 | 2000-02-15 | Shin Etsu Chem Co Ltd | Silane-surface-treated siliceous fine particles, their production and organic resin composition containing same |
| JP2008001781A (en) * | 2006-06-21 | 2008-01-10 | Koito Mfg Co Ltd | Composition for preventing adhesion of snow and ice and its use, and liquid spraying device |
Cited By (10)
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|---|---|---|---|---|
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| JP2011137097A (en) * | 2009-12-28 | 2011-07-14 | Jgc Catalysts & Chemicals Ltd | Coating liquid for transparent film formation, substrate with transparent film, and method for producing hydrophobic metal oxide particle |
| JP2012051762A (en) * | 2010-09-01 | 2012-03-15 | Nano Cube Japan Co Ltd | Method for producing tin oxide ultrafine particle |
| JP2013204029A (en) * | 2012-03-29 | 2013-10-07 | Admatechs Co Ltd | Optical resin composition |
| KR20150047429A (en) * | 2013-10-24 | 2015-05-04 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Photo-curable coating material, layered product and sheet for coating head lamp of automobile |
| JP2015212354A (en) * | 2013-10-24 | 2015-11-26 | 信越化学工業株式会社 | Photocurable coating, laminate and sheet for coating automobile head lamp |
| KR102157614B1 (en) * | 2013-10-24 | 2020-09-18 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Photo-curable coating material, layered product and sheet for coating head lamp of automobile |
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| JP2015212355A (en) * | 2013-11-01 | 2015-11-26 | 信越化学工業株式会社 | Titanium oxide-containing coating composition and coated article |
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