JP4741905B2 - Cosmetics containing composite particles for UV shielding - Google Patents
Cosmetics containing composite particles for UV shielding Download PDFInfo
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- JP4741905B2 JP4741905B2 JP2005243572A JP2005243572A JP4741905B2 JP 4741905 B2 JP4741905 B2 JP 4741905B2 JP 2005243572 A JP2005243572 A JP 2005243572A JP 2005243572 A JP2005243572 A JP 2005243572A JP 4741905 B2 JP4741905 B2 JP 4741905B2
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本発明は、紫外線遮蔽能を有する金属酸化物を複合化して成る紫外線遮蔽用の複合粒子を配合したパウダー、クリーム、リキッド状等の各種形態の化粧料に関する。 The present invention relates to various forms of cosmetics such as powders, creams, and liquids containing composite particles for ultraviolet shielding formed by complexing a metal oxide having ultraviolet shielding ability.
太陽光には、大きく分けて波長域が７８０ｎｍ以上の赤外線と、波長域が４００〜７８０ｎｍの可視光線と、波長域が４００ｎｍ以下の紫外線とが含まれている。このうち紫外線は、地球上に届く太陽光の５〜６％を占めており、さらに波長域が３２０〜４００ｎｍのＵＶ−Ａ、２９０〜３２０ｎｍのＵＶ−Ｂ、２９０ｎｍ以下のＵＶ−Ｃに分類される。 Sunlight broadly includes infrared rays having a wavelength range of 780 nm or more, visible rays having a wavelength range of 400 to 780 nm, and ultraviolet rays having a wavelength range of 400 nm or less. Among these, ultraviolet rays occupy 5 to 6% of sunlight reaching the earth, and are further classified into UV-A with a wavelength range of 320 to 400 nm, UV-B with 290 to 320 nm, and UV-C with 290 nm or less. The
従来、紫外線照射による人体、特に皮膚への悪影響が知られている。紫外線のうちＵＶ−Ａは、強い作用を起こさない代わりに、肌の奥（深部）まで浸透して紅斑を伴った黒化現象を起こし、肌の老化の主原因になると言われている。一方、ＵＶ−Ｂは、皮膚がんやシワの形成に関与すると言われており、シミ、ソバカスや皮膚の乾燥の原因にもなる。なお、ＵＶ−Ｃはオゾン層で吸収されるため地表には届かない。 Conventionally, adverse effects on human bodies, particularly skin, due to ultraviolet irradiation are known. It is said that UV-A among ultraviolet rays does not cause a strong action, but penetrates to the back (deep part) of the skin and causes a blackening phenomenon accompanied by erythema, which is a main cause of skin aging. On the other hand, UV-B is said to be involved in the formation of skin cancer and wrinkles, and also causes stains, buckwheat and dry skin. In addition, since UV-C is absorbed by the ozone layer, it does not reach the ground surface.
ところで、この紫外線を吸収、遮蔽する種々の紫外線遮蔽材料が知られている。紫外線遮蔽材料は、大きく有機系の紫外線吸収剤と無機粒子とに分類される。有機系の紫外線吸収剤としては、ベンゾフェノン誘導体、メトキシ桂皮酸誘導体、サリチル酸誘導体等があり、無機材料に比べ安価で皮膚に塗布した時の使用感に優れるという利点がある。 By the way, various ultraviolet shielding materials that absorb and shield the ultraviolet rays are known. Ultraviolet shielding materials are roughly classified into organic ultraviolet absorbers and inorganic particles. Examples of organic ultraviolet absorbers include benzophenone derivatives, methoxycinnamic acid derivatives, salicylic acid derivatives, and the like, which have an advantage that they are cheaper than inorganic materials and have excellent usability when applied to the skin.
無機粒子は、紫外線を散乱若しくは吸収して皮膚への吸収を抑制するものであり、３００ｎｍ付近の波長域に吸光度のピークを有するＵＶ−Ｂ波長域遮蔽能に優れた酸化チタン（ＴｉＯ2）、３８０ｎｍ付近の波長域に吸光度のピークを有するＵＶ−Ａ波長域遮蔽能に優れた酸化亜鉛（ＺｎＯ）、４００ｎｍ付近の波長域に吸光度のピークを有するＵＶ−Ａ波長域遮蔽能に優れた酸化セリウム（ＣｅＯ2）等の金属酸化物を複合させたものであり、有機系の紫外線吸収剤に比べて耐熱性や耐候性に優れるという利点がある。 Inorganic particles scatter or absorb ultraviolet rays to suppress absorption to the skin, and have a UV-B wavelength region shielding ability having a peak of absorbance in a wavelength region near 300 nm (TiO 2 ), Zinc oxide (ZnO) having excellent UV-A wavelength band shielding ability having an absorbance peak in the wavelength region near 380 nm, and cerium oxide having excellent UV-A wavelength band shielding ability having an absorbance peak in the wavelength region near 400 nm It is a composite of a metal oxide such as (CeO 2 ), and has the advantage of being superior in heat resistance and weather resistance as compared with an organic ultraviolet absorber.
前述したような紫外線の悪影響から皮膚を保護するため、紫外線遮蔽材料を含有させた化粧料が開発されている。従来、紫外線防御効果の高い化粧料には、安価で使用感の優れた有機系の紫外線吸収剤が用いられていた。しかし、有機系の紫外線吸収剤は耐熱性や耐候性が不十分で経時的に変化し易い上、皮膚に接触させた場合に紫外線吸収剤自体若しくはその分解生成物による刺激性の問題があり、炎症等を引き起こした事例も多数報告されている。 In order to protect the skin from the adverse effects of ultraviolet rays as described above, cosmetics containing an ultraviolet shielding material have been developed. Conventionally, organic UV absorbers that are inexpensive and have excellent usability have been used for cosmetics with a high UV protection effect. However, organic UV absorbers have insufficient heat resistance and weather resistance and are likely to change over time, and when exposed to the skin, there is a problem of irritation caused by the UV absorber itself or its decomposition products. Many cases that caused inflammation and the like have been reported.
そこで、安定性、安全性に優れた無機粒子を配合した紫外線防御用化粧料が種々提案されており、例えば特許文献１には、酸化亜鉛に不定形シリカを複合させて得られるシリカ被覆酸化亜鉛を配合したパウダーファンデーションが開示されている。特許文献２には、シリカ担体に酸化チタンを含有させて成るチタン−シリカ複合体を配合した化粧料が開示されている。また、特許文献３には、酸化チタン、酸化亜鉛、酸化セリウムなどの金属酸化物粒子をシリカ粒子に対して互いに微分散するように複合させた金属酸化物シリカ複合体を配合した化粧料が開示されている。 Therefore, various UV protective cosmetics containing inorganic particles having excellent stability and safety have been proposed. For example, Patent Document 1 discloses silica-coated zinc oxide obtained by combining amorphous oxide with zinc oxide. The powder foundation which mix | blended is disclosed. Patent Document 2 discloses a cosmetic in which a titanium-silica composite formed by incorporating titanium oxide into a silica carrier is blended. Patent Document 3 discloses a cosmetic containing a metal oxide silica composite in which metal oxide particles such as titanium oxide, zinc oxide and cerium oxide are finely dispersed with respect to silica particles. Has been.
また、特許文献４には、紫外線吸収剤を含有する金属酸化物ゲルで粉体の表面を被覆して成る紫外線吸収剤含有複合粉体を配合した化粧料が開示されている。特許文献５には、酸化亜鉛を内包したシリカと、超微粒子酸化チタン及び超微粒子酸化チタンが付着したタルク、マイカ及び／又はセリサイトとから成る無機粉体が配合された化粧料が開示されている。さらに、特許文献６には、所定の白色度を有する微粒子金属酸化物・酸化セリウム複合体を配合した化粧料が、特許文献７には、酸化セリウムに他の金属元素イオンを固溶（ドープ）させた金属酸化物固溶酸化セリウムを配合した化粧料がそれぞれ開示されている。 Patent Document 4 discloses a cosmetic containing an ultraviolet absorbent-containing composite powder obtained by coating a powder surface with a metal oxide gel containing an ultraviolet absorbent. Patent Document 5 discloses a cosmetic containing an inorganic powder composed of silica containing zinc oxide and talc, mica and / or sericite to which ultrafine titanium oxide and ultrafine titanium oxide are attached. Yes. Further, Patent Document 6 discloses cosmetics containing a fine particle metal oxide / cerium oxide composite having a predetermined whiteness, and Patent Document 7 discloses cerium oxide in which other metal element ions are dissolved (doped). Cosmetics containing the dissolved metal oxide solid solution cerium oxide are disclosed.
ここで、紫外線防御効果をより確実に発現させるためには、ＵＶ−Ａ及びＵＶ−Ｂの両方を遮蔽することが望ましい。しかしながら、上記特許文献１、２においては、ＵＶ−Ａを遮蔽する酸化亜鉛若しくはＵＶ−Ｂを遮蔽する酸化チタンのいずれか一方のみを配合しているため、紫外線防御効果が十分であるとは言えなかった。また、特許文献３に記載の複合粒子は、各金属酸化物粒子が凝集した構造であるため、紫外線遮蔽能が不均一になるおそれがあった。また、特許文献４に記載の複合粒子は、粉体表面をコーティング処理する工程が必要となる上、有機系の紫外線吸収剤を使用するため、耐熱性や耐候性の面で十分とはいえなかった。 Here, it is desirable to shield both UV-A and UV-B in order to develop the UV protection effect more reliably. However, in Patent Documents 1 and 2, only one of zinc oxide that blocks UV-A and titanium oxide that blocks UV-B is blended, so that it can be said that the ultraviolet protection effect is sufficient. There wasn't. Moreover, since the composite particles described in Patent Document 3 have a structure in which the respective metal oxide particles are aggregated, there is a possibility that the ultraviolet shielding ability is not uniform. In addition, the composite particles described in Patent Document 4 require a step of coating the powder surface, and use an organic ultraviolet absorber, which is not sufficient in terms of heat resistance and weather resistance. It was.
また、特許文献５に記載の化粧料では、酸化亜鉛を内包する酸化珪素粒子と微粒子酸化チタンを別々に配合するため、各粒子が凝集しないように均一に分散させるための取り扱いが難しくなり、紫外線遮蔽能が不均一になるおそれがあった。また、特許文献６、７に記載の複合粒子は、その製造法から考えて、いずれも単一粒子内に各金属酸化物成分が均一に分散したものではないため、ＵＶ−Ａ及びＵＶ−Ｂの両波長域の紫外線をバランス良く遮蔽するには、異なる複合粒子が凝集しないよう均一に分散させる必要が生じ、複合粒子の取り扱いが難しくなるとともに、全体として粒子材料の充填量、即ち使用量が増加するという不都合があった。 In addition, in the cosmetic described in Patent Document 5, since silicon oxide particles enclosing zinc oxide and fine particle titanium oxide are blended separately, handling for uniformly dispersing each particle so that the particles do not aggregate becomes difficult. There was a possibility that the shielding ability would be uneven. In addition, since the composite particles described in Patent Documents 6 and 7 are not obtained by uniformly dispersing each metal oxide component in a single particle in view of the production method, UV-A and UV-B In order to shield the ultraviolet rays in both wavelengths in a well-balanced manner, it is necessary to uniformly disperse different composite particles so as not to agglomerate. There was an inconvenience of increasing.
さらに、上記特許文献に記載の化粧料は、無機の紫外線遮蔽材料である複合粒子が微粒子であるために活性が強く、また摩擦抵抗が大きくて感触が良くないので、多量に用いた場合、活性が更に強まり感触も悪くなることから、いずれも処方の安定性、使用感の点において更なる改良が求められていた。
本発明は、上記問題点に鑑み、高い紫外線防御効果を有するとともに、紫外線遮蔽材料として無機粒子を用いた場合でも使用感が良く、安定性、安全性にも優れた紫外線防御用化粧料を提供することを目的とする。 In view of the above problems, the present invention provides a UV protection cosmetic that has a high UV protection effect, has good usability even when inorganic particles are used as a UV shielding material, and is excellent in stability and safety. The purpose is to do.
上記目的を達成するために本発明の第１の構成は、少なくともＵＶ−ＡとＵＶ−Ｂの両波長域の紫外線を遮蔽する複数種の金属酸化物成分の分子或いは分子集合体が単一粒子中に凝集することなく分散し、所定の組成比で構成された複合粒子を配合して成る化粧料であって、前記複合粒子は、ＵＶ−Ａ波長域の紫外線を遮蔽する金属酸化物成分として、酸化セリウムと酸化亜鉛のいずれか一方若しくは両方を含み、ＵＶ−Ｂ波長域の紫外線を遮蔽する金属酸化物成分として酸化チタンを含み、さらに安定保護材成分として酸化珪素を含み、前記複合粒子中の各金属酸化物成分の含有割合は、酸化セリウムと酸化亜鉛の合計が４０重量％以上、酸化チタンが５重量％以上、酸化珪素が５重量％以上であり、且つ、前記複合粒子の平均粒子径がＢＥＴ換算径で１０ｎｍ以上３００ｎｍ以下としたものである。 In order to achieve the above object, the first configuration of the present invention is a single particle in which molecules or molecular aggregates of a plurality of types of metal oxide components that shield at least ultraviolet rays in both the UV-A and UV-B wavelength regions are used. A cosmetic comprising composite particles dispersed without agglomerating therein and having a predetermined composition ratio , wherein the composite particles are used as a metal oxide component that shields ultraviolet rays in the UV-A wavelength region. , Containing one or both of cerium oxide and zinc oxide, containing titanium oxide as a metal oxide component that shields ultraviolet rays in the UV-B wavelength region, and further containing silicon oxide as a stable protective material component, The content of each metal oxide component is such that the total of cerium oxide and zinc oxide is 40% by weight or more, titanium oxide is 5% by weight or more, silicon oxide is 5% by weight or more, and the average particle of the composite particles Diameter is B It is obtained by a 10nm or 300nm or less in T terms diameter.
また本発明の第２の構成は、上記構成の化粧料において、前記各金属酸化物成分の含有割合は、酸化セリウムと酸化亜鉛の合計が４０重量％以上９０重量％以下、酸化チタンが５重量％以上２０重量％以下、酸化珪素が５重量％以上４０重量％以下の範囲にあることを特徴としている。 According to a second configuration of the present invention, in the cosmetic having the configuration described above, the content ratio of each metal oxide component is such that the total of cerium oxide and zinc oxide is 40 wt% or more and 90 wt% or less, and titanium oxide is 5 wt%. % To 20% by weight and silicon oxide in the range of 5% to 40% by weight .
また本発明の第３の構成は、上記構成の化粧料において、前記複合粒子の粒子径が１０ｎｍ以上１００ｎｍ以下であることを特徴としている。 According to a third configuration of the present invention, in the cosmetic having the above-described configuration, the composite particles have a particle size of 10 nm to 100 nm.
また本発明の第４の構成は、上記構成の化粧料において、前記複合粒子の配合割合が２重量％以上１５重量％以下であることを特徴としている。 According to a fourth configuration of the present invention, in the cosmetic having the above-described configuration, the blending ratio of the composite particles is 2 wt% or more and 15 wt% or less.
また本発明の第５の構成は、上記構成の化粧料において、前記複合粒子の表面が疎水化処理されていることを特徴としている。 According to a fifth configuration of the present invention, in the cosmetic having the above-described configuration, the surface of the composite particle is subjected to a hydrophobic treatment.
また本発明の第６の構成は、上記構成の化粧料が、さらに、着色剤、タルク、マイカ、酸化チタン、及びオイル成分を含むパウダーファンデーションであることを特徴としている。 A sixth configuration of the present invention is characterized in that the cosmetic having the above-described configuration is a powder foundation further including a colorant, talc, mica, titanium oxide, and an oil component.
また本発明の第７の構成は、上記構成の化粧料が、さらに、パラフィン、及びオイル成分を含むスキンクリームであることを特徴としている。 The seventh configuration of the present invention is characterized in that the cosmetic having the above-described configuration is a skin cream further containing paraffin and an oil component.
また本発明の第８の構成は、上記構成の化粧料が、さらに、着色剤、タルク、樹脂パウダー、セリサイト、マイカ、及びオイル成分を含むプレストパウダーであることを特徴としている。 The eighth configuration of the present invention is characterized in that the cosmetic having the above configuration is a pressed powder further containing a colorant, talc, resin powder, sericite, mica, and an oil component.
また本発明の第９の構成は、上記構成の化粧料が、さらに、着色剤、ベントナイト、及びオイル成分を含むリキッドファンデーションであることを特徴としている。 The ninth configuration of the present invention is characterized in that the cosmetic having the above configuration is a liquid foundation further containing a colorant, bentonite, and an oil component.
また本発明の第１０の構成は、上記構成の化粧料が、さらに、着色剤、ロウ、及びオイル成分を含む口紅であることを特徴としている。 The tenth configuration of the present invention is characterized in that the cosmetic having the above-described configuration is a lipstick that further contains a colorant, a wax, and an oil component.
本発明の第１の構成によれば、ＵＶ−ＡとＵＶ−Ｂの両波長域の紫外線を遮蔽する複数種の金属酸化物成分が単一粒子中に均一に分散された複合粒子を配合するため、ＵＶ−ＡとＵＶ−Ｂの両波長域の紫外線をバランス良く遮蔽するとともに、紫外線遮蔽能のバラツキが小さくて高い紫外線防御効果を有し、且つ使用感が良く、安定性及び安全性にも優れた紫外線遮蔽用化粧料が提供される。 According to the first configuration of the present invention, composite particles in which a plurality of types of metal oxide components that shield ultraviolet rays in both the UV-A and UV-B wavelength ranges are uniformly dispersed in a single particle are blended. Therefore, the UV-A and UV-B wavelength ranges are shielded in a well-balanced manner, and the UV-shielding ability is small and has a high UV protection effect. Excellent UV shielding cosmetics are also provided.
また、本発明の第２の構成によれば、上記第１の構成の化粧料において、複合粒子中の酸化セリウムと酸化亜鉛の合計を４０重量％以上９０重量％以下、酸化チタンを５重量％以上２０重量％以下、酸化珪素を５重量％以上４０重量％以下とすることにより、ＵＶ−ＡとＵＶ−Ｂの両波長域の紫外線遮蔽効果と触媒活性抑制効果とを好ましい範囲に調整することができる。 According to the second configuration of the present invention, in the cosmetic of the first configuration, the total of cerium oxide and zinc oxide in the composite particles is 40 wt% or more and 90 wt% or less, and titanium oxide is 5 wt%. By adjusting the content to 20% by weight or less and silicon oxide to 5% by weight or more and 40% by weight or less, the UV shielding effect and the catalyst activity suppression effect in both the UV-A and UV-B wavelength ranges are adjusted to a preferable range. Can do.
また、本発明の第３の構成によれば、上記第１または第２の構成の化粧料において、複合粒子の粒子径を１０ｎｍ以上１００ｎｍ以下とするとすることにより、高い紫外線遮蔽効果と優れた使用感を兼ね備えた紫外線遮蔽用化粧料となる。 Further, according to the third configuration of the present invention, in the cosmetic of the first or second configuration, the composite particle has a particle diameter of 10 nm or more and 100 nm or less, and thus has a high ultraviolet shielding effect and excellent. It is an ultraviolet shielding cosmetic material that has a feeling of use.
また、本発明の第４の構成によれば、上記第１乃至第３のいずれかの構成の化粧料において、複合粒子の配合割合を２重量％以上１５重量％以下とすることにより、複合粒子の摩擦抵抗によるきしみ感がなく使用感に優れ、且つ十分な紫外線防御効果を有する紫外線遮蔽用化粧料となる。 Further, according to the fourth configuration of the present invention, in the cosmetic composition of any one of the first to third configurations, the composite particles are mixed in an amount of 2 wt% or more and 15 wt% or less. Thus, there is no squeaky feeling due to the frictional resistance, and it is excellent in the feeling of use and has a sufficient ultraviolet protection effect.
また、本発明の第５の構成によれば、上記第１乃至第４のいずれかの構成の化粧料において、複合粒子の表面を疎水化処理することにより、複合粒子の表面活性を抑制するとともに、樹脂や油等の有機物系の化粧料原料と無機物である複合粒子との親和性を高め、化粧料中での複合粒子の分散性や安定性が向上する。 Further, according to the fifth configuration of the present invention, in the cosmetic having any one of the first to fourth configurations, the surface activity of the composite particles is suppressed by hydrophobizing the surface of the composite particles. In addition, the affinity between the organic cosmetic raw material such as resin and oil and the composite particles that are inorganic is increased, and the dispersibility and stability of the composite particles in the cosmetic are improved.
また、本発明の第６乃至第１０のいずれかの構成によれば、上記第１乃至第５のいずれかの構成の化粧料が、パウダーファンデーション、スキンクリーム、プレストパウダー、リキッドファンデーション、若しくは口紅であることにより、剤型の異なる上記化粧料において、いずれも優れた使用感と顕著な紫外線遮蔽効果とを得ることができる。
According to any of the sixth to tenth configurations of the present invention, the cosmetic material of any of the first to fifth configurations is a powder foundation, skin cream, pressed powder, liquid foundation, or lipstick. As a result, in the cosmetics having different dosage forms, it is possible to obtain an excellent feeling of use and a remarkable ultraviolet shielding effect.
本発明に用いられる紫外線遮蔽用の複合粒子は、単一粒子中に、少なくともＵＶ−ＡとＵＶ−Ｂの両波長域の紫外線を遮蔽するための複数種の金属酸化物が分散形成されている。具体的には、上記ＵＶ−Ａ波長域の紫外線遮蔽能に優れた金属酸化物成分として、酸化セリウム（ＣｅＯ2）と酸化亜鉛（ＺｎＯ）のいずれか一方若しくは両方を含み、ＵＶ−Ｂ波長域の紫外線遮蔽能に優れた金属酸化物成分として酸化チタン（ＴｉＯ2）を含み、さらに安定保護材成分として酸化珪素（ＳｉＯ2）を含む。 In the composite particle for ultraviolet shielding used in the present invention, a plurality of types of metal oxides for shielding ultraviolet rays in both wavelength ranges of at least UV-A and UV-B are dispersedly formed in a single particle. . Specifically, the metal oxide component excellent in ultraviolet shielding ability in the UV-A wavelength range includes one or both of cerium oxide (CeO 2 ) and zinc oxide (ZnO), and is in the UV-B wavelength range. Titanium oxide (TiO 2 ) is included as a metal oxide component excellent in ultraviolet shielding ability, and silicon oxide (SiO 2 ) is included as a stable protective material component.
つまり、本発明に用いられる複合粒子は、少なくともＵＶ−ＡとＵＶ−Ｂの両波長域の紫外線を遮蔽するための、複数種の金属酸化物それぞれの分子或いは分子集合体が単一粒子中に分散して存在し、ある組成比で構成されたものである。具体的には、酸化セリウムと酸化亜鉛の少なくとも一方、酸化チタン及び酸化珪素のそれぞれの分子或いは分子集合体が単一粒子中に分散して存在している。 That is, in the composite particles used in the present invention, molecules or molecular aggregates of each of a plurality of types of metal oxides for shielding at least UV-A and UV-B wavelength regions are contained in a single particle. It exists in a dispersed manner and is composed of a certain composition ratio. Specifically, at least one of cerium oxide and zinc oxide, each of titanium oxide and silicon oxide molecules or molecular aggregates are dispersed in a single particle.
これにより、複合粒子を化粧料に配合したとき、ＵＶ−ＡとＵＶ−Ｂの両波長域の紫外線がバランス良く遮蔽される。また、単一粒子であるので、各粒子が凝集しないよう均一に分散させるための取り扱いが容易であり、仮に凝集が起こったとしても、ＵＶ−Ａ用とＵＶ−Ｂ用の別々の紫外線遮蔽用粒子を混合させた場合に比較して、各波長域の紫外線遮蔽効果のばらつきが小さくなる。その結果、全体として複合粒子の使用量を減少させることができる。 Thereby, when a composite particle is mix | blended with cosmetics, the ultraviolet-ray of both wavelength range of UV-A and UV-B is shielded with sufficient balance. Moreover, since it is a single particle, it is easy to handle to uniformly disperse the particles so that they do not aggregate, and even if aggregation occurs, UV-A and UV-B are separately shielded from ultraviolet rays. Compared with the case where particles are mixed, the variation in the ultraviolet shielding effect in each wavelength region is reduced. As a result, the amount of composite particles used can be reduced as a whole.
また、酸化セリウム、酸化亜鉛、及び酸化チタンは触媒活性作用を有するため、この触媒活性作用による皮膚や基材等の劣化を防止、抑制する必要がある。本発明では安定保護材成分として酸化珪素を配合し、酸化セリウム、酸化亜鉛、及び酸化チタンの表面活性を抑制した複合粒子を用いることにより、皮膚に対する刺激が少なく安全性の高い化粧料としている。 Moreover, since cerium oxide, zinc oxide, and titanium oxide have a catalytic activity, it is necessary to prevent and suppress deterioration of the skin, the base material, and the like due to the catalytic activity. In the present invention, by using composite particles in which silicon oxide is blended as a stable protective material component and the surface activity of cerium oxide, zinc oxide, and titanium oxide is suppressed, cosmetics with less irritation to the skin and high safety are obtained.
複合粒子中の上記金属酸化物成分の含有割合は、遮蔽の対象とする紫外線の主波長域や、化粧料に要求される使用感等によって適宜設定することができるが、酸化セリウムと酸化亜鉛の合計が４０重量％より少ないと、ＵＶ−Ａ波長域の紫外線を効果的に遮蔽できず、酸化チタンが５重量％より少ないと、ＵＶ−Ｂ波長域の紫外線を効果的に遮蔽できない。一方、酸化チタンが２０重量％を超えると、表面活性により化粧料を使用した時のきしみ感が増加する。また、酸化珪素が５重量％より少ないと、酸化セリウム、酸化亜鉛、及び酸化チタンの触媒活性作用を十分に抑制できず、化粧料の使用感が悪くなる。 The content ratio of the metal oxide component in the composite particles can be set as appropriate depending on the dominant wavelength range of the ultraviolet rays to be shielded, the feeling of use required for cosmetics, etc. When the total is less than 40% by weight, the UV-A wavelength region cannot be effectively shielded, and when the titanium oxide is less than 5% by weight, the UV-B wavelength region cannot be effectively shielded. On the other hand, if the titanium oxide exceeds 20% by weight, the squeaky feeling when using cosmetics due to surface activity increases. On the other hand, when the amount of silicon oxide is less than 5% by weight, the catalytic activity of cerium oxide, zinc oxide, and titanium oxide cannot be sufficiently suppressed, and the feeling of use of the cosmetic is deteriorated.
従って、酸化セリウムと酸化亜鉛の合計が４０重量％以上９０重量％以下、酸化チタンが５重量％以上２０重量％以下、酸化珪素が５重量％以上４０重量％以下の範囲にあることが好ましい。即ち、上記配合割合にすることにより、ＵＶ−Ａ及びＵＶ−Ｂ波長域の紫外線をバランス良く遮蔽するとともに表面活性も効果的に抑制することができ、従来の無機粒子では遮蔽することが比較的困難であったＵＶ−Ａ波長域の遮蔽能に優れ、且つ化粧料中に配合した時の使用感にも優れた複合粒子となる。 Accordingly, the total of cerium oxide and zinc oxide is preferably in the range of 40 wt% to 90 wt%, titanium oxide 5 wt% to 20 wt%, and silicon oxide 5 wt% to 40 wt%. That is, by using the above blending ratio, it is possible to shield UV-A and UV-B wavelength regions in a well-balanced manner and to effectively suppress the surface activity. The composite particles have excellent shielding ability in the UV-A wavelength region, which has been difficult, and excellent usability when blended in cosmetics.
なお、複合粒子中のＵＶ−Ａ波長域の紫外線を遮蔽する金属酸化物成分として、酸化セリウムや酸化亜鉛以外の金属酸化物を含むようにしても良く、ＵＶ−Ｂ波長域の紫外線を遮蔽する金属酸化物成分として酸化チタン以外の金属酸化物を含むようにしても良い。また、安定保護材成分として酸化珪素以外の金属酸化物を含むようにしても良い。 In addition, as a metal oxide component that shields ultraviolet rays in the UV-A wavelength region in the composite particles, a metal oxide other than cerium oxide or zinc oxide may be included, and metal oxide that shields ultraviolet rays in the UV-B wavelength region. You may make it contain metal oxides other than a titanium oxide as a physical component. Moreover, you may make it contain metal oxides other than a silicon oxide as a stable protective material component.
本発明に用いられる複合粒子は、例えば気相反応法や燃焼噴霧法等の従来公知の製造方法を用いて製造することができる。気相反応法による複合粒子の製造方法について概要を説明すると、反応後の金属酸化物が所定の組成比となるように、各金属成分を含む原料液を調合する。次に、反応気体（酸素ガス）と共に噴霧ノズルを使用して、例えば高温プラズマにより発生させた高温雰囲気の反応空間に原料液を噴霧し、反応気体流で覆われた原料液の液滴流を生成するとともに、液滴の蒸発気化による粒子核形成と粒子成長を行わせた後、周囲の冷却ガスで急速冷却して所定サイズの複合粒子を製造する。 The composite particles used in the present invention can be produced using a conventionally known production method such as a gas phase reaction method or a combustion spray method. The outline of the method for producing composite particles by the gas phase reaction method will be described. The raw material liquid containing each metal component is prepared so that the metal oxide after the reaction has a predetermined composition ratio. Next, using a spray nozzle together with the reaction gas (oxygen gas), for example, the raw material liquid is sprayed into a reaction space in a high-temperature atmosphere generated by high-temperature plasma, and a droplet flow of the raw material liquid covered with the reaction gas flow is generated. At the same time, particle nucleation and particle growth are performed by evaporation of droplets, and then rapidly cooled with a surrounding cooling gas to produce composite particles of a predetermined size.
原料液は、テトラ（２−エチルヘキシル）チタネート等の有機チタン化合物、２−エチルヘキサン酸亜鉛等の有機亜鉛化合物、２−エチルヘキサン酸セリウム等の有機セリウム化合物、オクタメチルシクロテトラシロキサン等の有機珪素化合物を石油系炭化水素（ミネラルスピリット）中に溶解して調製される。 The raw material liquid is an organic titanium compound such as tetra (2-ethylhexyl) titanate, an organic zinc compound such as zinc 2-ethylhexanoate, an organic cerium compound such as cerium 2-ethylhexanoate, or an organic silicon such as octamethylcyclotetrasiloxane. Prepared by dissolving the compound in petroleum hydrocarbon (mineral spirit).
このようにして製造された複合粒子の平均粒子径は、複合粒子単位重量当たりの表面積（ＢＥＴ値）を実測し、ＢＥＴ値からＢＥＴ換算径を計算することにより求められる。複合粒子の平均粒子径が３００ｎｍを超えると、紫外線遮蔽効果が低下するとともに、きしみ感が増加して使用感が悪くなる。一方、複合粒子の平均粒子径が１０ｎｍよりも小さくなると、粒子が凝集し易くなり、取り扱いが困難となる。従って、平均粒子径が１０ｎｍ以上３００ｎｍ以下の複合粒子を用いることが好ましく、特に１００ｎｍ以下の複合粒子を用いた場合、より高い紫外線遮蔽効果と優れた使用感を兼ね備えた化粧料が得られる。 The average particle diameter of the composite particles produced in this manner is obtained by actually measuring the surface area (BET value) per unit weight of the composite particles and calculating the BET equivalent diameter from the BET value. When the average particle diameter of the composite particles exceeds 300 nm, the ultraviolet shielding effect is lowered, and the squeakiness is increased to deteriorate the feeling of use. On the other hand, when the average particle size of the composite particles is smaller than 10 nm, the particles are likely to aggregate and handling becomes difficult. Therefore, it is preferable to use composite particles having an average particle size of 10 nm or more and 300 nm or less, and in particular, when composite particles of 100 nm or less are used, a cosmetic having a higher ultraviolet shielding effect and an excellent usability can be obtained.
また、本発明の化粧料の剤型としては、乳液、化粧水、スキンクリーム等のスキンケア化粧料、パウダーファンデーション、リキッドファンデーション、口紅等のメイクアップ化粧料、頭髪用化粧料等が挙げられるが、例えばスキンケア化粧料のように透明性を確保する必要のある場合、複合粒子の粒子径を小さくするとともに、複合粒子の屈折率と後述するような他の配合材料の屈折率との差を小さくする必要がある。複合粒子の屈折率は、屈折率が１．５と小さい酸化珪素の含有率が多くなるほど小さくなるため、酸化珪素の含有割合によりある程度は調整可能である。 In addition, examples of the dosage form of the cosmetic of the present invention include skin care cosmetics such as emulsions, lotions, skin creams, makeup cosmetics such as powder foundations, liquid foundations, and lipsticks, and cosmetics for hair. For example, when it is necessary to ensure transparency as in skin care cosmetics, the particle diameter of the composite particles is reduced, and the difference between the refractive index of the composite particles and the refractive index of other compounding materials as described later is reduced. There is a need. The refractive index of the composite particles becomes smaller as the content ratio of silicon oxide, which is as small as 1.5, and can be adjusted to some extent by the content ratio of silicon oxide.
化粧料中への複合粒子の配合割合は、要求される紫外線遮蔽効果や化粧料の剤型等に応じて任意に設定することができるが、複合粒子の配合割合が２重量％以下の場合、十分な紫外線遮蔽効果を得られない。また、配合割合が１５重量％以上の場合、粒子の摩擦抵抗によるきしみ感が増加するとともに、剤型によっては成形性が悪くなる。即ち、上記方法により得られた複合粒子を２重量％以上１５重量％以下の割合で化粧料中に配合すれば、摩擦抵抗によるきしみ感がなく使用感に優れ、有機系の紫外線吸収剤を配合せずに高い紫外線防御効果を有する化粧料を得ることができる。 The blending ratio of the composite particles in the cosmetic can be arbitrarily set according to the required UV shielding effect, cosmetic dosage form, etc., but when the blending ratio of the composite particles is 2% by weight or less, A sufficient ultraviolet shielding effect cannot be obtained. On the other hand, when the blending ratio is 15% by weight or more, the squeaky feeling due to the frictional resistance of the particles increases, and the moldability deteriorates depending on the dosage form. That is, if the composite particles obtained by the above method are blended in cosmetics at a ratio of 2% by weight or more and 15% by weight or less, there is no squeaky feeling due to frictional resistance and an excellent feeling of use, and an organic UV absorber is blended. A cosmetic material having a high UV protection effect can be obtained without the use of this.
なお、複合粒子を化粧料に配合する場合、さらにシリコン処理、アミノ酸処理、レシチン処理、コラーゲン処理、ジアルキルリン酸処理、パーフルオロアルキル基を有する化合物によるフッ素化処理等の表面処理をしたものを用いても良い。中でも、シリコン処理により粒子表面を疎水化処理した場合、複合粒子の表面活性を抑制するとともに、樹脂や油等の有機物と無機物である複合粒子との親和性を高め、化粧料中での分散性や安定性を向上させることが可能となる。 In addition, when compound particles are blended in cosmetics, those that have been surface-treated such as silicon treatment, amino acid treatment, lecithin treatment, collagen treatment, dialkyl phosphate treatment, fluorination treatment with a compound having a perfluoroalkyl group are used. May be. In particular, when the particle surface is hydrophobized by silicon treatment, the surface activity of the composite particles is suppressed, and the affinity between organic particles such as resins and oils and inorganic composite particles is increased, and the dispersibility in cosmetics is increased. And stability can be improved.
シリコン処理に用いられるシリコン化合物としては、メチコン、ジメチコン、（ジメチコン／メチコン）コポリマー等が挙げられる。なお、シリコン化合物中の水素原子がフッ素原子に置換されたフッ素変性シリコンやフッ素化処理剤を用いて表面処理を行った場合、複合粒子に撥水性に加えて撥油性を付与することができる。フッ素化処理剤としては、パーフルオロアルキルリン酸ＤＥＡ等が挙げられる。 Examples of the silicon compound used for the silicon treatment include methicone, dimethicone, and (dimethicone / methicone) copolymer. In addition, when surface treatment is performed using fluorine-modified silicon in which hydrogen atoms in the silicon compound are substituted with fluorine atoms or a fluorination treatment agent, the composite particles can be given oil repellency in addition to water repellency. Examples of the fluorination treatment agent include perfluoroalkyl phosphoric acid DEA.
本発明の化粧料には、タルク、マイカ、セリサイト、酸化チタン、無水珪酸、カオリン、酸化亜鉛、雲母チタン、酸化鉄等の無機粉末、ポリエステル、ポリエチレン、ポリスチレン、ポリウレタン、アクリル酸樹脂、フェノール樹脂、フッ素樹脂、ジビニルベンゼン、スチレン共重合体等の各種樹脂粉体或いはそれらの２種以上から成る共重合樹脂粉体、アセチルセルロース、多糖類、タンパク質等の有機粉末、赤色２０２号、赤色２２６号、黄色２０５号、黄色４０１号、青色１号、青色２０４号、青色４０４号等の顔料粉末、ステアリン酸亜鉛、ステアリン酸マグネシウム、パルミチン酸亜鉛等の金属石鹸、ジメチコン、メチコン、シクロメチコン、ポリエーテル変性シリコン、フッ素変性シリコン等のシリコン化合物、トリオクタノイン、ジカプリル酸ネオペンチルグリコール、トリ（カプリル／カプリン酸）グリセリル、（ヒドロキシステアリン酸／ステアリン酸／ロジン酸）ジペンタエリスリチル、イソステアリン酸水添ヒマシ油等のエステル油、ミネラルオイル、ワセリン、ポリブテン等の鉱物油、カルナウバロウ、キャンデリラロウ、ミツロウ等のロウ、ホホバ油、オリーブ油、アロエ、ベニバナ等の天然系原料、ビタミンＡ、ビタミンＢ、ビタミンＣ、ビタミンＤ、ビタミンＥ、ビタミンＦ、ビタミンＫ、ビタミンＰ、ビタミンＵ、酢酸ｄｌ−α−トコフェロール、ニコチン酸−α−トコフェロール、コハク酸−α−トコフェロール等のビタミンまたはビタミン誘導体等の、任意の無機又は有機原料、或いは通常化粧料に配合される任意の成分、例えばエタノールや多価アルコール等のアルコール類、界面活性剤、保湿剤、着色料、香料、防腐剤等を、本発明の効果を妨げない範囲で配合することができる。 The cosmetics of the present invention include talc, mica, sericite, titanium oxide, silicic anhydride, kaolin, zinc oxide, mica titanium, iron oxide and other inorganic powders, polyester, polyethylene, polystyrene, polyurethane, acrylic resin, phenol resin , Various resin powders such as fluororesin, divinylbenzene, styrene copolymer or copolymer resin powders composed of two or more thereof, organic powders such as acetylcellulose, polysaccharides, proteins, red 202, red 226 , Yellow 205, Yellow 401, Blue 1, Blue 204, Blue 404, etc., metal soap such as zinc stearate, magnesium stearate, zinc palmitate, dimethicone, methicone, cyclomethicone, polyether Silicon compounds such as modified silicon and fluorine-modified silicon, trioctanoy , Ester oils such as neopentyl glycol dicaprylate, tri (capryl / capric acid) glyceryl, (hydroxystearic acid / stearic acid / rosinic acid) dipentaerythrityl, hydrogenated isostearic acid castor oil, mineral oils, mineral oils such as petroleum jelly and polybutene , Waxes such as carnauba wax, candelilla wax, beeswax, natural raw materials such as jojoba oil, olive oil, aloe, safflower, vitamin A, vitamin B, vitamin C, vitamin D, vitamin E, vitamin F, vitamin K, vitamin P, Vitamin U, vitamins such as dl-α-tocopherol acetate, nicotinic acid-α-tocopherol, succinic acid-α-tocopherol, and any inorganic or organic raw materials, or any ingredient that is usually added to cosmetics Such as ethanol or Alcohols such as polyhydric alcohols, surfactants, humectants, colorants, flavors, preservatives, etc., can be blended within a range which does not impair the effects of the present invention.
なお、本発明は上述した実施形態及び後述する各実施例に限定されるものではなく、課題を解決するための手段の項に示した範囲で種々の変更が可能であり、異なる実施形態及び実施例にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。 The present invention is not limited to the above-described embodiment and each example described later, and various modifications are possible within the scope shown in the section of means for solving the problem, and different embodiments and implementations are possible. Embodiments obtained by appropriately combining the technical means disclosed in the examples are also included in the technical scope of the present invention.
原料として、テトラ（２−エチルヘキシル）チタネート９重量％、２−エチルヘキサン酸亜鉛６５％溶液２０重量％、２−エチルヘキサン酸セリウム４９％溶液４０重量％、及びオクタメチルシクロテトラシロキサン２重量％をミネラルスピリット２９重量％に混合して原料液を調製した。次に、この原料液を酸素ガスと共に噴霧ノズルを用いて高温プラズマにより発生させた約３，０００℃の反応空間に噴霧し、酸素ガスで覆われた液滴流を生成するとともに、液滴の蒸発気化による粒子核形成と粒子成長を行わせた後、周囲の冷却ガスで急速冷却して、組成比が１０重量％ＴｉＯ2−３０重量％ＺｎＯ−５０重量％ＣｅＯ2−１０重量％ＳｉＯ2である紫外線遮蔽用複合粒子を得た。 The raw materials are 9% by weight of tetra (2-ethylhexyl) titanate, 20% by weight of zinc 2-ethylhexanoate 65%, 40% by weight of cerium 2-ethylhexanoate 49%, and 2% by weight of octamethylcyclotetrasiloxane. A raw material liquid was prepared by mixing with 29% by weight of mineral spirits. Next, this raw material liquid is sprayed together with oxygen gas into a reaction space of about 3,000 ° C. generated by high-temperature plasma using a spray nozzle to generate a droplet flow covered with oxygen gas, After particle nucleation and particle growth by evaporative vaporization are performed, rapid cooling is performed with a surrounding cooling gas, and the composition ratio is 10 wt% TiO 2 -30 wt% ZnO-50 wt% CeO 2 -10 wt% SiO 2. As a result, composite particles for ultraviolet shielding were obtained.
得られた複合粒子についてＢＥＴ値を実測すると２３ｍ2／ｇであり、ＢＥＴ換算径を計算すると４４ｎｍであった。この複合粒子をさらにメチコンで疎水化処理することにより、表面が疎水化処理された紫外線遮蔽用複合粒子を得た。 When the BET value of the obtained composite particles was measured, it was 23 m 2 / g, and the calculated BET diameter was 44 nm. The composite particles were further hydrophobized with methicone to obtain UV-shielding composite particles whose surface was hydrophobized.
原料として、テトラ（２−エチルヘキシル）チタネート４０重量％、２−エチルヘキサン酸亜鉛６５％溶液３０重量％、及びオクタメチルシクロテトラシロキサン２重量％をミネラルスピリット２８重量％に混合して原料液を調製した。次に、この原料液を用いて実施例１と同様の方法により、組成比が４５重量％ＴｉＯ2−４５重量％ＺｎＯ−１０重量％ＳｉＯ2である紫外線遮蔽用複合粒子を製造した。 As raw materials, 40% by weight of tetra (2-ethylhexyl) titanate, 30% by weight of 65% zinc 2-ethylhexanoate solution, and 2% by weight of octamethylcyclotetrasiloxane were mixed with 28% by weight of mineral spirit to prepare a raw material solution. did. Next, composite materials for ultraviolet shielding having a composition ratio of 45 wt% TiO 2 -45 wt% ZnO-10 wt% SiO 2 were produced by the same method as in Example 1 using this raw material solution.
得られた複合粒子についてＢＥＴ値を実測すると３１ｍ2／ｇであり、ＢＥＴ換算径を計算すると４２ｎｍであった。この複合粒子をさらにメチコンで疎水化処理することにより、表面が疎水化処理された紫外線遮蔽用複合粒子を得た。 The BET value of the obtained composite particles was measured to be 31 m 2 / g, and the BET equivalent diameter was calculated to be 42 nm. The composite particles were further hydrophobized with methicone to obtain UV-shielding composite particles whose surface was hydrophobized.
実施例１で得られた複合粒子及び表１に示す成分を用いて、下記製造方法によりパウダーファンデーションを製造した。なお、表１中のメチコン処理の材料は、メチルハイドロジェンポリシロキサン被覆原料である。 A powder foundation was produced by the following production method using the composite particles obtained in Example 1 and the components shown in Table 1. In addition, the material of methicone treatment in Table 1 is a methyl hydrogen polysiloxane coating raw material.
表１のＡに記載の粉体成分をヘンシェルミキサー（三井鉱山（株）製）にて攪拌混合し、表１のＢに記載の成分の加熱混合物を加えて更に混合し、均一にした。これをアトマイザーで処理し、ふるいを通した後、金皿中に圧縮成型してパウダーファンデーションを得た。 The powder components described in A of Table 1 were stirred and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), and the heated mixture of the components described in B of Table 1 was added and further mixed to make uniform. This was treated with an atomizer, passed through a sieve, and then compression molded into a metal pan to obtain a powder foundation.
実施例２で得られた複合粒子及び表１に示す成分（但し、実施例１で得られた複合粒子を除く）を用いて、実施例３の製造方法と同一条件にてパウダーファンデーションを製造した。 Using the composite particles obtained in Example 2 and the components shown in Table 1 (excluding the composite particles obtained in Example 1), a powder foundation was produced under the same conditions as in the production method of Example 3. .
実施例３、４の比較として、複合粒子の代わりにメチコン処理タルクを５．０重量％増量配合（合計で１１．２重量％になる）し、実施例３の製造方法と同一条件にてパウダーファンデーションを製造した。 As a comparison with Examples 3 and 4, a methicone-treated talc was added in an amount of 5.0% by weight (in total, 11.2% by weight) instead of composite particles, and powdered under the same conditions as in the production method of Example 3 A foundation was produced.
実施例１で得られた複合粒子及び表２に示す成分を用いて、下記製造方法によりスキンクリームを製造した。 A skin cream was produced by the following production method using the composite particles obtained in Example 1 and the components shown in Table 2.
表２のＡ及びＢに記載の成分を、それぞれ８０℃で加熱混合した。Ａに記載の成分の加熱混合物に、Ｂに記載の成分の加熱混合物を加え、ホモミキサー（ホモミキサーマークシリーズ；（株）特殊機化製）で攪拌しながら３０℃まで徐々に冷却してスキンクリームを得た。 The components described in A and B of Table 2 were heated and mixed at 80 ° C., respectively. To the heated mixture of the components described in A, add the heated mixture of the components described in B, and gradually cool to 30 ° C. with stirring with a homomixer (Homomixer Mark Series; manufactured by Special Machine Co., Ltd.). A cream was obtained.
実施例１で得られた複合粒子及び表３に示す成分を用いて、下記製造方法によりプレストパウダーを製造した。 Using the composite particles obtained in Example 1 and the components shown in Table 3, a pressed powder was produced by the following production method.
表３のＡに記載の成分をヘンシェルミキサー（三井鉱山（株）製）で約１０分間混合した。混合物にＢに記載の成分を加えて約１０分間混合し、さらにＣに記載の成分を加えて１分間混合した。得られた混合物をふるいにかけ粒度を揃えた後、成型してプレストパウダーを得た。 The components described in A of Table 3 were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) for about 10 minutes. The components described in B were added to the mixture and mixed for about 10 minutes, and further the components described in C were added and mixed for 1 minute. The obtained mixture was sieved to make the particle size uniform and then molded to obtain a pressed powder.
実施例１で得られた複合粒子及び表４に示す成分を用いて、下記製造方法によりリキッドファンデーションを製造した。 A liquid foundation was produced by the following production method using the composite particles obtained in Example 1 and the components shown in Table 4.
表４のＡ、Ｂ、及びＣに記載の成分を、それぞれ８０℃で加熱混合した。Ａに記載の成分の加熱混合物にＢに記載の成分の加熱混合物を加え、次いでＣに記載の成分の加熱混合物を加え、さらにＤに記載の成分を加えた後、４０℃まで徐々に冷却した。得られた混合物をホモミキサー（ホモミキサーマークシリーズ；（株）特殊機化製）を用いて５分間攪拌した後、３０℃まで冷却してリキッドファンデーションを得た。 The components described in A, B, and C of Table 4 were heated and mixed at 80 ° C., respectively. The heated mixture of the components described in B is added to the heated mixture of the components described in A, then the heated mixture of the components described in C is added, and the components described in D are further added, and then gradually cooled to 40 ° C. . The resulting mixture was stirred for 5 minutes using a homomixer (Homomixer Mark Series; manufactured by Special Machine Co., Ltd.) and then cooled to 30 ° C. to obtain a liquid foundation.
実施例１で得られた複合粒子及び表５に示す成分を用いて、下記製造方法により口紅を製造した。 Using the composite particles obtained in Example 1 and the components shown in Table 5, lipstick was produced by the following production method.
表５のＡ及びＢに記載の成分を、それぞれ８０℃で加熱混合した。加熱混合物を混合し、ロールを用いて混練した後、さらに加熱溶解した。得られた溶解物を減圧化で脱泡した後、成型して口紅を得た。 The components described in A and B of Table 5 were heated and mixed at 80 ° C., respectively. The heated mixture was mixed, kneaded using a roll, and further dissolved by heating. The resulting melt was degassed under reduced pressure and then molded to obtain a lipstick.
パネラー２０名により実施例３及び比較例１で得られたパウダーファンデーションの使用テストを行い、皮膚に対するのび、つき、しっとり感について官能評価を行い、以下の基準で判定した。結果を表６に示す。
（判定基準）
◎：１５名以上が良好と判断
○：１０名以上、１５名未満が良好と判断
△：５名以上、１０名未満が良好と判断
A panel test was carried out by 20 panelists using the powder foundations obtained in Example 3 and Comparative Example 1, and sensory evaluation was performed on the spread, stickiness and moist feeling on the skin, and the following criteria were used. The results are shown in Table 6.
(Criteria)
◎: 15 or more people judged good ○: 10 or more people, less than 15 judged good △: 5 people or more, less than 10 people judged good
表６に示すように、実施例３のパウダーファンデーションを使用した場合、皮膚に対するのび、つきについては２０名中１５名以上が良好と判断し、しっとり感についても１０名以上１５名未満が良好と判断し、使用感に優れた結果が得られた。一方、比較例１のパウダーファンデーションを使用した場合は、のび、つき、しっとり感のいずれについても、良好と判断したのは２０名中１０名以上１５名未満であった。 As shown in Table 6, when the powder foundation of Example 3 was used, it was judged that 15 or more out of 20 people were good about the spread and adhesion on the skin, and the moist feeling was 10 or more and less than 15 people were good. Judgment was made, and excellent results were obtained. On the other hand, when the powder foundation of Comparative Example 1 was used, 10 or more of the 20 people and less than 15 people judged that the spread, stickiness, and moist feeling were all good.
この結果より、酸化セリウム、酸化亜鉛、酸化チタン、及び酸化珪素を単一粒子中に分散させた複合粒子を配合した本発明のパウダーファンデーションは、酸化珪素及び疎水化処理により複合粒子の表面活性が抑制されるとともに、摩擦抵抗によるきしみ感がなく使用感に優れることが確認された。なお、ここでは記載しないが、酸化亜鉛、酸化チタン、及び酸化珪素を単一粒子中に分散させた複合粒子を用いて製造した実施例４のパウダーファンデーションについても、実施例３と同等の効果が確認されている。 From this result, the powder foundation of the present invention containing the composite particles in which cerium oxide, zinc oxide, titanium oxide, and silicon oxide are dispersed in a single particle has a surface activity of the composite particles by silicon oxide and hydrophobization treatment. In addition to being suppressed, it was confirmed that there was no squeaky feeling due to frictional resistance and excellent usability. Although not described here, the powder foundation of Example 4 manufactured using composite particles in which zinc oxide, titanium oxide, and silicon oxide are dispersed in a single particle has the same effect as Example 3. It has been confirmed.
実施例３、４及び比較例１で得られたパウダーファンデーションのＳＰＦ（Sun Protection Factor）値及びＰＡ（Protection grade of ＵＶＡ）値を測定した。結果を表７に示す。 The SPF (Sun Protection Factor) value and PA (Protection grade of UVA) value of the powder foundations obtained in Examples 3 and 4 and Comparative Example 1 were measured. The results are shown in Table 7.
表７に示すように、実施例３のパウダーファンデーションでは、ＳＰＦ値は３１、ＰＡ値は＋＋＋であった。また、実施例４のパウダーファンデーションでは、ＳＰＦ値は２９、ＰＡ値は＋＋であった。一方、比較例１のパウダーファンデーションでは、ＳＰＦ値は２５、ＰＡ値は＋＋であった。 As shown in Table 7, in the powder foundation of Example 3, the SPF value was 31 and the PA value was +++. In the powder foundation of Example 4, the SPF value was 29 and the PA value was ++. On the other hand, in the powder foundation of Comparative Example 1, the SPF value was 25 and the PA value was ++.
この結果より、本発明のパウダーファンデーションは、ＵＶ−Ｂに対する防御効果を表すＳＰＦ値、及びＵＶ−Ａに対する防御効果を表すＰＡ値が、比較例に比べていずれも同等若しくは高い値を示し、ＵＶ−ＡとＵＶ−Ｂの両波長域の紫外線を効果的に遮蔽することが確認された。 From this result, the powder foundation of the present invention shows that the SPF value representing the protective effect against UV-B and the PA value representing the protective effect against UV-A are both equal or higher than those in the comparative example. It was confirmed that ultraviolet rays in both wavelength ranges of -A and UV-B were effectively shielded.
即ち、実施例９及び１０の結果から、本発明によりＵＶ−Ａ及びＵＶ−Ｂの両波長域の紫外線遮蔽効果がともに高く、且つＵＶ−ＡとＵＶ−Ｂに対する遮蔽効果を任意に調整できるとともに、なめらかでのびが良く、使用感にも優れた化粧料を提供することができた。なお、ここでは記載しないが、酸化セリウム、酸化チタン、及び酸化珪素を単一粒子中に分散させた複合粒子を用いて製造したパウダーファンデーションについても、実施例４と同等の効果が確認されている。 That is, from the results of Examples 9 and 10, according to the present invention, both the UV-A and UV-B wavelength shielding effects are high, and the shielding effect against UV-A and UV-B can be arbitrarily adjusted. It was possible to provide cosmetics that were smooth and smooth, and also excellent in the feeling of use. Although not described here, the same effect as in Example 4 has been confirmed for the powder foundation manufactured using composite particles in which cerium oxide, titanium oxide, and silicon oxide are dispersed in a single particle. .
本発明の化粧料は、ＵＶ−ＡとＵＶ−Ｂの両波長域の紫外線を遮蔽する成分が単一粒子中に均一に分散された複合粒子を配合するため、ＵＶ−ＡとＵＶ−Ｂの両波長域の紫外線をバランス良く遮蔽するとともに、紫外線遮蔽能のバラツキを抑制し、且つ安全性も高めることができる。特に、ＵＶ−Ａ波長域の紫外線遮蔽成分として、酸化セリウムと酸化亜鉛のいずれか一方若しくは両方を含み、ＵＶ−Ｂ波長域の紫外線遮蔽成分として酸化チタンを含み、さらに安定保護材成分として酸化珪素を含む複合粒子用いた場合、高い紫外線遮蔽効果と共に優れた使用感が得られる。 Since the cosmetic of the present invention contains composite particles in which the components that shield ultraviolet rays in both wavelength ranges of UV-A and UV-B are uniformly dispersed in a single particle, UV-A and UV-B It is possible to shield the ultraviolet rays in both wavelength ranges with a good balance, suppress the variation in the ultraviolet shielding ability, and improve the safety. In particular, it contains one or both of cerium oxide and zinc oxide as an ultraviolet shielding component in the UV-A wavelength region, titanium oxide as an ultraviolet shielding component in the UV-B wavelength region, and silicon oxide as a stable protective material component. When composite particles containing are used, an excellent feeling of use can be obtained together with a high ultraviolet shielding effect.
また、配合される複合粒子の平均粒子径を１０ｎｍ以上３００ｎｍ以下とし、化粧料中への配合割合を２重量％以上１５重量％以下としたので、複合粒子の摩擦抵抗によるきしみ感を抑えつつ、十分な紫外線遮蔽効果を得ることができる。 Moreover, since the average particle diameter of the composite particles to be blended is 10 nm or more and 300 nm or less and the blending ratio in the cosmetic is 2 wt% or more and 15 wt% or less, while suppressing the squeaky feeling due to the frictional resistance of the composite particles, A sufficient ultraviolet shielding effect can be obtained.
また、複合粒子の表面をシリコン化合物等により疎水化処理しておけば、酸化珪素による表面活性の低下に加えて複合粒子の表面活性をさらに抑制するとともに、樹脂や油等の有機物系の化粧料原料と無機物である複合粒子との親和性を高め、化粧料中での複合粒子の分散性や安定性を一層向上させる。 Further, if the surface of the composite particles is hydrophobized with a silicon compound or the like, in addition to the reduction of the surface activity due to silicon oxide, the surface activity of the composite particles is further suppressed, and organic cosmetics such as resins and oils are used. The affinity between the raw material and the composite particles, which are inorganic substances, is increased, and the dispersibility and stability of the composite particles in cosmetics are further improved.
本発明によれば、パウダーファンデーション、スキンクリーム、プレストパウダー、リキッドファンデーション、口紅等、化粧料の剤型に関係なく、優れた使用感と顕著な紫外線遮蔽効果とを兼ね備えた紫外線遮蔽用化粧料を提供することができる。 According to the present invention, there is provided an ultraviolet shielding cosmetic that has both excellent use feeling and a remarkable ultraviolet shielding effect, regardless of the cosmetic dosage form, such as powder foundation, skin cream, pressed powder, liquid foundation, lipstick and the like. Can be provided.
Claims (10)
前記複合粒子は、ＵＶ−Ａ波長域の紫外線を遮蔽する金属酸化物成分として、酸化セリウムと酸化亜鉛のいずれか一方若しくは両方を含み、ＵＶ−Ｂ波長域の紫外線を遮蔽する金属酸化物成分として酸化チタンを含み、さらに安定保護材成分として酸化珪素を含み、前記複合粒子中の各金属酸化物成分の含有割合は、酸化セリウムと酸化亜鉛の合計が４０重量％以上、酸化チタンが５重量％以上、酸化珪素が５重量％以上であり、且つ、前記複合粒子の平均粒子径がＢＥＴ換算径で１０ｎｍ以上３００ｎｍ以下である化粧料。 A plurality of metal oxide component molecules or molecular aggregates that shield at least UV-A and UV-B wavelength ultraviolet rays are dispersed in a single particle without agglomeration, and are configured with a predetermined composition ratio. A cosmetic comprising a combination of composite particles ,
The composite particle includes one or both of cerium oxide and zinc oxide as a metal oxide component that shields ultraviolet rays in the UV-A wavelength region, and as a metal oxide component that shields ultraviolet rays in the UV-B wavelength region. It contains titanium oxide, further contains silicon oxide as a stable protective material component, and the content ratio of each metal oxide component in the composite particles is 40% by weight or more in total of cerium oxide and zinc oxide, and 5% by weight of titanium oxide. As mentioned above, cosmetics whose silicon oxide is 5 weight% or more and whose average particle diameter of the said composite particle is 10 nm or more and 300 nm or less in BET conversion diameter .
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| JP2006306641A (en) * | 2005-04-26 | 2006-11-09 | Hosokawa Funtai Gijutsu Kenkyusho:Kk | Composite particle for ultraviolet shielding |
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