JP3848458B2 - Method for producing UV blocker - Google Patents
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- JP3848458B2 JP3848458B2 JP06105498A JP6105498A JP3848458B2 JP 3848458 B2 JP3848458 B2 JP 3848458B2 JP 06105498 A JP06105498 A JP 06105498A JP 6105498 A JP6105498 A JP 6105498A JP 3848458 B2 JP3848458 B2 JP 3848458B2
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- zinc oxide
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- ultraviolet blocking
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【０００１】
【発明の属する技術分野】
本発明は、触媒活性がなく安定で、可視領域において透明性が高く、優れた紫外線遮断性を有する紫外線遮断剤及びその製造方法に関する。
【０００２】
【従来の技術】
紫外線はプラスチックの劣化を招き、人体に対しても悪影響を及ぼす。そのため、種々の有機系・無機系紫外線遮断剤が開発されており、これらはプラスチックや化粧品等に配合されている。
有機系紫外線遮断剤には、サリチル酸系、ベンゾトリアゾール系、シアノアクリレート系、ケイ皮酸系、ジベンゾイルメタン系等の種類があるが、いずれも耐熱性・耐候性、大量配合あるいは分解した際にできる生成物の安全性等の改善が課題となっている。
一方、無機系紫外線遮断剤には、微粒子酸化チタンや微粒子酸化亜鉛等があるが、いずれも分散性や触媒活性の改善が課題となっている。そこで、これらの課題を解決するため、シリカ・酸化セリウム複合粒子（特開平９−１１８６１０号公報）が開発されている。
【０００３】
一般に、紫外線は波長が３２０〜４００ｎｍのＵＶ−Ａ領域、２８０〜３２０ｎｍのＵＶ−Ｂ領域及び２８０ｎｍ以下のＵＶ−Ｃ領域に区分されるが、通常問題となるのはＵＶ−Ａ領域とＵＶ−Ｂ領域の紫外線である。
前記したシリカ・酸化セリウム複合粒子は、ＵＶ−Ｂ領域の遮断性には優れているが、ＵＶ−Ａ領域の遮断性は不十分であった。プラスチックの中には、ポリウレタンのようにＵＶ−Ａ領域に大きな吸収を示すものがあり、また、人体の皮膚はＵＶ−Ａ領域の紫外線によりメラニンが生成して褐色化することから、このＵＶ−Ａ領域の紫外線を吸収・遮断したいとの要望が強かった。
【０００４】
ＵＶ−Ａ領域の紫外線の吸収・遮断に優れている無機化合物として微粒子酸化亜鉛が知られている。しかし、微粒子酸化亜鉛は触媒活性が高いため、使用範囲が制限されていた。そこで、この問題を解決するために種々の紫外線遮断剤が検討され、例えば、特開平８−１０４５１２号公報や特開平９−１００１１２号公報に記載のものが開発されているが、触媒活性がなく、かつ、優れたＵＶ−Ａ領域の紫外線遮断性を有するまでには至っていない。そのため、これらの特性をすべて備えた技術の開発が望まれていた。
【０００５】
【発明が解決しようとする課題】
そこで、本発明は、触媒活性がなく、優れたＵＶ−Ａ領域の紫外線遮断性を有する紫外線遮断剤及びその製造方法の提供を課題とする。
【０００６】
【課題を解決するための手段】
本発明者らは、酸化亜鉛に不定形シリカを所定量複合化させることにより、上記課題を解決できることを知り、その知見に基づき鋭意検討した結果、本発明を完成するに至った。
すなわち、本発明は、ＳｉＯ2 の含有量が１５〜５０重量％であるシリカ・酸化亜鉛複合粒子からなる紫外線遮断剤と、平均粒子径が０．０１〜０．０８μｍの微粒子酸化亜鉛を５０℃以上の温水に分散し、水和させて水酸化亜鉛スラリーとし、７０〜１００℃、ｐＨ７〜１１の状態を保つようにして、該水酸化亜鉛スラリーに、ケイ酸塩溶液と鉱酸を加えて不定形シリカ・水酸化亜鉛複合化物スラリーを生成し、これを水洗、ろ過した後、乾燥又は焼成し粉砕することを特徴とする上記紫外線遮断剤の製造方法である。
【０００７】
【発明の実施の形態】
本発明の紫外線遮断剤は、複合粒子中におけるＳｉＯ2 の含有量が１５〜５０重量％となる量の不定形シリカと酸化亜鉛とを複合化したものである。ＳｉＯ2 の含有量が上記範囲外の場合は、紫外線遮断効果が不足又は可視領域の透明性が低下し触媒活性が高くなる。
この紫外線遮断剤を製造するには、まず、水酸化亜鉛スラリーの調製を行う。水酸化亜鉛スラリーを調製するには、平均粒子径が０．０１〜０．０８μｍ、好ましくは０．０１〜０．０４μｍである微粒子酸化亜鉛を、５０℃以上、好ましくは６０℃以上の温水に添加し、３０分以上好ましくは１時間以上、強撹拌して分散させる。このとき、分散機や乳化機を使って分散してもかまわない。また、微粒子酸化亜鉛の温水中における分散濃度は適当でよいが、好ましくは０．１ｇ／ｍｌ以下である。
【０００８】
水酸化亜鉛スラリーの調製においては、前記したように、顔料級酸化亜鉛ではなく微粒子酸化亜鉛を使用する。その理由は、図１に示すように、顔料級酸化亜鉛では紫外線遮断効果が悪く、シリカを複合化しても可視領域で十分な透明性が得られないからである。なお、図１は、各種試料の波長と光透過率との関係を示した図で、試料▲１▼はＳｉＯ2 ３２重量％含有シリカ・微粒子酸化亜鉛複合粒子、試料▲２▼は微粒子酸化亜鉛、試料▲３▼はＳｉＯ2 ３２重量％含有シリカ・顔料級酸化亜鉛複合粒子、試料▲４▼は顔料級酸化亜鉛である。
【０００９】
次に、不定形シリカ・水酸化亜鉛複合化物スラリーを以下の方法で生成させる。まず、ケイ酸塩溶液として、例えば、３号ケイ酸ナトリウム（ＪＩＳによる）溶液を水で希釈したケイ酸ナトリウム溶液を調製する。一方、塩酸、硝酸、硫酸等の鉱酸を水で希釈して鉱酸溶液を調製する。そして、このケイ酸ナトリウム溶液と鉱酸溶液を、７０〜１００℃に加熱してある上記水酸化亜鉛スラリーに適当なスピードで滴下して不定形シリカ・水酸化亜鉛複合化物スラリーを生成させる。このとき、水酸化亜鉛スラリーのｐＨは７〜１１、好ましくは８〜１０の状態に維持する。また、滴下するケイ酸ナトリウムの量は、紫外線遮断剤中におけるＳｉＯ2 の含有量が１５〜５０重量％となるように換算して求める。この不定形シリカ・水酸化亜鉛複合化物スラリーの生成反応は、前記した温度とｐＨの条件下で行うことが重要であり、これらの条件を逸脱すると均一な不定形シリカ・水酸化亜鉛複合化物スラリーが得られない。
最後に、このスラリーを水洗、ろ過、乾燥又は１３０〜１，０００℃程度で焼成して粉砕することで、シリカ・酸化亜鉛複合粒子からなる本発明の紫外線遮断剤が得られる。
【００１０】
本発明の紫外線遮断剤の紫外線遮断効果及び可視領域における透明性は、微粒子酸化亜鉛の粒径とシリカの量に応じて異なる。したがって、微粒子酸化亜鉛の粒径とシリカの量は、用途に応じて適宜、上記範囲内で決定すればよい。図２は、粒径の異なる微粒子酸化亜鉛にシリカ（ＳｉＯ2 ３２重量％）を複合化したシリカ・酸化亜鉛複合粒子の波長と光透過率の関係を示す図であり、試料▲５▼、▲６▼、▲７▼はそれぞれ平均粒子径０．０１μｍ、０．０２μｍ、０．０４μｍの微粒子酸化亜鉛である。なお、上記の光透過率は、樹脂固形分の添加率が３．０％となる量の試料に、ヒマシ油０．４ｍｌを加えてフーバーマーラー（５０回転×２）で分散し、さらにクリアラッカー６ｍｌを加えて混練した後、この液を透明石英板に３０μｍの厚さに塗布し、分光光度計「ＵＶ−２２００」（島津製作所製、商品名）で測定した。
【００１１】
また、試料▲６▼ＳｉＯ2 ３２重量％含有シリカ・酸化亜鉛複合粒子について、Ｘ線回折を測定したところ、図３に示すようなＸ線回折パターンが得られたが、ＺｎＯのパターンしか示さず、このことからシリカは不定形シリカになっていることが確認された。
【００１２】
さらに、本発明の紫外線遮断剤の触媒活性については、ポリエチレンに各種試料を配合して２００℃でプレートに射出成型し、そのプレートをサンシャインウェザーメーターに１０００時間かけた後、その表面を観察して触媒活性の程度を判定した。その結果、試料が微粒子酸化亜鉛の場合は、表面が白化しザラザラした状態であった。ＳｉＯ2 １０重量％含有シリカ・酸化亜鉛複合粒子の場合は、わずかに表面が白化していた。ＳｉＯ2 １８、３２、５０重量％含有シリカ・酸化亜鉛複合粒子の場合は、表面に白化は見られなかった。触媒活性を示さない場合を◎、わずかに示す場合を○、やや示す場合を×、かなり示す場合を××とすると、微粒子酸化亜鉛とシリカ・酸化亜鉛複合粒子の触媒活性度は表１のような結果であった。
【００１３】
【表１】
これら紫外線遮断効果、可視領域の透明性、触媒活性に関する上記実施例及び下記の実施例の結果から、紫外線遮断剤中の最適なＳｉＯ2 含有率は１５〜５０重量％であると判断した。
【００１５】
【実施例】
【００１６】
（実施例１）
平均粒子径０．０２μｍの市販の微粒子酸化亜鉛１ｋｇを、６０℃の温水１０，０００ｍｌに少量ずつ添加し、６０℃に保ったまま１時間強撹拌しながら水和させて水酸化亜鉛スラリーを調製した。
一方、３号ケイ酸ナトリウム溶液（ＳｉＯ2 ２８．５重量％）７７０．２ｇを水で希釈してケイ酸ナトリウム溶液２，５００ｍｌを調製した。また、９５重量％硫酸１０３．８ｇを水で希釈して希硫酸溶液２，５００ｍｌを調製した。そして、水酸化亜鉛スラリーを８０℃以上に加熱撹拌しながら、ケイ酸ナトリウム溶液と希硫酸溶液を、反応液のｐＨが８〜１０の状態となるようにして同時に滴下した。両液の滴下終了後、３０分撹拌し反応液のｐＨが６〜７になるように希硫酸で調整した。これをろ過、水洗、乾燥、焼成（５００℃）し粉砕して、ＳｉＯ2 １８重量％含有のシリカ・酸化亜鉛複合粒子を得た。
【００１７】
（実施例２）
３号ケイ酸ナトリウム溶液１６５１．２ｇを水で希釈して５，６００ｍｌとし、９５重量％硫酸２２２．５ｇを水で希釈して５，６００ｍｌに調製した以外は実施例１と同様にしてＳｉＯ2 ３２重量％含有のシリカ・酸化亜鉛複合粒子を得た。
【００１８】
（実施例３）
３号ケイ酸ナトリウム溶液３５０８．８ｇを水で希釈して１２，３００ｍｌとし、９５重量％硫酸４７２．９ｇを水で希釈して１２，３００ｍｌに調製した以外は、実施例１と同様にしてＳｉＯ2 ５０重量％含有のシリカ・酸化亜鉛複合粒子を得た。
【００１９】
（比較例）
３号ケイ酸ナトリウム溶液３８９．９ｇを水で希釈して１，１００ｍｌとし、９５重量％硫酸５２．５ｇを水で希釈して１，１００ｍｌに調製した以外は、実施例１と同様にしてＳｉＯ2 １０重量％含有のシリカ・酸化亜鉛複合粒子を得た。
【００２０】
実施例１〜３及び比較例で製造したシリカ・酸化亜鉛複合粒子の光透過率を測定した結果を図４に示す。試料ＡはＳｉＯ2 ５０重量％含有シリカ・酸化亜鉛複合粒子、試料ＢはＳｉＯ2 ３２重量％含有シリカ・酸化亜鉛複合粒子、試料ＣはＳｉＯ2 １８重量％含有シリカ・酸化亜鉛複合粒子、試料ＤはＳｉＯ2 １０重量％含有シリカ・酸化亜鉛複合粒子の光透過率曲線である。
【００２１】
【発明の効果】
本発明の紫外線遮断剤は、触媒活性を有さず、可視領域での透明性が高く、しかも、ＵＶ−Ａ領域の紫外線遮断効果に優れており、プラスチックや化粧品等の分野において広い利用が期待されるものである。
【図面の簡単な説明】
【図１】各種試料の波長と光透過率との関係を示した図である。
【図２】各種試料の波長と光透過率との関係を示した図である。
【図３】ＳｉＯ2 ３２重量％含有シリカ・酸化亜鉛複合粒子のＸ線回折パターン図である。
【図４】各種試料の波長と光透過率との関係を示した図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ultraviolet blocking agent having no catalytic activity, stable, high transparency in the visible region, and excellent ultraviolet blocking properties, and a method for producing the same.
[0002]
[Prior art]
Ultraviolet rays cause plastic deterioration and have a negative effect on the human body. Therefore, various organic and inorganic ultraviolet blocking agents have been developed, and these are blended in plastics and cosmetics.
Organic UV blocking agents include salicylic acid, benzotriazole, cyanoacrylate, cinnamic acid, dibenzoylmethane, and others, all of which have heat resistance, weather resistance, and when mixed or decomposed in large quantities. Improvements in the safety of products that can be produced have become issues.
On the other hand, inorganic ultraviolet blocking agents include fine particle titanium oxide, fine particle zinc oxide, and the like, all of which have been problems in improving dispersibility and catalytic activity. In order to solve these problems, silica / cerium oxide composite particles (Japanese Patent Laid-Open No. 9-118610) have been developed.
[0003]
In general, ultraviolet rays are divided into a UV-A region having a wavelength of 320 to 400 nm, a UV-B region having a wavelength of 280 to 320 nm, and a UV-C region having a wavelength of 280 nm or less. It is an ultraviolet ray in the B region.
The silica-cerium oxide composite particles described above are excellent in the blocking property in the UV-B region, but the blocking property in the UV-A region is insufficient. Some plastics, such as polyurethane, show a large absorption in the UV-A region, and the human skin is browned by the formation of melanin by the ultraviolet rays in the UV-A region. There was a strong demand to absorb and block ultraviolet rays in the A region.
[0004]
Fine particle zinc oxide is known as an inorganic compound that is excellent in absorbing and blocking ultraviolet rays in the UV-A region. However, since the fine zinc oxide has high catalytic activity, the range of use has been limited. Accordingly, in order to solve this problem, various ultraviolet blocking agents have been studied. For example, those described in JP-A-8-104512 and JP-A-9-100112 have been developed, but have no catalytic activity. And it has not yet reached | attained the outstanding ultraviolet-blocking property of the UV-A area | region. Therefore, development of a technology having all these characteristics has been desired.
[0005]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide an ultraviolet blocking agent having no catalytic activity and having an excellent ultraviolet blocking property in the UV-A region, and a method for producing the same.
[0006]
[Means for Solving the Problems]
The present inventors have found that the above-mentioned problems can be solved by combining a predetermined amount of amorphous silica with zinc oxide, and as a result of intensive studies based on the findings, the present invention has been completed.
That is, the present invention provides an ultraviolet blocking agent composed of silica / zinc oxide composite particles having a SiO 2 content of 15 to 50% by weight and fine particle zinc oxide having an average particle size of 0.01 to 0.08 μm at 50 ° C. Disperse in the above warm water and hydrate to make a zinc hydroxide slurry, and maintain a state of 70 to 100 ° C. and pH 7 to 11, and add a silicate solution and a mineral acid to the zinc hydroxide slurry. The method for producing an ultraviolet screening agent according to the above, wherein an amorphous silica / zinc hydroxide composite slurry is produced, washed with water, filtered, dried or fired and pulverized.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The ultraviolet blocking agent of the present invention is a composite of amorphous silica and zinc oxide in such an amount that the content of SiO 2 in the composite particles is 15 to 50% by weight. When the content of SiO 2 is out of the above range, the ultraviolet blocking effect is insufficient or the transparency in the visible region is lowered and the catalytic activity is increased.
In order to produce this ultraviolet blocking agent, first, a zinc hydroxide slurry is prepared. In order to prepare a zinc hydroxide slurry, fine zinc oxide having an average particle size of 0.01 to 0.08 μm, preferably 0.01 to 0.04 μm, is added to hot water of 50 ° C. or higher, preferably 60 ° C. or higher. Add and disperse with vigorous stirring for 30 minutes or more, preferably 1 hour or more. At this time, it may be dispersed using a disperser or an emulsifier. The dispersion concentration of fine zinc oxide in warm water may be appropriate, but is preferably 0.1 g / ml or less.
[0008]
In preparing the zinc hydroxide slurry, as described above, fine particle zinc oxide is used instead of pigment grade zinc oxide. The reason for this is that, as shown in FIG. 1, pigment grade zinc oxide has a poor ultraviolet blocking effect, and even if silica is combined, sufficient transparency cannot be obtained in the visible region. FIG. 1 is a graph showing the relationship between the wavelength and light transmittance of various samples. Sample (1) is a silica-fine particle zinc oxide composite particle containing 32% by weight of SiO 2 , and sample (2) is fine particle zinc oxide. Sample (3) is a silica / pigment grade zinc oxide composite particle containing 32 wt% of SiO 2 , and Sample (4) is pigment grade zinc oxide.
[0009]
Next, an amorphous silica / zinc hydroxide composite slurry is produced by the following method. First, as a silicate solution, for example, a sodium silicate solution is prepared by diluting a No. 3 sodium silicate (according to JIS) solution with water. On the other hand, a mineral acid solution is prepared by diluting mineral acids such as hydrochloric acid, nitric acid and sulfuric acid with water. Then, the sodium silicate solution and the mineral acid solution are added dropwise to the zinc hydroxide slurry heated to 70 to 100 ° C. at an appropriate speed to produce an amorphous silica / zinc hydroxide composite slurry. At this time, the pH of the zinc hydroxide slurry is maintained at 7 to 11, preferably 8 to 10. Further, the amount of sodium silicate to be dropped is determined by converting so that the content of SiO 2 in the ultraviolet blocking agent is 15 to 50% by weight. It is important that the formation reaction of this irregular silica / zinc hydroxide composite slurry is performed under the conditions of the temperature and pH described above, and if these conditions are deviated, a uniform amorphous silica / zinc hydroxide composite slurry is obtained. Cannot be obtained.
Finally, the slurry is washed with water, filtered, dried, or fired at about 130 to 1,000 ° C. and pulverized to obtain the ultraviolet blocking agent of the present invention composed of silica / zinc oxide composite particles.
[0010]
The ultraviolet blocking effect and transparency in the visible region of the ultraviolet blocking agent of the present invention vary depending on the particle size of the fine zinc oxide and the amount of silica. Accordingly, the particle size of the fine particle zinc oxide and the amount of silica may be appropriately determined within the above range depending on the application. FIG. 2 is a graph showing the relationship between the wavelength and light transmittance of silica / zinc oxide composite particles obtained by combining silica (SiO 2 32 wt%) with fine particle zinc oxide having different particle diameters. 6 and 7 are fine zinc oxide particles having average particle diameters of 0.01 μm, 0.02 μm, and 0.04 μm, respectively. The above light transmittance is obtained by adding 0.4 ml of castor oil to a sample having an amount of resin solid content of 3.0% and dispersing with a Hoovermarler (50 rotations × 2), and further clear lacquer. After adding 6 ml and kneading, this liquid was applied to a transparent quartz plate to a thickness of 30 μm and measured with a spectrophotometer “UV-2200” (trade name, manufactured by Shimadzu Corporation).
[0011]
Further, when X-ray diffraction was measured with respect to the silica / zinc oxide composite particles containing 6 wt% of SiO 2 sample 2 , an X-ray diffraction pattern as shown in FIG. 3 was obtained, but only a ZnO pattern was shown. From this, it was confirmed that the silica was amorphous silica.
[0012]
Further, regarding the catalytic activity of the ultraviolet blocking agent of the present invention, various samples were blended with polyethylene, injection molded onto a plate at 200 ° C., the plate was placed on a sunshine weather meter for 1000 hours, and the surface was observed. The degree of catalytic activity was determined. As a result, when the sample was fine particle zinc oxide, the surface was whitened and rough. In the case of silica / zinc oxide composite particles containing 10% by weight of SiO 2 , the surface was slightly whitened. In the case of silica / zinc oxide composite particles containing SiO 2 18, 32, 50% by weight, no whitening was observed on the surface. Table 1 shows the catalytic activity of fine particles of zinc oxide and silica / zinc oxide composite particles, where ◎ indicates no catalytic activity, ○ indicates slightly, × indicates slightly, and XX indicates a considerable amount. It was a result.
[0013]
[Table 1]
From the results of the above examples concerning the ultraviolet blocking effect, transparency in the visible region, and catalytic activity and the following examples, it was determined that the optimum SiO 2 content in the ultraviolet blocking agent was 15 to 50% by weight.
[0015]
【Example】
[0016]
Example 1
1 kg of commercially available fine particle zinc oxide with an average particle size of 0.02 μm was added little by little to 10,000 ml of warm water at 60 ° C. and hydrated with vigorous stirring for 1 hour while maintaining the temperature at 60 ° C. to prepare a zinc hydroxide slurry. did.
On the other hand, 770.2 g of No. 3 sodium silicate solution (SiO 2 28.5 wt%) was diluted with water to prepare 2,500 ml of sodium silicate solution. Further, 2,500 ml of dilute sulfuric acid solution was prepared by diluting 103.8 g of 95 wt% sulfuric acid with water. And while heating and stirring a zinc hydroxide slurry at 80 degreeC or more, the sodium silicate solution and the dilute sulfuric acid solution were simultaneously dripped so that the pH of a reaction liquid might be in the state of 8-10. After completion of the dropwise addition of both solutions, the mixture was stirred for 30 minutes and adjusted with dilute sulfuric acid so that the pH of the reaction solution was 6-7. This was filtered, washed with water, dried, fired (500 ° C.) and pulverized to obtain silica / zinc oxide composite particles containing 18% by weight of SiO 2 .
[0017]
(Example 2)
The SiO 2 solution was prepared in the same manner as in Example 1 except that 1651.2 g of No. 3 sodium silicate solution was diluted to 5,600 ml with water and 222.5 g of 95 wt% sulfuric acid was diluted with water to 5,600 ml. Silica / zinc oxide composite particles containing 32% by weight were obtained.
[0018]
Example 3
The same as in Example 1 except that 3508.8 g of No. 3 sodium silicate solution was diluted with water to 12,300 ml, and 472.9 g of 95 wt% sulfuric acid was diluted with water to 12,300 ml. 2 50% by weight of silica / zinc oxide composite particles were obtained.
[0019]
(Comparative example)
The same as in Example 1 except that 389.9 g of No. 3 sodium silicate solution was diluted to 1,100 ml with water and 52.5 g of 95% by weight sulfuric acid was diluted with water to make 1,100 ml. 2 Silica / zinc oxide composite particles containing 10% by weight were obtained.
[0020]
The result of having measured the light transmittance of the silica * zinc oxide composite particle manufactured by Examples 1-3 and the comparative example is shown in FIG. Sample A is a silica / zinc oxide composite particle containing 50 wt% SiO 2 , Sample B is a silica / zinc oxide composite particle containing 32 wt% SiO 2 , Sample C is a silica / zinc oxide composite particle containing 18 wt% SiO 2 , Sample D Is a light transmittance curve of silica / zinc oxide composite particles containing 10% by weight of SiO 2 .
[0021]
【The invention's effect】
The ultraviolet blocking agent of the present invention has no catalytic activity, is highly transparent in the visible region, and has an excellent ultraviolet blocking effect in the UV-A region, and is expected to be widely used in the fields of plastics and cosmetics. It is what is done.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between the wavelength and light transmittance of various samples.
FIG. 2 is a graph showing the relationship between the wavelength and light transmittance of various samples.
FIG. 3 is an X-ray diffraction pattern of silica / zinc oxide composite particles containing 32% by weight of SiO 2 .
FIG. 4 is a diagram showing the relationship between the wavelength and light transmittance of various samples.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06105498A JP3848458B2 (en) | 1998-03-12 | 1998-03-12 | Method for producing UV blocker |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06105498A JP3848458B2 (en) | 1998-03-12 | 1998-03-12 | Method for producing UV blocker |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11256133A JPH11256133A (en) | 1999-09-21 |
| JP3848458B2 true JP3848458B2 (en) | 2006-11-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP06105498A Expired - Lifetime JP3848458B2 (en) | 1998-03-12 | 1998-03-12 | Method for producing UV blocker |
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| JP (1) | JP3848458B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015072499A1 (en) | 2013-11-13 | 2015-05-21 | 住友大阪セメント株式会社 | Silicon-oxide-coated zinc oxide and method for manufacturing same, silicon-oxide-coated zinc-oxide-containing composition, and cosmetic |
| KR20170083043A (en) | 2014-11-13 | 2017-07-17 | 스미토모 오사카 세멘토 가부시키가이샤 | Silicon oxide-coated zinc oxide and method for preparing same, and composition and cosmetic material containing silicon oxide-coated zinc oxide |
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| US6660380B1 (en) | 1999-05-12 | 2003-12-09 | Sakai Chemical Industry Co., Ltd. | Zinc oxide particles having suppressed surface activity and production and use thereof |
| AU6269101A (en) * | 2000-06-05 | 2001-12-17 | Showa Denko Kk | Cosmetic preparation |
| US6500415B2 (en) | 2000-06-05 | 2002-12-31 | Showa Denko K.K. | Cosmetic composition |
| KR20030038046A (en) * | 2001-11-08 | 2003-05-16 | (주)나노플루이드 | Zinc oxide nanoparticle, and aqueous dispersion containing the same |
| DE10333029A1 (en) | 2003-07-21 | 2005-02-17 | Merck Patent Gmbh | Nanoparticulate UV protectants used in cosmetic, sunscreen, dermatological or other protective uses (e.g. as textile or packaging coatings) comprise a metal oxide with a silicon dioxide coating |
| JP4836232B2 (en) * | 2005-07-07 | 2011-12-14 | テイカ株式会社 | Method for producing silica-coated fine particle titanium oxide or silica-coated fine particle zinc oxide |
| TW201410758A (en) | 2012-08-02 | 2014-03-16 | Asahi Glass Co Ltd | Resin film, backsheet for solar cell module, and solar cell module |
| US20180161255A1 (en) | 2015-02-27 | 2018-06-14 | Sumitomo Osaka Cement Co., Ltd. | Silicon oxide-coated zinc oxide, composition containing silicon oxide-coated zinc oxide, and cosmetic product |
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Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2851885B2 (en) * | 1989-12-12 | 1999-01-27 | 住友大阪セメント株式会社 | Zinc oxide and cosmetics |
| JP3493717B2 (en) * | 1994-04-19 | 2004-02-03 | 旭硝子株式会社 | Zinc oxide-supported spherical silica for cosmetics, method for producing the same, and cosmetics |
| JP3453872B2 (en) * | 1994-09-30 | 2003-10-06 | 旭硝子株式会社 | Method for producing zinc oxide-containing spherical silica |
| JPH08104512A (en) * | 1994-09-30 | 1996-04-23 | Asahi Glass Co Ltd | Ultraviolet shielding material consisting of zinc oxide-containing spherical silica and cosmetic material |
| JP3848697B2 (en) * | 1995-03-10 | 2006-11-22 | 花王株式会社 | Ultraviolet shielding composite fine particles, production method thereof and cosmetics |
| JPH08268707A (en) * | 1995-03-28 | 1996-10-15 | Kao Corp | Ultraviolet-ray shielding platy composite fine particles and their production |
| JP3267508B2 (en) * | 1995-08-10 | 2002-03-18 | 日本電工株式会社 | Silica / cerium oxide composite particles, method for producing the same, resin composition containing the same, and cosmetics |
| JPH1111927A (en) * | 1997-06-20 | 1999-01-19 | Doukai Kagaku Kogyo Kk | Composite particle with silica matrix, its production and compounded cosmetic material |
| JPH11193354A (en) * | 1997-12-26 | 1999-07-21 | Fuji Shikiso Kk | Silica-coated zinc oxide particle, its preparation, and composition containing it |
-
1998
- 1998-03-12 JP JP06105498A patent/JP3848458B2/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015072499A1 (en) | 2013-11-13 | 2015-05-21 | 住友大阪セメント株式会社 | Silicon-oxide-coated zinc oxide and method for manufacturing same, silicon-oxide-coated zinc-oxide-containing composition, and cosmetic |
| KR20160079083A (en) | 2013-11-13 | 2016-07-05 | 스미토모 오사카 세멘토 가부시키가이샤 | Silicon-oxide-coated zinc oxide and method for manufacturing same, silicon-oxide-coated zinc-oxide-containing composition, and cosmetic |
| US9855197B2 (en) | 2013-11-13 | 2018-01-02 | Sumitomo Osaka Cement Co., Ltd. | Zinc oxide which is coated with silicon oxide, method for manufacturing the same, composition which includes the zinc oxide coated with silicon oxide, and cosmetic |
| US10363204B2 (en) | 2013-11-13 | 2019-07-30 | Sumitomo Osaka Cement Co., Ltd. | Zinc oxide which is coated with silicon oxide, method for manufacturing the same, composition which includes the zinc oxide coated with silicon oxide, and cosmetic |
| KR20170083043A (en) | 2014-11-13 | 2017-07-17 | 스미토모 오사카 세멘토 가부시키가이샤 | Silicon oxide-coated zinc oxide and method for preparing same, and composition and cosmetic material containing silicon oxide-coated zinc oxide |
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| JPH11256133A (en) | 1999-09-21 |
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