JP2009107872A - Modified zirconia fine particles, sol in which the fine particles are dispersed, and method for producing the sol - Google Patents
Modified zirconia fine particles, sol in which the fine particles are dispersed, and method for producing the sol Download PDFInfo
- Publication number
- JP2009107872A JP2009107872A JP2007280565A JP2007280565A JP2009107872A JP 2009107872 A JP2009107872 A JP 2009107872A JP 2007280565 A JP2007280565 A JP 2007280565A JP 2007280565 A JP2007280565 A JP 2007280565A JP 2009107872 A JP2009107872 A JP 2009107872A
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- Prior art keywords
- zirconia fine
- fine particles
- modified zirconia
- dispersion
- weight
- Prior art date
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 409
- 239000010419 fine particle Substances 0.000 title claims abstract description 195
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 123
- 239000006185 dispersion Substances 0.000 claims abstract description 122
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 60
- 239000007787 solid Substances 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims description 69
- 239000007864 aqueous solution Substances 0.000 claims description 40
- 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 claims description 25
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000003729 cation exchange resin Substances 0.000 claims description 19
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- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
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- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
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- 239000011591 potassium Substances 0.000 description 9
- 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 8
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- 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 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
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- 229920003303 ion-exchange polymer Polymers 0.000 description 6
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- 235000002906 tartaric acid Nutrition 0.000 description 6
- 239000011975 tartaric acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- 229910000410 antimony oxide Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 4
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 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
- 239000003957 anion exchange resin Substances 0.000 description 3
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 239000007771 core particle Substances 0.000 description 3
- -1 for example Substances 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
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- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 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
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- 150000002500 ions Chemical class 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
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- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
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- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 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
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- WDUXKFKVDQRWJN-UHFFFAOYSA-N triethoxysilylmethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C=C WDUXKFKVDQRWJN-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
本発明は、表面が五酸化アンチモンまたはシリカで被覆されているために分散液の広範囲のｐＨ領域にわたって分散性、安定性に優れたジルコニア微粒子、該微粒子分散ゾルおよびその製造方法に関する。
The present invention relates to zirconia fine particles having excellent dispersibility and stability over a wide pH range of a dispersion liquid because the surface is coated with antimony pentoxide or silica, the fine particle-dispersed sol, and a method for producing the same.
従来、シリカ、アルミナ、チタニア、ジルコニア、酸化亜鉛、五酸化アンチモン、酸化セリウム、酸化スズ、シリカ・アルミナ、シリカ・ジルコニアなどのコロイド粒子が知られており、光学材料として屈折率を調整するために被膜等に配合して用いられている。
例えば、シリカは低屈折材料として、アルミナは中程度の屈折率材料として、チタニア、ジルコニア等は高屈折率材料として用いられている。
Conventionally, colloidal particles such as silica, alumina, titania, zirconia, zinc oxide, antimony pentoxide, cerium oxide, tin oxide, silica-alumina, silica-zirconia, etc. are known, and to adjust the refractive index as an optical material It is blended and used for coatings.
For example, silica is used as a low refractive index material, alumina is used as a medium refractive index material, and titania, zirconia, and the like are used as high refractive index materials.
チタニア粒子は高屈折率ではあるものの、分散安定性や、用法、用途によっては光触媒活性のために耐光性、耐候性等に問題があった。このため他の成分、例えばシリカ成分などを複合化することによって分散安定性や、耐光性、耐候性等を向上させることが行われているが、複合化成分によっては屈折率を低下させることになることに加えて、光触媒活性を完全に抑制することが困難で、このため耐光性、耐候性等が不充分となることがあった（特許文献１：特開平８−４８９４０号公報参照）。 Although titania particles have a high refractive index, there are problems in light resistance, weather resistance, etc. due to dispersion stability, photocatalytic activity depending on usage and application. For this reason, dispersion stability, light resistance, weather resistance, etc. are improved by compounding other components such as silica components, but depending on the complexed component, the refractive index is lowered. In addition, it is difficult to completely suppress the photocatalytic activity, and thus light resistance, weather resistance and the like may be insufficient (see Patent Document 1: JP-A-8-48940).
一方、ジルコニア粒子は、光触媒活性は実質的になく、耐光性、耐候性等には優れているものの、均一な粒子径分布を有し、安定性に優れたコロイド領域のジルコニアゾルを得ることが困難であった。
そこで、本願の出願人は粒子成長調整剤の存在下でジルコニアゲルの調製および水熱処理を行うことによって均一な粒子径分布を有し、安定性に優れたジルコニアゾルが得られることを開示している（特許文献２：特開２００６−１４３５３５号公報参照）。
On the other hand, the zirconia particles have substantially no photocatalytic activity and are excellent in light resistance, weather resistance, etc., but have a uniform particle size distribution and can obtain a zirconia sol in a colloidal region with excellent stability. It was difficult.
Therefore, the applicant of the present application discloses that a zirconia sol having a uniform particle size distribution and excellent in stability can be obtained by preparing a zirconia gel and performing hydrothermal treatment in the presence of a particle growth regulator. (See Patent Document 2: JP-A-2006-143535).
しかしながら、従来公知のジルコニア粒子の分散液、あるいはジルコニア粒子を用いた塗布液は酸性域では容易にゲル化し、安定性に問題があった。
本願発明者等は鋭意検討した結果、ジルコニア粒子を五酸化アンチモンまたはシリカ系複合酸化物で被覆すると広範囲のｐＨ領域で安定なジルコニア微粒子が得られることを見出して本発明を完成するに至った。
However, a conventionally known dispersion of zirconia particles or a coating solution using zirconia particles easily gels in the acidic region and has a problem in stability.
As a result of intensive studies, the present inventors have found that when zirconia particles are coated with antimony pentoxide or a silica-based composite oxide, stable zirconia fine particles can be obtained in a wide pH range, and the present invention has been completed.
本発明は、アルカリ領域に加えて酸性領域でも安定な改質ジルコニア微粒子、該微粒子分散ゾルおよびその製造方法を提供することを目的としている。 An object of the present invention is to provide modified zirconia fine particles that are stable in the acidic region in addition to the alkaline region, the fine particle-dispersed sol, and a method for producing the same.
本発明の改質ジルコニア微粒子は、表面が五酸化アンチモンおよび／またはシリカで被覆されたジルコニア微粒子であって、該ジルコニア微粒子の表面電位が下記条件で測定した場合に、−１２０〜−１０ｍＶの範囲にあることを特徴とする。
条件(1)：改質ジルコニア微粒子分散液の固形分濃度が１重量％
条件(2)：改質ジルコニア微粒子分散液のｐＨが２〜１３の範囲
本発明の改質ジルコニア微粒子は、さらに、下記式（１）で表される有機ケイ素化合物で表面処理されていることが好ましい。
Ｒn−ＳiＸ4-n ・・・（１）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、水酸基、ハロゲン、水素、ｎ：１〜３の整数）
The modified zirconia fine particles of the present invention are zirconia fine particles whose surfaces are coated with antimony pentoxide and / or silica, and the surface potential of the zirconia fine particles is in the range of −120 to −10 mV when measured under the following conditions. It is characterized by that.
Condition (1): The solid content concentration of the modified zirconia fine particle dispersion is 1% by weight.
Condition (2): The pH of the modified zirconia fine particle dispersion is in the range of 2 to 13. The modified zirconia fine particles of the present invention are further surface-treated with an organosilicon compound represented by the following formula (1). preferable.
R n -Si x 4-n (1)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3)
前記改質ジルコニア微粒子は、平均粒子径が５〜１２０ｎｍの範囲にあることが好ましい。
前記改質ジルコニア微粒子は、屈折率が１．５〜２．１の範囲にあることが好ましい。
The modified zirconia fine particles preferably have an average particle diameter in the range of 5 to 120 nm.
The modified zirconia fine particles preferably have a refractive index in the range of 1.5 to 2.1.
本発明の改質ジルコニア微粒子分散ゾルは、前記改質ジルコニア微粒子が水および／または有機溶媒に分散してなり、固形分濃度が１〜５０重量％の範囲にあることを特徴とする。 The modified zirconia fine particle-dispersed sol of the present invention is characterized in that the modified zirconia fine particles are dispersed in water and / or an organic solvent, and the solid content concentration is in the range of 1 to 50% by weight.
本発明の改質ジルコニア微粒子の製造方法は、下記の工程（ａ）〜（ｃ）からなることを特徴とする。
（ａ）ＺrＯ2としての濃度０．１〜２０重量％のジルコニア微粒子水分散液（Ａ）と、Ｓb2Ｏ5としての濃度０．１〜２０重量％のアンチモン酸アルカリ水溶液（Ｂ）またはＳiＯ2としての濃度０．１〜２０重量％のケイ酸アルカリ水溶液または４官能アルコキシシラン溶液（Ｃ）とを混合した分散液を調製する工程
（ｂ）混合した分散液を陽イオン交換樹脂と接触させる工程
（ｃ）４０〜２００℃で熟成する工程
The method for producing modified zirconia fine particles of the present invention is characterized by comprising the following steps (a) to (c).
(A) A zirconia fine particle aqueous dispersion (A) having a concentration of 0.1 to 20% by weight as ZrO 2 and an alkali antimonate aqueous solution (B) or SiO having a concentration of 0.1 to 20% by weight as Sb 2 O 5 the concentration of 0.1 to 20 wt% of alkali silicate aqueous solution or tetrafunctional alkoxysilane solution (C) to prepare mixed dispersion and a step (b) mixed dispersion as 2 is contacted with a cation exchange resin Step (c) Step of aging at 40 to 200 ° C
前記工程（ａ）で、ジルコニア微粒子水分散液（Ａ）とアンチモン酸アルカリ水溶液（Ｂ）またはケイ酸アルカリ水溶液または４官能アルコキシシラン溶液（Ｃ）との混合比が、酸化物重量比Ｓb2Ｏ5／ＺrＯ2またはＳiＯ2／ＺrＯ2として０．０１〜２．３の範囲にあることが好ましい。 In the step (a), the mixing ratio of the zirconia fine particle aqueous dispersion (A) and the alkali antimonate aqueous solution (B), the alkali silicate aqueous solution or the tetrafunctional alkoxysilane solution (C) is the oxide weight ratio Sb 2 O. 5 / ZrO 2 or SiO 2 / ZrO 2 is preferably in the range of 0.01 to 2.3.
前記工程（ｃ）についで、下記の工程（ｄ）〜（ｇ）を行うことが好ましい。
（ｄ）工程（ｃ）で得られた改質ジルコニア微粒子水分散液を有機溶媒に溶媒置換する工程
（ｅ）下記式（２）で表される有機ケイ素化合物の水および／または有機溶媒溶液を加える工程
Ｒn−ＳiＸ4-n ・・・（２）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、水酸基、ハロゲン、水素、ｎ：１〜３の整数）
（ｆ）必要に応じて加水分解触媒を加え、有機ケイ素化合物を加水分解して改質ジルコニア微粒子を表面処理する工程
（ｇ）３０〜１２０℃で熟成する工程
Following the step (c), the following steps (d) to (g) are preferably performed.
(D) Step of replacing the modified zirconia fine particle aqueous dispersion obtained in step (c) with an organic solvent (e) Water and / or an organic solvent solution of an organosilicon compound represented by the following formula (2) Add step R n -SiX 4-n ··· ( 2)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3)
(F) A step of adding a hydrolysis catalyst as necessary, hydrolyzing the organosilicon compound and surface-treating the modified zirconia fine particles (g) A step of aging at 30 to 120 ° C.
本発明の改質ジルコニア微粒子の製造方法において、前記改質ジルコニア微粒子は、平均粒子径が５〜１２０ｎｍの範囲にあることが好ましい。
本発明の改質ジルコニア微粒子の製造方法において、前記改質ジルコニア微粒子は、屈折率が１．５〜２．１の範囲にあることが好ましい。
In the method for producing modified zirconia fine particles of the present invention, the modified zirconia fine particles preferably have an average particle diameter in the range of 5 to 120 nm.
In the method for producing modified zirconia fine particles of the present invention, the modified zirconia fine particles preferably have a refractive index in the range of 1.5 to 2.1.
本発明によれば、ジルコニア微粒子の表面が五酸化アンチモンまたはシリカで被覆されており、アルカリ領域に加えて酸性領域でも安定な改質ジルコニア微粒子、該微粒子分散ゾルおよびその製造方法を提供することができる。
本発明の改質ジルコニア微粒子は、高屈折率で、かつ、屈折率を調整することができ、分散性、安定性に優れているために高屈折率の透明被膜に好適に用いることができる。具体的には、基材と透明被膜の屈折率を同程度に調整することができ、このため干渉縞が生じることもなく、基材との密着性、耐擦傷性、スクラッチ強度、鉛筆硬度、ヘーズ等に優れた透明被膜を得ることができる。
According to the present invention, it is possible to provide modified zirconia fine particles whose surface is coated with antimony pentoxide or silica, which is stable in the acidic region in addition to the alkaline region, the fine particle-dispersed sol, and a method for producing the same. it can.
The modified zirconia fine particles of the present invention have a high refractive index, can adjust the refractive index, and are excellent in dispersibility and stability, and thus can be suitably used for a transparent film having a high refractive index. Specifically, the refractive index of the base material and the transparent film can be adjusted to the same extent, so that interference fringes do not occur, adhesion to the base material, scratch resistance, scratch strength, pencil hardness, A transparent film excellent in haze and the like can be obtained.
［改質ジルコニア微粒子］
以下に、まず本発明に係る改質ジルコニア微粒子について説明する。
本発明に係る改質ジルコニア微粒子は、表面が五酸化アンチモンまたはシリカで被覆されたジルコニア微粒子であって、該ジルコニア微粒子の表面電位が下記条件で測定した場合に、−１２０〜−１０ｍＶの範囲にあることを特徴としている。
条件(1)：改質ジルコニア微粒子分散液の固形分濃度が１重量％
条件(2)：改質ジルコニア微粒子分散液のｐＨが２〜１３の範囲
なお、本発明では、表面電位を以下、ゼータ電位ということがある。
[Modified zirconia fine particles]
The modified zirconia fine particles according to the present invention will be first described below.
The modified zirconia fine particles according to the present invention are zirconia fine particles whose surface is coated with antimony pentoxide or silica, and the surface potential of the zirconia fine particles is in the range of −120 to −10 mV when measured under the following conditions. It is characterized by being.
Condition (1): The solid content concentration of the modified zirconia fine particle dispersion is 1% by weight.
Condition (2): The pH of the modified zirconia fine particle dispersion is in the range of 2 to 13. In the present invention, the surface potential may be hereinafter referred to as zeta potential.
ジルコニア微粒子
本発明の改質ジルコニア微粒子を構成するジルコニア微粒子は、平均粒子径が概ね３〜１００ｎｍ、さらには５〜８０ｎｍの範囲にあることが好ましい。
ジルコニアコア微粒子の平均粒子径が３ｎｍ未満の場合は、得ることが困難であり、得られたとしても結晶性が不充分で、結晶性の高いジルコニア微粒子に比して屈折率が低く、分散安定性が低く、凝集することがあり、後述する五酸化アンチモンおよび／またはシリカによる被覆層の形成が困難である。
ジルコニアコア粒子の平均粒子径が１００ｎｍを越えると、得られる改質ジルコニア微粒子の平均粒子径が１２０ｎｍを越える場合があり、光の散乱が強くなり、これを用いた透明被膜の透明性が不充分であったり、ヘーズが高くなる場合がある。
Zirconia Fine Particles The zirconia fine particles constituting the modified zirconia fine particles of the present invention preferably have an average particle diameter of 3 to 100 nm, more preferably 5 to 80 nm.
When the average particle diameter of the zirconia core fine particles is less than 3 nm, it is difficult to obtain, and even if obtained, the crystallinity is insufficient, the refractive index is lower than the highly crystalline zirconia fine particles, and the dispersion stability It is difficult to form a coating layer with antimony pentoxide and / or silica described later.
If the average particle size of the zirconia core particles exceeds 100 nm, the average particle size of the resulting modified zirconia fine particles may exceed 120 nm, resulting in strong light scattering, and the transparency of the transparent film using this is insufficient. Or haze may be high.
前記ジルコニア微粒子としては、本願出願人の出願による特開２００６−１４３５３５号公報に開示したジルコニアゾルはジルコニア微粒子の平均粒子径が５〜１００ｎｍの範囲にあり、粒子径分布が均一で、結晶性および屈折率が高く、好適に用いることができる。
なお、前記平均粒子径は、透過型電子顕微鏡写真（ＴＥＭ）を撮影し、５０個の粒子について粒子径を測定し、これを平均して求めることができる。
As the zirconia fine particles, the zirconia sol disclosed in Japanese Patent Application Laid-Open No. 2006-143535 filed by the applicant of the present application has an average particle size of zirconia fine particles in the range of 5 to 100 nm, uniform particle size distribution, crystallinity and It has a high refractive index and can be suitably used.
The average particle size can be determined by taking a transmission electron micrograph (TEM), measuring the particle size of 50 particles, and averaging the particle sizes.
五酸化アンチモンおよび／またはシリカ被覆層
改質ジルコニア微粒子中の五酸化アンチモンおよび／またはシリカ被覆層の含有量は、酸化物として１〜７０重量％、さらには３〜５０重量％の範囲にあることが好ましい。
改質ジルコニア微粒子中の五酸化アンチモンまたはシリカ被覆層の含有量が酸化物として１重量％未満の場合は、被覆層が薄く、表面が酸化アンチモンコロイド粒子あるいはシリカコロイド粒子と同様に充分な負の帯電をせず、即ち、酸化アンチモンまたはシリカと同様のコロイド的特性が得られず、分散性、分散安定性が不充分となり、他の粒子を混合したり、バインダーと混合した際に凝集する場合がある。
改質ジルコニア微粒子中の五酸化アンチモンまたはシリカ被覆層の含有量が酸化物として７０重量％を越えると、コア粒子であるジルコニアの割合が少なく、得られる粒子の屈折率が低く、所望の屈折率を有する改質ジルコニア微粒子が得られない場合がある。
The content of antimony pentoxide and / or silica coating layer in the modified zirconia fine particles of antimony pentoxide and / or silica is in the range of 1 to 70% by weight, further 3 to 50% by weight as oxide. Is preferred.
When the content of the antimony pentoxide or silica coating layer in the modified zirconia fine particles is less than 1% by weight as an oxide, the coating layer is thin and the surface is sufficiently negative like the antimony oxide colloid particles or silica colloid particles. When charging is not performed, that is, colloidal properties similar to those of antimony oxide or silica are not obtained, dispersibility and dispersion stability are insufficient, and other particles are agglomerated when mixed or mixed with a binder There is.
When the content of the antimony pentoxide or silica coating layer in the modified zirconia fine particles exceeds 70% by weight as an oxide, the ratio of the core particles of zirconia is small, the resulting particles have a low refractive index, and a desired refractive index. In some cases, modified zirconia fine particles having the above cannot be obtained.
改質ジルコニア微粒子
本発明の改質ジルコニア微粒子は平均粒子径が５〜１２０ｎｍ、さらには１０〜１００ｎｍの範囲にあることが好ましい。
改質ジルコニア微粒子の平均粒子径が５ｎｍ未満のものは得ることが困難であり、得られたとしても分散性、安定性等が不充分となることがある。
改質ジルコニア微粒子の平均粒子径が１２０ｎｍを越えると、改質ジルコニア微粒子を用いた透明被膜のヘーズが悪化する傾向にある。
Modified Zirconia Fine Particles The modified zirconia fine particles of the present invention preferably have an average particle size in the range of 5 to 120 nm, more preferably 10 to 100 nm.
It is difficult to obtain modified zirconia fine particles having an average particle diameter of less than 5 nm, and even if obtained, dispersibility, stability, etc. may be insufficient.
When the average particle diameter of the modified zirconia fine particles exceeds 120 nm, the haze of the transparent coating using the modified zirconia fine particles tends to deteriorate.
また、本発明の改質ジルコニア微粒子は屈折率が１．５〜２．１、さらには１．８〜２．１の範囲にあることが好ましい。
改質ジルコニア微粒子の屈折率が１．５未満の場合は、本発明の改質ジルコニア微粒子によらずとも他の低屈折率の粒子、例えばシリカを主成分とする粒子を用いることができ、改質ジルコニア微粒子の屈折率が２．１を越えるものは、前記した組成範囲で五酸化アンチモンまたはシリカを被覆した粒子としては得ることが困難である。
本発明の改質ジルコニア微粒子の屈折率は標準屈折率液法によって測定することができる。なお、本発明では、ジルコニアの屈折率は２．１５、五酸化アンチモンの屈折率は１．６８、シリカの屈折率は１．４３である。
The modified zirconia fine particles of the present invention preferably have a refractive index in the range of 1.5 to 2.1, more preferably 1.8 to 2.1.
When the refractive index of the modified zirconia fine particles is less than 1.5, other low refractive index particles, for example, particles mainly composed of silica can be used regardless of the modified zirconia fine particles of the present invention. It is difficult to obtain particles in which the refractive index of the fine zirconia particles exceeds 2.1 as particles coated with antimony pentoxide or silica in the above composition range.
The refractive index of the modified zirconia fine particles of the present invention can be measured by a standard refractive index liquid method. In the present invention, the refractive index of zirconia is 2.15, the refractive index of antimony pentoxide is 1.68, and the refractive index of silica is 1.43.
本発明に係る改質ジルコニア微粒子は、固形分濃度を１重量％に調整したときの改質ジルコニア微粒子分散液のｐＨが２〜１３の範囲で表面電位が−１２０〜−１０ｍＶ、さらには−１２０〜−２０ｍＶの範囲にあることが好ましい。
表面電位が−１２０ｍＶ未満の改質ジルコニア微粒子は得ることが困難であり、−１０ｍＶを越えると改質ジルコニア微粒子相互間の静電的反発が弱く安定性が不充分になることがあり、透明被膜に用いた場合にヘーズが高くなり、場合によっては透明被膜が白化することがある。
The modified zirconia fine particles according to the present invention have a surface potential of −120 to −10 mV, and −120 when the pH of the modified zirconia fine particle dispersion is 2 to 13 when the solid content concentration is adjusted to 1% by weight. It is preferable to be in the range of -20 mV.
It is difficult to obtain modified zirconia fine particles having a surface potential of less than −120 mV, and if it exceeds −10 mV, electrostatic repulsion between the modified zirconia fine particles is weak and stability may be insufficient. When used, the haze is increased, and in some cases, the transparent film may be whitened.
表面処理
本発明の改質ジルコニア微粒子は、さらに、下記式(1)で表される有機ケイ素化合物で表面処理されていることが好ましい。
Ｒn−ＳiＸ4-n ・・・（１）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、水酸基、ハロゲン、水素、ｎ：１〜３の整数）
Surface Treatment The modified zirconia fine particles of the present invention are preferably surface-treated with an organosilicon compound represented by the following formula (1).
R n -Si x 4-n (1)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3)
このような有機ケイ素化合物としては、メチルトリメトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ジフェニルジエトキシシラン、イソブチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（βメトキシエトキシ）シラン、3,3,3−トリフルオロプロピルトリメトキシシラン、メチル-3,3,3−トリフルオロプロピルジメトキシシラン、β−（3,4-エポキシシクロヘキシル）エチルトリメトキシシラン、γ-グリシドキシメチルトリメトキシシラン、γ-グリシドキシメチルトリエキシシラン、γ-グリシドキシエチルトリメトキシシラン、γ-グリシドキシエチルトリエトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ−（β−グリシドキシエトキシ）プロピルトリメトキシシラン、γ-（メタ）アクリロオキシメチルトリメトキシシラン、γ-（メタ）アクリロオキシメチルトリエキシシラン、γ-（メタ）アクリロオキシエチルトリメトキシシラン、γ-（メタ）アクリロオキシエチルトリエトキシシラン、γ-（メタ）アクリロオキシプロピルトリメトキシシラン、γ-（メタ）アクリロオキシプロピルトリメトキシシラン、γ-（メタ）アクリロオキシプロピルトリエトキシシラン、γ-（メタ）アクリロオキシプロピルトリエトキシシラン、ブチルトリメトキシシラン、イソブチルトリエトキシシラン、ヘキシルトリエトキシシラオクチルトリエトキシシラン、デシルトリエトキシシラン、ブチルトリエトキシシラン、イソブチルトリエトキシシラン、ヘキシルトリエトキシシラン、オクチルトリエトキシシラン、デシルトリエトキシシラン、3-ウレイドイソプロピルプロピルトリエトキシシラン、パーフルオロオクチルエチルトリメトキシシラン、パーフルオロオクチルエチルトリエトキシシラン、パーフルオロオクチルエチルトリイソプロポキシシラン、トリフルオロプロピルトリメトキシシラン、γ-メルカプトプロピルトリメトキシシラン、トリメチルシラノール、メチルトリクロロシラン等、およびこれらの混合物が挙げられる。 Such organosilicon compounds include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxy. Silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyl Triethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycyl Sidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (Meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane, butyltrimeth Xysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropyl Propyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltri A chlorosilane etc., and these mixtures are mentioned.
この時の有機ケイ素化合物の処理量は、改質ジルコニア微粒子中の有機ケイ素化合物がＲn-ＳiＯ(4-n)/2として１〜５０重量％、さらには２〜３０重量％の範囲にあることが好ましい。
有機ケイ素化合物の処理量がＲn-ＳiＯ(4-n)/2として１重量％未満の場合は、表面処理が不充分で、分散安定性向上効果が充分得られないことがある。
有機ケイ素化合物の処理量がＲn-ＳiＯ(4-n)/2として５０重量％を越えると分散安定性向上効果は得られるが、得られる改質ジルコニア微粒子の屈折率が前記範囲を外れて低くなることがあり、透明被膜に用いた場合、基材の屈折率によっては基材との屈折率差が０．３以上になる場合があり、光学干渉（干渉縞）が発生する場合がある。
The treatment amount of the organosilicon compound at this time is in the range of 1 to 50% by weight, further 2 to 30% by weight of the organosilicon compound in the modified zirconia fine particles as R n —SiO 2 (4-n) / 2. It is preferable.
When the treatment amount of the organosilicon compound is less than 1% by weight as R n —SiO 2 (4-n) / 2 , the surface treatment is insufficient and the effect of improving the dispersion stability may not be sufficiently obtained.
When the treatment amount of the organosilicon compound exceeds 50% by weight as R n —SiO 2 (4-n) / 2 , an effect of improving dispersion stability is obtained, but the refractive index of the resulting modified zirconia fine particles is out of the above range. When used in a transparent coating, depending on the refractive index of the substrate, the difference in refractive index from the substrate may be 0.3 or more, and optical interference (interference fringes) may occur. .
改質ジルコニア微粒子の表面処理は従来公知の方法を採用することができ、例えば、改質ジルコニア微粒子のアルコール分散液に前記有機ケイ素化合物を所定量加え、これに水を加え、必要に応じて有機ケイ素化合物の加水分解用触媒として酸またはアルカリを加えて、有機ケイ素化合物を加水分解することにより行うことができる。
本発明に係る改質ジルコニア微粒子の態様には次の３種があり、その製造方法については、酸化ジルコニウムを五酸化アンチモンおよび／またはシリカで被覆した粒子が得られれば特に制限はないが、例えば、次のようにして製造することができる。
For the surface treatment of the modified zirconia fine particles, a conventionally known method can be employed. For example, a predetermined amount of the organosilicon compound is added to an alcohol dispersion of the modified zirconia fine particles, water is added thereto, and an organic material is added if necessary. It can be carried out by hydrolyzing the organosilicon compound by adding an acid or alkali as a catalyst for the hydrolysis of the silicon compound.
There are the following three types of modified zirconia fine particles according to the present invention, and the production method is not particularly limited as long as particles obtained by coating zirconium oxide with antimony pentoxide and / or silica are obtained. It can be manufactured as follows.
（１）五酸化アンチモンを被覆した改質ジルコニア微粒子
平均粒子径が概ね３〜１００ｎｍの酸化ジルコニウム粒子分散液に、アンチモン酸ナトリウム、アンチモン酸カリウム等の水溶液と混合し、熟成し、ついでイオン交換樹脂等によりイオン除去することにより得ることができる。
この時得られる改質ジルコニア微粒子の屈折率（Ｐn）は概ね１．８０〜２．１０の範囲にある。
(1) Modified zirconia fine particles coated with antimony pentoxide A zirconium oxide particle dispersion having an average particle size of approximately 3 to 100 nm is mixed with an aqueous solution of sodium antimonate, potassium antimonate, and the like, and then aged, and then an ion exchange resin. It can be obtained by removing ions by, for example.
The refractive index (P n ) of the modified zirconia fine particles obtained at this time is approximately in the range of 1.80 to 2.10.
（２）シリカを被覆した改質ジルコニア微粒子
平均粒子径が概ね３〜１００ｎｍの酸化ジルコニウム粒子分散液に、珪酸アルカリ水溶液を添加し、必要に応じて加熱し、熟成し、イオン交換樹脂等によりイオン除去することにより得ることができる。
また、別の方法として、平均粒子径が概ね３〜１００ｎｍの酸化ジルコニウム粒子分散液に、シリコンアルコキサイドのアルコール溶液を添加し、必要に応じて加水分解触媒として塩酸や硝酸等の酸もしくはアンモニア等の塩基を添加し、熟成することにより得ることができる。
この時得られる改質ジルコニア微粒子の屈折率（Ｐn）は概ね１．５０〜２．００の範囲にある。
(2) Modified zirconia fine particles coated with silica Add an aqueous alkali silicate solution to a zirconium oxide particle dispersion having an average particle size of approximately 3 to 100 nm, heat as necessary, age, and ionize with an ion exchange resin or the like. It can be obtained by removing.
As another method, an alcohol solution of silicon alkoxide is added to a zirconium oxide particle dispersion having an average particle diameter of about 3 to 100 nm, and an acid such as hydrochloric acid or nitric acid or ammonia as a hydrolysis catalyst as necessary. It can be obtained by adding a base such as aging and aging.
The refractive index (P n ) of the modified zirconia fine particles obtained at this time is approximately in the range of 1.50 to 2.00.
（３）シリカと五酸化アンチモンを被覆した改質ジルコニア微粒子
前記（１）と同様にして五酸化アンチモンで被覆した改質ジルコニア微粒子分散液を調製した後、前記（２）と同様にしてシリカを被覆することによって得ることができる。
また、前記（２）と同様にしてシリカで被覆した改質ジルコニア微粒子分散液を調製した後、前記（１）と同様にして五酸化アンチモンを被覆することによって得ることができる。
このとき得られる改質ジルコニア微粒子の屈折率（Ｐn）は概ね１．５５〜２．０５の範囲にある。
(3) Modified zirconia fine particles coated with silica and antimony pentoxide In the same manner as in (1) above, a modified zirconia fine particle dispersion coated with antimony pentoxide was prepared, and then silica as in (2) above was prepared. It can be obtained by coating.
Further, after preparing a modified zirconia fine particle dispersion coated with silica in the same manner as in (2), it can be obtained by coating with antimony pentoxide in the same manner as in (1).
The refractive index (P n ) of the modified zirconia fine particles obtained at this time is approximately in the range of 1.55 to 2.05.
上記に於いて、五酸化アンチモンおよび／またはシリカの使用量は被覆層の含有量が前記範囲となるように用いる。また、屈折率（Ｐn）が後述するように１．５０〜２．１０の範囲となるように用いる。
これらは、いずれも、五酸化アンチモンおよび／またはシリカで被覆した後、５０〜３００℃で熟成することが好ましい。熟成を行うと被覆した五酸化アンチモンおよび／またはシリカの結晶化が進むとともに表面電位が低下し、コロイド的性質が増して分散安定性に優れた複合酸化物粒子を得ることができる。
さらに、本発明の改質ジルコニア微粒子の製造方法としては、後述する本発明の改質ジルコニア微粒子の製造方法を採用することが好ましい。
In the above, the amount of antimony pentoxide and / or silica used is such that the content of the coating layer is in the above range. Further, the refractive index (P n ) is used in a range of 1.50 to 2.10 as will be described later.
Any of these is preferably aged at 50 to 300 ° C. after coating with antimony pentoxide and / or silica. When aging is performed, crystallization of the coated antimony pentoxide and / or silica proceeds and the surface potential is lowered, so that colloidal properties are increased and composite oxide particles having excellent dispersion stability can be obtained.
Furthermore, as the method for producing the modified zirconia fine particles of the present invention, it is preferable to employ the method for producing the modified zirconia fine particles of the present invention described later.
［改質ジルコニア微粒子分散ゾル］
次に、本発明に係る改質ジルコニア微粒子分散ゾルについて説明する。
本発明に係る改質ジルコニア微粒子分散ゾルは前記改質ジルコニア微粒子が水および／または有機溶媒に分散してなり、固形分濃度が１〜５０重量％の範囲にあることを特徴としている。
[Modified zirconia fine particle dispersed sol]
Next, the modified zirconia fine particle dispersed sol according to the present invention will be described.
The modified zirconia fine particle-dispersed sol according to the present invention is characterized in that the modified zirconia fine particles are dispersed in water and / or an organic solvent, and the solid content concentration is in the range of 1 to 50% by weight.
有機溶媒としては、従来公知の有機溶媒を用いることができ、具体的には、メタノール、エタノール、プロパノール、2-プロパノール（ＩＰＡ）、ブタノール、ジアセトンアルコール、フルフリルアルコール、テトラヒドロフルフリルアルコール、エチレングリコール、ヘキシレングリコール、イソプロピルグリコールなどのアルコール類；酢酸メチルエステル、酢酸エチルエステル、酢酸ブチルなどのエステル類；ジエチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルなどのエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、アセト酢酸エステルなどのケトン類、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、トルエン、シクロヘキサノン、イソホロン等およびこれらの混合溶媒が挙げられる。 As the organic solvent, conventionally known organic solvents can be used. Specifically, methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene Alcohols such as glycol, hexylene glycol and isopropyl glycol; esters such as acetic acid methyl ester, ethyl acetate, butyl acetate; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether , Ethers such as diethylene glycol monoethyl ether and propylene glycol monomethyl ether; acetone, methyl ethyl ketone Emissions, methyl isobutyl ketone, acetylacetone, ketones such as acetoacetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, toluene, cyclohexanone, isophorone and the like and mixed solvents thereof.
改質ジルコニア微粒子分散ゾルの濃度は、固形分として１〜５０重量％、さらには２〜４０重量％の範囲にあることが好ましい。
改質ジルコニア微粒子分散ゾルの濃度が固形分として１重量％未満の場合は、改質ジルコニア微粒子を含む透明被膜形成用塗布液を調製する場合に、高濃度の塗布液を調製できない場合があり、５０重量％を越えると改質ジルコニア微粒子分散ゾルの粘度が高くなるとともに安定性が不充分となり、ゲル化する場合がある。
The concentration of the modified zirconia fine particle-dispersed sol is preferably in the range of 1 to 50% by weight, more preferably 2 to 40% by weight as the solid content.
When the concentration of the modified zirconia fine particle-dispersed sol is less than 1% by weight as a solid content, when preparing a coating solution for forming a transparent film containing the modified zirconia fine particles, a high concentration coating solution may not be prepared. If it exceeds 50% by weight, the viscosity of the modified zirconia fine particle-dispersed sol becomes high and the stability becomes insufficient, which may cause gelation.
［改質ジルコニア微粒子分散ゾルの製造方法］
次に、本発明に係る改質ジルコニア微粒子分散ゾルの製造方法について説明する。
本発明に係る改質ジルコニア微粒子の製造方法は、下記の工程（ａ）〜（ｃ）からなることを特徴としている。
（ａ）ＺrＯ2としての濃度０．１〜２０重量％のジルコニア微粒子水分散液（Ａ）と、Ｓb2Ｏ5としての濃度０．１〜２０重量％のアンチモン酸アルカリ水溶液（Ｂ）またはＳiＯ2としての濃度０．１〜２０重量％のケイ酸アルカリ水溶液または４官能アルコキシシラン溶液（Ｃ）とを混合した分散液を調製する工程
（ｂ）混合した分散液を陽イオン交換樹脂と接触させる工程
（ｃ）５０〜１２０℃で熟成する工程
[Production Method of Modified Zirconia Fine Particle Dispersed Sol]
Next, a method for producing the modified zirconia fine particle dispersed sol according to the present invention will be described.
The method for producing modified zirconia fine particles according to the present invention is characterized by comprising the following steps (a) to (c).
(A) A zirconia fine particle aqueous dispersion (A) having a concentration of 0.1 to 20% by weight as ZrO 2 and an alkali antimonate aqueous solution (B) or SiO having a concentration of 0.1 to 20% by weight as Sb 2 O 5 the concentration of 0.1 to 20 wt% of alkali silicate aqueous solution or tetrafunctional alkoxysilane solution (C) to prepare mixed dispersion and a step (b) mixed dispersion as 2 is contacted with a cation exchange resin Step (c) Step of aging at 50 to 120 ° C
工程（ａ）
ジルコニア微粒子水分散液（Ａ）としては、前記したジルコニア微粒子の水分散液を用いることができる。特に、本発明に用いるジルコニア微粒子分散液としては、本願出願人の出願による特開２００６−１４３５３５号公報に開示したジルコニアゾルはジルコニア微粒子の平均粒子径が５〜１００ｎｍの範囲にあり、粒子径分布が均一で、結晶性および屈折率が高く好適に用いることができる。
Step (a)
As the zirconia fine particle aqueous dispersion (A), the above-described aqueous dispersion of zirconia fine particles can be used. In particular, as the zirconia fine particle dispersion used in the present invention, the zirconia sol disclosed in Japanese Patent Application Laid-Open No. 2006-143535 filed by the present applicant has an average particle size of zirconia fine particles in the range of 5 to 100 nm, and the particle size distribution Is uniform and has high crystallinity and refractive index and can be suitably used.
ジルコニア微粒子水分散液（Ａ）の濃度はＺrＯ2として０．１〜２０重量％、さらには０．２〜１５重量％の範囲にあることが好ましい。
ジルコニア微粒子水分散液（Ａ）の濃度がＺrＯ2として０．１重量％未満の場合は、濃度が低すぎて大きな処理設備を必要としたり、生産性が低く経済的でない。
ジルコニア微粒子水分散液（Ａ）の濃度がＺrＯ2として２０重量％を越えると、工程（ｂ）で得られる五酸化アンチモンまたはシリカを被覆したジルコニア微粒子が凝集する場合がある。
The concentration of the zirconia fine particle aqueous dispersion (A) is preferably 0.1 to 20% by weight, more preferably 0.2 to 15% by weight as ZrO 2 .
When the concentration of the zirconia fine particle aqueous dispersion (A) is less than 0.1% by weight as ZrO 2 , the concentration is too low to require a large treatment facility, and the productivity is low and not economical.
When the concentration of the zirconia fine particle aqueous dispersion (A) exceeds 20% by weight as ZrO 2 , the zirconia fine particles coated with antimony pentoxide or silica obtained in the step (b) may aggregate.
アンチモン酸アルカリ水溶液（Ｂ）としては、アンチモン酸ナトリウム、アンチモン酸カリウム等の水溶液を用いる。
アンチモン酸アルカリ水溶液（Ｂ）の濃度は、特に制限はないが、Ｓb2Ｏ5として０．１〜２０重量％、さらには０．２〜１５重量％の範囲にあることが好ましい。
As the alkali antimonate aqueous solution (B), an aqueous solution of sodium antimonate, potassium antimonate or the like is used.
The concentration of the alkali antimonate aqueous solution (B) is not particularly limited, but is preferably 0.1 to 20% by weight, more preferably 0.2 to 15% by weight as Sb 2 O 5 .
ケイ酸アルカリ水溶液または４官能アルコキシシラン溶液（Ｃ）としては、ケイ酸ナトリウム、ケイ酸カリウム等の水溶液、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシシラン、テトラブトキシシラン等のアルコールおよび／または水溶液を用いる。
ケイ酸アルカリ水溶液または４官能アルコキシシラン溶液（Ｃ）の濃度は、特に制限はないが、ＳiＯ2として濃度０．１〜２０重量％、さらには０．２〜１５重量％の範囲にあることが好ましい。
Examples of the alkali silicate aqueous solution or tetrafunctional alkoxysilane solution (C) include aqueous solutions such as sodium silicate and potassium silicate, alcohols such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane and / or aqueous solutions. Is used.
The concentration of the alkali silicate aqueous solution or the tetrafunctional alkoxysilane solution (C) is not particularly limited, but may be in the range of 0.1 to 20% by weight, more preferably 0.2 to 15% by weight as SiO 2. preferable.
ジルコニア微粒子水分散液（Ａ）とアンチモン酸アルカリ水溶液（Ｂ）またはケイ酸アルカリ水溶液または４官能アルコキシシラン溶液（Ｃ）とを混合した分散液の濃度は、酸化物の合計として０．１〜２０重量％、さらには０．２〜１５重量％の範囲にあることが好ましい。
混合分散液の濃度が、酸化物の合計として０．１重量未満の場合は、濃度が低すぎて大きな処理設備を必要としたり、生産性が低く経済的でない。
混合分散液の濃度が、酸化物の合計として２０重量％を越えると、工程（ｂ）で得られる五酸化アンチモンまたはシリカを被覆したジルコニア微粒子が凝集する場合がある。
The concentration of the dispersion obtained by mixing the zirconia fine particle aqueous dispersion (A) and the alkali antimonate aqueous solution (B), the alkali silicate aqueous solution or the tetrafunctional alkoxysilane solution (C) is 0.1 to 20 as the total of the oxides. It is preferable to be in the range of wt%, more preferably 0.2 to 15 wt%.
When the concentration of the mixed dispersion is less than 0.1 weight as the total of the oxides, the concentration is too low, requiring a large treatment facility, and the productivity is low and not economical.
When the concentration of the mixed dispersion exceeds 20% by weight as the total of oxides, the zirconia fine particles coated with antimony pentoxide or silica obtained in step (b) may aggregate.
ジルコニア微粒子水分散液（Ａ）とアンチモン酸アルカリ水溶液（Ｂ）またはケイ酸アルカリ水溶液または４官能アルコキシシラン溶液（Ｃ）との混合比が、酸化物重量比Ｓb2Ｏ5／ＺrＯ2またはＳiＯ2／ＺrＯ2として０．０１〜２．３、さらには０．０２〜１．５の範囲にあることが好ましい。
酸化物重量比Ｓb2Ｏ5／ＺrＯ2またはＳiＯ2／ＺrＯ2が０．０１未満の場合は、被覆層が薄く、表面が酸化アンチモンコロイド粒子あるいはシリカコロイド粒子と同様に充分な負の帯電をせず、即ち、酸化アンチモンまたはシリカと同様のコロイド的特性が得られず、分散性、分散安定性が不充分となり、他の粒子を混合したり、バインダーと混合した際に凝集する場合がある。
酸化物重量比Ｓb2Ｏ5／ＺrＯ2またはＳiＯ2／ＺrＯ2が２．３を越えると、コア粒子であるジルコニア微粒子の割合が少なく、得られる粒子の屈折率が低く、所望の屈折率を有する改質ジルコニア微粒子が得られない場合がある。
このとき、混合分散液のｐＨは概ね２〜５の範囲にある。
The mixing ratio of the zirconia fine particle aqueous dispersion (A) to the alkali antimonate aqueous solution (B), the alkali silicate aqueous solution or the tetrafunctional alkoxysilane solution (C) is an oxide weight ratio Sb 2 O 5 / ZrO 2 or SiO 2. / ZrO 2 is preferably in the range of 0.01 to 2.3, more preferably 0.02 to 1.5.
When the oxide weight ratio Sb 2 O 5 / ZrO 2 or SiO 2 / ZrO 2 is less than 0.01, the coating layer is thin and the surface is sufficiently negatively charged like the antimony oxide colloid particles or silica colloid particles. In other words, colloidal properties similar to those of antimony oxide or silica cannot be obtained, dispersibility and dispersion stability are insufficient, and other particles may be mixed or agglomerated when mixed with a binder. .
When the oxide weight ratio Sb 2 O 5 / ZrO 2 or SiO 2 / ZrO 2 exceeds 2.3, the ratio of the zirconia fine particles as the core particles is small, the refractive index of the obtained particles is low, and the desired refractive index is obtained. In some cases, the modified zirconia fine particles are not obtained.
At this time, the pH of the mixed dispersion is generally in the range of 2-5.
工程（ｂ）
工程（ａ）で混合した分散液を陽イオン交換樹脂と接触させる。
陽イオン交換樹脂としては、従来公知の陽イオン交換樹脂（Ｈ型）を用いることができ、混合した分散液を陽イオン交換樹脂と接触させることによって、アンチモン酸アルカリまたはケイ酸アルカリからアルカリが脱離し、アンチモン酸またはケイ酸がジルコニア微粒子表面に析出し、被覆層を形成することができる。
Step (b)
The dispersion mixed in step (a) is brought into contact with a cation exchange resin.
As the cation exchange resin, a conventionally known cation exchange resin (H type) can be used. By contacting the mixed dispersion with the cation exchange resin, the alkali is removed from the alkali antimonate or alkali silicate. Then, antimonic acid or silicic acid is deposited on the surface of the zirconia fine particles, and a coating layer can be formed.
陽イオン交換樹脂の使用量は、アンチモン酸アルカリまたはケイ酸アルカリの使用量によって異なるが、アンチモン酸アルカリまたはケイ酸アルカリからアルカリを脱離させ、混合分散液を陽イオン交換樹脂と接触させた後のアンチモン酸またはケイ酸を被覆したジルコニア微粒子分散液中にアルカリが実質的に残存しない程度に用いる。
ついで、分散液から陽イオン交換樹脂を分離する。陽イオン交換樹脂を分離した分散液のｐＨは１〜６、さらには２〜４の範囲にあることが好ましい。
The amount of cation exchange resin used varies depending on the amount of alkali antimonate or alkali silicate, but after the alkali is desorbed from the alkali antimonate or alkali silicate and the mixed dispersion is brought into contact with the cation exchange resin. It is used to such an extent that alkali does not substantially remain in the zirconia fine particle dispersion coated with antimonic acid or silicic acid.
The cation exchange resin is then separated from the dispersion. The pH of the dispersion from which the cation exchange resin has been separated is preferably in the range of 1 to 6, more preferably 2 to 4.
工程（ｃ）
ついで、分散液を熟成するが、熟成温度は４０〜２００℃、さらには６０〜１２０℃が好ましい。
熟成温度が４０℃未満の場合は、被覆層が五酸化アンチモンの場合は緻密化、結晶化が不充分なためか、得られる改質ジルコニア微粒子分散ゾルの安定性が不充分であり、被覆層がシリカの場合は緻密化が不充分なためか、得られる改質ジルコニア微粒子分散ゾルの安定性が不充分である。
熟成温度が２００℃を越えても改質ジルコニア微粒子分散ゾルの安定性がさらに向上することもなく、熟成時間を短縮できる効果もなく、経済性の点からも有意とはいえない。
なお、熟成時間は、温度によっても異なるが、通常０．５〜１２時間である。
Step (c)
Next, the dispersion is aged, and the aging temperature is preferably 40 to 200 ° C, more preferably 60 to 120 ° C.
When the ripening temperature is less than 40 ° C., if the coating layer is antimony pentoxide, the densification and crystallization are insufficient, or the resulting modified zirconia fine particle-dispersed sol is insufficiently stable. In the case of silica, the densification is insufficient, or the stability of the resulting modified zirconia fine particle-dispersed sol is insufficient.
Even if the aging temperature exceeds 200 ° C., the stability of the modified zirconia fine particle-dispersed sol is not further improved, the effect of shortening the aging time is not obtained, and it cannot be said that it is significant from the economical point of view.
The aging time varies depending on the temperature, but is usually 0.5 to 12 hours.
上記した方法は、酸化ジルコニウム粒子分散液に、アンチモン酸アルカリまたはケイ酸アルカリの水溶液を混合した後、イオン交換樹脂等によりイオン除去する前に熟成する方法に比して、安定性に優れた改質ジルコニア微粒子分散ゾルを得ることができる。
前記工程（ｃ）についで、下記の工程（ｄ）〜（ｇ）を行い、有機ケイ素化合物で表面処理した改質ジルコニア微粒子とすることが好ましい。
The above-described method is an improved method that is superior in stability to a method in which an aqueous solution of alkali antimonate or alkali silicate is mixed with the zirconium oxide particle dispersion and then aged before ion removal with an ion exchange resin or the like. Zirconia fine particle-dispersed sol can be obtained.
Following the step (c), the following steps (d) to (g) are preferably carried out to obtain modified zirconia fine particles surface-treated with an organosilicon compound.
工程（ｄ）
工程（ｃ）で得られた改質ジルコニア微粒子水分散液を有機溶媒に溶媒置換する。
有機溶媒としては、通常アルコールが用いられ、限外濾過膜法によって溶媒置換する。
改質ジルコニア微粒子の有機溶媒分散液の濃度は、特に制限はないが固形分として通常１〜４０重量％、さらには２〜３０重量％の範囲にあることが好ましい。
Step (d)
The modified zirconia fine particle aqueous dispersion obtained in the step (c) is solvent-substituted with an organic solvent.
As the organic solvent, alcohol is usually used, and the solvent is replaced by an ultrafiltration membrane method.
The concentration of the modified zirconia fine particle in the organic solvent dispersion is not particularly limited, but is preferably in the range of usually 1 to 40% by weight, more preferably 2 to 30% by weight as the solid content.
工程（ｅ）
工程（ｄ）で得られた有機溶媒分散液に、下記式（２）で表される有機ケイ素化合物の水および／または有機溶媒溶液を加える。
Ｒn−ＳiＸ4-n ・・・（２）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、水酸基、ハロゲン、水素、ｎ：１〜３の整数）
有機ケイ素化合物としては、前記式（１）で表される有機ケイ素化合物と同様の有機ケイ素化合物が用いられる。
有機ケイ素化合物は、得られる改質ジルコニア微粒子中にＲn-ＳiＯ(4-n)/2として１〜５０重量％、さらには２〜３０重量％の範囲となるように用いることが好ましい。
Step (e)
Water and / or an organic solvent solution of the organosilicon compound represented by the following formula (2) is added to the organic solvent dispersion obtained in the step (d).
R n -Si x 4-n (2)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3)
As the organosilicon compound, the same organosilicon compound as the organosilicon compound represented by the formula (1) is used.
The organosilicon compound is preferably used in the resulting modified zirconia fine particles in a range of 1 to 50% by weight, more preferably 2 to 30% by weight, as R n —SiO 2 (4-n) / 2 .
工程（ｆ）
必要に応じて加水分解触媒を加え、有機ケイ素化合物を加水分解して改質ジルコニア微粒子を表面処理する。
加水分解触媒としては、従来公知の酸またはアルカリが用いられる。
なお、分散液が予め水を含まない場合は水を添加するが、水の添加量は従来公知の量でよく、前記有機ケイ素化合物が充分に加水分解できる量とする。
Step (f)
If necessary, a hydrolysis catalyst is added to hydrolyze the organosilicon compound to surface-treat the modified zirconia fine particles.
A conventionally known acid or alkali is used as the hydrolysis catalyst.
In addition, when the dispersion does not contain water in advance, water is added, but the amount of water added may be a conventionally known amount so that the organosilicon compound can be sufficiently hydrolyzed.
工程（ｇ）
ついで、３０〜１２０℃で熟成する。さらに好ましい温度は５０〜８０℃である。
熟成温度が３０℃未満の場合は、加水分解が完結しない場合や、加水分解物の粒子表面への結合が不充分となり、表面処理効果が充分得られないことがある。
熟成温度が１２０℃を越えても表面処理効果がさらに増すこともなく、有意とはいえない。
なお、熟成時間は、温度によっても異なるが、通常０．５〜２時間である。
Step (g)
Then, it is aged at 30 to 120 ° C. A more preferable temperature is 50 to 80 ° C.
When the aging temperature is less than 30 ° C., hydrolysis may not be completed or the hydrolyzate may not be sufficiently bonded to the particle surface, and the surface treatment effect may not be sufficiently obtained.
Even if the aging temperature exceeds 120 ° C., the surface treatment effect is not further increased, which is not significant.
The aging time varies depending on the temperature, but is usually 0.5 to 2 hours.
上記で得られた改質ジルコニア微粒子分散液あるいは表面処理した改質ジルコニア微粒子分散液は所望の分散媒に溶媒置換して改質ジルコニア微粒子分散ゾルとすることができる。
分散媒としては、用途によって異なるが、前記した水および／または有機溶媒が用いられる。
得られた改質ジルコニア微粒子分散ゾルは、固形分濃度が１〜５０重量％、さらには２〜４０重量％の範囲にあることが好ましい。
The modified zirconia fine particle dispersion obtained above or the surface-treated modified zirconia fine particle dispersion can be made into a modified zirconia fine particle dispersed sol by replacing the solvent with a desired dispersion medium.
As a dispersion medium, although it changes with uses, the above-mentioned water and / or an organic solvent are used.
The obtained modified zirconia fine particle-dispersed sol preferably has a solid content concentration of 1 to 50% by weight, more preferably 2 to 40% by weight.
また、得られた改質ジルコニア微粒子は平均粒子径が５〜１２０ｎｍ、さらには１０〜１００ｎｍの範囲にあることが好ましい。
また、改質ジルコニア微粒子は屈折率が１．５〜２．１、さらには１．８〜２．１の範囲にあることが好ましい。
以下、実施例により説明するが、本発明はこれらの実施例により限定されるものではない。
The obtained modified zirconia fine particles preferably have an average particle size in the range of 5 to 120 nm, more preferably in the range of 10 to 100 nm.
The modified zirconia fine particles preferably have a refractive index in the range of 1.5 to 2.1, more preferably 1.8 to 2.1.
Hereinafter, although an example explains, the present invention is not limited by these examples.
改質ジルコニア微粒子(1)分散液の調製
ジルコニアゾル(1)の調製
純水１，３０２ｇにオキシ塩化ジルコニウム８水和物（ZrOCl2・8H2O）３５ｇを溶解し、これに濃度１０重量％のＫＯＨ水溶液１２２．８ｇ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。ついで、５時間静置してジルコニウム水酸化物ヒドロゲルを沈降させた後、上澄み液（pH11.0）７５０ｇ除去した。次に純水７５０ｇを添加し、攪拌した後、再び５時間静置した。以上の操作を上澄み液の電導度が０．５ｍｓ／ｃｍ以下になるまで繰り返し行った。
Preparation of modified zirconia fine particles (1) dispersion
Preparation of zirconia sol (1) 35 g of zirconium oxychloride octahydrate (ZrOCl 2 .8H 2 O) was dissolved in 1,302 g of pure water, and 122.8 g of a 10 wt% KOH aqueous solution was added thereto. Hydroxide hydrogel (ZrO 2 concentration 1 wt%) was prepared. Subsequently, after leaving still for 5 hours to precipitate the zirconium hydroxide hydrogel, 750 g of the supernatant (pH 11.0) was removed. Next, 750 g of pure water was added and stirred, and then allowed to stand again for 5 hours. The above operation was repeated until the conductivity of the supernatant liquid was 0.5 ms / cm or less.
得られたジルコニウム水酸化物ヒドロゲルに酒石酸０．９６ｇを加えて充分に攪拌を行った。ついで、ｐＨ１１．０になるまで濃度１０重量％のＫＯＨ水溶液を加え、超音波を1時間照射してヒドロゲルの分散処理をした後、限外濾過膜を用いて電導度が０．３５ｍｓ／ｃｍ以下になるまで洗浄した。次に、陰イオン交換樹脂（ROHM AND HAAS社製：デュオライトUP5000）を２．６ｇ加え、脱イオンを行った。ついで、得られたジルコニウム水酸化物ヒドロゲルをオートクレーブに充填し、１６５℃で６時間水熱処理を行った。このときｐＨは１０．７であった。ついで、水熱処理して得られた分散液を乾燥した後６５０℃で２時間焼成してジルコニア粉末を得た。得られたジルコニア粉末は立方晶，単斜晶の混晶体であった。 0.96 g of tartaric acid was added to the obtained zirconium hydroxide hydrogel and sufficiently stirred. Next, a 10% strength by weight KOH aqueous solution was added until the pH reached 11.0, and after ultrasonic treatment was applied for 1 hour to disperse the hydrogel, the conductivity was 0.35 ms / cm or less using an ultrafiltration membrane. Washed until Next, 2.6 g of anion exchange resin (manufactured by ROHM AND HAAS: Duolite UP5000) was added to perform deionization. Subsequently, the obtained zirconium hydroxide hydrogel was filled in an autoclave and hydrothermally treated at 165 ° C. for 6 hours. At this time, the pH was 10.7. Next, the dispersion obtained by hydrothermal treatment was dried and then calcined at 650 ° C. for 2 hours to obtain zirconia powder. The obtained zirconia powder was a mixed crystal of cubic and monoclinic crystals.
次に、純水１６１．９ｇに酒石酸４．４ｇを溶解した水溶液にジルコニア粉末３６ｇを加え、ついで、濃度１０重量％のＫＯＨ水溶液３０ｇを加えてｐＨ１２．３のジルコニア粉末分散液とした。ジルコニア粉末分散液を分散機（カンペ（株）製：BATCH SAND）にて分散させ、ジルコニアゾルとした。得られたジルコニアゾルを遠心分離器にセットし、２，５００ｒｐｍで5分間遠心分離処理を行なった後、限外濾過膜を用いて電導度が１００μｓ／ｃｍ程度になるまで洗浄し、ついで、陰イオン交換樹脂（デュオライトUP-5000）４０ｇを加えて脱イオン処理を行い、樹脂を分離し、ＺｒＯ2濃度１重量％のジルコニアゾル(1)を調製した。
ジルコニア微粒子を透過型電子顕微鏡写真（TEM）で観察したところ、粗大粒子等は無く、平均粒子径３０ｎｍのジルコニア微粒子であった。また、ジルコニア微粒子は立方晶、単斜晶の混晶体であった。また、屈折率は２．１であった。
Next, 36 g of zirconia powder was added to an aqueous solution in which 4.4 g of tartaric acid was dissolved in 161.9 g of pure water, and then 30 g of a 10 wt% KOH aqueous solution was added to obtain a zirconia powder dispersion having a pH of 12.3. The zirconia powder dispersion was dispersed with a disperser (manufactured by Campe Co., Ltd .: BATCH SAND) to obtain a zirconia sol. The obtained zirconia sol is set in a centrifuge, centrifuged at 2,500 rpm for 5 minutes, washed with an ultrafiltration membrane until the conductivity becomes about 100 μs / cm, and then negatively charged. Deionization treatment was performed by adding 40 g of ion exchange resin (Duolite UP-5000), and the resin was separated to prepare zirconia sol (1) having a ZrO 2 concentration of 1% by weight.
When the zirconia fine particles were observed with a transmission electron micrograph (TEM), there were no coarse particles and the like, and the zirconia fine particles had an average particle diameter of 30 nm. The zirconia fine particles were cubic and monoclinic mixed crystals. The refractive index was 2.1.
五酸化アンチモン被覆
ジルコニアゾル(1)２１０ｇとアンチモン酸カリウム水溶液（Sb2O5として濃度1重量％）９０ｇを混合し、陽イオン交換樹脂（三菱化学（株）製：DAIAION PK-216H）３３０ｇを充填したイオン交換塔を通過させた後、９０℃で1時間熟成して五酸化アンチモン被覆ジルコニアゾル(1)を調製した。得られたゾルのｐＨは２．６であった。
210 g of antimony pentoxide-coated zirconia sol (1) and 90 g of potassium antimonate aqueous solution (concentration of 1% by weight as Sb 2 O 5 ) were mixed, and 330 g of cation exchange resin (manufactured by Mitsubishi Chemical Corporation: DAIAION PK-216H) After passing through the packed ion exchange tower, it was aged at 90 ° C. for 1 hour to prepare antimony pentoxide-coated zirconia sol (1). The obtained sol had a pH of 2.6.
シリカ被覆
得られた五酸化アンチモン被覆ジルコニアゾル(1)２７７ｇにテトラエトキシシラン（多摩化学工業(株)製：エチルシリケート-A）１．１５ｇを加え、ついでメタノール２７７ｇを加えた後、５０℃で１５時間熟成を行った。ついで、限外濾過膜を用いて溶媒をメタノールに置換し、固形分濃度２重量％の五酸化アンチモン／シリカ被覆ジルコニア微粒子アルコール分散液(1)を調製した。
Silica coating To 277 g of the obtained antimony pentoxide-coated zirconia sol (1), 1.15 g of tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: ethyl silicate-A) was added, and then 277 g of methanol was added. Aging was performed for 15 hours. Subsequently, the solvent was replaced with methanol using an ultrafiltration membrane to prepare an antimony pentoxide / silica-coated zirconia fine particle alcohol dispersion (1) having a solid concentration of 2% by weight.
表面処理
次に、五酸化アンチモン／シリカ被覆ジルコニア微粒子アルコール分散液(1)１１９ｇにγ-メタアクリロオキシプロピルトリメトキシシラン（信越化学（株）製：KBM-503）０．１８ｇを加え、５０℃で１６時間熟成し、固形分濃度２重量％の改質ジルコニア微粒子(1)分散液を調製した。
得られた改質ジルコニア微粒子(1)について、平均粒子径および屈折率を測定し、結果を表に示した。また、表面電位は、改質ジルコニア微粒子(1)分散液の濃度を１重量％に調整し、分散液の１部を採取し、これに０．１ＮのＨＣｌ水溶液を加えてｐＨ３の分散液、他の１部に０．１ＮのＮａＯＨ水溶液を加えてｐＨ１０の分散液とし、ゼータ電位測定装置（ＳＹＳＭＥＸ社製：ゼータサイザー３０００ＨＳ）にてゼータ電位を測定し、結果を表に示した。
さらに、分散性の評価として、下記の方法で透明被膜付基材を調製し、透明被膜のヘーズを測定し、結果を表に示した。
Surface Treatment Next, 0.18 g of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) was added to 119 g of antimony pentoxide / silica-coated zirconia fine particle alcohol dispersion (1), and 50 Aged at 16 ° C. for 16 hours to prepare a modified zirconia fine particle (1) dispersion having a solid concentration of 2% by weight.
The obtained modified zirconia fine particles (1) were measured for average particle diameter and refractive index, and the results are shown in the table. The surface potential was adjusted by adjusting the concentration of the modified zirconia fine particle (1) dispersion to 1% by weight, collecting 1 part of the dispersion, adding 0.1N HCl aqueous solution thereto, and adding a pH 3 dispersion. A 0.1N NaOH aqueous solution was added to another part to obtain a pH 10 dispersion, and the zeta potential was measured with a zeta potential measuring device (manufactured by SYSMEX: Zeta Sizer 3000HS), and the results are shown in the table.
Furthermore, as evaluation of dispersibility, a substrate with a transparent coating was prepared by the following method, and the haze of the transparent coating was measured. The results are shown in the table.
透明被膜付基材(1)の調製
アクリル系樹脂（大日本インキ（株）製：17-824-9、樹脂濃度：７９.８重量％、溶媒：酢酸ブチル）をイソプロピルアルコール／メチルイソブチルケトン（1：1）で希釈して樹脂濃度３０重量％の透明被膜形成用樹脂成分を調製した。
この透明被膜形成用樹脂成分１０ｇに、改質ジルコニア微粒子(1)分散液１０ｇを混合して透明被膜形成用塗布液(1)を調製した。
Preparation of substrate with transparent coating (1) Acrylic resin (Dainippon Ink Co., Ltd .: 17-824-9, resin concentration: 79.8% by weight, solvent: butyl acetate) was added to isopropyl alcohol / methyl isobutyl ketone ( The resin component for forming a transparent film having a resin concentration of 30% by weight was prepared by dilution in 1: 1).
10 g of this transparent film forming resin component was mixed with 10 g of the modified zirconia fine particle (1) dispersion to prepare a coating liquid (1) for forming a transparent film.
透明被膜形成用塗布液(1)を、ＰＥＴフィルム（東洋紡製コスモシャイン Ａ４１００、厚さ：１８８μｍ、屈折率：１.６７、基材ヘーズ０．８％）にバーコーター法（＃１4）で塗布し、８０℃で１２０秒間乾燥した後、６００ｍＪ／ｃｍ2の紫外線を照射して硬化させて膜付基材(1)を製造した。得られた透明被膜のヘーズをヘーズメーター（スガ試験機（株）製）により測定し、ヘーズおよび透明被膜の外観観察結果から改質ジルコニア微粒子の透明被膜中の分散性を下記のように評価した。
評価基準
基材のヘーズと同等 ：◎
若干ヘーズが増加するが、目視では区別できない ：○
ヘーズが増加し、目視で白化が認められる ：△
ヘーズが大きく増加し、目視で顕著な白化が認められる：×
The coating solution (1) for forming a transparent coating is applied to a PET film (Toyobo Cosmo Shine A4100, thickness: 188 μm, refractive index: 1.67, substrate haze 0.8%) by the bar coater method (# 14). Then, after drying at 80 ° C. for 120 seconds, the film-coated substrate (1) was produced by irradiating and curing 600 mJ / cm 2 ultraviolet rays. The haze of the obtained transparent film was measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.), and the dispersibility of the modified zirconia fine particles in the transparent film was evaluated as follows from the observation results of the haze and the appearance of the transparent film. .
Equivalent to haze of evaluation base material: ◎
Slightly increased haze, but cannot be distinguished visually: ○
Haze increases and whitening is observed visually: △
Haze increases greatly, and noticeable whitening is observed visually: ×
改質ジルコニア微粒子(2)分散液の調製
五酸化アンチモン被覆
実施例1と同様にして調製したジルコニアゾル(1)２４０ｇとアンチモン酸カリウム水溶液（Sb2O5として濃度1重量％）６０ｇを混合し、陽イオン交換樹脂（三菱化学（株）製：DAIAION PK-216H）３３０ｇを充填したイオン交換塔を通過させた後、９０℃で1時間熟成して五酸化アンチモン被覆ジルコニアゾル(2)を調製した。得られたゾルのｐＨは２．５であった。
Preparation of modified zirconia fine particle (2) dispersion
Antimony pentoxide coating 240 g of zirconia sol (1) prepared in the same manner as in Example 1 and 60 g of potassium antimonate aqueous solution (concentration of 1% by weight as Sb 2 O 5 ) were mixed to form a cation exchange resin (Mitsubishi Chemical Corporation). (Product: DAIAION PK-216H) After passing through an ion exchange column packed with 330 g, the mixture was aged at 90 ° C. for 1 hour to prepare antimony pentoxide-coated zirconia sol (2). The pH of the obtained sol was 2.5.
シリカ被覆
五酸化アンチモン被覆ジルコニアゾル(2)２７７ｇを用いた以外は実施例１と同様にして固形分濃度１０重量％の五酸化アンチモン／シリカ被覆ジルコニア微粒子アルコール分散液(2)を調製した。
表面処理
次に、五酸化アンチモン／シリカ被覆ジルコニア微粒子アルコール分散液(2)１１９ｇを用いた以外は実施例１と同様にして、固形分濃度２重量％の改質ジルコニア微粒子(2)分散液を調製した。
得られた改質ジルコニア微粒子(2)について、平均粒子径、屈折率、表面電位および分散性を測定し、結果を表に示した。
An antimony pentoxide / silica-coated zirconia fine particle alcohol dispersion (2) having a solid concentration of 10% by weight was prepared in the same manner as in Example 1 except that 277 g of silica-coated antimony pentoxide-coated zirconia sol (2) was used.
Surface Treatment Next, a modified zirconia fine particle (2) dispersion having a solid content concentration of 2% by weight was prepared in the same manner as in Example 1 except that 119 g of antimony pentoxide / silica-coated zirconia fine particle alcohol dispersion (2) was used. Prepared.
The resulting modified zirconia fine particles (2) were measured for average particle diameter, refractive index, surface potential and dispersibility, and the results are shown in the table.
改質ジルコニア微粒子(3)分散液の調製
五酸化アンチモン被覆
実施例1と同様にして調製したジルコニアゾル(1)１５０ｇとアンチモン酸カリウム水溶液（Sb2O5として濃度1重量％）１５０ｇを混合し、陽イオン交換樹脂（三菱化学（株）製：DAIAION PK-216H）３３０ｇを充填したイオン交換塔を通過させた後、９０℃で1時間熟成して五酸化アンチモン被覆ジルコニアゾル(3)を調製した。得られたゾルのｐＨは２．７であった。
Preparation of modified zirconia fine particle (3) dispersion
Antimony pentoxide coating 150 g of zirconia sol (1) prepared in the same manner as in Example 1 and 150 g of potassium antimonate aqueous solution (concentration of 1% by weight as Sb 2 O 5 ) were mixed to form a cation exchange resin (Mitsubishi Chemical Corporation). (Product: DAIAION PK-216H) After passing through an ion exchange column packed with 330 g, the mixture was aged at 90 ° C. for 1 hour to prepare antimony pentoxide-coated zirconia sol (3). The obtained sol had a pH of 2.7.
シリカ被覆
五酸化アンチモン被覆ジルコニアゾル(3)２７７ｇを用いた以外は実施例１と同様にして固形分濃度１０重量％の五酸化アンチモン／シリカ被覆ジルコニア微粒子アルコール分散液(3)を調製した。
表面処理
次に、五酸化アンチモン／シリカ被覆ジルコニア微粒子アルコール分散液(3)１１９ｇを用いた以外は実施例１と同様にして、固形分濃度２重量％の改質ジルコニア微粒子(3)分散液を調製した。
得られた改質ジルコニア微粒子(3)について、平均粒子径、屈折率、表面電位および分散性を測定し、結果を表に示した。
An antimony pentoxide / silica-coated zirconia fine particle alcohol dispersion (3) having a solid concentration of 10% by weight was prepared in the same manner as in Example 1 except that 277 g of silica-coated antimony pentoxide-coated zirconia sol (3) was used.
Surface Treatment Next, a modified zirconia fine particle (3) dispersion having a solid content concentration of 2% by weight was prepared in the same manner as in Example 1 except that 119 g of antimony pentoxide / silica-coated zirconia fine particle alcohol dispersion (3) was used. Prepared.
The resulting modified zirconia fine particles (3) were measured for average particle diameter, refractive index, surface potential and dispersibility, and the results are shown in the table.
改質ジルコニア微粒子(4)分散液の調製
ジルコニアゾル(2)の調製
純水１，３０２ｇにオキシ塩化ジルコニウム８水和物（ZrOCl2・8H2O）３５ｇを溶解し、これに濃度１０重量％のＫＯＨ水溶液１２２．８ｇ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。ついで、５時間静置してジルコニウム水酸化物ヒドロゲルを沈降させた後、上澄み液（pH11.0）７５０ｇ除去した。次に純水７５０ｇを添加し、攪拌した後、再び５時間静置した。以上の操作を上澄み液の電導度が０．５ｍｓ／ｃｍ以下になるまで繰り返し行った。
Preparation of modified zirconia fine particle (4) dispersion
Dissolving zirconium oxychloride octahydrate (ZrOCl 2 · 8H 2 O) 35 g Preparation of pure water 1,302g of zirconia sol (2), to which was added a 10 wt% aqueous KOH solution 122.8g zirconium Hydroxide hydrogel (ZrO 2 concentration 1 wt%) was prepared. Subsequently, after leaving still for 5 hours to precipitate the zirconium hydroxide hydrogel, 750 g of the supernatant (pH 11.0) was removed. Next, 750 g of pure water was added and stirred, and then allowed to stand again for 5 hours. The above operation was repeated until the conductivity of the supernatant liquid was 0.5 ms / cm or less.
得られたジルコニウム水酸化物ヒドロゲルに酒石酸１．４４ｇを加えて充分に攪拌を行った。ついで、ｐＨ１１．０になるまで濃度１０重量％のＫＯＨ水溶液を加え、超音波を1時間照射してヒドロゲルの分散処理をした後、限外濾過膜を用いて電導度が０．３５ｍｓ／ｃｍ以下になるまで洗浄した。次に、陰イオン交換樹脂（ROHM AND HAAS社製：デュオライトUP5000）を２．６ｇ加え、脱イオンを行った。ついで、得られたジルコニウム水酸化物ヒドロゲルをオートクレーブに充填し、１４０℃で６時間水熱処理を行った。このときｐＨは１０．７であった。
ついで、水熱処理して得られた分散液を乾燥した後５００℃で２時間焼成してジルコニア粉末を得た。得られたジルコニア粉末は立方晶，単斜晶の混晶体であった。
1.44 g of tartaric acid was added to the obtained zirconium hydroxide hydrogel and sufficiently stirred. Next, a 10% strength by weight KOH aqueous solution was added until the pH reached 11.0, and after ultrasonic waves were irradiated for 1 hour to disperse the hydrogel, the conductivity was 0.35 ms / cm or less using an ultrafiltration membrane. Washed until Next, 2.6 g of anion exchange resin (manufactured by ROHM AND HAAS: Duolite UP5000) was added to perform deionization. Subsequently, the obtained zirconium hydroxide hydrogel was filled in an autoclave and hydrothermally treated at 140 ° C. for 6 hours. At this time, the pH was 10.7.
Next, the dispersion obtained by hydrothermal treatment was dried and then calcined at 500 ° C. for 2 hours to obtain zirconia powder. The obtained zirconia powder was a mixed crystal of cubic and monoclinic crystals.
次に、純水１６１．９ｇに酒石酸８．８ｇを溶解した水溶液にジルコニア粉末３６ｇを加え、ついで、濃度１０重量％のＫＯＨ水溶液３０ｇを加えてｐＨ１２．３のジルコニア粉末分散液とした。ジルコニア粉末分散液を分散機（カンペ（株）製：BATCH SAND）にて分散させ、ジルコニアゾルとした。得られたジルコニアゾルを遠心分離器にセットし、２，５００ｒｐｍで5分間遠心分離処理を行なった後、限外濾過膜を用いて電導度が１００μｓ／ｃｍ程度になるまで洗浄し、ついで、陰イオン交換樹脂（デュオライトUP-5000）４０ｇを加えて脱イオン処理を行い、樹脂を分離し、ＺｒＯ2濃度１重量％のジルコニアゾル(2)を調製した。
ジルコニア微粒子を透過型電子顕微鏡写真（TEM）で観察したところ、粗大粒子等は無く、平均粒子径１５ｎｍのジルコニア微粒子であった。また、ジルコニア微粒子は立方晶、単斜晶の混晶体であった。また、屈折率は２．０であった。
Next, 36 g of zirconia powder was added to an aqueous solution in which 8.8 g of tartaric acid was dissolved in 161.9 g of pure water, and then 30 g of a 10 wt% KOH aqueous solution was added to obtain a zirconia powder dispersion having a pH of 12.3. The zirconia powder dispersion was dispersed with a disperser (manufactured by Campe Co., Ltd .: BATCH SAND) to obtain a zirconia sol. The obtained zirconia sol is set in a centrifuge, centrifuged at 2,500 rpm for 5 minutes, washed with an ultrafiltration membrane until the conductivity becomes about 100 μs / cm, and then negatively charged. Deionization treatment was performed by adding 40 g of an ion exchange resin (Duolite UP-5000), and the resin was separated to prepare a zirconia sol (2) having a ZrO 2 concentration of 1% by weight.
When the zirconia fine particles were observed with a transmission electron micrograph (TEM), there were no coarse particles and the like, and the zirconia fine particles had an average particle diameter of 15 nm. The zirconia fine particles were cubic and monoclinic mixed crystals. The refractive index was 2.0.
五酸化アンチモン被覆
ジルコニアゾル(2)２１０ｇとアンチモン酸カリウム水溶液（Sb2O5として濃度1重量％）９０ｇを混合し、陽イオン交換樹脂（三菱化学（株）製：DAIAION PK-216H）３３０ｇを充填したイオン交換塔を通過させた後、９０℃で1時間熟成して五酸化アンチモン被覆ジルコニアゾル(4)を調製した。得られたゾルのｐＨは２．６であった。
シリカ被覆
五酸化アンチモン被覆ジルコニアゾル(4)２７７ｇを用いた以外は実施例１と同様にして固形分濃度１０重量％の五酸化アンチモン／シリカ被覆ジルコニア微粒子アルコール分散液(4)を調製した。
210 g of antimony pentoxide-coated zirconia sol (2) and 90 g of potassium antimonate aqueous solution (concentration 1% by weight as Sb 2 O 5 ) were mixed, and 330 g of cation exchange resin (manufactured by Mitsubishi Chemical Corporation: DAIAION PK-216H) After passing through the packed ion exchange tower, it was aged at 90 ° C. for 1 hour to prepare antimony pentoxide-coated zirconia sol (4). The obtained sol had a pH of 2.6.
An antimony pentoxide / silica-coated zirconia fine particle alcohol dispersion (4) having a solid concentration of 10% by weight was prepared in the same manner as in Example 1 except that 277 g of silica-coated antimony pentoxide-coated zirconia sol (4) was used.
表面処理
次に、五酸化アンチモン／シリカ被覆ジルコニア微粒子アルコール分散液(4)１１９ｇを用いた以外は実施例１と同様にして、固形分濃度２重量％の改質ジルコニア微粒子(4)分散液を調製した。
得られた改質ジルコニア微粒子(4)について、平均粒子径、屈折率、表面電位および分散性を測定し、結果を表に示した。
Surface Treatment Next, a modified zirconia fine particle (4) dispersion having a solid content concentration of 2% by weight was prepared in the same manner as in Example 1 except that 119 g of antimony pentoxide / silica-coated zirconia fine particle alcohol dispersion (4) was used. Prepared.
The resulting modified zirconia fine particles (4) were measured for average particle diameter, refractive index, surface potential and dispersibility, and the results are shown in the table.
改質ジルコニア微粒子(5)分散液の調製
ジルコニアゾル(3)の調製
純水１，３０２ｇにオキシ塩化ジルコニウム８水和物（ZrOCl2・8H2O）３５ｇを溶解し、これに濃度１０重量％のＫＯＨ水溶液１２２．８ｇ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。ついで、５時間静置してジルコニウム水酸化物ヒドロゲルを沈降させた後、上澄み液（pH11.0）７５０ｇ除去した。次に純水７５０ｇを添加し、攪拌した後、再び５時間静置した。以上の操作を上澄み液の電導度が０．５ｍｓ／ｃｍ以下になるまで繰り返し行った。
Preparation of modified zirconia fine particle (5) dispersion
Preparation of zirconia sol (3) 35 g of zirconium oxychloride octahydrate (ZrOCl 2 .8H 2 O) was dissolved in 1,302 g of pure water, and 122.8 g of a 10 wt% KOH aqueous solution was added thereto to add zirconium. Hydroxide hydrogel (ZrO 2 concentration 1 wt%) was prepared. Subsequently, after leaving still for 5 hours to precipitate the zirconium hydroxide hydrogel, 750 g of the supernatant (pH 11.0) was removed. Next, 750 g of pure water was added and stirred, and then allowed to stand again for 5 hours. The above operation was repeated until the conductivity of the supernatant liquid was 0.5 ms / cm or less.
得られたジルコニウム水酸化物ヒドロゲルに酒石酸０．６４ｇを加えて充分に攪拌を行った。ついで、ｐＨ１１．０になるまで濃度１０重量％のＫＯＨ水溶液を加え、超音波を1時間照射してヒドロゲルの分散処理をした後、限外濾過膜を用いて電導度が０．３５ｍｓ／ｃｍ以下になるまで洗浄した。次に、陰イオン交換樹脂（ROHM AND HAAS社製：デュオライトUP5000）を２．６ｇ加え、脱イオンを行った。ついで、得られたジルコニウム水酸化物ヒドロゲルをオートクレーブに充填し、２００℃で６時間水熱処理を行った。このときｐＨは１０．７であった。
ついで、水熱処理して得られた分散液を乾燥した後７００℃で２時間焼成してジルコニア粉末を得た。得られたジルコニア粉末は立方晶，単斜晶の混晶体であった。
0.64 g of tartaric acid was added to the obtained zirconium hydroxide hydrogel and sufficiently stirred. Next, a 10% strength by weight KOH aqueous solution was added until the pH reached 11.0, and after ultrasonic waves were irradiated for 1 hour to disperse the hydrogel, the conductivity was 0.35 ms / cm or less using an ultrafiltration membrane. Washed until Next, 2.6 g of anion exchange resin (manufactured by ROHM AND HAAS: Duolite UP5000) was added to perform deionization. Subsequently, the obtained zirconium hydroxide hydrogel was filled in an autoclave and hydrothermally treated at 200 ° C. for 6 hours. At this time, the pH was 10.7.
Subsequently, the dispersion obtained by hydrothermal treatment was dried and then calcined at 700 ° C. for 2 hours to obtain zirconia powder. The obtained zirconia powder was a mixed crystal of cubic and monoclinic crystals.
次に、純水１６１．９ｇに酒石酸２．２ｇを溶解した水溶液にジルコニア粉末３６ｇを加え、ついで、濃度１０重量％のＫＯＨ水溶液３０ｇを加えてｐＨ１２．３のジルコニア粉末分散液とした。ジルコニア粉末分散液を分散機（カンペ（株）製：BATCH SAND）にて分散させ、ジルコニアゾルとした。得られたジルコニアゾルを遠心分離器にセットし、２，５００ｒｐｍで5分間遠心分離処理を行なった後、限外濾過膜を用いて電導度が１００μｓ／ｃｍ程度になるまで洗浄し、ついで、陰イオン交換樹脂（デュオライトUP-5000）４０ｇを加えて脱イオン処理を行い、樹脂を分離し、ＺｒＯ2濃度１重量％のジルコニアゾル(3)を調製した。
ジルコニア微粒子を透過型電子顕微鏡写真（TEM）で観察したところ、粗大粒子等は無く、平均粒子径５０ｎｍのジルコニア微粒子であった。また、ジルコニア微粒子は立方晶、単斜晶の混晶体であった。また、屈折率は２．２であった。
Next, 36 g of zirconia powder was added to an aqueous solution in which 2.2 g of tartaric acid was dissolved in 161.9 g of pure water, and then 30 g of a 10% by weight aqueous KOH solution was added to obtain a zirconia powder dispersion having a pH of 12.3. The zirconia powder dispersion was dispersed with a disperser (manufactured by Campe Co., Ltd .: BATCH SAND) to obtain a zirconia sol. The obtained zirconia sol is set in a centrifuge, centrifuged at 2,500 rpm for 5 minutes, washed with an ultrafiltration membrane until the conductivity becomes about 100 μs / cm, and then negatively charged. Deionization treatment was performed by adding 40 g of an ion exchange resin (Duolite UP-5000), and the resin was separated to prepare a zirconia sol (3) having a ZrO 2 concentration of 1% by weight.
When the zirconia fine particles were observed with a transmission electron micrograph (TEM), there were no coarse particles and the like, and the zirconia fine particles had an average particle diameter of 50 nm. The zirconia fine particles were cubic and monoclinic mixed crystals. The refractive index was 2.2.
五酸化アンチモン被覆
ジルコニアゾル(3)２１０ｇとアンチモン酸カリウム水溶液（Sb2O5として濃度1重量％）９０ｇを混合し、陽イオン交換樹脂（三菱化学（株）製：DAIAION PK-216H）３３０ｇを充填したイオン交換塔を通過させた後、９０℃で1時間熟成して五酸化アンチモン被覆ジルコニアゾル(5)を調製した。得られたゾルのｐＨは２．６であった。
シリカ被覆
五酸化アンチモン被覆ジルコニアゾル(5)２７７ｇを用いた以外は実施例１と同様にして固形分濃度１０重量％の五酸化アンチモン／シリカ被覆ジルコニア微粒子アルコール分散液（5）を調製した。
210 g of antimony pentoxide-coated zirconia sol (3) and 90 g of potassium antimonate aqueous solution (concentration of 1% by weight as Sb 2 O 5 ) were mixed, and 330 g of cation exchange resin (manufactured by Mitsubishi Chemical Corporation: DAIAION PK-216H) After passing through the packed ion exchange tower, it was aged at 90 ° C. for 1 hour to prepare antimony pentoxide-coated zirconia sol (5). The obtained sol had a pH of 2.6.
An antimony pentoxide / silica-coated zirconia fine particle alcohol dispersion (5) having a solid concentration of 10% by weight was prepared in the same manner as in Example 1 except that 277 g of silica-coated antimony pentoxide-coated zirconia sol (5) was used.
表面処理
次に、五酸化アンチモン／シリカ被覆ジルコニア微粒子アルコール分散液(5)１１９ｇを用いた以外は実施例１と同様にして、固形分濃度２重量％の改質ジルコニア微粒子(5)分散液を調製した。
得られた改質ジルコニア微粒子(5)について、平均粒子径、屈折率、表面電位および分散性を測定し、結果を表に示した。
Surface Treatment Next, a modified zirconia fine particle (5) dispersion having a solid content concentration of 2% by weight was prepared in the same manner as in Example 1 except that 119 g of antimony pentoxide / silica-coated zirconia fine particle alcohol dispersion (5) was used. Prepared.
The obtained modified zirconia fine particles (5) were measured for average particle diameter, refractive index, surface potential and dispersibility, and the results are shown in the table.
改質ジルコニア微粒子(6)分散液の調製
シリカ被覆
実施例１と同様な方法でＺｒＯ2濃度１．５重量％のジルコニアゾル(1)を調製した。このジルコニアゾル（1）１００ｇとエタノール８７．６ｇおよび濃度２８重量％のアンモニア水溶液０．５ｇとの混合溶液を３５℃に加温した後、テトラエトキシシラン（多摩化学工業株式会社製：エチルシリケート-A）０．１５ｇを添加した。ついで、陽イオン交換樹脂（三菱化学（株）製：ダイアイオンSK-1BH）６０２．１ｇを用い、８０℃で３時間脱イオンを行った。得られたジルコニアゾルを限外濾過膜を用いて溶媒をアルコールに置換し、固形分濃度５重量％のシリカ被覆ジルコニア微粒子アルコール分散液(6)を調製した。
Preparation of modified zirconia fine particle (6) dispersion
Silica coating A zirconia sol (1) having a ZrO 2 concentration of 1.5% by weight was prepared in the same manner as in Example 1. A mixed solution of 100 g of this zirconia sol (1), 87.6 g of ethanol and 0.5 g of an aqueous ammonia solution having a concentration of 28% by weight was heated to 35 ° C., and then tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: ethyl silicate- A) 0.15 g was added. Subsequently, deionization was performed at 60 ° C. for 3 hours using 602.1 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: Diaion SK-1BH). The obtained zirconia sol was replaced with alcohol by using an ultrafiltration membrane to prepare a silica-coated zirconia fine particle alcohol dispersion (6) having a solid content concentration of 5% by weight.
表面処理
次に、シリカ被覆ジルコニア微粒子アルコール分散液（6）１１９ｇにγ-メタアクリロオキシプロピルトリメトキシシラン（信越化学（株）製：KBM-503）０．６ｇを加え、５０℃で１６時間熟成し、固形分濃度５重量％の改質ジルコニア微粒子(6)分散液を調製した。
得られた改質ジルコニア微粒子(6)について、平均粒子径、屈折率、表面電位および分散性を測定し、結果を表に示した。
Surface treatment Next, 0.6 g of γ-methacrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) was added to 119 g of silica-coated zirconia fine particle alcohol dispersion (6) and stirred at 50 ° C. for 16 hours. After aging, a modified zirconia fine particle (6) dispersion having a solid content concentration of 5% by weight was prepared.
The resulting modified zirconia fine particles (6) were measured for average particle diameter, refractive index, surface potential and dispersibility, and the results are shown in the table.
改質ジルコニア微粒子(7)分散液の調製
シリカ被覆
実施例６において、テトラエトキシシラン（多摩化学工業株式会社製：エチルシリケート-A）０．０５ｇを用いた以外は同様にして固形分濃度５重量％のシリカ被覆ジルコニア微粒子アルコール分散液(7)を調製した。
Preparation of modified zirconia fine particle (7) dispersion
Silica-coated Example 6 A silica-coated zirconia fine particle alcohol dispersion (7% solids concentration 5% by weight) except that 0.05 g of tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: ethyl silicate-A) was used. ) Was prepared.
表面処理
次に、シリカ被覆ジルコニア微粒子アルコール分散液(7)１１９ｇを用いた以外は実施例６と同様にして固形分濃度５重量％の改質ジルコニア微粒子(7)分散液を調製した。
得られた改質ジルコニア微粒子(7)について、平均粒子径、屈折率、表面電位および分散性を測定し、結果を表に示した。
Surface Treatment Next, a modified zirconia fine particle (7) dispersion having a solid content concentration of 5% by weight was prepared in the same manner as in Example 6 except that 119 g of silica-coated zirconia fine particle alcohol dispersion (7) was used.
The resulting modified zirconia fine particles (7) were measured for average particle diameter, refractive index, surface potential and dispersibility, and the results are shown in the table.
改質ジルコニア微粒子(8)分散液の調製
シリカ被覆
実施例６において、テトラエトキシシラン（多摩化学工業株式会社製：エチルシリケート-A）０．４５ｇを用いた以外は同様にして固形分濃度５重量％のシリカ被覆ジルコニア微粒子アルコール分散液(8)を調製した。
Preparation of modified zirconia fine particle (8) dispersion
In the same manner as Example 6 except that 0.45 g of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd .: ethyl silicate-A) was used in silica-coated Example 6, a silica-coated zirconia fine particle alcohol dispersion having a solid content concentration of 5% by weight (8 ) Was prepared.
表面処理
次に、シリカ被覆ジルコニア微粒子アルコール分散液(8)１１９ｇを用いた以外は実施例６と同様にして固形分濃度５重量％の改質ジルコニア微粒子(8)分散液を調製した。
得られた改質ジルコニア微粒子(8)について、平均粒子径、屈折率、表面電位および分散性を測定し、結果を表に示した。
Surface Treatment Next, a modified zirconia fine particle (8) dispersion having a solid content concentration of 5% by weight was prepared in the same manner as in Example 6 except that 119 g of silica-coated zirconia fine particle alcohol dispersion (8) was used.
The resulting modified zirconia fine particles (8) were measured for average particle diameter, refractive index, surface potential and dispersibility, and the results are shown in the table.
改質ジルコニア微粒子(9)分散液の調製
五酸化アンチモン被覆
実施例1と同様にして調製したジルコニアゾル(1)２１０ｇとアンチモン酸カリウム水溶液（Sb2O5として濃度1重量％）９０ｇを混合し、９０℃で1時間熟成を行った。ついで、陽イオン交換樹脂（三菱化学（株）製：DAIAION PK-216H）３３０ｇを充填したイオン交換塔を通過させて、五酸化アンチモン被覆ジルコニアゾル(9)を調製した。得られたゾルのｐＨは２．６であった。
Preparation of modified zirconia fine particle (9) dispersion
Coating with antimony pentoxide 210 g of zirconia sol (1) prepared in the same manner as in Example 1 and 90 g of an aqueous potassium antimonate solution (concentration of 1% by weight as Sb 2 O 5 ) were mixed and aged at 90 ° C. for 1 hour. Subsequently, the mixture was passed through an ion exchange column packed with 330 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: DAIAION PK-216H) to prepare antimony pentoxide-coated zirconia sol (9). The obtained sol had a pH of 2.6.
シリカ被覆
得られた五酸化アンチモン被覆ジルコニアゾル(9)２７７ｇにテトラエトキシシラン（多摩化学工業(株)製：エチルシリケート-A）１．１５ｇを加え、ついでメタノール２７７ｇを加えた後、５０℃で１５時間熟成を行った。ついで、限外濾過膜を用いて溶媒をメタノールに置換し、固形分濃度１０重量％の五酸化アンチモン／シリカ被覆ジルコニア微粒子アルコール分散液(9)を調製した。
1.15 g of tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: ethyl silicate-A) was added to 277 g of the obtained antimony pentoxide-coated zirconia sol (9) obtained by silica coating , and then 277 g of methanol was added. Aging was performed for 15 hours. Subsequently, the solvent was replaced with methanol using an ultrafiltration membrane to prepare an antimony pentoxide / silica-coated zirconia fine particle alcohol dispersion (9) having a solid concentration of 10% by weight.
表面処理
次に、五酸化アンチモン／シリカ被覆ジルコニア微粒子アルコール分散液(9)１１９ｇにγ-メタアクリロオキシプロピルトリメトキシシラン（信越化学（株）製：KBM-503）０．１８ｇを加え、５０℃で１６時間熟成し、固形分濃度５重量％の改質ジルコニア微粒子(9)分散液を調製した。
得られた改質ジルコニア微粒子(9)について、平均粒子径、屈折率、表面電位および分散性を測定し、結果を表に示した。
Surface Treatment Next, 0.18 g of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) was added to 119 g of antimony pentoxide / silica-coated zirconia fine particle alcohol dispersion (9), and 50 Aged at 16 ° C. for 16 hours, a modified zirconia fine particle (9) dispersion having a solid content concentration of 5% by weight was prepared.
The resulting modified zirconia fine particles (9) were measured for average particle diameter, refractive index, surface potential and dispersibility, and the results are shown in the table.
改質ジルコニア微粒子(10)分散液の調製
五酸化アンチモン被覆
実施例１と同様にして調製したジルコニアゾル(1)２１０ｇとアンチモン酸カリウム水溶液（Sb2O5として濃度１重量％）９０ｇを混合し、９０℃で１時間熟成を行った。ついで、陽イオン交換樹脂（三菱化学（株）製：DAIAION PK-216H）３３０ｇを充填したイオン交換塔を通過させて、五酸化アンチモンを被覆した改質ジルコニア微粒子(10)分散液を調製した。得られたゾルのｐＨは２．６であった。
得られた改質ジルコニア微粒子(10)について、平均粒子径、屈折率、表面電位および分散性を測定し、結果を表に示した。
Preparation of modified zirconia fine particle (10) dispersion
Coating with antimony pentoxide 210 g of zirconia sol (1) prepared in the same manner as in Example 1 and 90 g of an aqueous potassium antimonate solution (concentration of 1% by weight as Sb 2 O 5 ) were mixed and aged at 90 ° C. for 1 hour. Subsequently, it was passed through an ion exchange column packed with 330 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: DAIAION PK-216H) to prepare a modified zirconia fine particle (10) dispersion coated with antimony pentoxide. The obtained sol had a pH of 2.6.
The resulting modified zirconia fine particles (10) were measured for average particle diameter, refractive index, surface potential and dispersibility, and the results are shown in the table.
ジルコニア微粒子(R1)分散液の調製
実施例１と同様にして調製したＺｒＯ2濃度１重量％のジルコニアゾル(1)をジルコニア微粒子(R1)分散液とした。
ジルコニア粒子(R1)について、平均粒子径、屈折率、表面電位および分散性を測定し、結果を表に示した。
Preparation of zirconia fine particle (R1) dispersion A zirconia sol (1) having a ZrO 2 concentration of 1% by weight prepared in the same manner as in Example 1 was used as a zirconia fine particle (R1) dispersion.
The zirconia particles (R1) were measured for average particle diameter, refractive index, surface potential and dispersibility, and the results are shown in the table.
ジルコニア微粒子(R2)分散液の調製
実施例１と同様にして調製したＺｒＯ2濃度１重量％のジルコニアゾル(1)を 限外濾過膜を用いて溶媒をメタノールに置換し、固形分濃度１０重量％のジルコニア微粒子アルコール分散液(R2)を調製した。
表面処理
次に、ジルコニア微粒子アルコール分散液（R2）１１９ｇにγ-メタアクリロオキシプロピルトリメトキシシラン（信越化学（株）製：KBM-503）０．１８ｇを加え、５０℃で１６時間熟成し、固形分濃度５重量％の表面処理したジルコニア微粒子(R2)分散液を調製した。
得られたジルコニア粒子(R2)について、平均粒子径、屈折率、表面電位および分散性を測定し、結果を表に示した。
Preparation of zirconia fine particle (R2) dispersion A zirconia sol (1) having a ZrO 2 concentration of 1% by weight prepared in the same manner as in Example 1 was replaced with methanol using an ultrafiltration membrane, and the solid content concentration was 10%. % Zirconia fine particle alcohol dispersion (R2) was prepared.
Surface treatment Next, 0.18 g of γ-methacrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) was added to 119 g of zirconia fine particle alcohol dispersion (R2) and aged at 50 ° C. for 16 hours. A surface-treated zirconia fine particle (R2) dispersion having a solid content concentration of 5% by weight was prepared.
The resulting zirconia particles (R2) were measured for average particle diameter, refractive index, surface potential and dispersibility, and the results are shown in the table.
Claims (10)
条件(1)：改質ジルコニア微粒子分散液の固形分濃度が１重量％
条件(2)：改質ジルコニア微粒子分散液のｐＨが２〜１３の範囲 A zirconia fine particle whose surface is coated with antimony pentoxide and / or silica, and the surface potential of the zirconia fine particle is in the range of −120 to −10 mV when measured under the following conditions. Zirconia fine particles.
Condition (1): The solid content concentration of the modified zirconia fine particle dispersion is 1% by weight.
Condition (2): The pH of the modified zirconia fine particle dispersion is in the range of 2 to 13.
Ｒn−ＳiＸ4-n ・・・（１）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、水酸基、ハロゲン、水素、ｎ：１〜３の整数） Further, the modified zirconia fine particles according to claim 1, which are surface-treated with an organosilicon compound represented by the following formula (1).
R n -Si x 4-n (1)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3)
（ａ）ＺrＯ2としての濃度０．１〜２０重量％のジルコニア微粒子水分散液（Ａ）と、Ｓb2Ｏ5としての濃度０．１〜２０重量％のアンチモン酸アルカリ水溶液（Ｂ）またはＳiＯ2としての濃度０．１〜２０重量％のケイ酸アルカリ水溶液または４官能アルコキシシラン溶液（Ｃ）とを混合した分散液を調製する工程
（ｂ）混合した分散液を陽イオン交換樹脂と接触させる工程
（ｃ）４０〜２００℃で熟成する工程 A method for producing modified zirconia fine particles, comprising the following steps (a) to (c).
(A) A zirconia fine particle aqueous dispersion (A) having a concentration of 0.1 to 20% by weight as ZrO 2 and an alkali antimonate aqueous solution (B) or SiO having a concentration of 0.1 to 20% by weight as Sb 2 O 5 the concentration of 0.1 to 20 wt% of alkali silicate aqueous solution or tetrafunctional alkoxysilane solution (C) to prepare mixed dispersion and a step (b) mixed dispersion as 2 is contacted with a cation exchange resin Step (c) Step of aging at 40 to 200 ° C
（ｄ）工程（ｃ）で得られた改質ジルコニア微粒子水分散液を有機溶媒に溶媒置換する工程
（ｅ）下記式（２）で表される有機ケイ素化合物の水および／または有機溶媒溶液を加える工程
Ｒn−ＳiＸ4-n ・・・（２）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、水酸基、ハロゲン、水素、ｎ：１〜３の整数）
（ｆ）必要に応じて加水分解触媒を加え、有機ケイ素化合物を加水分解して改質ジルコニア微粒子を表面処理する工程
（ｇ）３０〜１２０℃で熟成する工程 The method for producing modified zirconia fine particles according to claim 6 or 7, wherein the following steps (d) to (g) are performed after the step (c).
(D) Step of replacing the modified zirconia fine particle aqueous dispersion obtained in step (c) with an organic solvent (e) Water and / or an organic solvent solution of an organosilicon compound represented by the following formula (2) Add step R n -SiX 4-n ··· ( 2)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3)
(F) A step of adding a hydrolysis catalyst as necessary, hydrolyzing the organosilicon compound and surface-treating the modified zirconia fine particles (g) A step of aging at 30 to 120 ° C.
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| JP2007280565A JP4994187B2 (en) | 2007-10-29 | 2007-10-29 | Method for producing modified zirconia fine particles |
| KR1020080083685A KR101571706B1 (en) | 2007-08-31 | 2008-08-27 | Substrate for hard coating film and coating solution for hard coating film |
| CN2008102150046A CN101397422B (en) | 2007-08-31 | 2008-08-29 | Substrate with hard coat film and coating solution for forming hard coat film |
| US12/201,172 US8748001B2 (en) | 2007-08-31 | 2008-08-29 | Substrate with hard coat film and coating solution for forming hard coat film comprising core-shell composite oxide surface-treated with an organic silicon compound |
| TW097133059A TWI448433B (en) | 2007-08-31 | 2008-08-29 | Substrate with hard coat film and coating solution for forming hard coat film |
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| JP2011136857A (en) * | 2009-12-28 | 2011-07-14 | Jgc Catalysts & Chemicals Ltd | Hydrophobic zirconium oxide particle, method of producing the same, resin composition containing the hydrophobic zirconium oxide particle and base material with cured resin film |
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