JP2851885B2 - Zinc oxide and cosmetics - Google Patents
Zinc oxide and cosmeticsInfo
- Publication number
- JP2851885B2 JP2851885B2 JP32224389A JP32224389A JP2851885B2 JP 2851885 B2 JP2851885 B2 JP 2851885B2 JP 32224389 A JP32224389 A JP 32224389A JP 32224389 A JP32224389 A JP 32224389A JP 2851885 B2 JP2851885 B2 JP 2851885B2
- Authority
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- Japan
- Prior art keywords
- zinc oxide
- weight
- oxide
- cosmetic
- ultraviolet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Landscapes
- Cosmetics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】 「産業上の利用分野」 本発明は、微粒子酸化亜鉛とこれを配合してなる紫外
線遮蔽化粧料に係り、詳しくはAl,Si,ZrあるいはSnの酸
化物もしくは水酸化物を微粒子酸化亜鉛の表面に被覆し
て諸物性を改善した表面改質酸化亜鉛と、これを配合し
てなる化粧料に関する。Description: TECHNICAL FIELD The present invention relates to a fine particle zinc oxide and an ultraviolet shielding cosmetic comprising the same, more specifically, an oxide or hydroxide of Al, Si, Zr or Sn. The present invention relates to a surface-modified zinc oxide in which various substances are improved by coating a substance on the surface of a fine-particle zinc oxide, and a cosmetic comprising the same.
「従来の技術」 地上に照射される太陽光の中には、中紫外線（280〜3
20nm;UV−Ｂ）と近紫外線（325〜400nm;UV−Ａ）とが含
まれている。このうち中紫外線は皮膚の紅斑水疱等の炎
症を引き起こし、一方近紫外線はメラニン生成を促して
皮膚の褐色化を生じさせることが知られている。そし
て、このような人体（皮膚）への悪影響に対処するため
のものとして、従来より紫外線遮蔽剤を配合して日焼け
化粧品並びに日焼け止め化粧品が知られている。"Conventional technology" The sunlight radiated to the ground contains medium ultraviolet rays (280-3
20 nm; UV-B) and near ultraviolet rays (325-400 nm; UV-A). Among them, medium ultraviolet rays are known to cause inflammation such as erythema blisters on the skin, while near ultraviolet rays are known to promote melanin production and cause browning of the skin. To cope with such adverse effects on the human body (skin), sunscreen cosmetics and sunscreen cosmetics containing an ultraviolet shielding agent are conventionally known.
このような化粧品に用いられる紫外線遮蔽剤として
は、大別するとベンゾフェノン系、ベンゾトリアゾール
系、サリチル酸系等の紫外線吸収剤と、酸化亜鉛、酸化
チタン、酸化セリウム等の紫外線散乱剤との２種類に分
類されている。このうち有機系化合物が主である紫外線
吸収剤は、その吸収端が330〜350nm付近に存在すること
から、近紫外線に対する遮蔽効果が十分でなく、したが
って日焼け化粧品に配合されて用いられることが多い。
またこの紫外線吸収剤では、皮膚に対する刺激性がある
ことから、多量に配合すると皮膚にアレルギー症状を引
き起こす恐れがあり、しかも紫外線を吸収することで紫
外線吸収剤自体が劣化するため、紫外線遮蔽効果が長続
きしないなどの問題点がある。There are roughly two types of ultraviolet shielding agents used in such cosmetics: ultraviolet absorbers such as benzophenone, benzotriazole and salicylic acid, and ultraviolet scattering agents such as zinc oxide, titanium oxide and cerium oxide. Classified. Among these, ultraviolet absorbers mainly composed of organic compounds have insufficient absorption effect against near ultraviolet rays because their absorption edges are present in the vicinity of 330 to 350 nm, and are therefore often used in sunburn cosmetics. .
In addition, since this UV absorber is irritating to the skin, it may cause allergic symptoms to the skin when it is used in a large amount. There are problems such as not lasting.
これに対し、主に無機系化合物である紫外線散乱剤
は、近紫外線をも吸収・散乱することから、近紫外線を
含む巾広い領域に渡って紫外線を遮蔽するという長所が
あり、したがって日焼け止め化粧品に配合されて効果を
発揮するものである。またこの紫外線散乱剤にあって
は、無機系化合物であるので皮膚にアレルギーを引き起
こしにくく、よって多量に配合することが可能となる。On the other hand, ultraviolet scattering agents, which are mainly inorganic compounds, also absorb and scatter near-ultraviolet rays, and thus have the advantage of shielding ultraviolet rays over a wide area including near-ultraviolet rays. It is effective when it is blended in. In addition, since this ultraviolet scattering agent is an inorganic compound, it does not easily cause allergy to the skin, and thus can be incorporated in a large amount.
ところで、このような紫外線散乱剤のうちで従来よく
用いられているものとしては酸化チタンがある。しか
し、酸化チタンは屈折率が2.5と大きいことから隠蔽力
が大きくなるので、化粧料に配合した場合透明感が損な
われ、白っぽくなって不自然な仕上がりとなる。このよ
うに酸化チタンにあっては種々の不都合があることか
ら、酸化チタンに代わって酸化亜鉛の使用が提案されて
いる。By the way, among such ultraviolet light scattering agents, titanium oxide is one which is often used in the past. However, since titanium oxide has a large refractive index of 2.5 and therefore has a high hiding power, when blended in cosmetics, the transparency is impaired, and it becomes whitish and has an unnatural finish. Since titanium oxide has various inconveniences, use of zinc oxide instead of titanium oxide has been proposed.
ここで、平均粒径が約0.02μｍの超微粒子酸化チタン
と、同サイズの超微粒子酸化亜鉛のそれぞれの分光反射
率を第１図に示す。第１図より、酸化亜鉛は400μｍ付
近から吸収が始まって、380μｍ付近に吸収端を有する
ことから、酸化チタンに比べより広い紫外線領域に渡っ
て遮蔽効果を有するものであることが分かる。また、酸
化亜鉛は屈折率が1.9程度と酸化チタンよりかなり小さ
いので、散乱の度合いが減少し透明感の点で酸化チタン
を大巾に凌ぐものとなる。そして、粒子径を0.1μｍ以
下の超微粒子に調整すれば、可視光線の波長よりずっと
小さくなるので、可視光線がほとんど吸収されずしたが
って透明感が増すものとなる。このように微粒子酸化亜
鉛は、紫外線遮蔽領域の広さ、透明感、皮膚に対する安
全性、紫外線遮蔽効果の持続性などの点で従来の紫外線
遮蔽材料、すなわち酸化チタンに比べて優れた特徴を有
するものである。FIG. 1 shows the respective spectral reflectances of ultrafine titanium oxide having an average particle size of about 0.02 μm and ultrafine zinc oxide of the same size. From FIG. 1, it can be seen that zinc oxide starts absorbing around 400 μm and has an absorption edge near 380 μm, and thus has a shielding effect over a wider ultraviolet region than titanium oxide. Further, since zinc oxide has a refractive index of about 1.9, which is considerably smaller than that of titanium oxide, the degree of scattering is reduced, and zinc oxide greatly exceeds titanium oxide in terms of transparency. If the particle diameter is adjusted to ultrafine particles of 0.1 μm or less, the wavelength becomes much smaller than the wavelength of visible light, so that visible light is hardly absorbed, and therefore, the sense of transparency increases. As described above, the fine zinc oxide has characteristics superior to the conventional ultraviolet shielding material, that is, titanium oxide, in terms of the size of the ultraviolet shielding area, transparency, safety to the skin, and sustainability of the ultraviolet shielding effect. Things.
「発明が解決しようとする課題」 しかしながら、このような微粒子酸化亜鉛にあって
も、これを紫外線散乱剤として化粧料に配合した場合に
以下に述べる問題点がある。"Problems to be Solved by the Invention" However, even in the case of such a fine particle zinc oxide, there is a problem described below when this is mixed into a cosmetic as an ultraviolet scattering agent.
微粒子酸化亜鉛には触媒活性があり、しかも微粒子で
あり表面積が大きいことからその触媒活性能がより大き
なものとなっている。そして、このような微粒子酸化亜
鉛を化粧料に配合する場合には、通常他の有機系のビヒ
クルと混合して用いるが、上述したように微粒子酸化亜
鉛に触媒活性があることから、保存期間中に微粒子酸化
亜鉛が有機系ビヒクルを変質させる触媒として機能して
しまい、そのため化粧料の保存性を著しく損なってしま
う。Fine-particle zinc oxide has catalytic activity, and since it is a fine particle and has a large surface area, its catalytic activity is greater. When such a particulate zinc oxide is blended into a cosmetic, it is usually used in a mixture with another organic vehicle. However, since the particulate zinc oxide has catalytic activity as described above, during the storage period, In addition, the finely divided zinc oxide functions as a catalyst for altering the organic vehicle, which significantly impairs the preservability of the cosmetic.
また、微粒子酸化亜鉛を化粧品に配合した場合、化粧
料の滑らかさを低下させてしまう。すなわち、酸化亜鉛
は元々シリカ、アルミナ等に比べて動摩擦係数が大きく
滑りが悪いものである。そして、これが微粒子となって
微細になることから動摩擦係数が更に大きなものとな
り、結果的に滑らかさの低下を引き起こし、感触の悪化
を招くのである。In addition, when the fine particles of zinc oxide are added to cosmetics, the smoothness of the cosmetics is reduced. That is, zinc oxide originally has a large coefficient of dynamic friction and is less slippery than silica, alumina or the like. Then, the particles become fine particles and become finer, so that the dynamic friction coefficient further increases, and as a result, the smoothness is reduced and the touch is deteriorated.
本発明は上記問題点を解決するためになされたもの
で、その目的とするところは、良好な透明性を有し、紫
外線遮蔽効果が高く、しかも保存性がよく十分な滑らか
さを有する化粧料を提供するとともに、これを得るため
の酸化亜鉛を提供することにある。The present invention has been made in order to solve the above problems, and has as its object to provide a cosmetic composition having good transparency, a high ultraviolet shielding effect, and good preservability and sufficient smoothness. And zinc oxide for obtaining the same.
「課題を解決するための手段」 本発明における請求項１記載の酸化亜鉛では、0.1μ
ｍ以下の平均粒子径を有する微粒子酸化亜鉛の粒子表面
に、Al,Si,ZrあるいはSnの酸化物もしくは水酸化物の内
の１種あるいは複数種を、酸化亜鉛に対し重量比で0.1
〜20％被覆したことを上記課題を解決手段とした。"Means for Solving the Problems" In the zinc oxide according to claim 1 of the present invention, 0.1 μm
m, one or more of oxides or hydroxides of Al, Si, Zr or Sn are added to the surface of the fine zinc oxide particles having an average particle diameter of 0.1 m or less in a weight ratio of 0.1 to zinc oxide.
The above problem was solved by covering up to 20%.
また、請求項２記載の化粧料では、請求項１記載の酸
化亜鉛を、0.1〜40重量％配合したことを上記課題の解
決手段とした。In addition, in the cosmetic according to the second aspect, the zinc oxide according to the first aspect is blended in an amount of 0.1 to 40% by weight as a means for solving the above problem.
以下、本発明について詳しく説明する。本発明におけ
る請求項１記載の酸化亜鉛は、金属酸化物もしくは金属
水酸化物で被覆された微粒子酸化亜鉛である。Hereinafter, the present invention will be described in detail. The zinc oxide according to the first aspect of the present invention is a particulate zinc oxide coated with a metal oxide or a metal hydroxide.
配合される微粒子酸化亜鉛としては、平均粒径が0.1
μｍ以下のものが用いられる。ここで平均粒径を0.1μ
ｍ以下としたのは、これより大きくすると紫外線遮蔽効
果が不十分となり、また可視光線の波長に近づくことに
よって可視光線をも吸収、散乱するため、透明性が著し
く低下するからである。The fine particle zinc oxide to be blended has an average particle size of 0.1
Those having a size of μm or less are used. Where the average particle size is 0.1μ
The reason for the value of m or less is that if it is larger than this, the effect of blocking ultraviolet rays becomes insufficient, and if the wavelength approaches the wavelength of visible light, visible light is also absorbed and scattered, so that the transparency is significantly reduced.
このような微粒子酸化亜鉛を作製するには種々の方法
が採用可能であるが、例えば本出願人が先に提案した超
微粒酸化亜鉛の製造方法（特願平１−130422）に基づい
て作製することができる。すなわちこの方法では、亜鉛
の酸性塩と酢酸アンモニウムの混合溶液に硫化水素を通
じ、得られた沈澱物から可溶性塩を除去し、次いで該沈
澱物を非水溶媒に分散し、これをオートクレーブにて25
0〜400℃で加熱してガス分を除去し、その後得られた乾
粉を500〜800℃で加熱処理して超微粒酸化亜鉛を得るの
である。Various methods can be adopted for producing such fine-particle zinc oxide. For example, the fine-particle zinc oxide is produced based on a method for producing ultrafine zinc oxide proposed by the present applicant (Japanese Patent Application No. 1-130422). be able to. That is, in this method, hydrogen sulfide is passed through a mixed solution of an acidic salt of zinc and ammonium acetate to remove a soluble salt from the obtained precipitate, and then the precipitate is dispersed in a non-aqueous solvent, and this is autoclaved for 25 minutes.
The heating is performed at 0 to 400 ° C. to remove gas components, and then the obtained dry powder is heat-treated at 500 to 800 ° C. to obtain ultrafine zinc oxide.
微粒子酸化亜鉛を被覆するのに用いられる金属酸化物
もしくは金属水酸化物の金属元素としては、Al,Si,Zrお
よびSnの内の１種あるいはこれらの複数種が組み合わさ
れて用いられる。このうちSi,Zrの酸化物あるいは水酸
化物は、酸化亜鉛を被覆することにより、主に酸化亜鉛
の触媒活性を低下せしめて酸化亜鉛を不活性化するもの
である。一方,Al,Zr,Snの酸化物あるいは水酸化物は、
酸化亜鉛を被覆してその動摩擦係数を低下せしめるもの
である。すなわちこれは、Al,Zr,Snの酸化物あるいは水
酸化物の動摩擦係数が小さいためである。そしてさら
に、微粒子酸化亜鉛の結晶型は六方晶系であり、粒子形
状が角柱状を呈しているが、Al,Zr,Snの酸化物あるいは
水酸化物で被覆されていることによって角が丸みを帯び
るようになり、全体として球状に近づくことから、上述
した動摩擦係数の低下が一層顕著になるのである。そし
て、これら酸化物あるいは水酸化物に被覆された酸化亜
鉛を化粧料に配合することにより、化粧料の滑りが改善
されるのである。As the metal element of the metal oxide or metal hydroxide used for coating the fine particle zinc oxide, one or more of Al, Si, Zr and Sn are used in combination. Of these, oxides or hydroxides of Si and Zr are mainly intended to reduce the catalytic activity of zinc oxide and inactivate zinc oxide by coating with zinc oxide. On the other hand, oxides or hydroxides of Al, Zr, Sn
It is coated with zinc oxide to reduce its dynamic friction coefficient. That is, this is because the dynamic friction coefficient of the oxide or hydroxide of Al, Zr, or Sn is small. Furthermore, the crystal form of the fine particle zinc oxide is hexagonal, and the particle shape is prismatic, but the corners are rounded by being coated with oxides or hydroxides of Al, Zr, Sn. Since it becomes tinged and approaches a spherical shape as a whole, the above-described decrease in the coefficient of dynamic friction becomes even more remarkable. Then, by blending zinc oxide coated with these oxides or hydroxides into the cosmetic, the slip of the cosmetic is improved.
酸化物あるいは水酸化物の酸化亜鉛表面への被覆量と
しては、0.1重量％から20重量％の範囲とされる。すな
わち、被覆量が0.1重量％より小さいと、表面被覆によ
る効果が十分発揮されず、よって触媒活性の十分な低下
や動摩擦係数の改善効果が望めないからであり、一方20
重量％を越えると、相対的に酸化亜鉛の含有量が減るこ
とから、紫外線遮蔽効果が十分でなくなるからである。The coating amount of the oxide or hydroxide on the zinc oxide surface is in the range of 0.1% by weight to 20% by weight. That is, if the coating amount is less than 0.1% by weight, the effect of the surface coating is not sufficiently exerted, and thus a sufficient reduction of the catalytic activity and an improvement effect of the dynamic friction coefficient cannot be expected.
If the content exceeds 10% by weight, the content of zinc oxide is relatively reduced, so that the ultraviolet shielding effect becomes insufficient.
SiあるいはZrの酸化物もしくは水酸化物による酸化亜
鉛表面の被覆は、例えばSi酸化物の場合以下の手順によ
って行われる。The zinc oxide surface is coated with an oxide or hydroxide of Si or Zr, for example, in the case of a Si oxide, by the following procedure.
まず、所定量の微粒子酸化亜鉛を珪酸ソーダ水溶液中
に加え、該溶液を強く撹拌して懸濁状態にし、さらに液
のpHに注意しながら該水溶液中に塩酸希釈液を徐々に添
加する。そして、pHが７程度になったら添加をやめてし
ばらく静置する。すると酸化亜鉛粒子表面には、Siの酸
化物が徐々に析出し、被膜が形成される。次に、この懸
濁液を過洗滌し、さらに乾燥器にて105℃で加熱乾燥
し、乾粉を得る。First, a predetermined amount of particulate zinc oxide is added to an aqueous sodium silicate solution, the solution is vigorously stirred to form a suspended state, and a hydrochloric acid diluent is gradually added to the aqueous solution while paying attention to the pH of the solution. When the pH becomes about 7, the addition is stopped and the mixture is left for a while. Then, the oxide of Si is gradually deposited on the surface of the zinc oxide particles to form a film. Next, the suspension is washed, and further dried by heating at 105 ° C. in a drier to obtain a dry powder.
また、Al,ZrあるいはSnの酸化物もしくは水酸化物に
よる酸化亜鉛表面の被覆は、例えばAlの酸化物の場合以
下の手順によって行われる。Further, the coating of the zinc oxide surface with an oxide or hydroxide of Al, Zr or Sn is performed by the following procedure in the case of, for example, an oxide of Al.
まず、所定量の微粒子酸化亜鉛をアルミン酸ソーダの
水溶液に加え、該溶液を強く攪拌して懸濁状態にし、さ
らに液のpHが７以下にならないよう注意しながら塩酸希
釈液を徐々に滴下する。すると酸化亜鉛粒子表面には、
Al2O3ゲルが析出する。そして、滴下終了後しばらく静
置した後、過洗滌し、さらに105℃程度の温度で加熱
乾燥し、乾粉を得る。First, a predetermined amount of particulate zinc oxide is added to an aqueous solution of sodium aluminate, the solution is vigorously stirred to form a suspended state, and a hydrochloric acid diluting solution is gradually dropped while taking care that the pH of the solution does not become 7 or less. . Then, on the zinc oxide particle surface,
Al 2 O 3 gel precipitates. Then, after the dropping is completed, the mixture is allowed to stand for a while, washed with water, and further dried by heating at a temperature of about 105 ° C. to obtain a dry powder.
また、請求項２記載の化粧料は、上記被覆処理後の酸
化亜鉛を0.1〜40重量％配合してなるものである。ここ
で、化粧料としては特に日焼け防止を目的とするものと
され、またその形態としてはクリーム、化粧水、乳液な
ど種々のものが適用される。そして、酸化亜鉛の配合量
を0.1〜40重量％としたのは、0.1重量％未満では酸化亜
鉛を配合した効果、すなわち紫外線遮蔽効果などが十分
発揮されないためであり、また40重量％を越えると化粧
料自身の効用などが低くなるとともに、被覆処理後の酸
化亜鉛のコストが高いことから化粧料自身のコストが高
くなってしまうからである。Further, the cosmetic according to claim 2 contains the zinc oxide after the coating treatment in an amount of 0.1 to 40% by weight. Here, the cosmetic is intended for the purpose of preventing sunburn in particular, and various forms such as cream, lotion, milky lotion and the like are applied. The reason why the content of zinc oxide is set to 0.1 to 40% by weight is that if the content is less than 0.1% by weight, the effect of adding zinc oxide, that is, the ultraviolet shielding effect is not sufficiently exhibited, and if it exceeds 40% by weight, This is because the utility of the cosmetic itself decreases and the cost of the zinc oxide after the coating treatment is high, so that the cost of the cosmetic itself increases.
このようにして得られ被覆処理後の酸化亜鉛にあって
は、被覆無しの場合に比べ酸化亜鉛の触媒活性が低下
し、かつ動摩擦係数が小さくなるなど、微粒子酸化亜鉛
の性状が大きく改善されたものとなる。そして、これを
配合して日焼け防止用の紫外線遮蔽化粧料を作製すれ
ば、従来の化粧料に比べて以下の利点を有するものとな
る。In the zinc oxide obtained in this way and after the coating treatment, the properties of the particulate zinc oxide were greatly improved, such as a decrease in the catalytic activity of the zinc oxide and a decrease in the dynamic friction coefficient as compared with the case without the coating. It will be. If this is blended to produce an ultraviolet shielding cosmetic for preventing sunburn, the following advantages are obtained as compared with conventional cosmetics.
すなわち、従来の微粒子酸化亜鉛を化粧品に配合した
場合、種々の化粧品用基剤と混合して用いられるため、
微粒子酸化亜鉛のように触媒活性が大きいと、他の成分
の分解や重合を促進することにより、酸化亜鉛含有化粧
品に変色、硬化、異臭の発生等の経時変化をもたらす。
しかし、上記の被覆処理後の酸化亜鉛を配合した化粧料
にあっては、酸化亜鉛の触媒活性が低下しているので、
上述した経時変化を促進することがなく、よって化粧料
の商品寿命を大巾に伸ばすことができる。また、従来の
微粒子酸化亜鉛では動摩擦係数が大きいため、化粧料に
配合した場合、滑りの悪さを引き起こし、使用した際滑
らかで良好な感触が得られない。しかし、被覆処理後の
酸化亜鉛を配合した化粧料にあっては、動摩擦係数が小
さくなっているので、使用した際滑らかな感触を得るこ
とができる。さらに、この被覆処理後の酸化亜鉛を配合
した化粧料にあっては、非常に透明で、かつ可視領域に
ごく近く近紫外部を含むほぼ紫外部全域に渡る遮蔽効果
を有するものとなる。That is, when the conventional fine particle zinc oxide is blended in cosmetics, it is used by being mixed with various cosmetic bases.
When the catalytic activity is high, as in the case of fine-particle zinc oxide, the decomposition and polymerization of other components are promoted, thereby causing the zinc oxide-containing cosmetic to undergo a temporal change such as discoloration, hardening, generation of an odor, and the like.
However, in cosmetics containing zinc oxide after the above-mentioned coating treatment, the catalytic activity of zinc oxide is reduced,
The above-mentioned change with time is not promoted, so that the product life of the cosmetic can be greatly extended. In addition, conventional particulate zinc oxide has a large coefficient of kinetic friction. Therefore, when it is blended in cosmetics, it causes poor slippage and does not provide a smooth and good feel when used. However, in the cosmetics containing zinc oxide after the coating treatment, the dynamic friction coefficient is small, so that a smooth feel can be obtained when used. Further, the cosmetic containing zinc oxide after the coating treatment is very transparent and has a shielding effect that is very close to the visible region and covers almost the entire ultraviolet region including near ultraviolet region.
（実験例） 微粒子酸化亜鉛の表面被覆処理前後での触媒活性の変
化を調べ、その結果を第１表に示す。なお、触媒活性の
目安としてはマイクロリアクターを用いたときのイソプ
ロピルアルコールの脱水素反応によるアセトンへの転化
率を用いた。(Experimental Example) The change in catalytic activity before and after the surface coating treatment of the fine particle zinc oxide was examined, and the results are shown in Table 1. In addition, the conversion rate of isopropyl alcohol to acetone by a dehydrogenation reaction using a microreactor was used as a standard of the catalyst activity.
第１表より、被覆無しの酸化亜鉛はイソプロピルアル
コールの転化率が58モル％であり、大きな触媒活性を有
するのが分かる。一方、SiO2あるいはZrO2を表面に被覆
した酸化亜鉛では、触媒活性が著しく低下しており、表
面被覆処理による効果が確認された。 From Table 1, it can be seen that the zinc oxide without coating has a conversion of isopropyl alcohol of 58 mol% and has a large catalytic activity. On the other hand, in the case of zinc oxide coated on the surface with SiO 2 or ZrO 2 , the catalytic activity was significantly reduced, and the effect of the surface coating treatment was confirmed.
また、微粒子酸化亜鉛の、Al、Zr、Sn等の酸化物もし
くは水酸化物の表面被覆処理前後の動摩擦係数の変化を
調べ、その結果を第２表に示す。なお、動摩擦係数の測
定としては、荷重を付した可動式アタッチメントを酸化
亜鉛粒子上で往復させ、そのときのズリ応力をストレン
メーターで読み取ることによって行った。Further, the change in the coefficient of kinetic friction before and after the surface coating treatment of the oxide or hydroxide such as Al, Zr and Sn of the fine particle zinc oxide was examined. The results are shown in Table 2. The dynamic friction coefficient was measured by reciprocating a movable attachment with a load on zinc oxide particles, and reading the shear stress at that time with a strain meter.
第２表より、被覆の無い酸化亜鉛は、粒径が小さいと
いうこともあって動摩擦係数が0.95と非常に大きく、し
たがってこれを配合して化粧料を作製した場合に、化粧
料の滑りが悪くなることが推察される。一方、酸化亜鉛
表面にAl2O3,ZrO2,SnO2を被覆したものにあっては、動
摩擦係数が被覆なしのものに比べて1/2〜1/3程度になっ
ているので、これらを配合して化粧料を作製すれば、被
覆無しの酸化亜鉛を配合した場合に比較して滑りの悪さ
が著しく改善されることが推察される。 From Table 2, it can be seen that zinc oxide without coating has a very large kinetic friction coefficient of 0.95 due to its small particle size. Therefore, when a cosmetic is prepared by blending this, the slip of the cosmetic is poor. It is presumed that it becomes. On the other hand, in the case where the surface of zinc oxide is coated with Al 2 O 3 , ZrO 2 , SnO 2 , the kinetic friction coefficient is about 1/2 to 1/3 compared to that without coating, so these It is presumed that, when a cosmetic is produced by blending the compound, the slipperiness is significantly improved as compared with the case where zinc oxide without a coating is blended.
「実施例」 本発明における請求項２記載の化粧料の実施例を以下
に示す。"Examples" Examples of the cosmetic according to claim 2 of the present invention are shown below.
（実施例１） 以下の配合により、クリームを作製した。(Example 1) A cream was prepared according to the following formulation.
微粒子酸化亜鉛 ５重量％ （ただし、平均粒径0.02μｍの酸化亜鉛表面に、SiO2を
３重量％、Al2O3を２重量％被覆したもの。） カオリン ２重量％ セチルアルコール ３重量％ ワセリン ６重量％ 流動パラフィン 12重量％ シリコン油 ２重量％ グリセルモノステアリン酸エステル 2.5重量％ ポリオキシエチレン （25モル） セチルアルコールエーテル 2.5重量％ プロピレングリコール ６重量％ 精製水 59重量％ 香料 適量 顔料 適量 防腐剤 適量 クリームの作製としては以下の手順で行った。Fine particle zinc oxide 5% by weight (However, zinc oxide with an average particle size of 0.02 μm is coated with 3 % by weight of SiO 2 and 2 % by weight of Al 2 O 3. ) Kaolin 2% by weight Cetyl alcohol 3% by weight Vaseline 6% by weight Liquid paraffin 12% by weight Silicone oil 2% by weight Glyceryl monostearate 2.5% by weight Polyoxyethylene (25 mol) Cetyl alcohol ether 2.5% by weight Propylene glycol 6% by weight Purified water 59% by weight Perfume appropriate amount Pigment appropriate amount Preservative An appropriate amount of cream was prepared according to the following procedure.
まず、平均粒径0.02μｍの微粒子酸化亜鉛を用意し、
これらの表面に、上述した方法によってSiO2とAl2O3と
をそれぞれ被覆した。なお、被覆量はSiO2を３重量％、
Al2O3を２重量％とした。次に、被覆処理後の微粒子酸
化亜鉛とカオリン、顔料とをブレンダーで混合して粉末
部とした。First, prepare fine particle zinc oxide with an average particle size of 0.02 μm,
These surfaces were coated with SiO 2 and Al 2 O 3 respectively by the method described above. The coating amount was 3% by weight of SiO 2 ,
Al 2 O 3 was 2% by weight. Next, the finely divided zinc oxide, kaolin, and pigment after the coating treatment were mixed with a blender to obtain a powder portion.
次いで、精製水にプロピレングリコールを加え70℃に
加熱し、上記粉末部を加えてホモミキサーで分散し、水
相とした。また、上記配合中の他の成分を混合し、加熱
溶解して70℃に保って油相とした。Next, propylene glycol was added to the purified water, and the mixture was heated to 70 ° C., and the above-mentioned powder portion was added and dispersed with a homomixer to obtain an aqueous phase. The other components in the above composition were mixed, dissolved by heating, and maintained at 70 ° C. to obtain an oil phase.
その後、上記水相に油相を加え、ホモミキサーで均一
に乳化・分散せしめ、乳化後冷却しながらかきまぜるこ
とによってクリームを得た。Thereafter, the oil phase was added to the aqueous phase, and the mixture was uniformly emulsified and dispersed with a homomixer. After emulsification, the mixture was stirred with cooling to obtain a cream.
得られたクリームを肌につけたところ、肌になじみが
よく、滑らかな感触が得られた。また、このクリームに
紫外線を照射してその遮蔽効果を調べたところ、十分な
紫外線遮蔽効果があることが確認された。When the obtained cream was applied to the skin, the cream was well adapted to the skin and a smooth feel was obtained. Further, when this cream was irradiated with ultraviolet rays and its shielding effect was examined, it was confirmed that the cream had a sufficient ultraviolet shielding effect.
（実施例２） 以下の配合により、化粧水を作製した。(Example 2) A lotion was prepared according to the following formulation.
微粒子酸化亜鉛 ５重量％ （ただし、平均粒径0.02μｍの酸化亜鉛表面に、SiO2を
３重量％、ZrO2を５重量％被覆したもの。） ポリエチレングリコール400 15重量％ グリセリン ７重量％ ポリオキシエチレン （60モル） 硬化ヒマシ油 1.5重量％ エチルアルコール 50重量％ 精製水 21.5重量％ 香料 適量 染料 適量 化粧水の作製としては以下の手順で行った。Zinc oxide particles 5 wt% (provided that the zinc oxide surface having an average particle size of 0.02 [mu] m, the SiO 2 3% by weight, those coated with ZrO 2 5% by weight.) Polyethylene glycol 400 15% Glycerin 7 wt% polyoxy Ethylene (60 mol) hydrogenated castor oil 1.5% by weight Ethyl alcohol 50% by weight Purified water 21.5% by weight Fragrance appropriate amount Dye appropriate amount Preparation of lotion was carried out by the following procedure.
まず、平均粒径0.02μｍの微粒子酸化亜鉛を用意し、
これらの表面に、上述した方法によってSiO2とZrO2とを
それぞれ被覆した。なお、被覆量はSiO2を３重量％、Zr
O2を５重量％とした。次に、精製水にポリエチレングリ
コールとグリセリンとを加えてこれらを溶解し、水相と
した。また、エチルアルコールに染料を除く他の成分を
加えてこれらを溶解し、油相とした。First, prepare fine particle zinc oxide with an average particle size of 0.02 μm,
These surfaces were respectively coated with SiO 2 and ZrO 2 by the method described above. The coating amount was 3% by weight of SiO 2 , Zr
O 2 was 5% by weight. Next, polyethylene glycol and glycerin were added to the purified water to dissolve them to form an aqueous phase. In addition, other components except for the dye were added to ethyl alcohol, and these were dissolved to form an oil phase.
その後、水相に上記被覆処理後の微粒子酸化亜鉛と油
相とを加えて可溶化を行い、さらに染料で着色した後
過して化粧水を得た。Thereafter, the fine particles of zinc oxide and the oil phase after the above-mentioned coating treatment were added to the aqueous phase to solubilize the solution, and the solution was colored with a dye and passed through to obtain a lotion.
得られた化粧水を肌につけたところ、のびがよく、滑
らかな感触が得られた。また、この化粧水に紫外線を照
射してその遮蔽効果を調べたところ、十分な紫外線遮蔽
効果があることが確認された。When the obtained lotion was applied to the skin, it spread well and gave a smooth feel. In addition, when this lotion was irradiated with ultraviolet rays and its shielding effect was examined, it was confirmed that there was a sufficient ultraviolet shielding effect.
（実施例３） 以下の配合により、乳液を作製した。(Example 3) An emulsion was prepared according to the following formulation.
微粒子酸化亜鉛 ７重量％ （ただし、平均粒径0.02μｍの酸化亜鉛表面に、ZrO2を
３重量％、SnO2を２重量％被覆したもの。） ステアリン酸 ３重量％ セチルアルコール ２重量％ ワセリン ６重量％ シリコン油 ２重量％ 流動パラフィン 12重量％ グリセリルモノステアリン酸エステル 1.5重量％ ポリオキシエチレン （25モル） モノオレイン酸エステル 1.5重量％ ポリエチレングリコール1500 ４重量％ ビーガム 0.5重量％ 精製水 60.5重量％ 香料 適量 防腐剤 適量 乳剤の作製としては以下の手順で行った。Zinc oxide particles 7 wt% (provided that the zinc oxide surface having an average particle size of 0.02 [mu] m, the ZrO 2 3 wt%, the SnO 2 2 wt% coated ones.) 3 wt% of stearic acid cetyl alcohol 2 wt% petrolatum 6 2% by weight Silicon oil 2% by weight Liquid paraffin 12% by weight Glyceryl monostearate 1.5% by weight Polyoxyethylene (25 mol) monooleate 1.5% by weight Polyethylene glycol 1500 4% by weight Vegum 0.5% by weight Purified water 60.5% by weight Fragrance Appropriate amount Preservative Appropriate amount Emulsion was prepared by the following procedure.
まず、平均粒径0.02μｍの微粒子酸化亜鉛を用意し、
これらの表面に、上述した方法によってZrO2とSnO2とを
それぞれ被覆した。なお、被覆量はZrO2を３重量％、Sn
O2を２重量％とした。First, prepare fine particle zinc oxide with an average particle size of 0.02 μm,
These surfaces were respectively coated with ZrO 2 and SnO 2 by the method described above. The coating amount was 3% by weight of ZrO 2 and Sn
O 2 was 2% by weight.
次に、精製水にプロピレングリコールを加えて加熱溶
解した後、被覆処理後の酸化亜鉛とビーガムとを加えて
ホモミキサーで均一に分散し、70℃に保って水相とし
た。また、上記配合中の他の成分を混合し、加熱溶解し
て70℃に保ち、これを油相とした。Next, propylene glycol was added to purified water and dissolved by heating. Then, zinc oxide and veegum after the coating treatment were added, and the mixture was uniformly dispersed with a homomixer, and kept at 70 ° C. to form an aqueous phase. The other components in the above composition were mixed, dissolved by heating and maintained at 70 ° C., and this was used as an oil phase.
その後、上記水相に油相を加え、ホモミキサーで均一
に乳化・分散せしめ、乳化後かきまぜながら35℃にまで
冷却して乳液を得た。Thereafter, the oil phase was added to the aqueous phase, and the mixture was uniformly emulsified and dispersed with a homomixer. After emulsification, the mixture was cooled to 35 ° C. while stirring to obtain an emulsion.
得られた乳液を肌につけたところ、のびがよく、滑ら
かな感触が得られた。また、この乳液に紫外線を照射し
てその遮蔽効果を調べたところ、十分な紫外線遮蔽効果
があることが確認された。When the obtained emulsion was applied to the skin, it spread well and a smooth feel was obtained. In addition, when this emulsion was irradiated with ultraviolet rays and its shielding effect was examined, it was confirmed that the emulsion had a sufficient ultraviolet shielding effect.
「発明の効果」 以上説明したように本発明における酸化亜鉛は、0.1
μｍ以下の平均粒子径を有する微粒子酸化亜鉛の粒子表
面に、AL,Si,ZrあるいはSnの酸化物もしくは水酸化物の
内の１種あるいは複数種を、酸化亜鉛に対し重量比で0.
1〜20％被覆したものである。そして、この被覆処理を
行った酸化亜鉛にあっては、被覆無しの場合に比べ酸化
亜鉛の触媒活性が低下し、かつ動摩擦係数が小さいもの
となる。`` Effect of the invention '' As described above, zinc oxide in the present invention is 0.1%
One or more kinds of oxides or hydroxides of AL, Si, Zr or Sn are added at a weight ratio of 0.5 to zinc oxide to the surface of the fine zinc oxide particles having an average particle diameter of μm or less.
It is 1-20% coated. Then, in the zinc oxide that has been subjected to the coating treatment, the catalytic activity of the zinc oxide is reduced and the dynamic friction coefficient is small as compared with the case without the coating.
請求項２記載の化粧料は、上記被覆処理後の酸化亜鉛
を0.1〜40重量％配合してなるものであるから、非常に
透明で、かつ可視領域にごく近い近紫外部を含むほぼ紫
外部全域に亘る遮蔽効果を有するものとなり、また配合
した酸化亜鉛の触媒活性が低下しているので、他の配合
成分の経時変化を促進することがなく、よって保存性の
高いものとなり、さらに配合した酸化亜鉛の動摩擦係数
が小さくなっているので、使用した際滑らかな感触を示
すものとなる。The cosmetic according to claim 2, wherein the zinc oxide after the coating treatment is blended in an amount of 0.1 to 40% by weight, so that it is very transparent and almost ultraviolet including near ultraviolet which is very close to the visible region. Since it has a shielding effect over the whole area, and the catalytic activity of the blended zinc oxide is reduced, it does not promote the aging of the other blended components, so that it becomes highly storable and further blended. Since the coefficient of kinetic friction of zinc oxide is small, it exhibits a smooth feel when used.
第１図は、超微粒子酸化チタンおよび同サイズの超微粒
子酸化亜鉛の分光反射率を示すグラフである。FIG. 1 is a graph showing the spectral reflectance of ultrafine titanium oxide and ultrafine zinc oxide of the same size.
Claims (2)
酸化亜鉛の粒子表面に、Al,Si,ZrあるいはSnの酸化物も
しくは水酸化物の内の１種あるいは複数種を、酸化亜鉛
に対し重量比で0.1〜20％被覆してなることを特徴とす
る酸化亜鉛。1. A method according to claim 1, wherein one or a plurality of oxides or hydroxides of Al, Si, Zr or Sn is coated on the surface of the fine zinc oxide particles having an average particle diameter of 0.1 μm or less. Zinc oxide characterized by being coated by 0.1 to 20% by weight.
％配合してなることを特徴とする化粧料。2. A cosmetic comprising the zinc oxide according to claim 1 in an amount of 0.1 to 40% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32224389A JP2851885B2 (en) | 1989-12-12 | 1989-12-12 | Zinc oxide and cosmetics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32224389A JP2851885B2 (en) | 1989-12-12 | 1989-12-12 | Zinc oxide and cosmetics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03183620A JPH03183620A (en) | 1991-08-09 |
| JP2851885B2 true JP2851885B2 (en) | 1999-01-27 |
Family
ID=18141509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32224389A Expired - Fee Related JP2851885B2 (en) | 1989-12-12 | 1989-12-12 | Zinc oxide and cosmetics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2851885B2 (en) |
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1989
- 1989-12-12 JP JP32224389A patent/JP2851885B2/en not_active Expired - Fee Related
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| JPH03183620A (en) | 1991-08-09 |
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