JPH08104515A - Production of zinc oxide-containing spherical silica - Google Patents
Production of zinc oxide-containing spherical silicaInfo
- Publication number
- JPH08104515A JPH08104515A JP23782694A JP23782694A JPH08104515A JP H08104515 A JPH08104515 A JP H08104515A JP 23782694 A JP23782694 A JP 23782694A JP 23782694 A JP23782694 A JP 23782694A JP H08104515 A JPH08104515 A JP H08104515A
- Authority
- JP
- Japan
- Prior art keywords
- zinc oxide
- spherical silica
- carbon dioxide
- dioxide gas
- producing
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、酸化亜鉛含有球状シリ
カの製造方法、特に、化粧品原料、塗料添加剤、樹脂添
加剤などに用いられる紫外線遮蔽能を有する酸化亜鉛含
有球状シリカの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing zinc oxide-containing spherical silica, and more particularly to a method for producing zinc oxide-containing spherical silica having an ultraviolet shielding ability, which is used as a raw material for cosmetics, paint additives, resin additives and the like. .
【０００２】[0002]
【従来の技術】従来より酸化亜鉛は、紫外線遮蔽剤とし
て、化粧品原料、樹脂添加剤、塗料添加剤、ガラス等の
コーティング剤成分に用いられている。2. Description of the Related Art Zinc oxide has heretofore been used as a UV shielding agent in cosmetic raw materials, resin additives, paint additives, and coating agent components such as glass.
【０００３】紫外線遮蔽効果の向上、透明性の向上を目
的として、粒子を微細化することが試みられている。例
えば、特開昭６０−２３１６０７号公報には、最大粒径
０．１μｍ以下で平均粒径１０〜６０ｎｍの微粒子酸化
亜鉛を化粧料に配合することが開示されている。特開昭
６２−８４０１７号公報には、平均粒子径２０ｎｍ以下
の酸化亜鉛が化粧用組成物として開示されている。特開
昭６２−２２８００６号公報には、平均粒径７０〜３０
０ｎｍの酸化亜鉛を配合した化粧料が開示されている。
また、粒径が０．１μｍ以下の酸化亜鉛を分散させた塗
料組成物が、特開平２−２６５９７６号公報に開示され
ている。Attempts have been made to make the particles finer for the purpose of improving the ultraviolet shielding effect and improving the transparency. For example, JP-A-60-231607 discloses that fine zinc oxide particles having a maximum particle size of 0.1 μm or less and an average particle size of 10 to 60 nm are mixed with a cosmetic. JP-A-62-84017 discloses zinc oxide having an average particle diameter of 20 nm or less as a cosmetic composition. JP 62-228006 A discloses an average particle size of 70-30.
Cosmetics containing 0 nm zinc oxide are disclosed.
A coating composition in which zinc oxide having a particle size of 0.1 μm or less is dispersed is disclosed in JP-A-2-265976.
【０００４】しかし、微粒子化した酸化亜鉛は、凝集し
やすく、分散配合することが困難であった。また、比表
面積が大きくなることにより活性が強くなり、いっしょ
に配合した有機成分を分解する傾向がある。そこで、分
散性を向上させるために、特開昭６３−１１９４１８号
公報では、担体表面に固着剤により酸化亜鉛微粒子を固
着した顔料が提案されている。また、分解活性を抑える
ために、特開平３−１８３６２０号公報では、表面をＡ
ｌ、Ｓｉなどの酸化物で被覆した酸化亜鉛が提案されて
いる。However, finely divided zinc oxide easily aggregates, and it is difficult to mix and disperse it. In addition, the larger specific surface area increases the activity and tends to decompose the organic components blended together. Therefore, in order to improve the dispersibility, JP-A-63-119418 proposes a pigment in which zinc oxide fine particles are fixed on the surface of a carrier with a fixing agent. Further, in order to suppress the decomposition activity, in Japanese Patent Laid-Open No. 183620/1993, the surface is
Zinc oxide coated with oxides such as l and Si has been proposed.
【０００５】しかし、担体表面に酸化亜鉛を固着したも
のは、表面に酸化亜鉛が露出しているために、活性が高
く、流動性が悪いという問題がある。また、微粒子の酸
化亜鉛を他の金属酸化物で被覆したものはもとの酸化亜
鉛の形状を保持しているため、流動性が低く化粧料に配
合した場合は使用感が悪いという問題があった。However, the one in which zinc oxide is fixed on the surface of the carrier has a problem that the activity is high and the fluidity is poor because the zinc oxide is exposed on the surface. In addition, since fine zinc oxide coated with another metal oxide retains the original zinc oxide shape, there is a problem that the fluidity is low and the feel of use is poor when blended in cosmetics. It was
【０００６】さらに、米国特許第４０９０８８７号明細
書において顔料を分散したケイ酸塩を酸でゲル化する球
状シリカの製造方法が開示されているが、紫外線遮蔽効
果の観点からは反応条件が適当でなく、性能が不十分で
ある。Further, US Pat. No. 4,090,887 discloses a method for producing spherical silica in which a silicate in which a pigment is dispersed is gelled with an acid. However, the reaction conditions are appropriate from the viewpoint of the ultraviolet shielding effect. No, the performance is insufficient.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、紫外
線の遮蔽効果が高く、かつ、流動性、滑沢性が良好で化
粧料などに容易に分散配合することが可能で、かつ、同
時に有機成分を配合した場合にそれを分解する活性が低
い紫外線遮蔽用の粉体を得ることを目的とする。The object of the present invention is to have a high ultraviolet ray shielding effect, good fluidity and lubricity, and can be easily dispersed and blended in cosmetics, and at the same time. The purpose of the present invention is to obtain an ultraviolet shielding powder having a low activity of decomposing an organic component when it is blended.
【０００８】[0008]
【課題を解決するための手段】本発明は、粒子径が０．
０１〜０．５μｍの酸化亜鉛を１０〜６０重量％の含有
量で分散させたアルカリケイ酸塩水溶液を、界面活性剤
を含む有機溶剤中で乳化した後、炭酸ガスによりゲル化
させる酸化亜鉛含有球状シリカの製造方法を提供するも
のである。SUMMARY OF THE INVENTION The present invention has a particle size of 0.
Zinc oxide-containing solution in which an alkaline silicate aqueous solution in which zinc oxide of 01 to 0.5 μm is dispersed at a content of 10 to 60% by weight is emulsified in an organic solvent containing a surfactant and then gelated by carbon dioxide gas. A method for producing spherical silica is provided.
【０００９】酸化亜鉛の粒子径は０．０１〜０．５μｍ
であることが必要である。粒子径が０．５μｍを超える
と紫外線の遮蔽効果が低くなるので不適当である。ま
た、０．０１μｍより小さい場合も紫外線の遮蔽効果が
低くなるとともに、遮蔽できる波長領域が短波長側にシ
フトするので好ましくない。酸化亜鉛の平均粒子径が
０．０３〜０．３μｍである場合はさらに好ましい。The particle size of zinc oxide is 0.01 to 0.5 μm.
It is necessary to be. When the particle size exceeds 0.5 μm, the ultraviolet ray shielding effect is lowered, and therefore it is not suitable. Also, when it is smaller than 0.01 μm, the ultraviolet ray shielding effect is lowered and the wavelength region capable of shielding is shifted to the short wavelength side, which is not preferable. It is more preferable that the average particle diameter of zinc oxide is 0.03 to 0.3 μm.
【００１０】ケイ酸アルカリ水溶液中の酸化亜鉛の含有
量は、アルカリケイ酸塩水溶液中のＳｉＯ2 と酸化亜鉛
の合計量に対して１０〜６０重量％が適当である。酸化
亜鉛の含有量が１０重量％に満たない場合は、紫外線の
遮蔽効果が不足するので好ましくない。酸化亜鉛の含有
量が６０重量％を超える場合は、球状のシリカが得るこ
とが困難であり、また、可視光における透過率が低下し
て、化粧料などの用途に適さなくなるので不適当であ
る。The content of zinc oxide in the alkali silicate aqueous solution is preferably 10 to 60% by weight based on the total amount of SiO 2 and zinc oxide in the alkali silicate aqueous solution. When the content of zinc oxide is less than 10% by weight, the effect of shielding ultraviolet rays is insufficient, which is not preferable. When the content of zinc oxide exceeds 60% by weight, it is difficult to obtain spherical silica, and the transmittance of visible light is lowered, which makes it unsuitable for applications such as cosmetics. .
【００１１】ケイ酸アルカリ水溶液において、アルカリ
としては特に制限はないが、経済的理由によりナトリウ
ムがもっとも好ましい。ケイ酸とアルカリの割合は、ア
ルカリがナトリウムであるとして、Ｎａ2 Ｏ／ＳｉＯ2
のモル比が、２．０〜３．５程度が好ましい。水溶液の
濃度は、ＳｉＯ2 として５〜３０重量％が好ましい。In the alkali silicate aqueous solution, the alkali is not particularly limited, but sodium is most preferable for economic reasons. The ratio of silicic acid and alkali is Na 2 O / SiO 2 assuming that the alkali is sodium.
The molar ratio of is preferably about 2.0 to 3.5. The concentration of the aqueous solution is preferably 5 to 30% by weight as SiO 2 .
【００１２】酸化亜鉛は、高速せん断式分散機、媒体撹
拌ミル、超音波分散機などによりアルカリケイ酸塩中に
分散させることができる。また、分散剤も適宜併用する
ことができる。Zinc oxide can be dispersed in the alkali silicate by a high-speed shearing disperser, a medium stirring mill, an ultrasonic disperser or the like. Further, a dispersant can also be used in combination as appropriate.
【００１３】有機溶剤としては、炭酸ガスが溶解できる
物質が好ましい。たとえば、ヘキサン、オクタンなどの
脂肪族炭化水素、キシレン、トルエンなどの芳香族炭化
水素、クロロホルム、トリクロロエチレン、テトラクロ
ロエチレンなどの塩素化炭化水素、トリクロロトリフル
オロエタン、ジクロロトリフルオロエタン、ジクロロフ
ルオロエタン、ジクロロペンタフルオロプロパンなどの
クロロフルオロカーボン類が好ましい。The organic solvent is preferably a substance capable of dissolving carbon dioxide gas. For example, hexane, octane and other aliphatic hydrocarbons, xylene, toluene and other aromatic hydrocarbons, chloroform, trichloroethylene, tetrachloroethylene and other chlorinated hydrocarbons, trichlorotrifluoroethane, dichlorotrifluoroethane, dichlorofluoroethane, dichloropentane. Chlorofluorocarbons such as fluoropropane are preferred.
【００１４】界面活性剤としては、ポリエチレングリコ
ール脂肪酸エステル、ポリオキシエチレンアルキルフェ
ニルエーテル、ポリオキシエチレンアルキルエーテル、
ソルビタン脂肪酸エステル、ポリオキシエチレンソルビ
タン脂肪酸エステルが好ましい。その使用量は、０．０
５〜１０重量％が好ましい。As the surfactant, polyethylene glycol fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether,
Sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester are preferable. The usage is 0.0
5-10% by weight is preferred.
【００１５】界面活性剤は、有機溶剤に溶解し、これに
酸化亜鉛を分散したアルカリケイ酸塩水溶液を加えて乳
化する。Ｗ／Ｏ型の乳化液が形成されるように、有機溶
剤に対し、水溶液が容積比で０．１〜１の範囲で加える
のが好ましい。乳化は、タービン式撹拌機、高速せん断
式乳化機などの手段によって行うのが好ましい。乳化液
において、アルカリケイ酸塩水溶液の粒子は、平均粒子
径が０．１〜１００μｍであることが好ましい。The surfactant is dissolved in an organic solvent, and an alkaline silicate aqueous solution in which zinc oxide is dispersed is added to this to emulsify. It is preferable to add the aqueous solution in a volume ratio of 0.1 to 1 with respect to the organic solvent so that a W / O type emulsion is formed. The emulsification is preferably performed by means such as a turbine stirrer or a high speed shearing emulsifier. In the emulsion, the particles of the aqueous alkali silicate solution preferably have an average particle size of 0.1 to 100 μm.
【００１６】次に、乳化液に炭酸ガスを導入することに
より、アルカリケイ酸塩水溶液をゲル化させる。本発明
においては乳化させた状態でゲル化させるため、球状の
シリカゲルが得られる。酸化亜鉛は、水溶液中に分散し
た状態を保持したままゲル化し、シリカゲルマトリック
ス中に分散する。Next, carbon dioxide gas is introduced into the emulsion to gelate the aqueous solution of alkali silicate. In the present invention, spherical silica gel is obtained because the gel is formed in the emulsified state. Zinc oxide gels while maintaining a state of being dispersed in an aqueous solution, and is dispersed in a silica gel matrix.
【００１７】ゲル化に当たっては、ゲル化開始時間が４
分以上になる条件で炭酸ガスを導入することが好まし
い。この乳化液に炭酸ガスを導入すると、ある時点で乳
化液の粘度が急激かつ明瞭に増大するのが目視でも十分
観察できるので、その時点をもってゲル化開始時間とし
た。ゲル化開始時間が４分より短い場合は、生成したシ
リカゲル粒子中の酸化亜鉛の分散状態が適当でなく紫外
線遮蔽効果が劣るので好ましくない。ゲル化開始時間
は、炭酸ガスの流量、分圧などを変えることにより調整
することが可能である。ゲル化開始時間が５分以上であ
る場合は、さらに好ましい。At the time of gelation, the gelation start time is 4
It is preferable to introduce carbon dioxide under the condition of not less than minutes. When carbon dioxide gas was introduced into this emulsion, the viscosity of the emulsion suddenly and sharply increased at a certain point, which can be sufficiently observed with the naked eye, so that point was taken as the gelation start time. When the gelation start time is shorter than 4 minutes, the dispersion state of zinc oxide in the produced silica gel particles is not appropriate and the ultraviolet ray shielding effect is poor, which is not preferable. The gelation start time can be adjusted by changing the flow rate of carbon dioxide, the partial pressure, and the like. It is more preferable that the gelation start time is 5 minutes or more.
【００１８】ゲル化の終了後は、有機溶媒を除去し、適
宜加熱処理や薬液処理することにより、酸化亜鉛含有球
状シリカの水系スラリー（以下、合成直後のスラリーと
いう）が得られる。合成直後のスラリーは、主として酸
化亜鉛含有球状シリカと炭酸アルカリとを含んでおり、
酸化亜鉛含有球状シリカは分離後、適宜洗浄し乾燥す
る。After completion of gelation, the organic solvent is removed, and heat treatment or chemical treatment is appropriately carried out to obtain an aqueous slurry of zinc oxide-containing spherical silica (hereinafter referred to as slurry immediately after synthesis). The slurry immediately after synthesis mainly contains zinc oxide-containing spherical silica and alkali carbonate,
After separating the zinc oxide-containing spherical silica, it is appropriately washed and dried.
【００１９】化粧品原料や塗料、樹脂の添加剤として用
いる場合、酸化亜鉛含有球状シリカを水に分散させたと
きのｐＨ（本明細書では、水に分散させて得た１０重量
％スラリーのｐＨとする。以下、単にシリカのｐＨとい
う）は７〜９のほぼ中性であることが望ましい。通常の
シリカの場合、シリカスラリーに酸を加えてｐＨを６以
下した後、濾過洗浄することによりシリカのｐＨを７程
度にすることができるが、酸化亜鉛を含有したシリカの
場合ｐＨを６以下にすると酸化亜鉛が溶解し、含有量が
減少するばかりでなく、排液の処理に多大の費用がかか
ることとなる。しかしながら次のような洗浄方法を採用
すると、酸化亜鉛の含有量をほとんど変化させずにシリ
カのｐＨを７〜８にすることができるので好ましい。When used as an additive for cosmetic raw materials, paints, and resins, the pH of zinc oxide-containing spherical silica when dispersed in water (in this specification, the pH of a 10 wt% slurry obtained by dispersing it in water is In the following, it is desirable that the pH of silica is referred to as "pH of silica"), which is substantially neutral from 7 to 9. In the case of normal silica, the pH of silica can be adjusted to about 7 by adding an acid to the silica slurry to adjust the pH to 6 or lower, and then filtering and washing. However, in the case of silica containing zinc oxide, the pH is 6 or lower. In this case, not only the zinc oxide is dissolved and the content is reduced, but also the waste liquid is expensive to treat. However, it is preferable to employ the following cleaning method because the pH of silica can be adjusted to 7 to 8 with almost no change in the content of zinc oxide.
【００２０】第１の方法は、合成直後のシリカスラリー
を濾過し、常圧若しくは加圧下で炭酸ガスを溶解した水
で所要の純度になるまで洗浄する方法である。炭酸ガス
は飽和していることが望ましいが、未飽和であってもよ
い。炭酸ガスが溶解した水のｐＨは、３．３（飽和の場
合）〜４の範囲にあることが好ましい。たとえば、同程
度のｐＨを有する希塩酸、希硫酸、希硝酸を使用する場
合は、所望のｐＨのシリカが得られないので不適切であ
る。The first method is a method in which a silica slurry immediately after synthesis is filtered and washed with water in which carbon dioxide gas is dissolved under atmospheric pressure or pressure until the required purity is reached. The carbon dioxide gas is preferably saturated, but may be unsaturated. The pH of water in which carbon dioxide gas is dissolved is preferably in the range of 3.3 (when saturated) to 4. For example, it is inappropriate to use dilute hydrochloric acid, dilute sulfuric acid, or dilute nitric acid having the same pH because silica having a desired pH cannot be obtained.
【００２１】第２の方法は、合成直後のスラリーに炭酸
ガスを吹き込み、ｐＨを５〜７にした後で濾過する方法
である。これを操作は、所要の純度になるまで１回以上
繰り返し行うことが望ましい。The second method is a method in which carbon dioxide gas is blown into the slurry immediately after the synthesis to adjust the pH to 5 to 7, and then the slurry is filtered. It is desirable to repeat this operation once or more until the required purity is reached.
【００２２】[0022]
【作用】炭酸ガスによりアルカリケイ酸塩をゲル化した
場合は、機構は不明であるが、シリカのゲル化が酸化亜
鉛の分散状態にとって好適な条件で進行するものと考え
られる。炭酸ガスは、いったん有機溶媒に溶解した後
で、アルカリケイ酸塩と反応していると考えられる。When the alkali silicate is gelled by carbon dioxide gas, the mechanism is unclear, but it is considered that the gelation of silica proceeds under conditions suitable for the dispersed state of zinc oxide. It is considered that carbon dioxide gas, once dissolved in an organic solvent, reacts with the alkali silicate.
【００２３】また、炭酸ガスを溶解した水による洗浄、
またはシリカスラリーへの炭酸ガスの吹き込みにより難
溶性の亜鉛の炭酸塩を形成することによりナトリウム等
の不純物のみを選択的に洗浄除去することが可能にな
り、シリカのｐＨをほぼ中性にし、かつ亜鉛の溶出を抑
えることができると考えられる。Further, washing with water in which carbon dioxide gas is dissolved,
Alternatively, it is possible to selectively wash and remove only impurities such as sodium by forming a sparingly soluble carbonate of zinc by blowing carbon dioxide gas into the silica slurry, and make the pH of the silica almost neutral, and It is considered that the elution of zinc can be suppressed.
【００２４】[0024]
実施例１ ３号珪曹（ＳｉＯ2 濃度２９重量％）２８８．４ｇを純
水８７．３ｇで希釈したケイ酸ナトリウム水溶液中に、
平均粒子径０．２６μｍの酸化亜鉛４５ｇを加え、ホモ
ミキサーで１０分撹拌して分散させた。この分散液を、
トリクロロトリフルオロエタン９６０ｍｌにソルビタン
モノオレイン酸エステル３．３６ｇを溶解した溶液に投
入し、ホモミキサーで乳化させた。この結果Ｗ／Ｏ型の
乳化液が形成され、ケイ酸ナトリウム水溶液の平均粒径
は約６μｍであった。Example 1 In a sodium silicate aqueous solution prepared by diluting 288.4 g of No. 3 silicic acid (SiO 2 concentration: 29% by weight) with 87.3 g of pure water,
45 g of zinc oxide having an average particle diameter of 0.26 μm was added, and the mixture was stirred for 10 minutes with a homomixer and dispersed. This dispersion is
A solution prepared by dissolving 3.36 g of sorbitan monooleate in 960 ml of trichlorotrifluoroethane was added and emulsified with a homomixer. As a result, a W / O type emulsion was formed, and the average particle size of the aqueous sodium silicate solution was about 6 μm.
【００２５】この乳化液に、空気で希釈した炭酸ガス
（ＣＯ2 濃度１０容積％）を吹き込みゲル化させた。ゲ
ル化開始時間は５．５分であった。炭酸ガスを１５分間
吹き込んだ後、トリクロロトリフルオロエタンを分離
し、球状シリカと水からなるスラリーを得た。このスラ
リーのｐＨは９．０であった。Carbon dioxide gas diluted with air (CO 2 concentration 10% by volume) was blown into the emulsion to gelate it. The gelation start time was 5.5 minutes. After blowing carbon dioxide gas for 15 minutes, trichlorotrifluoroethane was separated to obtain a slurry composed of spherical silica and water. The pH of this slurry was 9.0.
【００２６】このスラリーを濾過し、そのケーキを固形
分の１００倍の飽和炭酸水（ｐＨ＝３．３）で洗浄し、
乾燥した。得られた酸化亜鉛含有球状シリカの酸化亜鉛
の含有量は３２重量％、ｐＨは７．３、平均粒径は５．
５μｍであった。シリカのｐＨはシリカ５ｇを純水４５
ｇに入れ１０分間撹拌した後スラリーのｐＨを測定し
た。The slurry was filtered, and the cake was washed with 100 times the solid content of saturated carbonated water (pH = 3.3).
Dried. The obtained zinc oxide-containing spherical silica had a zinc oxide content of 32% by weight, a pH of 7.3, and an average particle size of 5.
It was 5 μm. The pH of silica is 5 g of silica and 45
After being placed in g and stirred for 10 minutes, the pH of the slurry was measured.
【００２７】実施例２ 実施例１で得られた合成直後のスラリーを濾過し、この
ケーキに固形分の２０倍の純水を加えて再度スラリー化
した後、炭酸ガスを吹き込んでｐＨを６．０にし、濾過
した。この操作を５回繰り返した後、乾燥した。得られ
た酸化亜鉛含有球状シリカの酸化亜鉛の含有量は３１重
量％、ｐＨは７．２、平均粒径は５．５μｍであった。Example 2 The slurry obtained in Example 1 immediately after synthesis was filtered, pure water having a solid content of 20 times was added to the cake to make a slurry again, and carbon dioxide gas was blown into the cake to adjust the pH to 6. 0 and filtered. This operation was repeated 5 times and then dried. The obtained zinc oxide-containing spherical silica had a zinc oxide content of 31% by weight, a pH of 7.2, and an average particle diameter of 5.5 μm.
【００２８】実施例３ 酸化亜鉛に平均粒子径０．０４μｍの酸化亜鉛を用いた
以外は実施例１と同様にして、酸化亜鉛含有球状シリカ
を得た。ただし、同一条件で炭酸ガスを導入してもゲル
化開始時間は６分であった。得られた酸化亜鉛含有球状
シリカの酸化亜鉛含有量は３１重量％であった。Example 3 A zinc oxide-containing spherical silica was obtained in the same manner as in Example 1 except that zinc oxide having an average particle diameter of 0.04 μm was used as the zinc oxide. However, even if carbon dioxide gas was introduced under the same conditions, the gelation start time was 6 minutes. The zinc oxide content in the obtained spherical silica containing zinc oxide was 31% by weight.
【００２９】実施例４ 炭酸ガスの濃度を８０容積％に変えて、ゲル化開始時間
を３分にした以外は実施例１と同様にして酸化亜鉛含有
球状シリカを製造した。この酸化亜鉛含有シリカの酸化
亜鉛含有量は３３重量％であった。Example 4 A zinc oxide-containing spherical silica was produced in the same manner as in Example 1 except that the concentration of carbon dioxide was changed to 80% by volume and the gelation start time was changed to 3 minutes. The zinc oxide content of this zinc oxide-containing silica was 33% by weight.
【００３０】実施例５ 炭酸ガスの濃度を８０容積％に変えて、ゲル化開始時間
を３分にした以外は実施例３と同様にして酸化亜鉛含有
シリカを製造した。この酸化亜鉛含有球状シリカの酸化
亜鉛含有量は３２重量％であった。Example 5 Zinc oxide-containing silica was produced in the same manner as in Example 3 except that the concentration of carbon dioxide was changed to 80% by volume and the gelation start time was changed to 3 minutes. The zinc oxide content of this zinc oxide-containing spherical silica was 32% by weight.
【００３１】（紫外線遮蔽特性の評価）実施例１および
実施例３〜５の酸化亜鉛担持球状シリカ３ｇと流動パラ
フィン７ｇを混合し、３本ロールを用いて分散させた。
これを石英板にはさみ厚みを３０μｍに調整した後、日
立製作所製、自記分光光度計Ｕ−４０００で透過率を測
定した。各波長での透過率を表１に示す。４００ｎｍは
可視光領域、３２０ｎｍは紫外光領域である。透過率が
小さいほど紫外線遮蔽特性が良いことを示す。いずれの
酸化亜鉛含有球状シリカも、可視光領域より高い吸収性
を紫外線領域で示した。実施例４、５に比べて、実施例
１、３は特にその特性が良好であった。(Evaluation of UV-shielding property) 3 g of the zinc oxide-supporting spherical silica of Example 1 and Examples 3 to 5 and 7 g of liquid paraffin were mixed and dispersed using a three-roll mill.
After sandwiching this with a quartz plate and adjusting the thickness to 30 μm, the transmittance was measured with a self-recording spectrophotometer U-4000 manufactured by Hitachi Ltd. Table 1 shows the transmittance at each wavelength. 400 nm is a visible light region and 320 nm is an ultraviolet light region. The smaller the transmittance is, the better the ultraviolet shielding property is. All of the zinc oxide-containing spherical silicas showed higher absorption in the ultraviolet region than in the visible light region. Compared with Examples 4 and 5, Examples 1 and 3 had particularly good characteristics.
【００３２】[0032]
【表１】 [Table 1]
【００３３】実施例６ 実施例１の合成直後のスラリーを濾過し、ケーキを固形
分の１００倍の純水で洗浄し、乾燥した。得られた酸化
亜鉛含有球状シリカの酸化亜鉛の含有量は３２重量％、
ｐＨは１０．３であった。実施例１および実施例２と同
量の水を使用したが、ｐＨはそれらより高かった。Example 6 The slurry obtained immediately after the synthesis of Example 1 was filtered, and the cake was washed with pure water having a solid content of 100 times and dried. The content of zinc oxide in the obtained spherical silica containing zinc oxide was 32% by weight,
The pH was 10.3. The same amount of water was used as in Examples 1 and 2, but the pH was higher than them.
【００３４】実施例７ 実施例１の合成直後のスラリーに希硫酸を加え、ｐＨを
５にした後濾過し、固形分の１００倍の純水で洗浄し、
乾燥した。得られた酸化亜鉛含有球状シリカの酸化亜鉛
の含有量は２５重量％、ｐＨは７．５であった。Example 7 Dilute sulfuric acid was added to the slurry immediately after synthesis in Example 1 to adjust the pH to 5, followed by filtration and washing with pure water having a solid content of 100 times.
Dried. The zinc oxide-containing spherical silica obtained had a zinc oxide content of 25% by weight and a pH of 7.5.
【００３５】実施例８ 実施例１の合成直後のスラリーを濾過し、ケーキを固形
分の１００倍の希塩酸（ｐＨ＝３．７）で洗浄し、乾燥
した。得られた酸化亜鉛含有球状シリカのｐＨは９．７
であった。実施例１および実施例２と同量の水を使用し
たが、ｐＨはそれらより高かった。Example 8 The slurry obtained immediately after the synthesis of Example 1 was filtered, and the cake was washed with 100 times the solid content of dilute hydrochloric acid (pH = 3.7) and dried. The pH of the obtained zinc oxide-containing spherical silica was 9.7.
Met. The same amount of water was used as in Examples 1 and 2, but the pH was higher than them.
【００３６】（排液中の亜鉛濃度）実施例１、２、７に
ついて洗浄排液（最初のろ液を含む）を全量混合し、Ｅ
ＤＴＡ法により亜鉛濃度を求めた。結果を表２に示す。
実施例７に比べると、実施例１および２では廃液中の亜
鉛濃度が極めて少なかった。(Zinc Concentration in Effluent) For Examples 1, 2, and 7, the cleaning effluent (including the first filtrate) was mixed in a total amount, and E
The zinc concentration was determined by the DTA method. Table 2 shows the results.
Compared to Example 7, in Examples 1 and 2, the zinc concentration in the waste liquid was extremely low.
【００３７】[0037]
【表２】 [Table 2]
【００３８】[0038]
【発明の効果】本発明の製造方法により、シリカ粒子中
の酸化亜鉛の分散状態が適当であり、紫外線遮蔽効果が
高い酸化亜鉛含有球状シリカが得られる。このシリカ
は、形状が球状であることにより、それを配合した化粧
料は紫外線遮蔽特性にすぐれ、すべり性等の使用感が良
好である。Industrial Applicability According to the production method of the present invention, zinc oxide-containing spherical silica having a suitable dispersion state of zinc oxide in silica particles and having a high ultraviolet shielding effect can be obtained. Since this silica has a spherical shape, the cosmetic containing it has excellent ultraviolet-shielding properties and a good feeling of use such as slipperiness.
【００３９】また、炭酸ガスを溶解した水による洗浄、
またはスラリーへの炭酸ガスの吹き込みにより、シリカ
のｐＨをほぼ中性にし、かつ亜鉛の溶出を抑えることが
できる。Further, washing with water in which carbon dioxide gas is dissolved,
Alternatively, by blowing carbon dioxide gas into the slurry, the pH of silica can be made almost neutral and the elution of zinc can be suppressed.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 平野 八朗 千葉県市原市五井海岸10番地 旭硝子株式 会社千葉工場内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hachiro Hirano 10 Goi Kaigan, Ichihara City, Chiba Asahi Glass Co., Ltd. Chiba Factory
Claims (9)
０１〜０．５μｍの酸化亜鉛を、アルカリケイ酸塩水溶
液中のＳｉＯ2 と酸化亜鉛の合計量に対して１０〜６０
重量％の含有量で分散させた分散液を、界面活性剤を含
む有機溶剤中で乳化した後、炭酸ガスによりゲル化させ
る酸化亜鉛含有球状シリカの製造方法。1. An alkaline silicate aqueous solution having a particle size of 0.
01 to 0.5 μm of zinc oxide is added to 10 to 60 with respect to the total amount of SiO 2 and zinc oxide in the aqueous alkali silicate solution.
A process for producing zinc oxide-containing spherical silica, which comprises emulsifying a dispersion liquid having a content of wt% in an organic solvent containing a surfactant and then gelling the mixture with carbon dioxide gas.
件でゲル化する請求項１の酸化亜鉛含有球状シリカの製
造方法。2. The method for producing spherical silica containing zinc oxide according to claim 1, wherein the gelling is carried out under the condition that the gelling start time is 4 minutes or more.
がナトリウムであり、Ｎａ2 Ｏ／ＳｉＯ2 モル比が、
２．０〜３．５で、水溶液の濃度がＳｉＯ2 として５〜
３０重量％である請求項１または請求項２の酸化亜鉛含
有球状シリカの製造方法。3. An alkali silicate aqueous solution, wherein the alkali is sodium and the Na 2 O / SiO 2 molar ratio is
It is 2.0 to 3.5, and the concentration of the aqueous solution is 5 as SiO 2.
30% by weight of the zinc oxide-containing spherical silica according to claim 1 or 2.
ある請求項１〜３いずれか１の酸化亜鉛含有球状シリカ
の製造方法。4. The method for producing spherical silica containing zinc oxide according to claim 1, wherein the organic solvent is an organic solvent in which carbon dioxide gas is soluble.
水素、塩素化炭化水素、クロロフルオロカーボン類から
なる群より選ばれる少なくとも１種である請求項１〜４
いずれか１の酸化亜鉛含有球状シリカの製造方法。5. The organic solvent is at least one selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons and chlorofluorocarbons.
1. A method for producing a spherical silica containing zinc oxide according to any one of the items.
解させた水で洗浄する請求項１〜５いずれか１の酸化亜
鉛含有球状シリカの製造方法。6. The method for producing spherical silica containing zinc oxide according to claim 1, wherein the gel produced by the reaction is washed with water in which carbon dioxide gas is dissolved.
４である請求項６の酸化亜鉛含有球状シリカの製造方
法。7. The pH of water in which carbon dioxide gas is dissolved is 3.3 to.
4. The method for producing spherical silica containing zinc oxide according to claim 6, which is No. 4.
後、炭酸ガスを吹き込みｐＨを５〜７に調整し濾過する
操作を少なくとも一回行う請求項１〜５いずれか１の酸
化亜鉛含有球状シリカの製造方法。8. The zinc oxide-containing spherical silica according to claim 1, wherein after the gel produced by the reaction is made into a slurry, the operation of blowing carbon dioxide gas to adjust the pH to 5 to 7 and filtering is performed at least once. Manufacturing method.
得た１０重量％スラリーのｐＨが７〜８になるまで処理
を行う請求項６〜８いずれか１の酸化亜鉛含有球状シリ
カの製造方法。9. A process for producing a zinc oxide-containing spherical silica according to claim 6, wherein a 10 wt% slurry obtained by dispersing the zinc oxide-containing spherical silica in water has a pH of 7-8. Method.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23782694A JP3453872B2 (en) | 1994-09-30 | 1994-09-30 | Method for producing zinc oxide-containing spherical silica |
| EP95115362A EP0704502B1 (en) | 1994-09-30 | 1995-09-28 | Zink-oxide containing spherical silica and process for its production |
| DE69502788T DE69502788T2 (en) | 1994-09-30 | 1995-09-28 | Silicic acid containing zinc oxide and process for its preparation |
| US08/833,427 US5738718A (en) | 1994-09-30 | 1997-04-07 | Zinc oxide-containing spherical silica and process for its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23782694A JP3453872B2 (en) | 1994-09-30 | 1994-09-30 | Method for producing zinc oxide-containing spherical silica |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08104515A true JPH08104515A (en) | 1996-04-23 |
| JP3453872B2 JP3453872B2 (en) | 2003-10-06 |
Family
ID=17020982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23782694A Expired - Fee Related JP3453872B2 (en) | 1994-09-30 | 1994-09-30 | Method for producing zinc oxide-containing spherical silica |
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| Country | Link |
|---|---|
| JP (1) | JP3453872B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11256133A (en) * | 1998-03-12 | 1999-09-21 | Nippon Muki Kagaku Kogyo Kk | Ultraviolet light-screening agent and its production |
| JP2002363018A (en) * | 2001-06-04 | 2002-12-18 | Shiseido Co Ltd | Antibacterial gel composition |
| JP2003516296A (en) * | 1999-12-08 | 2003-05-13 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Continuous production method of silica-based microgel |
| JP2020511394A (en) * | 2017-09-08 | 2020-04-16 | エルジー・ケム・リミテッド | Method for producing metal oxide-silica composite aerogel and metal oxide-silica composite aerogel produced thereby |
| CN115057466A (en) * | 2022-08-04 | 2022-09-16 | 安徽进化硅纳米材料科技有限公司 | Modified nano zinc oxide composite material and preparation method and application thereof |
-
1994
- 1994-09-30 JP JP23782694A patent/JP3453872B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11256133A (en) * | 1998-03-12 | 1999-09-21 | Nippon Muki Kagaku Kogyo Kk | Ultraviolet light-screening agent and its production |
| JP2003516296A (en) * | 1999-12-08 | 2003-05-13 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Continuous production method of silica-based microgel |
| JP4808350B2 (en) * | 1999-12-08 | 2011-11-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Continuous production method of silica-based microgel |
| JP2002363018A (en) * | 2001-06-04 | 2002-12-18 | Shiseido Co Ltd | Antibacterial gel composition |
| JP2020511394A (en) * | 2017-09-08 | 2020-04-16 | エルジー・ケム・リミテッド | Method for producing metal oxide-silica composite aerogel and metal oxide-silica composite aerogel produced thereby |
| US11478770B2 (en) | 2017-09-08 | 2022-10-25 | Lg Chem, Ltd. | Method of preparing metal oxide-silica composite aerogel and metal oxide-silica composite aerogel prepared by the same |
| US11666880B2 (en) | 2017-09-08 | 2023-06-06 | Lg Chem, Ltd. | Method of preparing metal oxide-silica composite aerogel and metal oxide-silica composite aerogel prepared by the same |
| CN115057466A (en) * | 2022-08-04 | 2022-09-16 | 安徽进化硅纳米材料科技有限公司 | Modified nano zinc oxide composite material and preparation method and application thereof |
| CN115057466B (en) * | 2022-08-04 | 2024-03-08 | 安徽进化硅纳米材料科技有限公司 | Modified nano zinc oxide composite material and preparation method and application thereof |
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