JP3520785B2 - Zinc oxide particle composition with suppressed surface activity, method for producing the same, and cosmetic containing the composition - Google Patents
Zinc oxide particle composition with suppressed surface activity, method for producing the same, and cosmetic containing the compositionInfo
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- JP3520785B2 JP3520785B2 JP33631698A JP33631698A JP3520785B2 JP 3520785 B2 JP3520785 B2 JP 3520785B2 JP 33631698 A JP33631698 A JP 33631698A JP 33631698 A JP33631698 A JP 33631698A JP 3520785 B2 JP3520785 B2 JP 3520785B2
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- Prior art keywords
- zinc oxide
- particle composition
- weight
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- composition according
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- Inorganic Compounds Of Heavy Metals (AREA)
- Silicon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、すぐれた紫外線遮
蔽性と透明性を有するうえに、ケイ素酸化物からなる高
密度の被覆層を表面に設けることによって、表面活性を
大幅に抑制した酸化亜鉛粒子組成物、その製造方法及び
上記組成物を含有する化粧料に関する。TECHNICAL FIELD The present invention relates to zinc oxide having excellent ultraviolet ray shielding property and transparency, and further having a high-density coating layer made of silicon oxide on the surface thereof, thereby significantly suppressing the surface activity. The present invention relates to a particle composition, a method for producing the particle composition, and a cosmetic containing the composition.
【０００２】[0002]
【従来の技術】近年、オゾン層が一部、破壊されている
ことによって、地表に到達する紫外線量の増加が問題に
されており、従来に増して、効果の高い日焼け止め化粧
料が要望されている。従来、このような日焼け止め化粧
料における紫外線吸収剤としては、ベンゾフェノン系、
安息香酸系、メトキシケイ皮酸系等の有機化合物が用い
られているが、これら有機化合物では、広い範囲の波長
域の紫外線を吸収することができないことや、皮膚への
刺激性の問題等から、より安全な紫外線遮蔽剤が求めら
れている。2. Description of the Related Art In recent years, due to the partial destruction of the ozone layer, an increase in the amount of ultraviolet rays reaching the surface of the earth has become a problem, and sunscreen cosmetics with higher effects than ever have been demanded. ing. Conventionally, as an ultraviolet absorber in such sunscreen cosmetics, benzophenone-based,
Benzoic acid-based and methoxycinnamic acid-based organic compounds are used, but these organic compounds cannot absorb ultraviolet rays in a wide range of wavelength range, and have a problem of irritation to the skin. There is a need for safer UV screening agents.
【０００３】地表に到達する紫外線には、水疱、紅斑等
の炎症（所謂日焼け）を起こす短波長（Ｂ領域）の紫外
線（２８０〜３２０ｎｍ）に加え、より長波長（Ａ領
域）の紫外線（３２０〜４００ｎｍ）が相乗して、皮膚
の老化や発癌性を引き起こすことが明らかにされてお
り、近年、特に、Ａ領域の紫外線の遮蔽に大きな関心が
もたれている。In addition to ultraviolet rays of short wavelength (B region) (280 to 320 nm) that cause inflammation (so-called sunburn) such as blisters and erythema, ultraviolet rays of longer wavelength (A region) (320) It has been revealed that synergistic effects (.about.400 nm) cause skin aging and carcinogenicity, and in recent years, in particular, there has been great interest in shielding ultraviolet rays in the A region.
【０００４】ところで、酸化亜鉛は、本来、３８０ｎｍ
付近に鋭い吸収端を有するので、Ａ領域の紫外線に対す
る遮蔽効果が高いが、更に、その後になって、超微粒子
酸化亜鉛が開発され、この超微粒子酸化亜鉛は、Ｂ領域
からＡ領域の広い波長域にわたる紫外線を遮蔽するのみ
ならず、超微粒子ルチル型酸化チタンが屈折率2.７を有
するところ、超微粒子酸化亜鉛は屈折率が2.０と小さ
く、透明性にすぐれているので、紫外線遮蔽剤として注
目されている。By the way, zinc oxide originally has a wavelength of 380 nm.
Since it has a sharp absorption edge in the vicinity, it has a high shielding effect against ultraviolet rays in the A region, but after that, ultrafine zinc oxide was developed, and this ultrafine zinc oxide has a wide wavelength range from the B region to the A region. In addition to blocking ultraviolet rays over a range, ultrafine particle rutile type titanium oxide has a refractive index of 2.7, but ultrafine particle zinc oxide has a small refractive index of 2.0 and has excellent transparency, so it can block ultraviolet rays. It is drawing attention as an agent.
【０００５】他方、酸化亜鉛は、元来、水に微量溶解す
る性質があり、その溶出亜鉛イオンによる生理作用が化
粧品分野では古くより収斂剤として利用されている。更
に、脂肪酸と反応して金属石ケンを生成する化学反応性
は、皮膚から分泌される皮脂を吸収して、化粧持ちをよ
くしたり、また、体臭成分を吸収するデオドラント効果
として利用されることもある。On the other hand, zinc oxide originally has a property of being dissolved in water in a trace amount, and the physiological action of the eluted zinc ion has been used as an astringent agent in the field of cosmetics for a long time. Furthermore, the chemical reactivity of reacting with fatty acids to form metallic soap is used as a deodorant effect that absorbs sebum secreted from the skin, improves makeup retention, and absorbs body odor components. There is also.
【０００６】しかし、これらの生理活性と化学反応性
は、酸化亜鉛を超微粒子化することによって一層強くな
る傾向にあり、今後、皮膚組織に対する安全性がより求
められた場合、粒子表面の活性を抑制することが望まし
い。However, these physiological activities and chemical reactivity tend to become stronger by making zinc oxide into ultrafine particles, and in the future, when the safety for skin tissue is further required, the activity of the particle surface will be increased. It is desirable to suppress it.
【０００７】更に、安全性に関連して、超微粒子酸化亜
鉛の光触媒能による活性酸素の生成を危惧する見方があ
る。元来、酸化亜鉛は、その結合エネルギーに相当する
紫外線を吸収することによって励起され、酸化チタンよ
りは非常に弱いが、粒子表面に接触している物質を酸化
する能力を有する。従って、化粧料に使用されたとき
に、活性酸素を生成するかもしれないとの疑いをもたれ
ていることから、超微粒子酸化亜鉛の光触媒活性を抑制
することが望ましい。Further, regarding safety, there is a view that there is a concern that active oxygen is produced by the photocatalytic activity of ultrafine zinc oxide. Originally, zinc oxide is excited by absorbing ultraviolet rays corresponding to its binding energy, and although it is much weaker than titanium oxide, it has an ability to oxidize a substance in contact with the particle surface. Therefore, since it is suspected that active oxygen may be generated when used in cosmetics, it is desirable to suppress the photocatalytic activity of ultrafine zinc oxide.
【０００８】また、上述した酸化亜鉛の水への溶解性と
化学反応性は、化粧料の配合設計上、種々の不都合を来
している。即ち、化粧料の最も重要な原料成分は、人体
の主要な構成成分でもある水であるが、超微粒子酸化亜
鉛を含む化粧料の場合、溶出亜鉛イオンが他成分と反応
するために、水の比率を高めることができず、処方の自
由度が狭められている。例えば、従来の超微粒子酸化亜
鉛を含む日焼け止め化粧料の場合、水の比率を５０％以
上にすることは困難であり、乳化製品の殆どは、油中水
型（Ｗ／Ｏ）に限定されている。Further, the above-mentioned solubility and chemical reactivity of zinc oxide in water have various inconveniences in designing the formulation of cosmetics. That is, the most important raw material component of cosmetics is water, which is also a major constituent of the human body, but in the case of cosmetics containing ultrafine zinc oxide, the dissolved zinc ions react with other components, and The ratio cannot be increased, and the degree of freedom in prescription is narrowed. For example, in the case of conventional sunscreen cosmetics containing ultrafine zinc oxide, it is difficult to adjust the water ratio to 50% or more, and most emulsified products are limited to the water-in-oil type (W / O). ing.
【０００９】更に、超微粒子酸化亜鉛の化粧料への使用
は、超微粒子酸化亜鉛が化粧品の他の配合成分である種
々の油剤、香料、色料、有機紫外線吸収剤、水溶性高分
子等と反応して、化粧料の粘度の増加や低減、異臭の発
生、変色等を起こす問題からも、処方の自由度を狭めて
いる。Further, the use of ultrafine zinc oxide in cosmetics is to use various oils, fragrances, colorants, organic UV absorbers, water-soluble polymers, etc., in which ultrafine zinc oxide is another component of cosmetics. The degree of freedom in prescription is also narrowed due to problems such as increase and decrease in viscosity of cosmetics, generation of offensive odor, discoloration, etc. by reaction.
【００１０】そこで、特開平３−１８３６２０号公報に
は、微粒子酸化亜鉛の表面にアルミニウム、ケイ素、ジ
ルコニウム又はスズの酸化物若しくは水酸化物を被覆
し、酸化亜鉛の触媒活性を低下させて、化粧料中の有機
系ベヒクルの変質を抑制し、また、微粒子酸化亜鉛の動
摩擦係数を低減させて、滑りや感触の悪化を防止するこ
とができることが記載されている。しかし、従来より知
られているこのような被覆層を表面に設けた微粒子酸化
亜鉛では、光触媒活性の抑制は、尚、非常に不十分であ
り、特に、酸化亜鉛が本来、有する水への溶解性と化学
反応性は、殆ど抑制することができない。Therefore, in JP-A-3-183620, the surface of fine particle zinc oxide is coated with an oxide or hydroxide of aluminum, silicon, zirconium or tin to reduce the catalytic activity of zinc oxide and It is described that the deterioration of the organic vehicle in the material can be suppressed, and the coefficient of kinetic friction of the particulate zinc oxide can be reduced to prevent slippage and deterioration of the feel. However, the suppression of photocatalytic activity is still very insufficient with the conventionally known fine particle zinc oxide provided with such a coating layer on the surface, and in particular, zinc oxide is originally dissolved in water. Properties and chemical reactivity can hardly be suppressed.
【００１１】以上のほか、超微粒子酸化チタンや超微粒
子酸化亜鉛をオルガノポリシロキサンで表面処理するこ
とによって、アセトアルデヒドの光化学的酸化反応に対
する光触媒作用を小さくすることができることが報告さ
れている（Cosmetics &Toiletries magazine, Vol. 11
2, June 1997, pp. 83-86)。In addition to the above, it has been reported that the surface treatment of ultrafine titanium oxide or ultrafine zinc oxide with an organopolysiloxane can reduce the photocatalytic action for the photochemical oxidation reaction of acetaldehyde (Cosmetics & Toiletries). magazine, Vol. 11
2, June 1997, pp. 83-86).
【００１２】しかし、化粧料分野においては、超微粒子
酸化亜鉛は、既に、実際に、オルガノポリシロキサン処
理したうえで配合されることが多く、それにもかかわら
ず、上述した溶出亜鉛イオンによる不具合や、他成分と
の反応性等の問題がみられることから、超微粒子酸化亜
鉛は、単純に、オルガノポリシロキサンで表面処理して
も、酸化亜鉛本来の表面活性を実質的に抑制することが
できないのみならず、光触媒活性についても、無害なま
でに制御することはできない。However, in the field of cosmetics, ultrafine zinc oxide is often already actually added after being treated with an organopolysiloxane, nevertheless, there are problems due to the above-mentioned eluted zinc ions, and Since there are problems such as reactivity with other components, ultrafine zinc oxide cannot substantially suppress the original surface activity of zinc oxide even if it is simply surface-treated with organopolysiloxane. In addition, the photocatalytic activity cannot be controlled harmlessly.
【００１３】[0013]
【発明が解決しようとする課題】本発明は、酸化亜鉛、
特に、超微粒子酸化亜鉛における上述した種々の問題、
なかでも、日焼け止め化粧料に用いるための超微粒子酸
化亜鉛における上述した種々の問題を解決するためにな
されたものであって、表面にケイ素酸化物からなる高密
度の被覆層を有し、純水や硫酸水溶液への溶解度が著し
く小さく、また、光触媒機能も、殆ど無害なまでに抑制
された酸化亜鉛粒子組成物、好ましくは、酸化亜鉛超微
粒子組成物とその製造方法と、更には、そのような酸化
亜鉛超微粒子組成物を配合した日焼け止め化粧料を提供
することを目的とする。The present invention is directed to zinc oxide,
In particular, the various problems described above in ultrafine zinc oxide,
Among them, what was made in order to solve the various problems described above in the ultrafine zinc oxide for use in sunscreen cosmetics, having a high-density coating layer of silicon oxide on the surface, pure Solubility in water or sulfuric acid aqueous solution is remarkably small, and the photocatalytic function is also almost harmlessly suppressed zinc oxide particle composition, preferably zinc oxide ultrafine particle composition and its production method, and further, An object is to provide a sunscreen cosmetic containing such a zinc oxide ultrafine particle composition.
【００１４】[0014]
【課題を解決するための手段】本発明による表面活性を
抑制した酸化亜鉛粒子組成物は、酸化亜鉛粒子の表面に
酸化亜鉛に対して１〜５０重量％の範囲でケイ素酸化物
からなる高密度の被覆層を有し、純水への溶解度がＺｎ
として２ｐｐｍ以下であると共に、0.０００５重量％硫
酸水溶液への溶解度がＺｎとして２０ｐｐｍ以下である
ことを特徴とする。The zinc oxide particle composition with suppressed surface activity according to the present invention has a high density of silicon oxide on the surface of zinc oxide particles in the range of 1 to 50% by weight with respect to zinc oxide. With a coating layer of
Is 2 ppm or less, and the solubility in a 0.0005 wt% sulfuric acid aqueous solution is 20 ppm or less as Zn.
【００１５】このような表面活性を抑制した酸化亜鉛粒
子組成物は、本発明に従って、酸化亜鉛粒子の水性懸濁
液に酸化亜鉛の重量に対してＳｉＯ2 として１〜５０重
量％の水溶性ケイ酸塩を加え、温度を６０℃以上に保持
しつつ、４０分以上の時間をかけて酸を加えて、ｐＨが
6.０〜8.０の範囲となるまで、懸濁液を中和して、酸化
亜鉛粒子の表面にケイ素酸化物からなる高密度の被覆層
を形成することによって得ることができる。According to the present invention, such a zinc oxide particle composition having suppressed surface activity has a water-soluble silica content of 1 to 50% by weight as SiO 2 based on the weight of zinc oxide in an aqueous suspension of zinc oxide particles. While adding the acid salt and maintaining the temperature at 60 ° C or higher, the acid is added over 40 minutes or longer to adjust the pH.
It can be obtained by neutralizing the suspension to a range of 6.0 to 8.0 to form a dense coating layer of silicon oxide on the surface of the zinc oxide particles.
【００１６】また、別の方法として、本発明に従って、
酸化亜鉛粒子の水性懸濁液に、温度を６０℃以上に保持
すると共に、ｐＨを９〜１0.５の範囲に保持しつつ、酸
化亜鉛の重量に対してＳｉＯ2 として１〜５０重量％の
水溶性ケイ酸塩と酸とを４０分以上の時間をかけて同時
に加えた後、更に、酸を加えて、ｐＨが6.０〜8.０の範
囲となるまで、懸濁液を中和して、酸化亜鉛粒子の表面
にケイ素酸化物からなる高密度の被覆層を形成すること
によって得ることができる。As another method, according to the present invention,
In an aqueous suspension of zinc oxide particles, the temperature was maintained at 60 ° C. or higher and the pH was maintained in the range of 9 to 10.5, while the SiO 2 content was 1 to 50% by weight as SiO 2. After simultaneously adding water-soluble silicate and acid over 40 minutes or more, further add acid to neutralize the suspension until the pH is in the range of 6.0 to 8.0. Then, it can be obtained by forming a high-density coating layer made of silicon oxide on the surface of the zinc oxide particles.
【００１７】更に、本発明による化粧料は、上記酸化亜
鉛粒子組成物を含むことを特徴とする。Furthermore, the cosmetic according to the present invention is characterized by containing the above zinc oxide particle composition.
【００１８】[0018]
【発明の実施の形態】本発明において用いる酸化亜鉛粒
子は、電気亜鉛地金を蒸発酸化して得られるものや、硫
酸亜鉛、塩化亜鉛のような水溶性塩の水溶液を中和して
得られる水酸化亜鉛、炭酸亜鉛、硫化亜鉛、シュウ酸亜
鉛等を焼成して得られるもの等、特に、限定されるもの
ではなく、いずれでもよい。しかし、本発明において、
酸化亜鉛粒子は、高い透明性を有するように、平均一次
粒子径が0.１５μｍ以下であることが好ましい。酸化亜
鉛粒子の平均一次粒子径が0.１５μｍより大きいとき
は、隠蔽力が大きく、白くなり、透明性が低い。しか
し、必要に応じて、平均一次粒子径が0.１５μｍを越え
るものを用いてもよい。酸化亜鉛粒子の平均一次粒子径
の下限は、特に、限定されるものではないが、通常、0.
０１μｍである。ここに、平均一次粒子径とは、透過型
電子顕微鏡写真の１０万倍の視野で一定方向径（所謂 F
ERET 径）で定義されるものである。BEST MODE FOR CARRYING OUT THE INVENTION Zinc oxide particles used in the present invention are obtained by evaporating and oxidizing electro-zinc metal or by neutralizing an aqueous solution of a water-soluble salt such as zinc sulfate and zinc chloride. Those obtained by firing zinc hydroxide, zinc carbonate, zinc sulfide, zinc oxalate and the like are not particularly limited and any of them may be used. However, in the present invention,
The zinc oxide particles preferably have an average primary particle diameter of 0.15 μm or less so as to have high transparency. When the average primary particle diameter of the zinc oxide particles is larger than 0.15 μm, the hiding power is large, whitening occurs, and the transparency is low. However, if necessary, particles having an average primary particle size of more than 0.15 μm may be used. The lower limit of the average primary particle diameter of the zinc oxide particles is not particularly limited, but is usually 0.
It is 01 μm. Here, the average primary particle diameter means a constant direction diameter (so-called F
ERET diameter).
【００１９】本発明による酸化亜鉛粒子組成物は、酸化
亜鉛粒子の表面に酸化亜鉛に対して１〜５０重量％、好
ましくは、５〜２０重量％の範囲でケイ素酸化物からな
る高密度の被覆層を有する。ケイ素酸化物は、限定され
るものではないが、好ましくは、含水ケイ素酸化物であ
る。酸化亜鉛粒子組成物におけるケイ素酸化物の割合が
１重量％よりも少ないときは、酸化亜鉛の表面活性を抑
えることができず、他方、５０重量％を越えるときは、
得られる酸化亜鉛粒子組成物が分散性において著しく低
下する。The zinc oxide particle composition according to the present invention has a high-density coating made of silicon oxide in the range of 1 to 50% by weight, preferably 5 to 20% by weight, based on zinc oxide, on the surface of the zinc oxide particles. With layers. The silicon oxide is preferably, but not limited to, hydrous silicon oxide. When the proportion of silicon oxide in the zinc oxide particle composition is less than 1% by weight, the surface activity of zinc oxide cannot be suppressed, while when it exceeds 50% by weight,
The resulting zinc oxide particle composition has a markedly reduced dispersibility.
【００２０】本発明によれば、酸化亜鉛粒子の水性懸濁
液に、酸化亜鉛に対してＳｉＯ2 として１〜５０重量％
の水溶性ケイ酸塩を加え、温度を６０℃以上に保持しつ
つ、４０分以上の時間をかけて酸を中和剤として加え
て、ｐＨが6.０〜8.０の範囲となるまで、懸濁液を中和
することによって、酸化亜鉛粒子の表面にケイ素酸化物
からなる高密度の被覆層を形成して、本発明による酸化
亜鉛粒子組成物を得ることができる。水性懸濁液におけ
る酸化亜鉛粒子の濃度は、５０〜２５０ｇ／Ｌの範囲が
好ましく、また、酸化亜鉛粒子は、サンドミル等の粉砕
機によって、酸化亜鉛原体を十分に粉砕しておくことが
望ましい。上記水溶性ケイ酸塩としては、ケイ酸ナトリ
ウム又はケイ酸カリウムが好ましく用いられるが、しか
し、これらに限定されるものではない。上記中和剤とし
ては、限定されるものではないが、硫酸等の無機酸や、
酢酸、シュウ酸等の有機酸が好ましく用いられる。According to the present invention, an aqueous suspension of zinc oxide particles contains 1 to 50% by weight of SiO 2 as zinc oxide.
Of water-soluble silicate is added, and while keeping the temperature at 60 ° C. or higher, the acid is added as a neutralizing agent over 40 minutes or longer until the pH is in the range of 6.0 to 8.0. By neutralizing the suspension, a zinc oxide particle composition according to the present invention can be obtained by forming a high density coating layer of silicon oxide on the surface of the zinc oxide particles. The concentration of zinc oxide particles in the aqueous suspension is preferably in the range of 50 to 250 g / L, and it is desirable that the zinc oxide particles are sufficiently crushed with a crusher such as a sand mill. . As the water-soluble silicate, sodium silicate or potassium silicate is preferably used, but the water-soluble silicate is not limited thereto. The neutralizing agent is not limited, but an inorganic acid such as sulfuric acid,
Organic acids such as acetic acid and oxalic acid are preferably used.
【００２１】本発明によれば、酸化亜鉛粒子の水性懸濁
液に水溶性ケイ酸塩を加えた後、これに中和剤として酸
を加えて、水溶性ケイ酸塩を中和する際の温度条件と中
和剤を加える時間条件（時間幅）が重要である。即ち、
本発明によれば、酸化亜鉛粒子の水性懸濁液に水溶性ケ
イ酸塩を加え、この懸濁液の温度を６０℃以上、好まし
くは、８０℃以上に保持しながら、４０分以上、好まし
くは、６０分以上の時間をかけて、中和剤を加え、ｐＨ
が6.０〜8.０の範囲まで、懸濁液を中和することによっ
て、含水ケイ素酸化物からなる高密度の被覆層を酸化亜
鉛の表面に形成することができる。According to the present invention, a water-soluble silicate is added to an aqueous suspension of zinc oxide particles, and then an acid is added as a neutralizing agent to neutralize the water-soluble silicate. The temperature condition and the time condition (time range) for adding the neutralizing agent are important. That is,
According to the present invention, a water-soluble silicate is added to an aqueous suspension of zinc oxide particles, and the temperature of this suspension is kept at 60 ° C or higher, preferably 80 ° C or higher, for 40 minutes or longer, preferably Over 60 minutes, add the neutralizing agent and
By neutralizing the suspension to a range of 6.0 to 8.0, a dense coating layer of hydrous silicon oxide can be formed on the surface of zinc oxide.
【００２２】別の方法として、酸化亜鉛粒子の水性懸濁
液に、その温度を６０℃以上、好ましくは、８０℃以上
に保持しながら、水溶性ケイ酸塩と中和剤とを、４０分
以上、好ましくは、６０分以上の時間をかけて、同時に
加えた後、更に、中和剤を加えて、ｐＨが6.０〜8.０の
範囲まで、懸濁液を中和することによっても、含水ケイ
素酸化物からなる高密度の被覆層を酸化亜鉛の表面に形
成することができる。As another method, an aqueous suspension of zinc oxide particles is treated with a water-soluble silicate and a neutralizing agent for 40 minutes while maintaining the temperature at 60 ° C. or higher, preferably 80 ° C. or higher. Above, preferably, over 60 minutes or more, after adding at the same time, by further adding a neutralizing agent, by neutralizing the suspension to a pH range of 6.0-8.0 Also, a high-density coating layer made of hydrous silicon oxide can be formed on the surface of zinc oxide.
【００２３】このような本発明の方法によって、酸化亜
鉛の表面に含水ケイ素酸化物からなる高密度の被覆層を
形成することができる。そして、本発明によれば、この
ような含水ケイ素酸化物からなる高密度の被覆層が酸化
亜鉛粒子を媒体から隔絶するので、酸化亜鉛本来の性質
である水への溶解性と化学反応性を著しく抑制すること
ができ、更には、光触媒能をもほぼ完全に抑制すること
ができ、かくして、本発明によれば、特に、超微粒子酸
化亜鉛の表面活性を実質的に抑制することができる。更
に、本発明による酸化亜鉛粒子組成物は、水への分散性
や水中における分散安定性が向上するという利点も有す
る。By the method of the present invention as described above, a high-density coating layer made of hydrous silicon oxide can be formed on the surface of zinc oxide. Further, according to the present invention, since the high-density coating layer made of such a hydrous silicon oxide isolates the zinc oxide particles from the medium, the solubility and chemical reactivity in water, which are the original properties of zinc oxide, are maintained. It can be remarkably suppressed, and further, the photocatalytic activity can be almost completely suppressed. Thus, according to the present invention, the surface activity of the ultrafine zinc oxide can be substantially suppressed. Further, the zinc oxide particle composition according to the present invention also has an advantage that the dispersibility in water and the dispersion stability in water are improved.
【００２４】本発明によれば、酸化亜鉛にケイ素酸化物
からなる高密度の被覆層を形成する前に、酸化亜鉛に、
上記被覆層の形成を妨げない範囲で、Ｔｉ、Ｚｒ、Ｓｎ
や、その他の含水酸化物又は酸化物を少量、含有させて
もよい。According to the present invention, before forming a high density coating layer of silicon oxide on zinc oxide,
Ti, Zr, Sn within a range that does not hinder the formation of the coating layer.
Alternatively, a small amount of other hydrous oxide or oxide may be contained.
【００２５】更に、本発明によれば、上述したようにし
て、酸化亜鉛の表面に含水ケイ素酸化物からなる高密度
の被覆層を形成した後、その上に酸化亜鉛に対して0.５
〜３０重量％、好ましくは、２〜１５重量％の範囲のＡ
ｌ、Ｔｉ、Ｚｒ、Ｓｎ、Ｓｂ及び希土類元素よりなる群
から選ばれる少なくとも１種の酸化物からなる第２の被
覆層を形成してもよい。ここに、希土類元素としては、
例えば、イットリウム、ランタン、セリウム、ネオジム
等を挙げることができる。Further, according to the present invention, as described above, after forming a high-density coating layer made of hydrous silicon oxide on the surface of zinc oxide, 0.5 to zinc oxide is formed thereon.
-30% by weight, preferably 2-15% by weight of A
You may form the 2nd coating layer which consists of at least 1 sort (s) of oxide selected from the group which consists of 1, Ti, Zr, Sn, Sb, and a rare earth element. Here, as the rare earth element,
For example, yttrium, lanthanum, cerium, neodymium, etc. can be mentioned.
【００２６】このような第２の被覆層を有する酸化亜鉛
粒子組成物は、含水酸化ケイ素からなる第１の被覆層を
有する酸化亜鉛粒子組成物の水性懸濁液を調製し、これ
に上記元素の水溶性化合物の水溶液を加え、酸又はアル
カリを中和剤として加えて、上記元素の化合物を中和し
て、上記酸化亜鉛粒子組成物の表面に上記元素の酸化物
からなる被覆層を形成することによって得ることができ
る。The zinc oxide particle composition having the second coating layer is prepared by preparing an aqueous suspension of the zinc oxide particle composition having the first coating layer made of hydrous silicon oxide, and adding the above-mentioned element to the suspension. Solution of water-soluble compound is added, and acid or alkali is added as a neutralizing agent to neutralize the compound of the above-mentioned element to form a coating layer made of oxide of the above-mentioned element on the surface of the zinc oxide particle composition. Can be obtained by doing.
【００２７】Ａｌの水溶性化合物としては、例えば、硝
酸アルミニウム、硫酸アルミニウム、アルミン酸ナトリ
ウム等を、Ｔｉの水溶性化合物としては、例えば、チタ
ニル硫酸等を、Ｚｒの水溶性化合物としては、例えば、
硝酸ジルコニウム、硫酸ジルコニウム等を、Ｓｎの水溶
性化合物としては、例えば、塩化スズを、Ｓｂの水溶性
化合物としては、例えば、塩化アンチモン等を、また、
希土類元素の水溶性化合物としては、例えば、硝酸セリ
ウム等を挙げることができる。As the water-soluble compound of Al, for example, aluminum nitrate, aluminum sulfate, sodium aluminate and the like, as the water-soluble compound of Ti, for example, titanyl sulfuric acid and the like, and as the water-soluble compound of Zr, for example,
Zirconium nitrate, zirconium sulfate, etc., as a water-soluble compound of Sn, for example, tin chloride, as a water-soluble compound of Sb, for example, antimony chloride, etc.
Examples of water-soluble compounds of rare earth elements include cerium nitrate.
【００２８】上記中和剤である酸としては、前述したも
のと同じく、硫酸等の無機酸や、酢酸、シュウ酸等の有
機酸が好ましく用いられる。他方、上記中和剤であるア
ルカリとしては、例えば、水酸化ナトリウム、水酸化カ
リウム、水酸化アンモニウム等が好ましく用いられる。As the above-mentioned neutralizing agent, an inorganic acid such as sulfuric acid or an organic acid such as acetic acid or oxalic acid is preferably used as in the above-mentioned ones. On the other hand, as the alkali that is the neutralizing agent, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide and the like are preferably used.
【００２９】含水ケイ素酸化物からなる第１の被覆層を
有する酸化亜鉛粒子組成物に上記元素の酸化物からなる
第２の被覆層を形成するに際して、２種以上の元素の酸
化物からなる被覆層を形成する場合、複数の元素の水溶
性化合物の水溶液を用いて、一度に複数の元素の酸化物
の混合物からなる被覆層を形成してもよいが、しかし、
個々の元素の水溶性化合物の水溶液を用いて、一層ず
つ、酸化物からなる被覆層を形成して、第２の被覆層を
多層とするのが好ましい。アルミニウム酸化物を含む複
数の元素の酸化物からなる被覆層を形成する場合には、
アルミニウム酸化物からなる被覆層を最後に形成するこ
とが好ましい。When forming the second coating layer made of the oxide of the above element on the zinc oxide particle composition having the first coating layer made of the hydrous silicon oxide, the coating made of the oxide of two or more elements is formed. When forming a layer, an aqueous solution of a water-soluble compound of a plurality of elements may be used to form a coating layer composed of a mixture of oxides of a plurality of elements at one time, but
It is preferable that a coating layer made of an oxide is formed one by one using an aqueous solution of a water-soluble compound of each element to form the second coating layer as a multi-layer. When forming a coating layer composed of oxides of a plurality of elements including aluminum oxide,
It is preferable to finally form the coating layer made of aluminum oxide.
【００３０】また、本発明によれば、例えば、化粧料中
の油剤への分散性を高め、また、撥水性を高めるため
に、酸化亜鉛粒子の表面に含水ケイ素酸化物からなる第
１の被覆層を形成した後、又は上記第２の被覆層を形成
した後、そのような酸化亜鉛粒子組成物をオルガノポリ
シロキサンで表面処理してもよい。このような表面処理
に用いるオルガノポリシロキサンは、酸化亜鉛に対し
て、通常、１〜２０重量％の範囲であり、好ましくは、
３〜１０重量％の範囲である。オルガノポリシロキサン
としては、例えば、ジメチルポリシロキサンやメチルハ
イドロジェンポリシロキサン等が好ましく用いられる。
このようなオルガノポリシロキサンが酸化亜鉛に対して
１重量％よりも少ないときは、化粧料中の油剤への分散
性の改善効果に乏しく、他方、２０重量％を越えても、
化粧料中の油剤への分散性や撥水性が飽和するので、経
済的にも不利である。Further, according to the present invention, for example, in order to enhance dispersibility in an oil agent in cosmetics and enhance water repellency, the surface of zinc oxide particles is coated with a first coating of hydrous silicon oxide. After forming the layer, or after forming the second coating layer, such a zinc oxide particle composition may be surface treated with an organopolysiloxane. The organopolysiloxane used for such surface treatment is usually in the range of 1 to 20% by weight with respect to zinc oxide, and preferably,
It is in the range of 3 to 10% by weight. As the organopolysiloxane, for example, dimethylpolysiloxane and methylhydrogenpolysiloxane are preferably used.
When the content of such an organopolysiloxane is less than 1% by weight with respect to zinc oxide, the effect of improving dispersibility in an oil agent in cosmetics is poor, and even when it exceeds 20% by weight,
It is economically disadvantageous because the dispersibility in oils and the water repellency in cosmetics are saturated.
【００３１】このように、オルガノポリシロキサンによ
る表面処理のほか、例えば、ステアリン酸等の高級脂肪
酸、パルミチン酸オクチル等の高級脂肪酸エステル、ト
リメチロールエタン、トリメチロールプロパン、ペンタ
エリスリトール等の多価アルコール、ジエタノールアミ
ン、トリエタノールアミン等のアミン化合物で表面処理
することもできる。Thus, in addition to the surface treatment with the organopolysiloxane, for example, higher fatty acids such as stearic acid, higher fatty acid esters such as octyl palmitate, polyhydric alcohols such as trimethylolethane, trimethylolpropane and pentaerythritol, The surface can be treated with an amine compound such as diethanolamine or triethanolamine.
【００３２】本発明による酸化亜鉛粒子組成物は、その
表面にケイ素酸化物からなる高密度の被覆層を有し、純
水及び硫酸水溶液への溶解度が著しく小さく、また、光
触媒機能が抑制されている一方、Ａ領域紫外線の遮蔽能
と透明性においてすぐれているので、人体への安全性を
危惧することなく、紫外線遮蔽用化粧料に好適に用いる
ことができる。本発明において、ケイ素酸化物からなる
高密度の被覆層とは、酸化亜鉛の溶解性、特に、酸化亜
鉛の純水及び硫酸水溶液への溶解度をこのように低くす
ることができる緻密さを有するという意味である。The zinc oxide particle composition according to the present invention has a high-density coating layer made of silicon oxide on the surface thereof, its solubility in pure water and sulfuric acid aqueous solution is extremely small, and its photocatalytic function is suppressed. On the other hand, since it is excellent in A-region ultraviolet ray shielding ability and transparency, it can be suitably used for ultraviolet ray shielding cosmetics without concern for safety to human body. In the present invention, the high-density coating layer made of silicon oxide means that the solubility of zinc oxide, especially the density of zinc oxide in pure water and aqueous sulfuric acid solution, can be reduced in this way. Is the meaning.
【００３３】本発明による酸化亜鉛粒子組成物は、これ
を配合する化粧料の剤形を大幅に拡大することができ
る。本発明による酸化亜鉛粒子組成物は、油性タイプは
勿論、水への溶解性が殆どないことから、水の比率が５
０％を越える乳化製品や化粧水にも安定的に用いること
ができる。更に、化粧料における他の配合成分である種
々の油剤、香料、色料、有機紫外線吸収剤、水溶性高分
子等との反応性を殆どもたないから、本発明による酸化
亜鉛粒子は、任意の剤形、例えば、パウダー、プレスド
パウダー、ケーキ状、乳液状、溶液状、ゲル状等のいず
れの剤形の日焼け止め化粧料にも用いることができる。The zinc oxide particle composition according to the present invention can greatly expand the dosage form of cosmetics containing the same. Since the zinc oxide particle composition according to the present invention has almost no solubility in water as well as an oily type, the ratio of water is 5%.
It can be stably used for emulsified products and lotions exceeding 0%. Furthermore, the zinc oxide particles according to the present invention have almost no reactivity with various oil agents, fragrances, coloring agents, organic UV absorbers, water-soluble polymers, etc., which are other compounding ingredients in cosmetics. Can be used for the sunscreen cosmetics in any of the dosage forms such as powder, pressed powder, cake, emulsion, solution and gel.
【００３４】[0034]
【実施例】以下に比較例と共に実施例を挙げて本発明を
説明するが、本発明はこれら実施例により何ら限定され
るものではない。以下の実施例及び比較例においては、
特に、記載がない限りは、酸化亜鉛原体として、電気亜
鉛地金を蒸発酸化して得られた平均一次粒子径0.０６μ
ｍの超微粒子酸化亜鉛（堺化学工業（株）製ＦＩＮＥＸ
−２５）を用いた。EXAMPLES The present invention will be described below with reference to examples together with comparative examples, but the present invention is not limited to these examples. In the following examples and comparative examples,
Unless otherwise specified, the average primary particle size obtained by evaporative oxidation of electro-zinc metal was 0.06μ unless otherwise specified.
Ultrafine zinc oxide of m (Finex manufactured by Sakai Chemical Industry Co., Ltd.)
-25) was used.
【００３５】実施例１
超微粒子酸化亜鉛の水性懸濁液（ＺｎＯ濃度５０ｇ／
Ｌ）を８０℃に昇温し、攪拌下、酸化亜鉛に対して、Ｓ
ｉＯ2 として１０重量％のケイ酸ナトリウムの水溶液を
加えた。１０分間、熟成した後、６０分かけて撹拌下に
硫酸を加え、ｐＨ6.５に中和した。３０分間、熟成した
後、得られた懸濁液を濾過、水洗した後、１３０℃で５
時間、加熱乾燥した。このようにして得られた乾燥品を
ジェットミル粉砕して、含水ケイ素酸化物からなる高密
度の被覆層を表面に有する酸化亜鉛超微粒子組成物粉末
を得た。Example 1 Aqueous suspension of ultrafine zinc oxide (ZnO concentration 50 g /
L) is heated to 80 ° C., and S is added to zinc oxide under stirring.
An aqueous solution of 10 wt% sodium silicate was added as iO 2 . After aging for 10 minutes, sulfuric acid was added with stirring over 60 minutes to neutralize to pH 6.5. After aging for 30 minutes, the resulting suspension was filtered, washed with water, and then washed at 130 ° C for 5 minutes.
Heat dried for hours. The dried product thus obtained was pulverized with a jet mill to obtain a zinc oxide ultrafine particle composition powder having a high-density coating layer made of hydrous silicon oxide on the surface.
【００３６】実施例２
超微粒子酸化亜鉛の水性懸濁液（ＺｎＯ濃度５０ｇ／
Ｌ）を８０℃に昇温し、攪拌下、酸化亜鉛に対して、Ｓ
ｉＯ2 として１０重量％のケイ酸ナトリウムの水溶液を
加えた。１０分間、熟成した後、６０分かけて撹拌下に
硫酸を加え、ｐＨ6.５に中和した。３０分間、熟成した
後、撹拌下に、酸化亜鉛に対して、Ａｌ2Ｏ3 として５
重量％のアルミン酸ナトリウムの水溶液を加え、１０分
間、熟成した後、１０分かけて硫酸を加えて、ｐＨ7.０
に中和した。３０分間、熟成した後、得られた懸濁液を
濾過、水洗し、１３０℃で５時間加熱乾燥した。このよ
うにして得られた乾燥品をジェットミル粉砕して、内側
に含水ケイ素酸化物からなる高密度の被覆層を有し、外
側に含水アルミニウム酸化物からなる被覆層を有する酸
化亜鉛超微粒子組成物粉末を得た。Example 2 Aqueous suspension of ultrafine zinc oxide (ZnO concentration 50 g /
L) is heated to 80 ° C., and S is added to zinc oxide under stirring.
An aqueous solution of 10 wt% sodium silicate was added as iO 2 . After aging for 10 minutes, sulfuric acid was added with stirring over 60 minutes to neutralize to pH 6.5. After aging for 30 minutes, with stirring, zinc oxide was mixed with Al 2 O 3 to give 5
Add an aqueous solution of sodium aluminate in an amount of 10% by weight, age for 10 minutes, and add sulfuric acid over 10 minutes to adjust the pH to 7.0.
Neutralized. After aging for 30 minutes, the obtained suspension was filtered, washed with water, and dried by heating at 130 ° C. for 5 hours. The dried product thus obtained is subjected to jet mill pulverization to have a zinc oxide ultrafine particle composition having a high-density coating layer made of hydrous silicon oxide on the inside and a coating layer made of hydrous aluminum oxide on the outside. The product powder was obtained.
【００３７】実施例３
実施例２で調製した酸化亜鉛超微粒子組成物粉末をスー
パーミキサー中で撹拌しながら、酸化亜鉛に対して１０
重量％のジメチルポリシロキサン（信越化学（株）製シ
リコーンオイルＫＦ−９６）を噴霧して、ジメチルポリ
シロキサン処理した酸化亜鉛超微粒子組成物粉末を得
た。Example 3 The zinc oxide ultrafine particle composition powder prepared in Example 2 was stirred in a supermixer with 10 parts by weight of zinc oxide.
A dimethylpolysiloxane-treated zinc oxide ultrafine particle composition powder was obtained by spraying dimethylpolysiloxane (silicone oil KF-96 manufactured by Shin-Etsu Chemical Co., Ltd.) in a weight percentage.
【００３８】比較例１
実施例１と同様にして、超微粒子酸化亜鉛の水性懸濁液
を調製し、２５〜３５℃の範囲の温度で、酸化亜鉛に対
して、ＳｉＯ2 として１０重量％のケイ酸ナトリウムの
水溶液を加えた。１０分間、熟成した後、１０分かけて
硫酸を加えて、ｐＨ6.５に中和した。次に、この懸濁液
に攪拌下、酸化亜鉛に対して、Ａｌ2 Ｏ 3 として５重量
％のアルミン酸ナトリウムの水溶液を加えた後、１０分
かけて硫酸を加えて、ｐＨ7.０に中和した。この後、実
施例１と同様に処理して、内側に含水ケイ素酸化物から
なる被覆層を有すると共に、外側に含水アルミニウム酸
化物からなる被覆層を有する酸化亜鉛超微粒子組成物粉
末を得た。Comparative Example 1
Aqueous suspension of ultrafine zinc oxide in the same manner as in Example 1.
Was prepared and treated with zinc oxide at a temperature in the range of 25 to 35 ° C.
Then SiO2As 10% by weight of sodium silicate
Aqueous solution was added. After aging for 10 minutes, take 10 minutes
Sulfuric acid was added to neutralize to pH 6.5. Then this suspension
Under stirring, with respect to zinc oxide, Al2O 3As 5 weight
% Aqueous sodium aluminate solution for 10 minutes
Sulfuric acid was added thereto to neutralize it to pH 7.0. After this, the real
The same treatment as in Example 1 was carried out, and hydrous silicon oxide was applied to the inside.
And a hydrous aluminum oxide on the outside.
Zinc Oxide Ultrafine Particle Composition Powder Having a Coating Layer Made of a Compound
I got the end.
【００３９】比較例２
実施例１と同様にして、超微粒子酸化亜鉛の水性懸濁液
を調製し、８０℃に昇温し、攪拌下、酸化亜鉛に対し
て、Ａｌ2 Ｏ3 として５重量％のアルミン酸ナトリウム
の水溶液を加えた後、１０分かけて硫酸を加えて、ｐＨ
7.０に中和した。この後、実施例１と同様に処理して、
表面が含水アルミニウム酸化物で被覆された酸化亜鉛超
微粒子組成物粉末を得た。Comparative Example 2 In the same manner as in Example 1, an aqueous suspension of ultrafine zinc oxide was prepared, heated to 80 ° C., and stirred to give 5% by weight of Al 2 O 3 with respect to zinc oxide. % Aqueous solution of sodium aluminate, then sulfuric acid is added over 10 minutes to adjust the pH.
Neutralized to 7.0. After that, the same processing as in Example 1 is performed,
A zinc oxide ultrafine particle composition powder having a surface coated with a hydrous aluminum oxide was obtained.
【００４０】比較例３
超微粒子酸化亜鉛原体の粉末をスーパーミキサー中で撹
拌しながら、粉体に対して１０重量％のジメチルポリシ
ロキサン（信越化学（株）製シリコーンオイルＫＦ−９
６）を噴霧して、ジメチルポリシロキサン処理した酸化
亜鉛超微粒子組成物粉末を得た。Comparative Example 3 While stirring powder of ultrafine zinc oxide raw material in a super mixer, 10% by weight of dimethylpolysiloxane (silicone oil KF-9 manufactured by Shin-Etsu Chemical Co., Ltd.) based on the powder was stirred.
6) was sprayed to obtain zinc oxide ultrafine particle composition powder treated with dimethylpolysiloxane.
【００４１】比較例４
超微粒子酸化亜鉛原体そのもの（堺化学工業（株）製Ｆ
ＩＮＥＸ−２５）を比較例としての酸化亜鉛粒子組成物
とした。Comparative Example 4 Ultrafine zinc oxide raw material itself (F manufactured by Sakai Chemical Industry Co., Ltd.)
INEX-25) was used as a zinc oxide particle composition as a comparative example.
【００４２】試験１
上記実施例１〜３及び比較例１〜４において得た酸化亜
鉛超微粒子組成物粉末について、２５℃における純水及
びｐＨ４の硫酸酸性水溶液（0.０００５重量％硫酸水溶
液）への酸化亜鉛の溶解度を原子吸光分析にて測定し
た。結果を表１に示す。Test 1 The zinc oxide ultrafine particle composition powders obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were added to pure water at 25 ° C. and a sulfuric acid aqueous solution having a pH of 4 (0.0005% by weight sulfuric acid aqueous solution). The solubility of zinc oxide of was measured by atomic absorption spectrometry. The results are shown in Table 1.
【００４３】[0043]
【表１】 [Table 1]
【００４４】表１から明らかなように、本発明による酸
化亜鉛超微粒子組成物粉末は、水及び硫酸水溶液への溶
解性が著しく小さい。As is apparent from Table 1, the zinc oxide ultrafine particle composition powder according to the present invention has remarkably low solubility in water and a sulfuric acid aqueous solution.
【００４５】試験２
本発明による酸化亜鉛超微粒子組成物粉末のサンスクリ
ーンゲルへの使用適性を調べるために、カルボキシビニ
ルポリマー（アクリル酸−アルキルアクリレート共重合
体）0.２％水溶液に超微粒子酸化亜鉛を１２％濃度で仕
込み、得られたスラリーの粘度（２５℃、Ｂ型粘度計）
を測定した。即ち、カルボキシビニルポリマーとして、
グッドリッチ社製カーボポール９３４を水に溶解させ、
これに水酸化カリウムを加えて、ｐＨ6.５に調整し、こ
れに酸化亜鉛超微粒子組成物粉末を１２％濃度で仕込
み、ホモミキサー５０００ｒｐｍで攪拌して分散させ
た。但し、実施例３と比較例３による酸化亜鉛超微粒子
組成物粉末は、撥水性であるので、試験に供しなかっ
た。結果を表２に示す。Test 2 In order to examine the suitability of the zinc oxide ultrafine particle composition powder according to the present invention for use in a sunscreen gel, a carboxyvinyl polymer (acrylic acid-alkyl acrylate copolymer) 0.2% aqueous solution was used for ultrafine particle oxidation. Zinc was charged at a concentration of 12% and the viscosity of the obtained slurry (25 ° C, B type viscometer)
Was measured. That is, as a carboxyvinyl polymer,
Dissolve Goodrich Carbopol 934 in water,
To this, potassium hydroxide was added to adjust the pH to 6.5, and the zinc oxide ultrafine particle composition powder was charged at a concentration of 12%, and the mixture was dispersed by stirring at 5000 rpm with a homomixer. However, since the zinc oxide ultrafine particle composition powders of Example 3 and Comparative Example 3 were water repellent, they were not subjected to the test. The results are shown in Table 2.
【００４６】[0046]
【表２】 [Table 2]
【００４７】表２から明らかなように、本発明による酸
化亜鉛超微粒子組成物は、カルボキシビニルポリマーと
の反応性を殆どもたないために、ポリマー水溶液のゲル
構造が保持される結果、ポリマー水溶液は時間の経過後
も高粘度が維持されている。これに対して、比較例によ
る従来法による酸化亜鉛超微粒子組成物と被覆層をもた
ない超微粒子酸化亜鉛は、いずれも、カルボキシビニル
ポリマーのカルボキシル基と反応して、ポリマーの水和
度を小さくするためであるとみられるが、ポリマー水溶
液のゲル構造が変質し、時間の経過と共に粘度が著しく
低下する。As is clear from Table 2, since the zinc oxide ultrafine particle composition according to the present invention has almost no reactivity with the carboxyvinyl polymer, the gel structure of the polymer aqueous solution is retained, resulting in the polymer aqueous solution. Has a high viscosity even after the passage of time. In contrast, the conventional zinc oxide ultrafine particle composition according to the comparative example and the ultrafine zinc oxide without a coating layer both react with the carboxyl groups of the carboxyvinyl polymer to increase the hydration degree of the polymer. It seems that this is because the size is made smaller, but the gel structure of the aqueous polymer solution is altered and the viscosity remarkably decreases with the passage of time.
【００４８】試験３
酸化亜鉛粒子組成物の耐光性、Ａ領域紫外線の遮蔽能及
び透明性を調べた。
（耐光性の試験）酸化亜鉛超微粒子組成物粉末0.７ｇと
白色ワセリン（日本薬局方）6.３ｇとをフーバー式マラ
ーで混練した後、内径３０ｍｍ、深さ１０ｍｍのポリエ
チレン製容器に入れて、試験片とし、ハンディ型紫外線
ランプ（ウルトラバイオレットプロダクツ社製ＵＶＧＬ
−２５型）を用いて、紫外線（３６５ｎｍ）を１０時間
照射して、照射前後の色差ΔＥを求めた。Test 3 The zinc oxide particle composition was examined for light resistance, A region ultraviolet ray shielding ability and transparency. (Light resistance test) 0.7 g of zinc oxide ultrafine particle composition powder and 6.3 g of white petrolatum (Japanese Pharmacopoeia) were kneaded with a Hoover type muller and then put in a polyethylene container having an inner diameter of 30 mm and a depth of 10 mm. , As a test piece, handy type UV lamp (UVGL manufactured by Ultra Violet Products Co., Ltd.
-25 type), ultraviolet rays (365 nm) were irradiated for 10 hours, and the color difference ΔE before and after irradiation was determined.
【００４９】色差は、色差計（スガ試験機（株）製ＳＭ
−５型）を用いて、ハンター系のＬ、ａ及びｂ値を測定
し、これに基づいて、照射前後の間の色差ΔＥを計算に
て求めた。この値が小さいほど、耐光性がよいことを示
す。The color difference is measured by a color difference meter (SM manufactured by Suga Test Instruments Co., Ltd.
-5 type), the L, a, and b values of the Hunter system were measured, and based on this, the color difference ΔE before and after irradiation was calculated. The smaller this value is, the better the light resistance is.
【００５０】（Ａ領域紫外線の遮蔽能及び透明性の評
価）酸化亜鉛超微粒子組成物粉末1.５ｇをスクワラン
（日光ケミカルズ（株）製）7.９ｇと界面活性剤（花王
（株）製スパン８０）0.６ｇに加え、ペイントシェーカ
ー（レッドデビル社製５４１０型）で分散させ、塗料化
した後、これをポリエチレンテレフタレートフィルム上
にバーコーター＃３にて塗布して、試験片とした。分光
光度計（日本分光（株）製Ｖ−５５０型）を用いて、波
長３５０ｎｍ及び５５０ｎｍにおけるこの試験片の透過
率を測定して、Ａ領域紫外線の遮蔽能と透明性を評価し
た。結果を表３に示す。(Evaluation of A-area UV-shielding ability and transparency) 1.9 g of squalane (manufactured by Nikko Chemicals Co., Ltd.) and 1.5 g of zinc oxide ultrafine particle composition powder and a spanner (spun by Kao Co., Ltd.) 80) In addition to 0.6 g, it was dispersed with a paint shaker (type 5410, manufactured by Red Devil Co.) to form a paint, which was coated on a polyethylene terephthalate film with a bar coater # 3 to give a test piece. Using a spectrophotometer (V-550 type, manufactured by JASCO Corporation), the transmittance of this test piece at wavelengths of 350 nm and 550 nm was measured to evaluate the A-region ultraviolet ray shielding ability and transparency. The results are shown in Table 3.
【００５１】[0051]
【表３】 [Table 3]
【００５２】表３から明らかなように、本発明による酸
化亜鉛超微粒子組成物粉末を配合したワセリンは、光黄
変度が小さく、従って、本発明による酸化亜鉛超微粒子
組成物は、光触媒能が著しく抑制されている。更に、本
発明による酸化亜鉛超微粒子組成物は、Ａ領域紫外線の
遮蔽能と透明性においても高いレベルにあるが、オルガ
ノポリシロキサン処理した実施例３による組成物は、ワ
セリンへの分散性が改善された結果、Ａ領域紫外線の遮
蔽能と透明性が一層すぐれている。As is clear from Table 3, the petrolatum containing the zinc oxide ultrafine particle composition powder according to the present invention has a small degree of photoyellowing, and therefore the zinc oxide ultrafine particle composition according to the present invention has a photocatalytic activity. Remarkably suppressed. Further, although the zinc oxide ultrafine particle composition according to the present invention has a high level in the A-region ultraviolet ray shielding ability and transparency, the composition according to Example 3 treated with organopolysiloxane has improved dispersibility in petrolatum. As a result, the ability to block ultraviolet rays in the A region and the transparency are further improved.
【００５３】実施例４
酸化亜鉛原体として、電気亜鉛地金を蒸発酸化して得ら
れた平均一次粒子径0.０４μｍの超微粒子酸化亜鉛を用
いて、水性懸濁液（ＺｎＯ濃度２００ｇ／Ｌ）を調製
し、これを７０℃に加熱し、酸化亜鉛に対して、ＳｉＯ
2 として３重量％のケイ酸ナトリウムの水溶液を３０分
かけて加えた後、６０分かけて撹拌下に硫酸を加え、ｐ
Ｈ7.０に中和した。３０分間、熟成した後、撹拌下に、
酸化亜鉛に対して、Ａｌ2 Ｏ3 として３重量％のアルミ
ン酸ナトリウムの水溶液を３０分間かけて加え、１０分
間、熟成した後、１０分かけて硫酸を加えて、ｐＨ7.０
に中和した。３０分間、熟成した後、得られた懸濁液を
濾過、水洗し、１３０℃で５時間加熱乾燥した。このよ
うにして得られた乾燥品をハンマーミル粉砕して、内側
に含水ケイ素酸化物からなる高密度の被覆層を有し、外
側に含水アルミニウム酸化物からなる被覆層を有する酸
化亜鉛超微粒子組成物粉末を得た。Example 4 As the zinc oxide raw material, ultrafine zinc oxide having an average primary particle diameter of 0.04 μm obtained by evaporative oxidation of electrozinc metal was used, and an aqueous suspension (ZnO concentration: 200 g / L) was used. ) Was prepared, and this was heated to 70 ° C.
An aqueous solution of 3 wt% sodium silicate as 2 was added over 30 minutes, and then sulfuric acid was added over 60 minutes with stirring, and p
Neutralized to H7.0. After aging for 30 minutes, with stirring,
An aqueous solution of 3% by weight of sodium aluminate as Al 2 O 3 was added to zinc oxide over 30 minutes, aged for 10 minutes, and sulfuric acid was added over 10 minutes to adjust the pH to 7.0.
Neutralized. After aging for 30 minutes, the obtained suspension was filtered, washed with water, and dried by heating at 130 ° C. for 5 hours. The dried product thus obtained is subjected to hammer mill pulverization to have a zinc oxide ultrafine particle composition having a high-density coating layer made of hydrous silicon oxide on the inside and a coating layer made of hydrous aluminum oxide on the outside. The product powder was obtained.
【００５４】このようにして得られた酸化亜鉛粒子組成
物の耐光性は、前述したと同じ歩にて測定した色差ΔＥ
値で2.３であった。また、酸化亜鉛粒子組成物のＡ領域
紫外線の遮蔽能と透明性を前述したと同じ方法で評価し
たところ、３５０ｎｍ及び５５０ｎｍにおける透過率は
それぞれ１３％及び８４％であった。The light resistance of the zinc oxide particle composition thus obtained is determined by the color difference ΔE measured in the same step as described above.
The value was 2.3. Further, when the zinc oxide particle composition was evaluated for its ability to block ultraviolet rays in the A region and its transparency by the same method as described above, the transmittances at 350 nm and 550 nm were 13% and 84%, respectively.
【００５５】[0055]
【発明の効果】以上のように、本発明による酸化亜鉛粒
子組成物は、その表面に含水ケイ素酸化物からなる高密
度の被覆層を有し、純水及び硫酸水溶液への溶解度が著
しく小さく、また、光触媒機能が抑制されている一方、
Ａ領域紫外線の遮蔽能と透明性においてすぐれていの
で、紫外線遮蔽用化粧料に好適に用いることができる。As described above, the zinc oxide particle composition according to the present invention has a high-density coating layer made of hydrous silicon oxide on the surface thereof, and has extremely low solubility in pure water and sulfuric acid aqueous solution. Also, while the photocatalytic function is suppressed,
Since it is excellent in A-region ultraviolet ray shielding ability and transparency, it can be suitably used for ultraviolet ray shielding cosmetics.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平９−315939（ＪＰ，Ａ) 特開 平11−199458（ＪＰ，Ａ) 特開 平10−17730（ＪＰ，Ａ) 特開 平10−47476（ＪＰ，Ａ) 特開 平９−188517（ＪＰ，Ａ) 欧州特許出願公開824086（ＥＰ，Ａ １) (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 9/00 C01G 9/02 A61K 7/42 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-9-315939 (JP, A) JP-A-11-199458 (JP, A) JP-A-10-17730 (JP, A) JP-A-10- 47476 (JP, A) JP-A-9-188517 (JP, A) European Patent Application Publication 824086 (EP, A 1) (58) Fields investigated (Int.Cl. 7 , DB name) C01G 9/00 C01G 9 / 02 A61K 7/42
Claims (9)
量に対してＳｉＯ2 として１〜５０重量％の水溶性ケイ
酸塩を加え、温度を６０℃以上に保持しつつ、６０分以
上の時間をかけて酸を加え、ｐＨが6.０〜8.０の範囲と
なるまで、懸濁液を中和して、酸化亜鉛粒子の表面に含
水ケイ素酸化物からなる高密度の被覆層を酸化亜鉛に対
して１〜５０重量％の範囲で形成して得られる、純水へ
の溶解度がＺｎとして２ｐｐｍ以下であると共に、0.０
００５重量％硫酸水溶液への溶解度がＺｎとして２０ｐ
ｐｍ以下である表面活性を抑制した酸化亜鉛粒子組成
物。1. A water-soluble silicate of 1 to 50% by weight as SiO 2 relative to the weight of zinc oxide is added to an aqueous suspension of zinc oxide particles, and the temperature is kept at 60 ° C. or higher for 60 minutes. Acid is added over the above time, the suspension is neutralized until the pH is in the range of 6.0 to 8.0, and the surface of the zinc oxide particles is a high-density coating made of hydrous silicon oxide. The solubility in pure water obtained by forming the layer in the range of 1 to 50% by weight with respect to zinc oxide is 2 ppm or less as Zn, and 0.0
Solubility in 005 wt% sulfuric acid aqueous solution is 20 p as Zn
A zinc oxide particle composition having a surface activity of pm or less and suppressed.
径を有する請求項１記載の酸化亜鉛粒子組成物。2. The zinc oxide particle composition according to claim 1, wherein the zinc oxide particles have an average particle size of 0.15 μm or less.
範囲のオルガノポリシロキサンで更に処理してなる請求
項１又は２に記載の酸化亜鉛粒子組成物。3. The zinc oxide particle composition according to claim 1, wherein the surface is further treated with an organopolysiloxane in the range of 1 to 20% by weight based on zinc oxide.
に酸化亜鉛に対して0.５〜３０重量％の範囲のＡｌ、Ｔ
ｉ、Ｚｒ、Ｓｎ、Ｓｂ及び希土類元素よりなる群から選
ばれる少なくとも１種の酸化物からなる第２の被覆層を
有する請求項１に記載の酸化亜鉛粒子組成物。4. Al, T in the range of 0.5 to 30% by weight, based on zinc oxide, on a dense coating layer of silicon oxide.
The zinc oxide particle composition according to claim 1, comprising a second coating layer made of at least one oxide selected from the group consisting of i, Zr, Sn, Sb, and a rare earth element.
範囲のオルガノポリシロキサンで更に処理してなる請求
項４に記載の酸化亜鉛粒子組成物。5. The zinc oxide particle composition according to claim 4, wherein the surface is further treated with an organopolysiloxane in the range of 1 to 20% by weight based on zinc oxide.
量に対してＳｉＯ2 として１〜５０重量％の水溶性ケイ
酸塩を加え、温度を６０℃以上に保持しつつ、６０分以
上の時間をかけて酸を加えて、ｐＨが6.０〜8.０の範囲
となるまで、懸濁液を中和して、酸化亜鉛粒子の表面に
ケイ素酸化物からなる高密度の被覆層を酸化亜鉛に対し
て１〜５０重量％の範囲で形成することを特徴とする、
純水への溶解度がＺｎとして２ｐｐｍ以下であると共
に、0.０００５重量％硫酸水溶液への溶解度がＺｎとし
て２０ｐｐｍ以下である表面活性を抑制した酸化亜鉛粒
子組成物の製造方法。6. A water-soluble silicate of 1 to 50% by weight as SiO 2 relative to the weight of zinc oxide is added to an aqueous suspension of zinc oxide particles, and the temperature is kept at 60 ° C. or higher for 60 minutes. Acid is added over the above time, the suspension is neutralized until the pH is in the range of 6.0 to 8.0, and the surface of the zinc oxide particles is a high-density coating made of silicon oxide. A layer is formed in the range of 1 to 50% by weight with respect to zinc oxide,
A method for producing a zinc oxide particle composition, which has a solubility in pure water of 2 ppm or less as Zn and a solubility of 0.0005% by weight in a sulfuric acid aqueous solution of 20 ppm or less as Zn and which suppresses surface activity.
径を有する請求項６に記載の酸化亜鉛粒子組成物の製造
方法。7. The method for producing a zinc oxide particle composition according to claim 6, wherein the zinc oxide particles have an average particle diameter of 0.15 μm or less.
鉛粒子組成物を１〜８０重量％の範囲で含有することを
特徴とする化粧料。8. A cosmetic comprising the zinc oxide particle composition according to any one of claims 1 to 5 in a range of 1 to 80% by weight.
鉛粒子組成物を１〜８０重量％の範囲で含有することを
特徴とする日焼け止め化粧料。9. A sunscreen cosmetic comprising the zinc oxide particle composition according to any one of claims 1 to 5 in an amount of 1 to 80% by weight.
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|---|---|---|---|
| JP33631698A JP3520785B2 (en) | 1998-02-20 | 1998-11-26 | Zinc oxide particle composition with suppressed surface activity, method for producing the same, and cosmetic containing the composition |
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|---|---|---|---|
| JP8015498 | 1998-02-20 | ||
| JP10-80154 | 1998-02-20 | ||
| JP33631698A JP3520785B2 (en) | 1998-02-20 | 1998-11-26 | Zinc oxide particle composition with suppressed surface activity, method for producing the same, and cosmetic containing the composition |
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| Publication Number | Publication Date |
|---|---|
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| JP3520785B2 true JP3520785B2 (en) | 2004-04-19 |
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| CN100369601C (en) * | 1999-08-19 | 2008-02-20 | 株式会社资生堂 | Cosmetic sunscreen prpearation |
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- 1998-11-26 JP JP33631698A patent/JP3520785B2/en not_active Expired - Lifetime
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