JP2852487B2 - Titanium dioxide aqueous dispersion - Google Patents
Titanium dioxide aqueous dispersionInfo
- Publication number
- JP2852487B2 JP2852487B2 JP6071364A JP7136494A JP2852487B2 JP 2852487 B2 JP2852487 B2 JP 2852487B2 JP 6071364 A JP6071364 A JP 6071364A JP 7136494 A JP7136494 A JP 7136494A JP 2852487 B2 JP2852487 B2 JP 2852487B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- aqueous dispersion
- ultrafine
- dispersion
- ultrafine titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、超微粒子二酸化チタン
の水性分散体、その製造方法およびその用途に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous dispersion of ultrafine titanium dioxide, a method for producing the same and a use thereof.
【０００２】[0002]
【従来の技術】超微粒子二酸化チタンは、可視部透明
性、紫外線遮蔽能に優れ、かつ安全性が高いことから、
紫外線遮蔽剤として、化粧料、塗料、化学繊維に広く利
用されている。ところで、一般に、超微粒子二酸化チタ
ンは、一次粒子径が、０．１μｍ以下と非常に小さいた
め、凝集した粗大粒子になり易く、ことに超微粒子二酸
化チタンも製造過程で焼成処理が適用される場合は一層
強固に凝集した粗大粒子になり易く、このままでは本来
の紫外線遮蔽能、可視部透明性は十分には発揮され難
い。従って、このものを種々の用途適用媒体系において
使用するに際して多大の分散エネルギーの適用を必要と
するが、強力な分散エネルギーの適用は、用途適用媒体
系の配合成分の特性を損なうおそれがあって嫌忌されて
おり、そのために十分な紫外線遮蔽性能や可視部透明性
をもたらし得るに至っていない。これがため、かねてよ
り、用途適用系において比較的簡単な分散処理操作で高
分散度に配合し得、配合分散時の省エネルギー、工程簡
略化、粉塵発生の防止に有用な水性分散体の提供が強く
希求されている。2. Description of the Related Art Ultrafine titanium dioxide is excellent in transparency in the visible part, ultraviolet shielding ability and high safety.
As an ultraviolet shielding agent, it is widely used in cosmetics, paints, and chemical fibers. By the way, in general, ultrafine titanium dioxide has a very small primary particle diameter of 0.1 μm or less, so that it tends to become agglomerated coarse particles. Is liable to become more agglomerated coarse particles, and it is difficult to sufficiently exhibit the original ultraviolet shielding ability and visible part transparency. Therefore, when this is used in various application medium systems, a large amount of dispersion energy needs to be applied, but the application of strong dispersion energy may impair the properties of the components of the application medium system. It is disliked and has not yet been able to provide sufficient ultraviolet shielding performance and visible part transparency. For this reason, it has long been possible to provide an aqueous dispersion which can be blended with a high degree of dispersion by a relatively simple dispersion treatment operation in an application application system, and which is useful for energy saving at the time of blending and dispersing, simplifying the process, and preventing generation of dust. Wanted.
【０００３】これに対し、種々の提案がなされている例
えば特開平２−２１２３１５公報には、超微粒二酸化チ
タンをポリカルボン酸系分散剤の存在下で分散させて水
性分散体を調製する方法が提案されている。しかしなが
ら、前記方法による場合には、十分な固形分濃度の分散
体が得難く、また用途適用媒体系において電解質成分が
存在すると、二酸化チタン粒子が凝集系を惹起し易く、
所望の透明性や紫外線遮蔽特性を奏し難い。On the other hand, various proposals have been made, for example, in JP-A-2-212315, which discloses a method for preparing an aqueous dispersion by dispersing ultrafine titanium dioxide in the presence of a polycarboxylic acid-based dispersant. Proposed. However, in the case of the above method, it is difficult to obtain a dispersion having a sufficient solid content, and when an electrolyte component is present in the application medium system, the titanium dioxide particles easily cause an aggregation system,
It is difficult to achieve desired transparency and ultraviolet shielding properties.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、超微粒子二
酸化チタンが高固形分濃度で分散されていて、かつその
分散状態が電解質成分の影響を受け難い安定な二酸化チ
タン水性分散体を提供することにある。DISCLOSURE OF THE INVENTION The present invention provides a stable aqueous titanium dioxide dispersion in which ultrafine titanium dioxide is dispersed at a high solid content and whose dispersion state is hardly affected by electrolyte components. It is in.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、かねてよ
り種々の用途適用系で有用な超微粒子二酸化チタンの高
濃度水性分散体を提供すべく種々検討を進める過程で、
例えば化粧料などの用途適用系で使用される例えば塩化
ナトリウムや塩化カリウムなどの電解質成分の影響が極
めて大きいことに着目し、その影響を回避する二酸化チ
タン水性分散体を調製すべく、さらに検討を進めた結
果、疎水化処理された二酸化チタンを特定の界面活性剤
の存在下で分散して得られる水性分散体は、電解質成分
の存在する用途適用系で凝集系を惹起することなく、超
微粒子二酸化チタンに由来する透明性と紫外線遮蔽性の
性能を用途適用系で十分発揮し得ること、用途適用系で
の当該配合調製作業の効率化、工程簡略化、安全性など
を一層好ましいものとすることができることの知見を
得、本発明を完成したものである。Means for Solving the Problems The present inventors have been conducting various studies in order to provide a high-concentration aqueous dispersion of ultrafine titanium dioxide which is useful in various application systems.
Focusing on the extremely large effect of electrolyte components such as sodium chloride and potassium chloride used in application systems such as cosmetics, further study was conducted to prepare an aqueous dispersion of titanium dioxide to avoid the effect. As a result, the aqueous dispersion obtained by dispersing the hydrophobized titanium dioxide in the presence of a specific surfactant can be used as an ultrafine particle without causing an aggregation system in an application system in which an electrolyte component is present. The transparency and ultraviolet shielding performance derived from titanium dioxide can be sufficiently exhibited in the application system, and the efficiency of the compounding preparation work in the application system, the process simplification, the safety, etc. are made more preferable. The inventors have found that the present invention can be performed, and have completed the present invention.
【０００６】すなわち、本発明は、 １．分散媒としての水、超微粒子二酸化チタンおよび非
イオン性界面活性剤を含む水性分散体であって、該超微
粒子二酸化チタンの粒子表面が疎水化処理されたもので
ある二酸化チタン水性分散体。 ２．超微粒子二酸化チタンを、２０〜６０重量％含有し
ている前記１記載の二酸化チタン水性分散体。 ３．超微粒子二酸化チタンの平均一次粒子径が１０〜１
００ｎｍである前記１記載の二酸化チタン水性分散体。 ４．超微粒子二酸化チタンが、アルミニウム、珪素、ジ
ルコニウム、チタン、亜鉛およびスズの少なくとも１種
の酸化物または含水酸化物で被覆されている前記１記載
の二酸化チタン水性分散体。 ５．超微粒子二酸化チタンが、鉄成分を含有している前
記１記載の二酸化チタン水性分散体。 ６．超微粒子二酸化チタンの粒子表面が、シロキサン
類、シラン系、チタネート系、アルミニウム系またはフ
ッ素系のカップリング剤、高級脂肪酸類、高級アルコー
ル系および高級アルキル基を有するアミン類の少なくと
も１種で疎水化処理されたものである前記１記載の二酸
化チタン水性分散体。 ７．超微粒子二酸化チタンの粒子表面が、シロキサン類
および高級脂肪酸類の少なくとも１種で疎水化処理され
たものである前記１記載の二酸化チタン水性分散体。 ８．非イオン性界面活性剤が、超微粒子二酸化チタンの
重量基準に対して、１〜４０％である前記１記載の二酸
化チタン水性分散体。 ９．非イオン性界面活性剤が、ポリエーテル基を持つソ
ルビタンと高級脂肪酸とのエステルである前記１記載の
二酸化チタン水性分散体。 １０．非イオン性界面活性剤が、ポリエーテル変性ジメ
チルポリシロキサンである前記１記載の二酸化チタン水
性分散体。 １１．超微粒子二酸化チタンの粒子表面を疎水化処理
し、しかる後このものを非イオン性界面活性剤の存在下
で水性媒液に分散させてなる二酸化チタン水性分散体の
製造方法。 １２．水性媒液への分散を粉砕機で行なう前記１１記載
の二酸化チタン水性分散体の製造方法。 １３．前記１〜１０のいづれかの二酸化チタン水性分散
体を使用した紫外線遮蔽性化粧料。 １４．前記１〜１０のいづれかの二酸化チタン水性分散
体を使用した紫外線遮蔽性医薬品。 １５．前記１〜１０のいづれかの二酸化チタン水性分散
体を使用した紫外線遮蔽性塗料。That is, the present invention provides: An aqueous dispersion containing water as a dispersion medium, ultrafine titanium dioxide and a nonionic surfactant, wherein the surface of the ultrafine titanium dioxide particles is subjected to a hydrophobic treatment. 2. 2. The aqueous dispersion of titanium dioxide according to the above 1, which contains 20 to 60% by weight of ultrafine titanium dioxide. 3. Average primary particle diameter of ultrafine titanium dioxide is 10-1
2. The aqueous dispersion of titanium dioxide according to the above 1, which has a thickness of 00 nm. 4. 2. The aqueous titanium dioxide dispersion according to the above 1, wherein the ultrafine titanium dioxide is coated with at least one oxide or hydrated oxide of aluminum, silicon, zirconium, titanium, zinc and tin. 5. 2. The aqueous dispersion of titanium dioxide according to the above 1, wherein the ultrafine titanium dioxide contains an iron component. 6. The surface of the ultrafine titanium dioxide particles is hydrophobized with at least one of siloxanes, silanes, titanates, aluminum or fluorine coupling agents, higher fatty acids, higher alcohols and amines having higher alkyl groups. 2. The aqueous dispersion of titanium dioxide according to the above 1, which has been treated. 7. 2. The aqueous dispersion of titanium dioxide according to the above 1, wherein the particle surface of the ultrafine titanium dioxide is subjected to a hydrophobic treatment with at least one of siloxanes and higher fatty acids. 8. 2. The aqueous dispersion of titanium dioxide according to the above 1, wherein the nonionic surfactant is 1 to 40% based on the weight of the ultrafine titanium dioxide. 9. 2. The aqueous dispersion of titanium dioxide according to the above 1, wherein the nonionic surfactant is an ester of sorbitan having a polyether group and a higher fatty acid. 10. 2. The aqueous dispersion of titanium dioxide according to the above 1, wherein the nonionic surfactant is a polyether-modified dimethylpolysiloxane. 11. A process for producing an aqueous dispersion of titanium dioxide, comprising subjecting the surface of ultrafine titanium dioxide particles to a hydrophobizing treatment and then dispersing the particles in an aqueous medium in the presence of a nonionic surfactant. 12. 12. The method for producing an aqueous dispersion of titanium dioxide according to the above item 11, wherein the dispersion in the aqueous medium is performed by a pulverizer. 13. An ultraviolet shielding cosmetic using any one of the aqueous dispersions of titanium dioxide according to any one of the above 1 to 10. 14． An ultraviolet ray shielding drug using any one of the aqueous dispersions of titanium dioxide according to any one of 1 to 10 above. 15. An ultraviolet shielding paint using any one of the aqueous dispersions of titanium dioxide described in 1 to 10.
【０００７】本発明において、使用する超微粒子二酸化
チタンは、種々の方法で製造し得るが、例えば四塩化チ
タン水溶液をアルカリで中和加水分解し、得られた含水
二酸化チタンを焼成するか、あるいは含水二酸化チタン
を水酸化ナトリウムで加熱処理し、得られた反応生成物
を酸で加熱熟成して得ることができる。このものは、さ
らに必要に応じて焼成して粒子径や粒子形状の調整、さ
らに耐候性の向上をはかってもよい。In the present invention, the ultrafine titanium dioxide used can be produced by various methods. For example, an aqueous titanium tetrachloride solution is neutralized and hydrolyzed with an alkali, and the obtained hydrous titanium dioxide is calcined, or The hydrous titanium dioxide is heat-treated with sodium hydroxide, and the obtained reaction product can be obtained by heating and aging with an acid. This may be further baked, if necessary, to adjust the particle diameter and particle shape, and to further improve the weather resistance.
【０００８】なお、前記のようにして得られる超微粒子
二酸化チタンでは、紫外線Ａ波（４００〜３２０ｎｍ）
の遮蔽が不十分であったり、日焼け止め化粧料に配合し
て肌に塗布した場合に、しばしば青みの色調を与えて肌
を不健康に見せるきらいがある。このような場合には、
例えば、鉄含有超微粒子二酸化チタンを使用することが
有用である。前記鉄含有超微粒子二酸化チタンは、例え
ば、基体物質としてルチル核を有する微小チタニアゾル
を用い、このものの存在下に鉄の水溶性塩を中和して該
チタニアの表面に含水酸化鉄を沈殿、被覆させ、しかる
後３００〜８５０℃で焼成する方法、チタン塩の酸性水
溶液と鉄塩の酸性水溶液をアルカリ物質の存在下で同時
に加水分解させ、しかる後、加水分解生成物を３００〜
８００℃で焼成する方法などによって得られるものを使
用することができる。In the ultrafine titanium dioxide obtained as described above, ultraviolet A wave (400 to 320 nm)
Inadequately shielding or sunscreen cosmetics, when applied to the skin, often imparts a bluish hue to make the skin look unhealthy. In such a case,
For example, it is useful to use iron-containing ultrafine titanium dioxide. The iron-containing ultrafine titanium dioxide is, for example, using a fine titania sol having a rutile nucleus as a base substance, and neutralizing a water-soluble salt of iron in the presence of the substance to precipitate and coat iron-containing hydroxide on the surface of the titania. And then calcining at 300 to 850 ° C., an acidic aqueous solution of a titanium salt and an acidic aqueous solution of an iron salt are simultaneously hydrolyzed in the presence of an alkaline substance.
What is obtained by a method of firing at 800 ° C. can be used.
【０００９】次に前記のようにして得られた超微粒子二
酸化チタンを用いて、本発明の水性分散体とするために
は、，まず疎水化処理されることが重要である。疎水化
されていないと、非イオン性界面活性剤による分散は十
分になされない。本発明において、超微粒子二酸化チタ
ンの疎水化処理は、乾式、あるいは湿式で疎水性付与剤
を二酸化チタン粒子表面に処理することによってなされ
る。例えば、乾式法として、ミキサー等で攪拌されてい
る二酸化チタン粉体に、疎水性付与剤を、そのままある
いは溶剤で希釈して添加し、必要ならば加熱処理するこ
とによって行なうことができる。また、湿式法として
は、例えば、二酸化チタンがよく分散されたスラリー
に、疎水性付与剤の溶液または乳化分散液を加えて攪拌
し、濾過・乾燥する方法や、さらには疎水性付与剤の溶
解度のｐＨ依存性や温度依存性等を利用して、二酸化チ
タン表面に均一に処理する方法などで行なうこともでき
る。Next, in order to use the ultrafine titanium dioxide obtained as described above to make the aqueous dispersion of the present invention, it is important to first perform a hydrophobic treatment. If it is not hydrophobized, it will not be sufficiently dispersed by the nonionic surfactant. In the present invention, the hydrophobic treatment of the ultrafine titanium dioxide is performed by treating the surface of the titanium dioxide particles with a hydrophobicity-imparting agent in a dry or wet manner. For example, the dry method can be carried out by adding a hydrophobicity-imparting agent to a titanium dioxide powder stirred by a mixer or the like as it is or by diluting it with a solvent, and, if necessary, by heating. Examples of the wet method include, for example, a method of adding a solution of a hydrophobicity-imparting agent or an emulsified dispersion to a slurry in which titanium dioxide is well dispersed, stirring, filtering and drying, and a method of further dissolving the hydrophobicity-imparting agent. Titanium dioxide can be uniformly treated on the surface thereof by utilizing the pH dependence, temperature dependence, etc.
【００１０】また、疎水性付与剤としては、種々のもの
を使用しうるが、例えばジメチルポリシロキサン、メチ
ル水素ポリシロキサン、有機変性シリコーンオイルなど
のシロキサン類、シラン系カップリング剤、チタネート
系カップリング剤、アルミニウム系カップリング剤、フ
ッ素系カップリング剤などのカップリング剤、高級脂肪
酸類、高級アルコール類、高級アルキル基を有するアミ
ン類等が挙げられる。As the hydrophobicity-imparting agent, various ones can be used. For example, siloxanes such as dimethylpolysiloxane, methylhydrogenpolysiloxane, and organic-modified silicone oil, silane-based coupling agents, and titanate-based coupling agents can be used. Agents, coupling agents such as aluminum-based coupling agents and fluorine-based coupling agents, higher fatty acids, higher alcohols, amines having a higher alkyl group, and the like.
【００１１】処理される疎水性付与剤の量は、二酸化チ
タン粒子表面を均一に被覆できる最低量であることが望
ましい。処理量が少なく、均一に被覆されていないと、
分散体にしたときの分散が十分でなく、安定性にも劣る
ことになる。一方、処理量が多すぎると、余分な疎水性
付与剤が遊離して、分散体に著しい発泡が惹起し易く好
ましくない。処理量としては普通TiO2重量基準で０．５
〜８％、好ましくは２〜５％である。The amount of the hydrophobicity-imparting agent to be treated is desirably the minimum amount that can uniformly coat the surface of the titanium dioxide particles. If the throughput is small and not evenly coated,
Dispersion when formed into a dispersion is not sufficient, resulting in poor stability. On the other hand, if the treatment amount is too large, an excessive hydrophobicity-imparting agent is released, and remarkable foaming is easily caused in the dispersion, which is not preferable. The processing amount is usually 0.5 based on TiO 2 weight.
８8%, preferably 2-5%.
【００１２】疎水化処理される二酸化チタン粒子は、そ
の処理に先立って、予め、疎水性付与剤との親和性や耐
光性の向上をはかるべく、例えばアルミニウム、珪素、
ジルコニウム、チタン、亜鉛およびスズの少なくとも１
種の酸化物または含水酸化物を被覆してもよい。Prior to the treatment, the titanium dioxide particles to be subjected to the hydrophobizing treatment are, for example, made of aluminum, silicon, or the like in order to improve the affinity with the hydrophobicity-imparting agent and the light resistance.
At least one of zirconium, titanium, zinc and tin
Seed oxides or hydrated oxides may be coated.
【００１３】本発明において、使用する非イオン界面活
性剤は、種々のものを挙げることができるが、例えばポ
リオキシエチレンソルビタン脂肪酸エステル、ポリオキ
シエチレンアルキルエーテル、ポリオキシエチレン変性
ジメチルポリシロキサン等、主にエチレンオキサイド鎖
を親水基として有する界面活性剤、ソルビタン脂肪酸エ
ステル、ショ糖脂肪酸エステル等、主に非解離性水酸基
を親水基として有する界面活性剤である。In the present invention, various nonionic surfactants can be used. Examples of the nonionic surfactant include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, and polyoxyethylene-modified dimethylpolysiloxane. Surfactants mainly having a non-dissociable hydroxyl group as a hydrophilic group, such as a surfactant having an ethylene oxide chain as a hydrophilic group, a sorbitan fatty acid ester and a sucrose fatty acid ester.
【００１４】非イオン性界面活性剤の使用量は、二酸化
チタンの粒子径、非イオン性界面活性剤の種類などによ
って異なり、一概に言えないが、例えば、二酸化チタン
の重量基準で３％の含水酸化アルミニウムと３％のステ
アリン酸で表面を被覆された平均一次粒子径４０ｎｍの
超微粒子二酸化チタンを、ポリオキシエチレンソルビタ
ンモノステアレートを用いて、精製水に分散させるなら
ば、二酸化チタンの重量基準で１５〜２０％の配合量
が、分散性、粘度、安定性などの上で好ましい。The amount of the nonionic surfactant used depends on the particle size of the titanium dioxide, the type of the nonionic surfactant and the like, and cannot be specified unconditionally. For example, the amount of the nonionic surfactant is 3% by weight based on the weight of the titanium dioxide. If ultrafine titanium dioxide having an average primary particle diameter of 40 nm, the surface of which is coated with aluminum oxide and 3% stearic acid, is dispersed in purified water using polyoxyethylene sorbitan monostearate, the weight basis of titanium dioxide is used. Is preferable in terms of dispersibility, viscosity, stability and the like.
【００１５】本発明の二酸化チタン水性分散体には、必
要に応じて防腐剤、例えばアルキルパラベン等を添加す
ることができる。A preservative, for example, an alkyl paraben can be added to the aqueous titanium dioxide dispersion of the present invention, if necessary.
【００１６】次に、本発明の二酸化チタン水性分散体の
製造方法について述べる。本発明の二酸化チタン水性分
散体は、非イオン性界面活性剤を溶解した水性媒液に、
疎水化処理された超微粒子二酸化チタンを、種々の方法
によって分散させることによって得られるが、例えば羽
根型攪拌機、ディスパー、ホモミキサー等を用いて予備
混合した後、例えばサンドミル、ペブルミル、ディスク
ミル等の粉砕機を用いて、超微粒子二酸化チタンを分散
せしめることによって調製することができる。前記にお
いて疎水化処理された超微粒子二酸化チタンは、粉末を
使用してもよいが、疎水化処理を湿式で行った場合に
は、その工程途中の仕上げ乾燥前のケーキを使用しても
よい。この場合、乾燥による凝集を避けることができ、
分散体製造時の粉砕工程を簡略化できる。前記超微粒子
二酸化チタンの分散に際しては、粉砕機の種類、粉砕メ
ディアの選定、最適粉砕条件の設定は、高度な分散体を
調製する上で重要である。超微粒子二酸化チタンを十分
に分散し得るシェアーが付与されることが必要である
が、疎水性付与剤を剥離するほど強力であってはならな
い。例えば縦型、横型のサンドミルで直径１ｍｍのガラ
スビーズを用いて粉砕するのが望ましい。本発明の二酸
化チタン水性分散体を製造する際には、必要に応じて消
泡剤、例えば、ＨＬＢの小さい界面活性剤を添加するこ
とができる。Next, a method for producing the aqueous titanium dioxide dispersion of the present invention will be described. Titanium dioxide aqueous dispersion of the present invention, an aqueous medium in which a nonionic surfactant is dissolved,
Hydrophobized ultrafine titanium dioxide, obtained by dispersing by various methods, for example, after premixed using a blade-type stirrer, disper, homomixer, etc., for example, sand mill, pebble mill, disk mill, etc. It can be prepared by dispersing ultrafine titanium dioxide using a pulverizer. As the ultrafine titanium dioxide subjected to the hydrophobic treatment in the above, a powder may be used, but when the hydrophobic treatment is performed by a wet method, a cake before finish drying in the middle of the process may be used. In this case, aggregation due to drying can be avoided,
The pulverizing step at the time of manufacturing the dispersion can be simplified. In dispersing the ultrafine titanium dioxide, the type of the pulverizer, the selection of the pulverization medium, and the setting of the optimum pulverization conditions are important for preparing an advanced dispersion. It is necessary to provide a shear capable of sufficiently dispersing the ultrafine titanium dioxide, but it must not be so strong as to peel off the hydrophobicity-imparting agent. For example, it is desirable to grind with a vertical or horizontal sand mill using glass beads having a diameter of 1 mm. When producing the titanium dioxide aqueous dispersion of the present invention, an antifoaming agent, for example, a surfactant having a small HLB can be added as necessary.
【００１７】このようにして得られた二酸化チタン水性
分散体は、超微粒子二酸化チタンを非常によく分散され
た状態で含有し、その分散状態が電解質の影響をほとん
ど受けないために、紫外線遮蔽剤として、塗料、繊維、
化粧品、医薬品などに広くかつ有効に利用可能な材料で
ある。本発明の高濃度超微粒子二酸化チタン水性分散体
を日焼け止め化粧料として利用する場合には、例えば油
性成分、保湿剤、界面活性剤、顔料、香料、防腐剤、
水、アルコール類、増粘剤等と配合し、ローション状、
クリーム状、ペースト状、スティック状、乳液状など、
各種の形態で用いることができる。また、紫外線防止用
塗料として利用するには、例えばポリビニルアルコール
樹脂、塩ビー酢ビ樹脂、アクリル樹脂、エポキシ樹脂、
ウレタン樹脂、アルキッド樹脂、ポリエステル樹脂、エ
チレン酢酸ビニル共重合体、アクリルースチレン共重合
体、繊維素樹脂、フェノール樹脂、アミノ樹脂などに配
合され、水または溶媒中で分散される。The aqueous titanium dioxide dispersion thus obtained contains ultrafine titanium dioxide in a very dispersed state, and the dispersion state is hardly affected by the electrolyte. As paints, textiles,
It is a material that can be widely and effectively used in cosmetics and pharmaceuticals. When the high-concentration ultrafine titanium dioxide aqueous dispersion of the present invention is used as a sunscreen cosmetic, for example, an oily component, a humectant, a surfactant, a pigment, a fragrance, a preservative,
Formulated with water, alcohols, thickeners, etc.
Cream, paste, stick, emulsion, etc.
It can be used in various forms. In addition, in order to use as a coating for preventing ultraviolet rays, for example, polyvinyl alcohol resin, vinyl chloride vinyl chloride resin, acrylic resin, epoxy resin,
It is blended with urethane resin, alkyd resin, polyester resin, ethylene vinyl acetate copolymer, acryl-styrene copolymer, cellulose resin, phenol resin, amino resin, etc., and dispersed in water or a solvent.
【００１８】[0018]
【実施例】実施例１ 四塩化チタン水溶液（ＴｉＯ２２００ｇ／ｌ）を室温に
保持しながら、水酸化ナトリウム水溶液で中和してコロ
イド状の非晶質水酸化チタンを析出させ、その後熟成し
てルチル型の微小チタニアゾルを得た。このゾルを濾
過、洗浄し、得られた洗浄ケーキを６００℃で３時間焼
成し、サンドミルで湿式粉砕して、超微粒子二酸化チタ
ンのスラリーとした。このスラリーを７０℃に加熱して
この温度を保ち、よく攪拌しながらアルミン酸ナトリウ
ムをＡｌ２Ｏ３としてＴｉＯ２重量基準で３％添加、熟
成してアルミニウムの水和酸化物を該二酸化チタン粒子
上に沈殿、被覆させた。引き続き７０℃に保ってよく攪
拌しながら、この中にＴｉＯ２重量基準３％のステアリ
ン酸ナトリウムを投入、溶解し、熟成してから３０℃ま
で冷却してステアリン酸を該二酸化チタン粒子上に被覆
させた。これを濾過、洗浄し、乾燥したのち、ハンマー
タイプミルで粉砕して電子顕微鏡写真法による平均一次
粒子径４０ｎｍの超微粒子二酸化チタンを得た。精製水
４９重量部にポリオキシエチレン変性ジメチルポリシロ
キサン６重量部を加えて混合し、これを攪拌しながらこ
の中に前記の疎水化処理超微粒子二酸化チタン４５重量
部を徐々に投入、ディスーパーで十分に予備混合した。
つぎにこれをガラスビーズを粉砕メディアとして用いて
サンドミルで粉砕したところ、粘度２３０ｃＰの水性分
散体（Ａ）を得た。EXAMPLES Example 1 While maintaining an aqueous solution of titanium tetrachloride (TiO 2 200 g / l) at room temperature, it was neutralized with an aqueous solution of sodium hydroxide to precipitate colloidal amorphous titanium hydroxide, which was then aged. Thus, a rutile-type fine titania sol was obtained. This sol was filtered and washed, and the obtained washed cake was baked at 600 ° C. for 3 hours and wet-pulverized with a sand mill to obtain a slurry of ultrafine titanium dioxide. The slurry was heated to 70 ° C. and maintained at this temperature, and sodium aluminate was added as Al 2 O 3 at 3% by weight based on TiO 2 while agitating well, and the mixture was aged to hydrate the aluminum hydrated oxide and obtain the titanium dioxide particles. Precipitated and coated on top. Then, while maintaining the temperature at 70 ° C. and stirring well, 3% by weight of TiO 2 sodium stearate is added and dissolved therein, and the mixture is aged and cooled to 30 ° C. to coat the stearic acid on the titanium dioxide particles. I let it. This was filtered, washed, dried, and then pulverized with a hammer type mill to obtain ultrafine titanium dioxide having an average primary particle diameter of 40 nm as measured by electron micrograph. 6 parts by weight of polyoxyethylene-modified dimethylpolysiloxane was added to 49 parts by weight of purified water and mixed. While stirring, 45 parts by weight of the above-mentioned hydrophobized ultrafine titanium dioxide was gradually added thereto. Premix well.
Next, when this was pulverized by a sand mill using glass beads as a pulverizing medium, an aqueous dispersion (A) having a viscosity of 230 cP was obtained.
【００１９】実施例２ 実施例１の超微粒子二酸化チタンスラリー（ＴｉＯ2 ２
００ｇ／ｌ）を７０℃に加熱した後よく攪拌しながらケ
イ酸ナトリウムをＳｉＯ2 としてTiO2重量基準で４％添
加し、引き続き熟成してケイ素の水和酸化物を該二酸化
チタン粒子上に沈殿、被覆させた。更に、このスラリー
をよく攪拌しながら、アルミン酸ナトリウムをＡｌ2 Ｏ
3 としてＴｉＯ2 重量基準で２％添加し、引き続き熟成
してアルミニウムの水和酸化物を該二酸化チタン粒子上
に沈殿、被覆させた。その固形分を濾過、洗浄し、洗浄
ケーキを乾燥したのちハンマータイプミルで粉砕して超
微粒子二酸化チタン粉末を得た。この超微粒子二酸化チ
タン粉末をヘンシェルミキサーで攪拌しながら、この中
にメチル水素ポリシロキサンをＴｉＯ2 重量基準で３％
添加し、引き続き１５０℃で加熱処理して疎水化した。
精製水４９重量部にポリオキシエチレンソルビタンモノ
ステアレート６重量部を加えて混合し、これを攪拌しな
がらこの中に前記の疎水化処理超微粒子二酸化チタン４
５重量部を徐々に投入、ディスーパーで十分に予備混合
した。つぎに、これをガラスビーズを粉砕メディアとし
て用い、サンドミルで粉砕したところ、粘度２６０ｃＰ
の水性分散体（Ｂ）を得た。[0019] Example 2 ultrafine titanium dioxide slurry of Example 1 (TiO 2 2
After heating to 70 ° C., sodium silicate was added as 4% by weight as SiO 2 and 4% by weight based on TiO 2 , followed by aging to precipitate hydrated oxides of silicon on the titanium dioxide particles. , Coated. Further, while stirring this slurry well, sodium aluminate was added to Al 2 O
3 as added 2% TiO 2 by weight, subsequently aged to precipitate the aluminum hydrated oxide on the titanium dioxide particles were coated. The solid content was filtered and washed, and the washed cake was dried and then pulverized with a hammer type mill to obtain ultrafine titanium dioxide powder. While stirring this ultrafine titanium dioxide powder with a Henschel mixer, 3% by weight of methyl hydrogen polysiloxane was added thereto based on TiO 2 weight.
The mixture was added and subsequently heated at 150 ° C. to make it hydrophobic.
6 parts by weight of polyoxyethylene sorbitan monostearate was added to 49 parts by weight of purified water and mixed, and the resulting mixture was stirred while stirring.
5 parts by weight were gradually added, and the mixture was sufficiently preliminarily mixed in a dispenser. Next, when this was crushed by a sand mill using glass beads as a crushing medium, the viscosity was 260 cP.
Thus, an aqueous dispersion (B) was obtained.
【００２０】実施例３ 実施例１で使用したルチル型微小チタニアゾルを濾過、
洗浄した後、ＴｉＯ２として２００ｇ／ｌの濃度の含水
チタン水性スラリーとした。このスラリーを７０℃に加
熱し、よく攪拌しながら、この中にＴｉＯ２に対してＦ
ｅとして７重量％の硫酸第一鉄水溶液（Ｆｅ濃度５０ｇ
／ｌ）を３０分を要して添加した後、水酸化ナトリウム
水溶液を４０分を要して添加てｐＨ９に調整して含水酸
化チタン粒子表面に含水酸化鉄を沈殿、被覆させた。そ
の後６０分間熟成し、濾過、洗浄した。得られた洗浄ケ
ーキを６００℃で３時間焼成し、サンドミルで湿式粉砕
して、超微粒子二酸化チタンのスラリーとした。 ひき
つづき、実施例１と同様にしてＡｌ２Ｏ３とステアリン
酸を二酸化チタン粒子上に沈殿、被覆し、これを濾過、
洗浄し、乾燥したのち、ハンマータイプミルで粉砕して
電子顕微鏡写真法による平均一次粒子径４０ｎｍの超微
粒子二酸化チタンを得た。精製水４９重量部にポリオキ
シエチレン変性ジメチルポリシロキサン６重量部を加え
て混合し、これを攪拌しながらこの中に前記の疎水化処
理超微粒子二酸化チタン４５重量部を徐々に投入、ディ
スーパーで十分に予備混合した。つぎにこれをガラスビ
ーズを粉砕メディアとして用いてサンドミルで粉砕した
ところ、粘度１５０ｃＰの水性分散体（Ｃ）を得た。Example 3 The rutile microtitania sol used in Example 1 was filtered and
After washing, a hydrated titanium aqueous slurry having a concentration of 200 g / l as TiO 2 was obtained. The slurry was heated to 70 ° C., with good stirring, F relative TiO 2 in this
e as a 7% by weight aqueous ferrous sulfate solution (Fe concentration 50 g)
/ L) was added over a period of 30 minutes, and an aqueous solution of sodium hydroxide was added over a period of 40 minutes to adjust the pH to 9, to precipitate and coat the surface of the hydrous titanium oxide particles with hydrous iron oxide. After aging for 60 minutes, the mixture was filtered and washed. The obtained washed cake was baked at 600 ° C. for 3 hours, and wet-pulverized with a sand mill to obtain a slurry of ultrafine titanium dioxide. Subsequently, Al 2 O 3 and stearic acid were precipitated and coated on the titanium dioxide particles in the same manner as in Example 1, and this was filtered,
After being washed and dried, it was pulverized with a hammer type mill to obtain ultrafine titanium dioxide having an average primary particle diameter of 40 nm as measured by electron microscopy. 6 parts by weight of polyoxyethylene-modified dimethylpolysiloxane was added to 49 parts by weight of purified water and mixed. While stirring, 45 parts by weight of the above-mentioned hydrophobized ultrafine titanium dioxide was gradually added thereto. Premix well. Next, when this was pulverized by a sand mill using glass beads as a pulverizing medium, an aqueous dispersion (C) having a viscosity of 150 cP was obtained.
【００２１】比較例１ 精製水４９重量部に塩化ステアリルトリメチルアンモニ
ウム６重量部を加えて混合し、これを攪拌しながらこの
中に実施例１で使用の超微粒子二酸化チタン４５重量部
を徐々に投入、ディスーパーで十分に予備混合した。つ
ぎに、これをガラスビーズを粉砕メディアとして用い、
サンドミルで粉砕したところ、粘度５８ｃＰの水性分散
体（Ｄ）を得たComparative Example 1 6 parts by weight of stearyltrimethylammonium chloride was added to 49 parts by weight of purified water and mixed. While stirring, 45 parts by weight of the ultrafine titanium dioxide used in Example 1 was gradually added thereto. And pre-mixed well in a dispenser. Next, using this as a grinding medium with glass beads,
When pulverized by a sand mill, an aqueous dispersion (D) having a viscosity of 58 cP was obtained.
【００２２】比較例２ 実施例１において、ステアリン酸ナトリウムの添加を省
いて水性分散体を調製しようと試みたが、予備混合の段
階で全く流動性がなくなり、サンドミルによる分散が不
可能となった。そこで、超微粒子二酸化チタンの使用量
４５重量部を２３重量部に減量した。即ち、精製水７４
重量部にポリオキシエチレン変性ジメチルポリシロキサ
ン３重量部を加えて混合し、これを攪拌しながらこの中
に実施例１においてステアリン酸ナトリウムの添加を省
いて得られた超微粒子二酸化チタン２３重量部を徐々に
投入し、ディスーパーで十分に予備混合した。つぎに、
これをガラスビーズを粉砕メディアとして用い、サンド
ミルで粉砕したところ、粘度５３０ｃＰの水性分散体
（Ｅ）を得た。Comparative Example 2 In Example 1, an attempt was made to prepare an aqueous dispersion by omitting the addition of sodium stearate. However, at the stage of premixing, there was no fluidity at all, and dispersion by a sand mill became impossible. . Therefore, the used amount of ultrafine titanium dioxide was reduced from 45 parts by weight to 23 parts by weight. That is, the purified water 74
3 parts by weight of polyoxyethylene-modified dimethylpolysiloxane was added to and mixed with parts by weight, and while stirring, 23 parts by weight of ultrafine titanium dioxide obtained by omitting the addition of sodium stearate in Example 1 was added thereto while stirring. Gradually, the mixture was preliminarily mixed in a supermarket. Next,
This was pulverized with a sand mill using glass beads as a pulverizing medium, to obtain an aqueous dispersion (E) having a viscosity of 530 cP.
【００２３】試験例 試験例１ 超微粒子二酸化チタン水性分散体を、５％食塩水で４０
ｍｇ／ｌに希釈し、１ｃｍのセルに入れて分光光度計に
て波長７５０〜３００ｎｍの紫外線の吸光度を測定、吸
収係数を算出し、精製水で同様に希釈して測定した吸収
係数と比較した。この結果を表１に示した。Test Example Test Example 1 An ultrafine titanium dioxide aqueous dispersion was treated with a 5% saline solution for 40 minutes.
mg / l, put into a 1 cm cell, measure the absorbance of ultraviolet light having a wavelength of 750 to 300 nm with a spectrophotometer, calculate the absorption coefficient, and compare it with the absorption coefficient measured by dilution with purified water in the same manner. . The results are shown in Table 1.
【００２４】[0024]
【表１】 [Table 1]
【００２５】試験例２ 超微粒子二酸化チタン水性分散体を下記の処方で配合し
て日焼け止めクリーム（Ｏ／Ｗエマルジョン）を得た。 （１）ステアリン酸 ３．５重量部 （２）サラシミツロウ ５．０重量部 （３）セタノール ５．０重量部 （４）スクワラン ２０．０重量部 （５）モノステアリン酸グリセリン ３．５重量部 （６）ポリオキシエチレンソルビタンモノステアレート ２．５重量部 （７）二酸化チタン水性分散体 ＴｉＯ2 として６．０重量部 （８）塩化ナトリウム ３．０重量部 （９）メチルパラベン ０．１重量部 （１０）グリセリン １７．０重量部 （１１）トリエタノールアミン １．５重量部 （１２）精製水 残部 （１３）香料 ０．３重量部 成分（１）〜（８）を８０℃で加熱混合したものを、成
分（９）〜（１２）を８０℃で加熱混合したものに加
え、ホモミキサーでよく混合し、強く攪拌する。４５℃
付近で（１３）を添加し日焼け止めクリームを調整し
た。このクリームを石英ガラス板上に１２μｍとなるよ
うに塗布し、分光光度計にて７５０〜３００ｎｍの透過
率を測定した。この試験結果を表２に示した。Test Example 2 An ultrafine titanium dioxide aqueous dispersion was blended according to the following formulation to obtain a sunscreen cream (O / W emulsion). (1) 3.5 parts by weight of stearic acid (2) 5.0 parts by weight of beeswax (3) 5.0 parts by weight of cetanol (4) 20.0 parts by weight of squalane (5) 3.5 parts by weight of glycerin monostearate (6) Polyoxyethylene sorbitan monostearate 2.5 parts by weight (7) Titanium dioxide aqueous dispersion 6.0 parts by weight as TiO 2 (8) Sodium chloride 3.0 parts by weight (9) Methyl paraben 0.1 parts by weight (10) Glycerin 17.0 parts by weight (11) Triethanolamine 1.5 parts by weight (12) Purified water remainder (13) Perfume 0.3 parts by weight Components (1) to (8) were heated and mixed at 80 ° C. The components are added to a mixture obtained by heating and mixing components (9) to (12) at 80 ° C., mixed well with a homomixer, and stirred vigorously. 45 ° C
In the vicinity, (13) was added to prepare a sunscreen cream. This cream was applied on a quartz glass plate so as to have a thickness of 12 μm, and the transmittance at 750 to 300 nm was measured with a spectrophotometer. The test results are shown in Table 2.
【００２６】[0026]
【表２】 [Table 2]
【００２７】[0027]
【発明の効果】本発明の二酸化チタン水性分散体は、電
解質成分の存在する種々の用途適用系で凝集系を惹起す
ることなく、超微粒子二酸化チタンとの優れた可視光透
明性や紫外線遮蔽性を用途適用系で十分発揮する上で極
めて有用な高濃度水性分散体であって、用途適用系での
配合調製作業の効率化、工程の簡略化、安全性を図る上
で工業的に甚だ有用なものである。The titanium dioxide aqueous dispersion of the present invention has excellent visible light transparency and ultraviolet shielding properties with ultrafine titanium dioxide without causing an agglomeration system in various application systems where an electrolyte component is present. Is a highly concentrated aqueous dispersion that is extremely useful for fully exhibiting application in application systems, and is extremely industrially useful for improving the efficiency of formulation and preparation work, simplifying processes, and ensuring safety in application systems. It is something.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C01G 23/047 A61K 7/02 B01J 13/00──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. 6 , DB name) C01G 23/047 A61K 7/02 B01J 13/00
Claims (15)
および非イオン性界面活性剤を含む水性分散体であっ
て、該超微粒子二酸化チタンの粒子表面が疎水化処理さ
れたものである二酸化チタン水性分散体。1. An aqueous dispersion containing water as a dispersion medium, ultrafine titanium dioxide and a nonionic surfactant, wherein the surface of the ultrafine titanium dioxide particles is subjected to a hydrophobic treatment. Aqueous dispersion.
％含有している請求項１記載の二酸化チタン水性分散
体。2. The aqueous dispersion of titanium dioxide according to claim 1, which contains 20 to 60% by weight of ultrafine titanium dioxide.
１０〜１００ｎｍである請求項１記載の二酸化チタン水
性分散体。3. The aqueous dispersion of titanium dioxide according to claim 1, wherein the average primary particle diameter of the ultrafine titanium dioxide is 10 to 100 nm.
珪素、ジルコニウム、チタン、亜鉛およびスズの少なく
とも１種の酸化物または含水酸化物で被覆されている請
求項１記載の二酸化チタン水性分散体。4. The ultrafine titanium dioxide is aluminum,
2. The aqueous dispersion of titanium dioxide according to claim 1, which is coated with at least one oxide or hydrated oxide of silicon, zirconium, titanium, zinc and tin.
ている請求項１記載の二酸化チタン水性分散体。5. The titanium dioxide aqueous dispersion according to claim 1, wherein the ultrafine titanium dioxide contains an iron component.
キサン類、シラン系、チタネート系、アルミニウム系ま
たはフッ素系のカップリング剤、高級脂肪酸類、高級ア
ルコール系および高級アルキル基を有するアミン類の少
なくとも１種で疎水化処理されたものである請求項１記
載の二酸化チタン水性分散体。6. The particle surface of ultrafine titanium dioxide has at least one of siloxanes, silanes, titanates, aluminum or fluorine coupling agents, higher fatty acids, higher alcohols and amines having higher alkyl groups. 2. The aqueous dispersion of titanium dioxide according to claim 1, wherein the dispersion is one kind subjected to a hydrophobic treatment.
キサン類および高級脂肪酸類の少なくとも１種で疎水化
処理されたものである請求項１記載の二酸化チタン水性
分散体。7. The aqueous dispersion of titanium dioxide according to claim 1, wherein the particle surface of the ultrafine titanium dioxide is subjected to a hydrophobic treatment with at least one of siloxanes and higher fatty acids.
チタンの重量基準に対して、１〜４０％である請求項１
記載の二酸化チタン水性分散体。8. The method according to claim 1, wherein the amount of the nonionic surfactant is 1 to 40% based on the weight of the ultrafine titanium dioxide.
The aqueous dispersion of titanium dioxide as described in the above.
を持つソルビタンと高級脂肪酸とのエステルである請求
項１記載の二酸化チタン水性分散体。9. The aqueous dispersion of titanium dioxide according to claim 1, wherein the nonionic surfactant is an ester of sorbitan having a polyether group and a higher fatty acid.
変性ジメチルポリシロキサンである請求項１記載の二酸
化チタン水性分散体。10. The aqueous dispersion of titanium dioxide according to claim 1, wherein the nonionic surfactant is a polyether-modified dimethylpolysiloxane.
化処理し、しかる後このものを非イオン性界面活性剤の
存在下で水性媒液に分散させてなる二酸化チタン水性分
散体の製造方法。11. A process for producing an aqueous dispersion of titanium dioxide, comprising subjecting the surface of ultrafine titanium dioxide particles to a hydrophobizing treatment and then dispersing the particles in an aqueous medium in the presence of a nonionic surfactant.
項１１記載の二酸化チタン水性分散体の製造方法。12. The method for producing an aqueous dispersion of titanium dioxide according to claim 11, wherein the dispersion in the aqueous medium is performed by a pulverizer.
ン水性分散体を使用した紫外線遮蔽性化粧料。13. An ultraviolet shielding cosmetic comprising the aqueous dispersion of titanium dioxide according to claim 1.
ン水性分散体を使用した紫外線遮蔽性医薬品。14. An ultraviolet-screening pharmaceutical product using the aqueous dispersion of titanium dioxide according to claim 1.
ン水性分散体を使用した紫外線遮蔽性塗料。15. An ultraviolet shielding paint using the aqueous dispersion of titanium dioxide according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6071364A JP2852487B2 (en) | 1994-03-15 | 1994-03-15 | Titanium dioxide aqueous dispersion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6071364A JP2852487B2 (en) | 1994-03-15 | 1994-03-15 | Titanium dioxide aqueous dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07247119A JPH07247119A (en) | 1995-09-26 |
| JP2852487B2 true JP2852487B2 (en) | 1999-02-03 |
Family
ID=13458379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6071364A Expired - Lifetime JP2852487B2 (en) | 1994-03-15 | 1994-03-15 | Titanium dioxide aqueous dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2852487B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006104342A (en) * | 2004-10-06 | 2006-04-20 | Shin Etsu Chem Co Ltd | Surface-treated inorganic powder, method for treating surface of inorganic powder and cosmetic |
| KR20160115922A (en) | 2014-02-20 | 2016-10-06 | 사까이가가꾸고오교가부시끼가이샤 | Aqueous dispersion of inorganic powder particles subjected to hydrophobic organic surface treatment, and cosmetic including same |
| US10717297B2 (en) | 2013-12-26 | 2020-07-21 | Ricoh Company, Ltd. | Inkjet recording method and inkjet recording apparatus |
| CN111961304A (en) * | 2020-08-21 | 2020-11-20 | 安徽江淮汽车集团股份有限公司 | Polymethyl methacrylate composite material and preparation method thereof |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3237855B2 (en) * | 1996-12-18 | 2001-12-10 | ザ、プロクター、エンド、ギャンブル、カンパニー | Stable high SPF foundation |
| US5891237A (en) * | 1997-10-08 | 1999-04-06 | Millennium Inorganic Chemicals, Ltd. | Production of free flowing spheres using partially neutralized fatty acid |
| JP3693317B2 (en) * | 1998-05-21 | 2005-09-07 | レジノカラー工業株式会社 | Bath preparation composition |
| GB0323665D0 (en) * | 2003-10-09 | 2003-11-12 | Ici Plc | Water-in-silicone oil emulsion |
| JP5109122B2 (en) * | 2007-02-28 | 2012-12-26 | 国立大学法人 千葉大学 | Fluid composition |
| JP5000684B2 (en) * | 2009-05-20 | 2012-08-15 | 信越化学工業株式会社 | Method for producing titanium oxide fine particle dispersion |
| JP5327714B2 (en) * | 2009-07-30 | 2013-10-30 | Ｔｏｔｏ株式会社 | Photocatalyst-coated body and photocatalyst coating liquid |
| WO2011037238A1 (en) * | 2009-09-27 | 2011-03-31 | アクテイブ株式会社 | Resin composition for carbon dioxide emission reduction, method for producing same, and use thereof |
| US8986580B2 (en) | 2010-05-18 | 2015-03-24 | Shin-Etsu Chemical Co., Ltd. | Visible-light-responsive titanium oxide microparticle dispersion, and process for production thereof |
| JP5617489B2 (en) * | 2010-09-28 | 2014-11-05 | 旭硝子株式会社 | Method for producing coating composition and coated article |
| JP5633571B2 (en) * | 2010-10-08 | 2014-12-03 | 信越化学工業株式会社 | Method for producing rutile type titanium oxide fine particle dispersion |
| KR20140025454A (en) | 2011-05-24 | 2014-03-04 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Method for manufacturing microparticulate anatase or rutile titanium oxide dispersion and component having photocatalytic thin film on surface |
| JPWO2013018827A1 (en) * | 2011-08-03 | 2015-03-05 | 堺化学工業株式会社 | Dispersion |
| JP5655827B2 (en) | 2011-11-14 | 2015-01-21 | 信越化学工業株式会社 | Visible light responsive titanium oxide fine particle dispersion, method for producing the same, and member having a photocatalytic thin film formed on the surface using the dispersion |
| CN104640630B (en) | 2012-09-19 | 2017-10-24 | 信越化学工业株式会社 | Visible-light-responsive photocatalyst particle dispersion liquid, its manufacture method and the part on surface with photocatalyst film |
| KR102170489B1 (en) | 2013-10-16 | 2020-10-28 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Dispersion liquid of titanium oxide-tungsten oxide composite photocatalytic fine particles, production method for same, and member having photocatalytic thin film on surface thereof |
| CN103919693A (en) * | 2014-03-26 | 2014-07-16 | 上海得高实业有限公司 | Water dispersible powder syrup for oleophylic treatment and product applying powder syrup |
| JP6682200B2 (en) * | 2015-05-29 | 2020-04-15 | テイカ株式会社 | Surface-treated powder, water-dispersible cosmetic composition using the surface-treated powder, and O / W type cosmetic using the surface-treated powder |
| JP6949823B2 (en) * | 2016-03-28 | 2021-10-13 | 株式会社Uacj | Paints, printing materials for dot printing and PTP packaging |
| JP6733312B2 (en) * | 2016-05-27 | 2020-07-29 | 堺化学工業株式会社 | Liquid dispersion and its use |
| JP6733326B2 (en) * | 2016-06-09 | 2020-07-29 | 堺化学工業株式会社 | Liquid dispersion and its use |
| MX2018016028A (en) * | 2016-07-05 | 2019-09-09 | Timilon Tech Acquisitions Llc | Compositions and methods for forming stable, liquid metal oxide/hydroxide formulations. |
| EP3747965B1 (en) | 2018-01-29 | 2024-02-28 | Ishihara Sangyo Kaisha, Ltd. | Titanium dioxide aqueous dispersion and method for producing same |
| CN111683904B (en) * | 2018-05-23 | 2023-05-02 | 株式会社高丝 | Novel titanium oxide powder and cosmetic matched with same |
| CN113698769B (en) * | 2021-07-26 | 2023-03-24 | 广东天跃新材料股份有限公司 | Silicone rubber leather material for medical industry and preparation method thereof |
-
1994
- 1994-03-15 JP JP6071364A patent/JP2852487B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006104342A (en) * | 2004-10-06 | 2006-04-20 | Shin Etsu Chem Co Ltd | Surface-treated inorganic powder, method for treating surface of inorganic powder and cosmetic |
| US10717297B2 (en) | 2013-12-26 | 2020-07-21 | Ricoh Company, Ltd. | Inkjet recording method and inkjet recording apparatus |
| KR20160115922A (en) | 2014-02-20 | 2016-10-06 | 사까이가가꾸고오교가부시끼가이샤 | Aqueous dispersion of inorganic powder particles subjected to hydrophobic organic surface treatment, and cosmetic including same |
| JPWO2015125622A1 (en) * | 2014-02-20 | 2017-03-30 | 堺化学工業株式会社 | Hydrophobic organic surface-treated fine particle inorganic powder aqueous dispersion and cosmetic containing the same |
| CN111961304A (en) * | 2020-08-21 | 2020-11-20 | 安徽江淮汽车集团股份有限公司 | Polymethyl methacrylate composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07247119A (en) | 1995-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2852487B2 (en) | Titanium dioxide aqueous dispersion | |
| JP2781433B2 (en) | Aqueous dispersion system of titanium dioxide and method for producing the same | |
| JPH0661457B2 (en) | Oil dispersion and method for producing the same | |
| US8668955B2 (en) | Single step milling and surface coating process for preparing stable nanodispersions | |
| EP0684208B1 (en) | Ultrafine iron-containing rutile titanium dioxide particle and process for producing the same | |
| JP3224750B2 (en) | Fine particle titanium dioxide silicone dispersion | |
| KR100791555B1 (en) | A disperse system having fine powder-typed inorganic metal oxide dispersed in water and preparing method for the same | |
| JPH11193354A (en) | Silica-coated zinc oxide particle, its preparation, and composition containing it | |
| KR100831820B1 (en) | Metal oxide/silica composite and cosmetic comprising the same | |
| KR20050111621A (en) | Porous titanium oxide powder and method for production thereof | |
| JP3020408B2 (en) | High concentration titanium dioxide aqueous dispersion | |
| JPH1081517A (en) | Superfine titanium oxide and its production | |
| JP7185143B2 (en) | Titanium dioxide aqueous dispersion and method for producing the same | |
| JP2717904B2 (en) | Iron-containing ultrafine rutile titanium dioxide and method for producing the same | |
| JP2001058821A (en) | Zinc oxide particle having suppressed surface activity, its production and utilization thereof | |
| JP2008273760A (en) | Method for producing surface-coated zinc oxide | |
| JP3115760B2 (en) | Iron-containing ultrafine titanium dioxide dispersion | |
| JPH02194065A (en) | Minute titanium dioxide composition | |
| JP4256133B2 (en) | Method for producing acicular titanium dioxide fine particles | |
| JP2852482B2 (en) | Iron-containing titanium dioxide and method for producing the same | |
| JPH07751B2 (en) | Fine particle titanium dioxide powder | |
| JPH09175821A (en) | Spindle-shaped fine particle titanium dioxide and its production | |
| JP3401039B2 (en) | Cosmetics | |
| JP4275796B2 (en) | Method for producing zinc oxide dispersion | |
| JPH10139434A (en) | Production of spindle-type titanium dioxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081120 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081120 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091120 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101120 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101120 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101120 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111120 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111120 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121120 Year of fee payment: 14 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131120 Year of fee payment: 15 |
|
| EXPY | Cancellation because of completion of term |