JP2005187284A - Modified silica-based sol and method for producing the modified silica-based sol - Google Patents
Modified silica-based sol and method for producing the modified silica-based sol Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000002245 particle Substances 0.000 claims abstract description 73
- 150000003819 basic metal compounds Chemical class 0.000 claims abstract description 52
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 150000001768 cations Chemical class 0.000 claims abstract description 18
- 150000001450 anions Chemical group 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001447 ferric ion Inorganic materials 0.000 claims abstract description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 34
- 229910004298 SiO 2 Inorganic materials 0.000 description 24
- 238000009826 distribution Methods 0.000 description 15
- 239000010408 film Substances 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 9
- 229910000358 iron sulfate Inorganic materials 0.000 description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- -1 Fe 3+ include Al-Fe Chemical class 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229910018084 Al-Fe Inorganic materials 0.000 description 1
- 229910018192 Al—Fe Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910011212 Ti—Fe Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 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
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Silicon Compounds (AREA)
Abstract
【課題】 屈折率が高く、分散安定性に優れ、また、塩基性金属化合物の金属の種類によっては紫外線遮蔽能を有する。
【解決手段】 改質シリカ系ゾルは、シリカ系粒子の表面に、下記式（１）で表される塩基性金属化合物が結合してなるものである。
[Ｍ2(ＯＨ)nＸ(2a-n)/b]m ・・・（１）
（式中、Ｍは１種または２種以上の３価および／または４価の金属カチオン、Ｘはアニオンであり、ａは金属カチオンの価数、ｂはアニオンの価数を示し、１≦ｎ≦７、ｎ＜２ａであり、１≦ｍ≦２０である。）
塩基性金属化合物の金属カチオンは、少なくとも第２鉄イオンを含むことが好ましく、改質シリカ系粒子の平均粒子径が５〜８０ｎｍの範囲にあり、ｐＨが０.１〜５の範囲にあり、濃度が固形分として５〜６０重量％の範囲にあることが好ましい。
【選択図】 なし
PROBLEM TO BE SOLVED: To provide a high refractive index, excellent dispersion stability, and UV shielding ability depending on the type of metal of a basic metal compound.
A modified silica-based sol is formed by bonding a basic metal compound represented by the following formula (1) to the surface of a silica-based particle.
[M 2 (OH) n X (2a-n) / b] m ··· (1)
(Wherein M is one or more trivalent and / or tetravalent metal cations, X is an anion, a is the valence of the metal cation, b is the valence of the anion, and 1 ≦ n ≦ 7, n <2a, and 1 ≦ m ≦ 20.)
The metal cation of the basic metal compound preferably contains at least ferric ion, the average particle diameter of the modified silica particles is in the range of 5 to 80 nm, and the pH is in the range of 0.1 to 5, The concentration is preferably in the range of 5 to 60% by weight as the solid content.
[Selection figure] None
Description
本発明は、粒子表面が塩基性金属化合物により改質されたシリカ系ゾルおよび該シリカ系ゾルの製造方法に関する。 The present invention relates to a silica-based sol having a particle surface modified with a basic metal compound and a method for producing the silica-based sol.
従来、シリカゾル、アルミナゾル、チタニアゾル、ジルコニアゾル、酸化アンチモンゾル、酸化亜鉛ゾル、炭酸カルシウム等の無機酸化物ゾル、無機化合物ゾル、シリカ・アルミナ等の複合酸化物ゾル等は耐摩耗性、耐擦傷性、硬度、耐候性、耐光性を不付与するために、あるいは屈折率調整剤、光学材料、着色剤、紫外線遮蔽剤等として基材上の樹脂被膜あるいは樹脂フイルム等に配合して用いられている。また、フィラーあるいは結合材等としても用いられている。
特に、シリカゾル、シリカ・アルミナ等の複合酸化物ゾルは球状の微粒子ゾルが得られ、安定性等に優れていることから、前記被膜形成用塗料への分散性が良く、得られる被膜は、ボイドやピンホールが無く、膜厚が均一で強度に優れた薄膜を得ることができる。
Conventionally, silica sol, alumina sol, titania sol, zirconia sol, antimony oxide sol, zinc oxide sol, inorganic oxide sol such as calcium carbonate, inorganic compound sol, composite oxide sol such as silica / alumina, etc. have abrasion resistance and scratch resistance. In addition, it is used in a resin film or a resin film on a substrate for imparting hardness, weather resistance, light resistance, or as a refractive index adjusting agent, optical material, colorant, ultraviolet shielding agent, etc. . It is also used as a filler or a binder.
Particularly, composite oxide sols such as silica sol and silica / alumina have a spherical fine particle sol and are excellent in stability and the like. Therefore, the dispersibility in the coating material for film formation is good. In addition, it is possible to obtain a thin film that has no or pinholes, a uniform film thickness, and excellent strength.
ところで、前記シリカゾルは屈折率が低く、紫外線遮蔽能を持たないので、これらの性能を付与させるためには、他の成分のゾルを混合することが必要となるが、この場合、安定性が低下したり、ゲル化する等の問題があった。
高屈折率で、紫外線遮蔽能を有するシリカ系ゾルとして、シリカ・アルミナ、シリカ・チタニア、シリカ・鉄等の複合酸化物ゾルが知られてはいるが、ゾル中の粒子径を精度よく、安定性において再現性良く製造することは容易なことではなかった。
By the way, since the silica sol has a low refractive index and does not have an ultraviolet shielding ability, it is necessary to mix sols of other components in order to impart these performances. Or gelled.
Silica-alumina, silica-titania, and silica-iron composite oxide sols are known as silica-based sols with high refractive index and UV shielding ability, but the particle size in the sol is stable and accurate. It was not easy to produce with good reproducibility.
また、負に帯電した酸性水性シリカゾルに、アルミニウムの塩基性塩またはジルコニウムの塩基性塩の水溶液を混合して、正に帯電したシリカゾルを得ることが特開平４−２１４０２２号公報（特許文献１）により公知であるが、濃度や温度によっては安定性が不十分であったり、ゲル化することがあった。特に、ｐＨが約４以下の低ｐＨ域では、安定性が低く、安定したゾルが得られにくい。
本発明は、シリカ系粒子の表面に塩基性金属化合物を結合・吸着させることにより、従来のシリカゾルに比べて屈折率が高く、分散安定性に優れ、また、塩基性金属化合物の金属の種類によっては紫外線遮蔽能を有する改質シリカ系ゾルおよび該シリカ系ゾルの製造方法を提供することを目的とする。 In the present invention, by binding and adsorbing a basic metal compound to the surface of silica-based particles, the refractive index is higher than that of a conventional silica sol, excellent in dispersion stability, and depending on the type of metal of the basic metal compound. An object of the present invention is to provide a modified silica-based sol having an ultraviolet shielding ability and a method for producing the silica-based sol.
本発明の改質シリカ系ゾルは、シリカ系粒子の表面に、下記式（１）で表される塩基性金属化合物が結合してなるものである。
[Ｍ2(ＯＨ)nＸ(2a-n)/b]m ・・・（１）
（式中、Ｍは１種または２種以上の３価および／または４価の金属カチオン、Ｘはアニオンであり、ａは金属カチオンの価数、ｂはアニオンの価数を示し、１≦ｎ≦７、ｎ＜２ａであり、１≦ｍ≦２０である。）
前記塩基性金属化合物の金属カチオンは、少なくとも第２鉄イオンを含むことが好ましい。
前記改質シリカ系ゾルの改質シリカ系粒子の平均粒子径が５〜８０ｎｍの範囲にあり、ｐＨが０.１〜５の範囲にあり、濃度が固形分として５〜６０重量％の範囲にあることが好ましい。
The modified silica-based sol of the present invention is formed by bonding a basic metal compound represented by the following formula (1) to the surface of silica-based particles.
[M 2 (OH) n X (2a-n) / b] m ··· (1)
(Wherein M is one or more trivalent and / or tetravalent metal cations, X is an anion, a is the valence of the metal cation, b is the valence of the anion, and 1 ≦ n ≦ 7, n <2a, and 1 ≦ m ≦ 20.)
The metal cation of the basic metal compound preferably contains at least a ferric ion.
The average particle size of the modified silica particles of the modified silica sol is in the range of 5 to 80 nm, the pH is in the range of 0.1 to 5, and the concentration is in the range of 5 to 60% by weight as the solid content. Preferably there is.
本発明の改質シリカ系ゾルの製造方法は、シリカ系ゾルを下記式（１）で表される塩基性金属化合物水溶液に添加して混合することからなることを特徴とする。
[Ｍ2(ＯＨ)nＸ(2a-n)/b]m ・・・（１）
（式中、Ｍは１種または２種以上の３価および／または４価の金属カチオン、Ｘはアニオンであり、ａは金属カチオンの価数、ｂはアニオンの価数を示し、１≦ｎ≦７、ｎ＜２ａであり、１≦ｍ≦２０である。）
前記シリカ系ゾルと塩基性金属化合物水溶液との混合液のｐＨを０.１〜５に調整することが好ましい。
The method for producing a modified silica-based sol of the present invention is characterized in that the silica-based sol is added to a basic metal compound aqueous solution represented by the following formula (1) and mixed.
[M 2 (OH) n X (2a-n) / b ] m (1)
(Wherein M is one or more trivalent and / or tetravalent metal cations, X is an anion, a is the valence of the metal cation, b is the valence of the anion, and 1 ≦ n ≦ 7, n <2a, and 1 ≦ m ≦ 20.)
It is preferable to adjust the pH of the mixed solution of the silica-based sol and the basic metal compound aqueous solution to 0.1 to 5.
本発明に係る改質シリカ系ゾルは、屈折率が高く、分散安定性に優れている。また、塩基性金属化合物の金属の種類によっては紫外線遮蔽能を有し、被膜に配合して用いた場合、基材の種類によっては密着性が向上したり、被膜の種類によっては高い絶縁性を維持することができたり、緻密な被膜を得ることができる。
本発明に係る改質シリカ系ゾルの製造方法によってよって得られる改質シリカ系ゾルは、シリカ系粒子の表面に塩基性金属化合物が結合および／または吸着しているので、粒子径分布が均一であり、表面が正に帯電し、このため分散安定性に優れる。従って、このような改質シリカ系ゾルを用いて形成した被膜、フィルムは改質シリカ系ゾルの塩基性金属化合物の種類あるいは量によって、屈折率を調整することが可能であり、耐光性、遮蔽性等にも優れている。
さらに、前記塩基性金属化合物はシリカ系粒子表面との結合性に優れている他、塩基性金属化合物の種類によっては他の被膜形成剤、フィルム形成剤、被膜やフィルム充填剤と容易に結合し、粒子径分布が均一であることから、被膜やフィルムは強度、耐擦傷性等に優れている。
The modified silica sol according to the present invention has a high refractive index and excellent dispersion stability. In addition, depending on the type of metal of the basic metal compound, it has an ultraviolet shielding ability, and when used in a coating, the adhesion improves depending on the type of the base material, and the high insulating property depends on the type of coating. It can be maintained or a dense film can be obtained.
The modified silica sol obtained by the method for producing a modified silica sol according to the present invention has a uniform particle size distribution because the basic metal compound is bound and / or adsorbed on the surface of the silica particles. Yes, the surface is positively charged, so that the dispersion stability is excellent. Therefore, the coating film and film formed using such a modified silica-based sol can be adjusted in refractive index depending on the type or amount of the basic metal compound in the modified silica-based sol. Excellent in properties.
In addition, the basic metal compound has excellent binding properties to the surface of the silica-based particles, and depending on the type of the basic metal compound, it easily binds to other film forming agents, film forming agents, coating films and film fillers. Since the particle size distribution is uniform, the coating and film are excellent in strength, scratch resistance and the like.
改質シリカ系ゾル
本発明に係る改質シリカ系ゾルは、シリカ系粒子の表面に、前記式（１）で表される塩基性金属化合物が結合したものである。
前記シリカ系ゾルとしては、シリカ系ゾル中のシリカ系粒子の平均粒子径が概ね５〜８０ｎｍの範囲にあり、粒子径分布が均一であれば特に制限はなく、従来公知のシリカゾル、シリカ系複合ゾルを用いることができる。例えば、本願出願人の出願による、特開昭６３−４５１１３号公報、特開昭６３−１２３８０７号公報等に開示したシリカゾル、特開平５−１３２３０９号公報、特開平７−１３３１０５号公報等に開示したシリカ系複合酸化物ゾルは好適に用いることができる。
Modified silica-based sol The modified silica-based sol according to the present invention is obtained by bonding the basic metal compound represented by the formula (1) to the surface of the silica-based particles.
The silica-based sol is not particularly limited as long as the average particle size of the silica-based particles in the silica-based sol is in the range of about 5 to 80 nm and the particle size distribution is uniform. A sol can be used. For example, disclosed in Japanese Patent Application Laid-Open No. 63-45113, Japanese Patent Application Laid-Open No. 63-123807, etc., Japanese Patent Application Laid-Open No. 5-132309, Japanese Patent Application Laid-Open No. 7-133105, etc. The silica-based composite oxide sol can be suitably used.
次に、前記塩基性金属化合物としては前記式（１）で表される塩基性金属化合物が用いられる。
Ｍは３価および／または４価の金属カチオンであり、例えば、周期律表の第３Ｂ族、第４Ａ族の元素の金属カチオンが用いられる。これらは同一化合物においてＭが１種または２種以上の元素の金属カチオンを含んでいてもよい。
このような金属カチオンとしては、例えば、Ａl3+、Ｆe3+、Ｇa4+、Ｔi4+、Ｚr4+等が挙げられる。なかでもＦe3+を含む化合物は好適に用いることができる。Ｆe3+を含む化合物は屈折率を高めることができるとともに、得られる改質シリカ系粒子は紫外線遮蔽能を有し、耐光性に優れている。Ｆe3+を含む２種以上の金属カチオンからなる場合の組み合わせとしてはＡl−Ｆe、Ｔi−Ｆe、Ｚr−Ｆe等が挙げられる。
Next, as the basic metal compound, a basic metal compound represented by the formula (1) is used.
M is a trivalent and / or tetravalent metal cation. For example, metal cations of elements of Group 3B and Group 4A of the periodic table are used. In these same compounds, M may contain a metal cation of one or more elements.
Examples of such metal cations include Al 3+ , Fe 3+ , Ga 4+ , Ti 4+ and Zr 4+ . Of these, compounds containing Fe 3+ can be preferably used. The compound containing Fe 3+ can increase the refractive index, and the resulting modified silica-based particles have an ultraviolet shielding ability and are excellent in light resistance. Examples of combinations of two or more metal cations including Fe 3+ include Al-Fe, Ti-Fe, Zr-Fe, and the like.
Ｘはアニオンであり、例えばハロゲンイオン、硫酸イオン、硝酸イオン、有機アニオン等が挙げられる。
具体的には、｛Ａl2（ＯＨ）1（ＳＯ4）2.5｝4 、｛Ｆe2（ＯＨ）1（ＳＯ4）2.5｝4 、｛Ｚr2（ＯＨ）1（ＳＯ4）3.5｝4 、Ａl2（ＯＨ）2（ＳＯ4）2｝4 、｛Ｆe2（ＯＨ）2（ＳＯ4）2｝4 、｛Ｆe2（ＯＨ）1（ＳＯ4）2.5｝6 、｛Ｆe2ーxＡlx（ＯＨ）1（ＳＯ4）2.5｝4 （０＜ｘ＜２） 等の他、前記（ＳＯ4）を他の前記アニオンに置換した化合物等が挙げられる。
また、式中、ｍは１≦ｍ≦２０ 、好ましくは２≦ｍ≦１０ の範囲にある。ｍが２０を越えると、シリカ系粒子表面への結合が起こりにくくなり、また表面電荷が付与できないために得られる改質シリカ系ゾルが不安定であったり、凝集することがある。
なお、本発明において前記「結合」は狭義の結合に限られず、化学吸着、物理吸着等の「吸着」を含んで意味している。即ち、前記塩基性金属化合物が吸着状態にあってもシリカ系粒子の表面に電荷を付与でき、安定したゾルが得られる場合がある。一般に、前記塩基性金属化合物のｍの大きいものは結合より吸着、ｍの小さいものは吸着より結合の傾向が強い。
X is an anion, and examples thereof include a halogen ion, a sulfate ion, a nitrate ion, and an organic anion.
Specifically, {Al 2 (OH) 1 (SO 4 ) 2.5 } 4 , {Fe 2 (OH) 1 (SO 4 ) 2.5 } 4 , {Zr 2 (OH) 1 (SO 4 ) 3.5 } 4 , Al 2 (OH) 2 (SO 4) 2} 4, {Fe 2 (OH) 2 (SO 4) 2} 4, {Fe 2 (OH) 1 (SO 4) 2.5} 6, {Fe 2 over x Al x (OH) 1 (SO 4 ) 2.5} 4 (0 <x <2) other such, the (SO 4) was replaced with another of said anionic compounds.
In the formula, m is in the range of 1 ≦ m ≦ 20, preferably 2 ≦ m ≦ 10. When m exceeds 20, bonding to the surface of the silica-based particles is difficult to occur, and the modified silica-based sol obtained because the surface charge cannot be imparted may be unstable or aggregate.
In the present invention, the “bond” is not limited to a narrowly defined bond, but includes “adsorption” such as chemical adsorption and physical adsorption. That is, even when the basic metal compound is in an adsorbed state, a charge can be imparted to the surface of the silica-based particles, and a stable sol may be obtained. In general, the basic metal compound having a large m is more adsorbed than the bond, and the one having a small m has a stronger tendency to bond than the adsorption.
このような塩基性金属化合物の改質シリカ系ゾル中の含有量は、用いるシリカ系粒子の粒子径、あるいは塩基性金属化合物のｍの値によっても異なるが、塩基性金属化合物を金属酸化物モル数（Ｍox）で表し、シリカ系ゾルの合計酸化物モル数（シリカのモル数とシリカ以外の酸化物のモル数）をＭsで表したときのモル比Ｍox／Ｍs が０.０２〜１、さらには０.０５〜０.５の範囲にあることが好ましい。
前記モル比Ｍox／Ｍs が０.０２未満の場合は、安定性が不充分となる他、金属の種類によって異なるが、耐光性、屈折率、遮蔽性が不充分となる。前記モル比Ｍox／Ｍs が１を越えてはシリカ系粒子表面に結合あるいは吸着することが困難である。
The content of the basic metal compound in the modified silica-based sol varies depending on the particle diameter of the silica-based particles to be used or the value of m of the basic metal compound. the number (M ox) expressed in the silica-based molar ratio M ox / M s at which the total oxide moles (the number of moles of oxides other than the moles of silica of the silica) were expressed as M s sols 0. It is preferably in the range of 02 to 1, more preferably 0.05 to 0.5.
When the molar ratio M ox / M s is less than 0.02, the stability is insufficient and the light resistance, refractive index, and shielding properties are insufficient, depending on the type of metal. When the molar ratio M ox / M s exceeds 1, it is difficult to bond or adsorb to the surface of the silica-based particles.
本発明の改質シリカ系ゾルに用いる分散媒としては水および／または有機溶媒を用いることができ、有機溶媒としてはメチルアルコール、エチルアルコール、グリコール類、エチレングリコールモノエチルエーテル等が挙げられる。 Water and / or an organic solvent can be used as the dispersion medium used in the modified silica-based sol of the present invention, and examples of the organic solvent include methyl alcohol, ethyl alcohol, glycols, ethylene glycol monoethyl ether, and the like.
本発明に係る改質シリカ系ゾルは、改質シリカ系ゾル中の改質シリカ系粒子の平均粒子径が５〜８０ｎｍ、さらには５〜５０ｎｍの範囲にあることが好ましい。改質シリカ系粒子の平均粒子径が５ｎｍ未満の場合は、凝集することがあり、安定性が不充分となることがある。一方、８０ｎｍを越えると、改質用塩基性化合物の結合量あるいは吸着量が減少するので耐光性、紫外線遮蔽性等の改質効果が不充分となる。 In the modified silica sol according to the present invention, the average particle diameter of the modified silica particles in the modified silica sol is preferably in the range of 5 to 80 nm, more preferably 5 to 50 nm. When the average particle size of the modified silica-based particles is less than 5 nm, the modified silica-based particles may aggregate and the stability may be insufficient. On the other hand, if the thickness exceeds 80 nm, the amount of the basic compound for modification or the amount of adsorption decreases, so that the modification effects such as light resistance and ultraviolet shielding are insufficient.
改質シリカ系ゾル中の改質シリカ系粒子の濃度は、固形分として５〜６０重量％、さらには１０〜４０重量％の範囲にあることが好ましい。濃度が固形分として５重量％未満の場合は、薄過ぎるために用途に制限があり、被膜形成用塗布液等として用いる場合は、１回の塗布で充分な膜厚の被膜が得られなかったり、このため目的の改質効果、例えば、屈折率、耐光性、紫外線遮蔽性が充分得られないことがある。他方、濃度が固形分として６０重量％を越えると、ゾルの安定性が低下するとともに、粘度が高くなる等の問題がある。 The concentration of the modified silica particles in the modified silica sol is preferably in the range of 5 to 60% by weight, more preferably 10 to 40% by weight as the solid content. When the concentration is less than 5% by weight as a solid content, the use is limited because it is too thin, and when it is used as a coating forming coating solution, a coating with a sufficient film thickness cannot be obtained by one coating. For this reason, the intended modification effects, for example, refractive index, light resistance, and ultraviolet shielding properties may not be sufficiently obtained. On the other hand, when the concentration exceeds 60% by weight as the solid content, there are problems such as a decrease in sol stability and an increase in viscosity.
また、改質シリカ系ゾルのｐＨは０.１〜５、さらには０.５〜３.８の範囲にあることが好ましい。ｐＨが０.１未満の場合は、酸性による腐食性が問題となることがあり、ｐＨが５を越えると塩基性金属化合物が金属水酸化物になりやすく、安定性が低下する傾向にある。
なお、本発明に係る改質シリカ系ゾルは、前記したシリカ系粒子の表面に結合等した塩基性金属化合物以外に、改質シリカ系ゾルの分散媒に溶解した塩基性金属化合物を含んでいてもよい。このときの分散媒に溶解した塩基性金属化合物の濃度は概ね３０重量％以下である。
The pH of the modified silica-based sol is preferably in the range of 0.1 to 5, more preferably 0.5 to 3.8. When the pH is less than 0.1, the corrosiveness due to acidity may be a problem. When the pH exceeds 5, the basic metal compound tends to be a metal hydroxide, and the stability tends to be lowered.
The modified silica sol according to the present invention contains a basic metal compound dissolved in a dispersion medium of the modified silica sol, in addition to the basic metal compound bonded to the surface of the silica particles. Also good. The concentration of the basic metal compound dissolved in the dispersion medium at this time is approximately 30% by weight or less.
改質シリカ系ゾルの製造方法
本発明に係る改質シリカ系ゾルの製造方法は、シリカ系ゾルと前記式（１）で表される塩基性金属化合物水溶液とを混合するものであるが、シリカ系ゾルとしては前述したシリカ系ゾルを用いることができ、このときシリカ系ゾル中のシリカ系粒子の濃度は酸化物として５〜５０重量％、さらには１０〜３０重量％の範囲にあることが好ましい。
シリカ系ゾル中のシリカ系粒子の濃度が酸化物として５重量％未満の場合は生産効率が低く、５０重量％を越えると、粘度が高いために均一に速やかに塩基性金属化合物水溶液と混合できないことがあり、凝集することがある。
Method for producing a modified silica-based sol according to the production method the present invention of the modified silica sol, but is intended to mix the basic metal compound solution represented by the silica-based sols in the formula (1), silica As the silica-based sol, the silica-based sol described above can be used. At this time, the concentration of the silica-based particles in the silica-based sol may be in the range of 5 to 50% by weight, more preferably 10 to 30% by weight as an oxide. preferable.
When the concentration of the silica-based particles in the silica-based sol is less than 5% by weight as an oxide, the production efficiency is low, and when it exceeds 50% by weight, the viscosity is high and cannot be uniformly and quickly mixed with the basic metal compound aqueous solution. And may agglomerate.
また、塩基性金属化合物としては、前述した塩基性金属化合物を用いることができ、塩基性金属化合物水溶液中の塩基性金属化合物の濃度は、固形分として０.５〜３０重量％、さらには１〜２０重量％の範囲にあることが好ましい。
塩基性金属化合物の濃度が、固形分として０.５重量％未満の場合は、所望量の塩基性金属化合物が結合・吸着しないことがある。一方、濃度が、固形分として３０重量％を越えると、シリカとの混合が迅速にかつ均一にできない場合があり、得られる改質シリカ系ゾルの安定性が不充分となることがある。
Moreover, as a basic metal compound, the basic metal compound mentioned above can be used, and the density | concentration of the basic metal compound in a basic metal compound aqueous solution is 0.5-30 weight% as solid content, Furthermore, 1 It is preferably in the range of ˜20% by weight.
When the concentration of the basic metal compound is less than 0.5% by weight as the solid content, a desired amount of the basic metal compound may not be bound or adsorbed. On the other hand, if the concentration exceeds 30% by weight as the solid content, mixing with silica may not be performed quickly and uniformly, and the resulting modified silica-based sol may have insufficient stability.
本発明に係る改質シリカ系ゾルの製造方法では、シリカ系ゾルと塩基性金属化合物水溶液とを混合する際に、塩基性金属化合物水溶液にシリカ系ゾルを添加する方法が好ましい。これとは逆に、シリカ系ゾルに塩基性金属化合物水溶液を添加すると、得られるゾルの安定性が低く、凝集粒子が生成することがある。 In the method for producing the modified silica sol according to the present invention, a method of adding the silica sol to the basic metal compound aqueous solution when the silica sol and the basic metal compound aqueous solution are mixed is preferable. On the contrary, when a basic metal compound aqueous solution is added to a silica-based sol, the stability of the obtained sol is low and aggregated particles may be generated.
シリカ系ゾルと塩基性金属化合物水溶液との混合比率は、得られる改質シリカ系ゾルの改質シリカ系粒子中の塩基性金属化合物の含有量が、塩基性金属化合物を金属酸化物モル数（Ｍox）で表し、シリカ系ゾルの合計酸化物モル数（シリカのモル数とシリカ以外の酸化物のモル数）をＭsで表したときのモル比Ｍox／Ｍs が０.０２〜２、さらには０.０５〜１の範囲となるように用いることが好ましい。
前記モル比Ｍox／Ｍs が０.０２未満の場合は、安定性が不充分となる他、金属の種類によって異なるが、耐光性、屈折率、遮蔽性が不充分となる。前記モル比Ｍox／Ｍs が２を越えてはシリカ系粒子表面に結合あるいは吸着することができず、ゾル中に溶解した塩基性金属化合物が多くなり、塩基性金属化合物の利用効率が低下する。
The mixing ratio between the silica-based sol and the aqueous solution of the basic metal compound is such that the content of the basic metal compound in the modified silica-based particles of the resulting modified silica-based sol is the number of moles of metal oxide of the basic metal compound ( expressed as M ox), silica-based total oxide moles of sol (molar ratio M ox / M s when the number of moles) were expressed as M s of moles of oxides other than silica of silica 0.02 2, more preferably 0.05 to 1 in range.
When the molar ratio M ox / M s is less than 0.02, the stability is insufficient and the light resistance, refractive index, and shielding properties are insufficient, depending on the type of metal. If the molar ratio M ox / M s exceeds 2, it cannot be bound or adsorbed on the surface of the silica-based particles, so that the basic metal compound dissolved in the sol increases and the utilization efficiency of the basic metal compound decreases. To do.
このとき、必要に応じてシリカ系ゾルと塩基性金属化合物水溶液との混合液のｐＨを０.１〜５、さらには０.５〜３.８の範囲に調整することが好ましい。ｐＨが０.１未満の場合は、酸性による腐食性が問題となることがある。一方、ｐＨが５を越えると塩基性金属化合物が金属水酸化物になりやすく、安定性が低下する傾向にある。
なお、混合液のｐＨを前記範囲に調整する方法としては酸またはアルカリを添加すればよい。また、混合後のｐＨが前記範囲となるようにあらかじめシリカ系ゾルおよび／または塩基性化合物水溶液に酸またはアルカリを加えて混合することもできる。
At this time, it is preferable to adjust the pH of the mixed solution of the silica-based sol and the basic metal compound aqueous solution to a range of 0.1 to 5, more preferably 0.5 to 3.8 as necessary. When the pH is less than 0.1, corrosivity due to acidity may be a problem. On the other hand, if the pH exceeds 5, the basic metal compound tends to be a metal hydroxide, and the stability tends to decrease.
In addition, what is necessary is just to add an acid or an alkali as a method of adjusting pH of a liquid mixture to the said range. Further, it is possible to add an acid or an alkali to the silica-based sol and / or the basic compound aqueous solution in advance so that the pH after mixing is in the above range.
混合時の混合液の温度は概ね１０〜９０℃、さらには２０〜５０℃の範囲にあることが好ましい。１０℃未満の場合は、シリカ系粒子への塩基性金属化合物の結合あるいは吸着が不充分となり、所望の安定性、性能を有した改質シリカ系ゾルが得られない場合があり、９０℃を越えると塩基性金属化合物が単独で加水分解・重合、さらには微粒子化し、所望の改質シリカ系ゾルが得られないことがある。 The temperature of the mixed solution at the time of mixing is preferably in the range of about 10 to 90 ° C, more preferably 20 to 50 ° C. When the temperature is lower than 10 ° C, the binding or adsorption of the basic metal compound to the silica-based particles becomes insufficient, and a modified silica-based sol having desired stability and performance may not be obtained. If it exceeds, the basic metal compound alone may be hydrolyzed / polymerized and further made into fine particles, and the desired modified silica sol may not be obtained.
得られた改質シリカ系ゾルは、必要に応じて濃縮あるいは希釈することができる。濃縮する方法としては、限外濾過膜法、エバポレーターによる加熱濃縮等が挙げられる。さらに、必要に応じて限外濾過膜法、エバポレーター法により有機溶媒に溶媒置換し、改質シリカ系オルガノゾルとすることもできる。 The resulting modified silica-based sol can be concentrated or diluted as necessary. Examples of the concentration method include an ultrafiltration membrane method and heat concentration using an evaporator. Furthermore, if necessary, the solvent can be replaced with an organic solvent by an ultrafiltration membrane method or an evaporator method to obtain a modified silica-based organosol.
このようにして得られた改質シリカ系ゾルは、平均粒子径が５〜８０ｎｍ、さらには５〜５０ｎｍの範囲にあり、ｐＨが０.１〜５、さらには０.５〜３.８の範囲にあり、濃度が固形分として５〜６０重量％、さらには１０〜４０重量％の範囲にあり、改質シリカ系粒子中の塩基性金属化合物の含有量が、塩基性金属化合物を金属酸化物モル数（Ｍox）で表し、シリカ系ゾルの合計酸化物モル数（シリカのモル数とシリカ以外の酸化物のモル数）をＭsで表したときのモル比Ｍox／Ｍs が０.０２〜１、さらには０.０５〜０.５の範囲にあることが好ましい。
以下、実施例により本発明を具体的に詳述する。
The modified silica-based sol thus obtained has an average particle size in the range of 5 to 80 nm, more preferably 5 to 50 nm, and a pH of 0.1 to 5, further 0.5 to 3.8. In the range, the concentration is in the range of 5 to 60% by weight as a solid content, and further in the range of 10 to 40% by weight, and the content of the basic metal compound in the modified silica-based particles is obtained by metal oxidation of the basic metal compound. expressed in object moles (M ox), the molar ratio M ox / M s at which the silica-based total oxide moles of sol (the number of moles of oxides other than the moles of silica of the silica) was expressed in M s It is preferably in the range of 0.02 to 1, more preferably 0.05 to 0.5.
Hereinafter, the present invention will be described in detail by way of examples.
改質シリカ系ゾル(1)の調製
塩基性硫酸鉄水溶液（多木化学（株）製：ダンパワー、ｐＨ２.５、Ｆe2Ｏ3濃度１６.４重量％）５００ｇを５Ｌの攪拌機付きガラス容器に採取し、温度２５℃にした。その後、攪拌しながら、この溶液に２５℃のシリカゾル（触媒化成工業（株）製：カタロイドＳＮ、ｐＨ３.０、ＳiＯ2濃度２０重量％、平均粒子径１２ｎｍ）１５００ｇを２分間かけて添加した。その後、２５℃に保ちながら６０分間攪拌を継続して改質シリカ系ゾル(1)を調製した。
この改質シリカ系ゾル(1)は、酸化物合計濃度（ＳiＯ2＋Ｆe2Ｏ3）が１９.１重量％、平均粒子径１３ｎｍ、Ｆe2Ｏ3／ＳiＯ2モル比０.１０、ｐＨ１.５であった。粒径分布は均一であった。
Preparation of modified silica-based sol (1 ) 500 g of a basic iron sulfate aqueous solution (manufactured by Taki Chemical Co., Ltd .: Danpower, pH 2.5, Fe 2 O 3 concentration 16.4% by weight) in a 5 L glass container equipped with a stirrer. The sample was collected and brought to a temperature of 25 ° C. Then, 1500 g of silica sol (catalyst chemical industry Co., Ltd. product: Cataloid SN, pH 3.0, SiO 2 concentration 20 wt%, average particle diameter 12 nm) at 25 ° C. was added to this solution over 2 minutes while stirring. Thereafter, stirring was continued for 60 minutes while maintaining at 25 ° C. to prepare a modified silica-based sol (1).
This modified silica-based sol (1) has a total oxide concentration (SiO 2 + Fe 2 O 3 ) of 19.1% by weight, an average particle diameter of 13 nm, a Fe 2 O 3 / SiO 2 molar ratio of 0.10, and a pH of 1. It was 5. The particle size distribution was uniform.
平均粒子径は透過型電子顕微鏡写真（ＴＥＭ）を撮影し、１００個の粒子について粒子径を測定し、その平均値を用いた。また、粒子径分布はＴＥＭ写真を観察し、粒子径が平均粒子径の１／２、あるいは２倍の粒子および凝集粒子の有無を観察した。
安定性の評価
得られた改質シリカ系ゾル(1)をガラス容器に採り、２５℃の恒温槽に浸漬し、ゾルの状況を観察し、以下の基準で評価し、結果を表に示した。
２ヶ月以上安定であった。 ：◎
３１日〜２ヶ月の間に白濁、ゲル化が開始した。：○
８〜３０日の間に白濁、ゲル化が開始した。 ：△
７日以内に白濁、ゲル化が開始した。 ：×
The average particle size was obtained by taking a transmission electron micrograph (TEM), measuring the particle size of 100 particles, and using the average value. Further, the particle size distribution was observed by TEM photographs, and the presence or absence of particles and aggregated particles whose particle size was 1/2 or twice the average particle size was observed.
Evaluation of stability The modified silica-based sol (1) obtained was taken in a glass container and immersed in a thermostatic bath at 25 ° C., the state of the sol was observed, evaluated according to the following criteria, and the results are shown in the table. .
Stable for over 2 months. : ◎
Cloudiness and gelation started between 31 days and 2 months. : ○
White turbidity and gelation started during 8-30 days. : △
The cloudiness and gelation started within 7 days. : ×
屈折率の測定
改質シリカ系ゾル(1)中の改質シリカ系粒子の屈折率を以下の方法で測定した。
（１） 改質シリカ系ゾルをエバポレーターに採り、分散媒を蒸発させる。
（２）これを１２０℃で乾燥し、粉末とする。
（３）屈折率が既知の標準屈折液を２，３滴ガラス基板に滴下し、これに上記粉末を混合する。
（４）上記（３）の操作を種々の標準屈折液で行い、混合液が最も透明性を有したときの標準屈折液の屈折率を改質シリカ系粒子の屈折率とした。
Measurement of Refractive Index The refractive index of the modified silica particles in the modified silica sol (1) was measured by the following method.
(1) Take the modified silica sol in an evaporator and evaporate the dispersion medium.
(2) This is dried at 120 ° C. to obtain a powder.
(3) A standard refraction liquid having a known refractive index is dropped on a few drops of glass substrate, and the above powder is mixed therewith.
(4) The above operation (3) was performed with various standard refractive liquids, and the refractive index of the standard refractive liquid when the mixed liquid had the most transparency was defined as the refractive index of the modified silica-based particles.
耐光性の評価
水溶性樹脂（日本合成化学（株）製：ポリエスター９７０、樹脂濃度２０重量％）１００重量部に、酸化物濃度を２０重量％に調整した改質シリカ系ゾル(1)３０重量部を混合して塗料とした。この塗料をポリカーボネート基板（厚さ：３ｍｍ）にワイヤバーにて塗布し、１００℃で３０分間乾燥して、厚さ３μｍの透明被膜を得た。
透明被膜を形成した基板を耐光性試験機（スガ試験機（株）製、サンシャインスーパーロングライフウェザーメーター）に設置し、塗布基板の表面温度を６０℃に維持しながら紫外線を２５０時間照射した後、透明被膜付基板の変化を観察し、以下の基準により評価した。
変色が認められなかった。 ：◎
僅かに変色が認められた。 ：○
明らかに変色が認められた。：△
濃い変色が認められた。 ：×
改質シリカ系ゾル(1) の安定性、改質シリカ系粒子の屈折率、耐光性の測定結果を、酸化物合計濃度、平均粒子径、ｐＨ等と共に表１に示した。
Evaluation of light resistance Modified silica-based sol (1) 30 in which 100 parts by weight of water-soluble resin (manufactured by Nippon Synthetic Chemical Co., Ltd .: Polyester 970, resin concentration 20% by weight) is adjusted to an oxide concentration of 20% by weight. The paint was mixed with parts by weight. This paint was applied to a polycarbonate substrate (thickness: 3 mm) with a wire bar and dried at 100 ° C. for 30 minutes to obtain a transparent film having a thickness of 3 μm.
The substrate on which the transparent film was formed was placed in a light resistance tester (Suga Test Instruments Co., Ltd., Sunshine Super Long Life Weather Meter) and irradiated with ultraviolet rays for 250 hours while maintaining the surface temperature of the coated substrate at 60 ° C. The change of the substrate with the transparent coating was observed and evaluated according to the following criteria.
No discoloration was observed. : ◎
Slight discoloration was observed. : ○
Clearly discoloration was observed. : △
A deep discoloration was observed. : ×
The stability of the modified silica-based sol (1), the refractive index of the modified silica-based particles, and the light resistance measurement results are shown in Table 1 together with the total oxide concentration, average particle diameter, pH, and the like.
改質シリカ系ゾル(2)の調製
実施例１において、塩基性硫酸鉄水溶液を８００ｇを用いた以外は同様にして改質シリカ系ゾル(2)を調製した。この改質シリカ系ゾル(2)は、酸化物合計濃度（ＳiＯ2＋Ｆe2Ｏ3）が１８.７重量％、平均粒子径１３ｎｍ、Ｆe2Ｏ3／ＳiＯ2モル比０.１６、ｐＨ１.４であった。粒径分布は均一であった。
実施例１と同様にして、改質シリカ系ゾル(2)の安定性、改質シリカ系粒子の屈折率、耐光性を測定し、結果を表１に示した。
Preparation of modified silica-based sol (2) A modified silica-based sol (2) was prepared in the same manner as in Example 1 except that 800 g of a basic iron sulfate aqueous solution was used. This modified silica-based sol (2) has a total oxide concentration (SiO 2 + Fe 2 O 3 ) of 18.7% by weight, an average particle diameter of 13 nm, a Fe 2 O 3 / SiO 2 molar ratio of 0.16, and a pH of 1. 4. The particle size distribution was uniform.
The stability of the modified silica-based sol (2), the refractive index of the modified silica-based particles, and the light resistance were measured in the same manner as in Example 1, and the results are shown in Table 1.
改質シリカ系ゾル(3)の調製
実施例１において、塩基性硫酸鉄水溶液を２００ｇを用いた以外は同様にして改質シリカ系ゾル(3)を調製した。この改質シリカ系ゾル(3)は、酸化物合計濃度（ＳiＯ2＋Ｆe2Ｏ3）が１９.６重量％、平均粒子径１２ｎｍ、Ｆe2Ｏ3／ＳiＯ2モル比０.０４、ｐＨ２.０であった。粒径分布は均一であった。
Preparation of modified silica-based sol (3) A modified silica-based sol (3) was prepared in the same manner as in Example 1 except that 200 g of a basic iron sulfate aqueous solution was used. This modified silica-based sol (3) has a total oxide concentration (SiO 2 + Fe 2 O 3 ) of 19.6% by weight, an average particle diameter of 12 nm, a Fe 2 O 3 / SiO 2 molar ratio of 0.04, and a pH of 2.0. 0. The particle size distribution was uniform.
改質シリカ系ゾル(4)の調製
塩基性硫酸鉄水溶液（多木化学（株）製：ダンパワー、ｐＨ２.５、Ｆe2Ｏ3濃度１６.４重量％）５００ｇを５Ｌの攪拌機付きガラス容器に採取し、温度２５℃にした。
別途、シリカゾル（触媒化成工業（株）製：カタロイドＳＩ-５０、ｐＨ９.５、ＳiＯ2濃度２０重量％、平均粒子径２５ｎｍ）に濃度４重量％の硫酸１００ｇを加えてｐＨを３.０とした。
ついで、塩基性硫酸鉄水溶液を攪拌しながら、これに２５℃のｐＨ調整したシリカゾル１５００ｇを２分間かけて添加した。その後、２５℃に保ちながら６０分間攪拌を継続して改質シリカ系ゾル(4)を調製した。
この改質シリカ系ゾル(4)は、酸化物合計濃度（ＳiＯ2＋Ｆe2Ｏ3）が１８.２重量％、平均粒子径３０ｎｍ、Ｆe2Ｏ3／ＳiＯ2モル比０.１０、ｐＨ１.４であった。粒径分布は均一であった。
Preparation basic iron sulfate aqueous solution of modified silica-based sol (4) (Taki Chemical Co., Ltd.: Danpawa, pH2.5, Fe 2 O 3 concentration of 16.4 wt%) 500 g of a stirrer with a glass container 5L The sample was collected and brought to a temperature of 25 ° C.
Separately, silica sol (Catalysts & Chemicals Industries Co., Ltd.: Cataloid SI-50, pH9.5, SiO 2 concentration of 20 wt%, average particle size 25 nm) and 3.0 to pH by adding a concentration of 4% by weight of sulfuric acid 100g did.
Next, while stirring the basic iron sulfate aqueous solution, 1500 g of silica sol having a pH adjusted at 25 ° C. was added over 2 minutes. Thereafter, stirring was continued for 60 minutes while maintaining at 25 ° C. to prepare a modified silica-based sol (4).
This modified silica-based sol (4) has a total oxide concentration (SiO 2 + Fe 2 O 3 ) of 18.2% by weight, an average particle diameter of 30 nm, a Fe 2 O 3 / SiO 2 molar ratio of 0.10, and a pH of 1. 4. The particle size distribution was uniform.
改質シリカ系ゾル(5)の調製
塩基性硫酸鉄水溶液（多木化学（株）製：ダンパワー-ＦＡ、ｐＨ２.１、Ｆe2Ｏ3濃度７.９重量％、Ａl2Ｏ3濃度４.７重量％）５００ｇを５Ｌの攪拌機付きガラス容器に採取し、温度４０℃にした。その後、攪拌しながら、この溶液に２５℃のシリカゾル（触媒化成工業（株）製：カタロイドＳＮ、ｐＨ３.０、ＳiＯ2濃度２０重量％、平均粒子径１２ｎｍ）１５００ｇを３０分間かけて添加した。その後、４０℃に保ちながら６０分間攪拌を継続して改質シリカ系ゾル(5)を調製した。この改質シリカ系ゾル(5)は、酸化物合計濃度（ＳiＯ2＋Ｆe2Ｏ3＋Ａl2Ｏ3）が１８.１重量％、平均粒子径１３ｎｍ、（Ｆe2Ｏ3＋Ａl2Ｏ3）／ＳiＯ2モル比０.０９、ｐＨ１.６であった。粒径分布は均一であった。
Preparation basic iron sulfate aqueous solution of modified silica-based sol (5) (Taki Chemical Co., Ltd.: Danpawa -FA, pH2.1, Fe 2 O 3 concentration of 7.9 wt%, Al 2 O 3 concentration of 4. (7 wt%) 500 g was collected in a 5 L glass container equipped with a stirrer, and the temperature was adjusted to 40 ° C. Thereafter, 1500 g of silica sol (manufactured by Catalytic Chemical Industry Co., Ltd .: Cataloid SN, pH 3.0, SiO 2 concentration 20 wt%, average particle diameter 12 nm) was added to this solution over 30 minutes while stirring. Thereafter, stirring was continued for 60 minutes while maintaining the temperature at 40 ° C. to prepare a modified silica-based sol (5). This modified silica-based sol (5) has a total oxide concentration (SiO 2 + Fe 2 O 3 + Al 2 O 3 ) of 18.1 wt%, an average particle diameter of 13 nm, (Fe 2 O 3 + Al 2 O 3 ) / The SiO 2 molar ratio was 0.09 and the pH was 1.6. The particle size distribution was uniform.
改質シリカ系ゾル(6)の調製
実施例１において、塩基性硫酸鉄水溶液５００ｇの代わりに塩基性塩化アルミニウム（多木化学（株）製：タンホワイト、ｐＨ３.７、Ａl2Ｏ3濃度２０.０重量％）５００ｇを用いた以外は同様にして改質シリカ系ゾル(6)を調製した。この改質シリカ系ゾル(6)は、酸化物合計濃度（ＳiＯ2＋Ａl2Ｏ3）が２０重量％、平均粒子径１３ｎｍ、Ａl2Ｏ3／ＳiＯ2モル比０.１９、ｐＨ２.６であった。粒径分布は均一であった。
Preparation of modified silica-based sol (6) In Example 1, instead of 500 g of the basic iron sulfate aqueous solution, basic aluminum chloride (manufactured by Taki Chemical Co., Ltd .: Tan White, pH 3.7, Al 2 O 3 concentration 20) 0.0 wt%) A modified silica-based sol (6) was prepared in the same manner except that 500 g was used. This modified silica-based sol (6) has an oxide total concentration (SiO 2 + Al 2 O 3 ) of 20% by weight, an average particle diameter of 13 nm, an Al 2 O 3 / SiO 2 molar ratio of 0.19, and a pH of 2.6. there were. The particle size distribution was uniform.
改質シリカ系ゾル(7)の調製
実施例１で得た改質シリカ系ゾル(1)１００ｇに塩基性硫酸鉄水溶液（多木化学（株）製：ダンパワー、ｐＨ２.５、Ｆe2Ｏ3濃度１６.４重量％）２０ｇを混合して改質シリカ系ゾル(7)を調製した。
この改質シリカ系ゾル(7)は、酸化物合計濃度（ＳiＯ2＋Ｆe2Ｏ3）が１８.６重量％、平均粒子径１３ｎｍ、Ｆe2Ｏ3／ＳiＯ2モル比０.１８、ｐＨ１.９であった。粒径分布は均一であった。
Preparation of modified silica sol (7) 100 g of the modified silica sol (1) obtained in Example 1 was added to a basic iron sulfate aqueous solution (manufactured by Taki Chemical Co., Ltd .: Danpower, pH 2.5, Fe 2 O 3 A modified silica-based sol (7) was prepared by mixing 20 g of a 16.4 wt% concentration.
The modified silica-based sol (7), an oxide total concentration (SiO 2 + Fe 2 O 3 ) 18.6% by weight, average particle diameter 13nm, Fe 2 O 3 / SiO 2 molar ratio 0.18, pH 1. It was 9. The particle size distribution was uniform.
改質シリカ系ゾル(8)の調製
実施例４において、シリカゾルの代わりにシリカ・アルミナゾル（触媒化成工業（株）製：ファインカタロイドＵＳＢＢ-１２０、ｐＨ１０.０、（ＳiＯ2＋Ａl2Ｏ3）濃度２０重量％、平均粒子径２５ｎｍ）に濃度４重量％の硫酸８０ｇを加えてｐＨを５.０として用いた以外は同様にして改質シリカ系ゾル(8)を調製した。粒径分布は均一であった。
この改質シリカ系ゾル(8)は、酸化物合計濃度（ＳiＯ2＋Ｆe2Ｏ3＋Ａl2Ｏ3）が１８.４重量％、平均粒子径２６ｎｍ、Ｆe2Ｏ3／（ＳiＯ2＋Ａl2Ｏ3）モル比０.１１、ｐＨ３.５であった。粒径分布は均一であった。
Preparation of modified silica-based sol (8) In Example 4, instead of silica sol, silica-alumina sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Fine Cataloid USBB-120, pH 10.0, (SiO 2 + Al 2 O 3 ) A modified silica-based sol (8) was prepared in the same manner except that 80 g of sulfuric acid having a concentration of 4% by weight was added to 20% by weight and an average particle diameter of 25 nm, and the pH was adjusted to 5.0. The particle size distribution was uniform.
The modified silica-based sol (8), an oxide total concentration (SiO 2 + Fe 2 O 3 + Al 2 O 3) 18.4% by weight, average particle diameter 26nm, Fe 2 O 3 / ( SiO 2 + Al 2 O 3 ) The molar ratio was 0.11, and the pH was 3.5. The particle size distribution was uniform.
シリカ系ゾル(R1)
シリカ系ゾル(R1)としてシリカゾル（触媒化成工業（株）製：カタロイドＳＮ、ｐＨ３.０、ＳiＯ2濃度２０重量％、平均粒子径１２ｎｍ）を用いた。粒径分布は均一であった。
Silica-based sol (R1)
As the silica-based sol (R1), silica sol (manufactured by Catalytic Chemical Industry Co., Ltd .: Cataloid SN, pH 3.0, SiO 2 concentration 20% by weight, average particle size 12 nm) was used. The particle size distribution was uniform.
シリカ系ゾル(R2)
シリカ系ゾル(R2)としてシリカゾル（触媒化成工業（株）製：カタロイドＳＩ-５０、ＳiＯ2濃度２０重量％、平均粒子径２５ｎｍ）を用いた。粒径分布は均一であった。
Silica-based sol (R2)
As silica-based sol (R2), silica sol (manufactured by Catalytic Chemical Industry Co., Ltd .: Cataloid SI-50, SiO 2 concentration 20% by weight, average particle diameter 25 nm) was used. The particle size distribution was uniform.
改質シリカ系ゾル(R3)の調製
実施例１において、塩基性硫酸鉄水溶液５００ｇの代わりに、ｐＨ１.１、Ｆe2Ｏ3濃度１６.４重量％の硫酸鉄水溶液（Ｆe2（ＳＯ４）3）５００ｇを用いた以外は同様にして改質シリカ系ゾル(R3)を調製した。この改質シリカ系ゾル(R3)は、酸化物合計濃度（ＳiＯ2＋Ｆe2Ｏ3）が１９.１重量％、Ｆe2Ｏ3／ＳiＯ2モル比０.１０、ｐＨ１.３であった。しかしながら、改質シリカ系ゾル(R3)は不安定で平均粒子径は５０ｎｍを越える凝集粒子であった。
In example 1 modified silica-based sol (R3), in place of the basic iron sulfate aqueous solution 500g, pH1.1, Fe 2 O 3 concentration of 16.4 wt% sulfuric acid aqueous solution of iron (Fe 2 (SO4) 3 A modified silica-based sol (R3) was prepared in the same manner except that 500 g was used. The modified silica-based sol (R3) had a total oxide concentration (SiO 2 + Fe 2 O 3 ) of 19.1% by weight, a Fe 2 O 3 / SiO 2 molar ratio of 0.10, and a pH of 1.3. However, the modified silica-based sol (R3) was unstable and was an aggregated particle having an average particle diameter exceeding 50 nm.
Claims (6)
[Ｍ2(ＯＨ)nＸ(2a-n)/b]m ・・・（１）
（式中、Ｍは１種または２種以上の３価および／または４価の金属カチオン、Ｘはアニオンであり、ａは金属カチオンの価数、ｂはアニオンの価数を示し、１≦ｎ≦７、ｎ＜２ａであり、１≦ｍ≦２０である。） A modified silica-based sol in which a basic metal compound represented by the following formula (1) is bonded to the surface of silica-based particles.
[M 2 (OH) n X (2a-n) / b ] m (1)
(Wherein M is one or more trivalent and / or tetravalent metal cations, X is an anion, a is the valence of the metal cation, b is the valence of the anion, and 1 ≦ n ≦ 7, n <2a, and 1 ≦ m ≦ 20.)
[Ｍ2(ＯＨ)nＸ(2a-n)/b]m ・・・（１）
（式中、Ｍは１種または２種以上の３価および／または４価の金属カチオン、Ｘはアニオンであり、ａは金属カチオンの価数、ｂはアニオンの価数を示し、１≦ｎ≦７、ｎ＜２ａであり、１≦ｍ≦２０である。） A method for producing a modified silica sol comprising adding a silica-based sol to a basic metal compound aqueous solution represented by the following formula (1) and mixing.
[M 2 (OH) n X (2a-n) / b ] m (1)
(Wherein M is one or more trivalent and / or tetravalent metal cations, X is an anion, a is the valence of the metal cation, b is the valence of the anion, and 1 ≦ n ≦ 7, n <2a, and 1 ≦ m ≦ 20.)
The method for producing a modified silica-based sol according to claim 5, wherein the pH of the mixed solution of the silica-based sol and the basic metal compound aqueous solution is adjusted to 0.1-5.
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| JP2015535798A (en) * | 2012-09-26 | 2015-12-17 | スリーエム イノベイティブ プロパティズ カンパニー | COATING COMPOSITION, Abrasion Resistant Composition, Abrasion Resistant Article, and Method for Producing the Same |
| CN110316737A (en) * | 2015-01-19 | 2019-10-11 | 福吉米株式会社 | Modified colloidal sifica and its manufacturing method and the grinding agent for using it |
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| JP2015535798A (en) * | 2012-09-26 | 2015-12-17 | スリーエム イノベイティブ プロパティズ カンパニー | COATING COMPOSITION, Abrasion Resistant Composition, Abrasion Resistant Article, and Method for Producing the Same |
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