JP6037899B2 - Oil-in-water emulsified cosmetic - Google Patents
Oil-in-water emulsified cosmetic Download PDFInfo
- Publication number
- JP6037899B2 JP6037899B2 JP2013047349A JP2013047349A JP6037899B2 JP 6037899 B2 JP6037899 B2 JP 6037899B2 JP 2013047349 A JP2013047349 A JP 2013047349A JP 2013047349 A JP2013047349 A JP 2013047349A JP 6037899 B2 JP6037899 B2 JP 6037899B2
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- JP
- Japan
- Prior art keywords
- oil
- mass
- water emulsified
- emulsified cosmetic
- component
- 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.)
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- 239000002537 cosmetic Substances 0.000 title claims description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 64
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- 238000011282 treatment Methods 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 32
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- 239000000203 mixture Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000010419 fine particle Substances 0.000 claims description 12
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical compound OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 claims description 11
- 229920002050 silicone resin Polymers 0.000 claims description 11
- 238000004381 surface treatment Methods 0.000 claims description 10
- JGUMTYWKIBJSTN-UHFFFAOYSA-N 2-ethylhexyl 4-[[4,6-bis[4-(2-ethylhexoxycarbonyl)anilino]-1,3,5-triazin-2-yl]amino]benzoate Chemical compound C1=CC(C(=O)OCC(CC)CCCC)=CC=C1NC1=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=N1 JGUMTYWKIBJSTN-UHFFFAOYSA-N 0.000 claims description 7
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Description
本発明は、日焼け止め効果に優れた水中油型乳化化粧料に関する。 The present invention relates to an oil-in-water emulsified cosmetic excellent in sunscreen effect.
近年、日常生活における日焼け止め対策の重要性が指摘されてきており、紫外線に対する防御効果を有する化粧料においても、さっぱりとした使用感で連用しやすい、水中油型乳化型の日焼け止め化粧料が開発されてきている。 In recent years, the importance of sunscreen countermeasures in daily life has been pointed out, and even in cosmetics that have a protective effect against ultraviolet rays, oil-in-water emulsified sunscreen cosmetics that are easy to use with a refreshing feeling are used. It has been developed.
紫外線防御効果を高めるため、これらの水中油型乳化化粧料には、酸化亜鉛や酸化チタン等の紫外線散乱剤が用いられている。しかし、紫外線散乱剤を多く配合すると、経時で粉末の凝集、沈降等が生じるばかりでなく、粘度低下、乳化分離、析出などの経時安定性が低下するという問題があった。さらに感触の面でも、のびが悪い、べたつく、きしみ感を感じる等の使用感が悪くなるという問題があった。 In order to enhance the ultraviolet protection effect, ultraviolet scattering agents such as zinc oxide and titanium oxide are used in these oil-in-water emulsion cosmetics. However, when a large amount of the ultraviolet scattering agent is blended, there is a problem that not only the powder aggregates and settles with time, but also the stability with time such as viscosity reduction, emulsification separation and precipitation decreases. Furthermore, in terms of feel, there was a problem that the feeling of use deteriorated, such as poor spread, stickiness, and squeaky feeling.
これらの問題を改善するために、ポリアクリル酸アミド、キサンタンガム、（アクリル酸ナトリウム／アクリロイルジメチルタウリン）コポリマー等の水溶性高分子を用いた水中油型乳化化粧料（特許文献１、２参照）が提案されている。 In order to improve these problems, an oil-in-water emulsified cosmetic using a water-soluble polymer such as polyacrylamide, xanthan gum, (sodium acrylate / acryloyldimethyltaurine) copolymer (see Patent Documents 1 and 2) Proposed.
一方、イソソルビドのジ脂肪酸エステルが、こってりとした油であるが、皮膚に塗布すると拡散性が良く、さっぱりとした感触を有することから油相成分として化粧料に用いることが提案されている（特許文献３参照）。 On the other hand, the difatty acid ester of isosorbide is a solid oil, but when applied to the skin, it has good diffusibility and has a refreshing feel, so it has been proposed to be used in cosmetics as an oil phase component (patent) Reference 3).
しかしながら、特許文献１、２に記載された水中油型乳化組成物では、組成物自体の経時安定性は改善されてはいるが、用いる油剤の種類によっては十分な紫外線防御効果が得られない場合があった。また、特許文献３には、イソソルビドのジ脂肪酸エステルが化粧料の油相成分として使用できることは記載されているが、紫外線散乱剤と併用したときにどのような作用が生じるかについては何も知られていない。 However, in the oil-in-water emulsion compositions described in Patent Documents 1 and 2, the stability over time of the composition itself is improved, but depending on the type of oil used, a sufficient UV protection effect cannot be obtained. was there. Patent Document 3 describes that a difatty acid ester of isosorbide can be used as an oil phase component of cosmetics, but nothing is known about what action occurs when used in combination with an ultraviolet scattering agent. It is not done.
本発明の課題は、優れた紫外線防御効果を有し、経時安定性が良好で、かつ使用感の良好な水中油型乳化化粧料を提供することにある。 An object of the present invention is to provide an oil-in-water emulsified cosmetic having an excellent UV protection effect, good stability over time, and good usability.
そこで、本発明者らは上記事情に鑑み、紫外線散乱剤の高配合による使用感の低下を改善し得る成分を見出すべく、鋭意検討した結果、無水ヘキシトールのジ脂肪酸エステル自身は、ほとんど紫外線吸収作用を示さないにもかかわらず、全く意外にも、無水ヘキシトールのジ脂肪酸エステルを疎水化処理紫外線散乱剤及び水溶性高分子と併用することで、紫外線防御効果を顕著に向上させることができ、さらに使用感の低下を大幅に改善でき、しかも安定性も良好な水中油型乳化組成物が得られることを見出し、本発明を完成させた。 Therefore, in view of the above circumstances, the present inventors have intensively studied to find a component that can improve the deterioration of the feeling of use due to the high blending of the ultraviolet scattering agent. As a result, the difatty acid ester of anhydrous hexitol itself has almost no ultraviolet absorbing action. Despite the fact that it does not show, quite surprisingly, by using a difatty acid ester of anhydrous hexitol in combination with a hydrophobized UV scattering agent and a water-soluble polymer, the UV protection effect can be remarkably improved. The present inventors have found that an oil-in-water emulsified composition that can greatly improve the feeling of use and that has good stability can be obtained.
すなわち、本発明は、下記の（Ａ）〜（Ｃ）成分を含有し、（Ｃ）成分と（Ａ）成分の含有質量比（（Ｃ）／（Ａ））が０．５〜１５である水中油型乳化化粧料を提供するものである。
（Ａ）下記一般式（１）で表される無水ヘキシトールのジ脂肪酸エステル、
（Ｂ）水溶性高分子、
（Ｃ）疎水化処理紫外線散乱剤
That is, the present invention contains the following components (A) to (C), and the mass ratio ((C) / (A)) of the components (C) and (A) is 0.5 to 15. An oil-in-water emulsified cosmetic is provided.
(A) difatty acid ester of anhydrous hexitol represented by the following general formula (1),
(B) a water-soluble polymer,
(C) Hydrophobized UV scattering agent
（式中、Ｒ1及びＲ2は、同一又は異なって、炭素数７〜９の飽和又は不飽和の直鎖又は分岐の炭化水素基示す。） (In the formula, R 1 and R 2 are the same or different and represent a saturated or unsaturated linear or branched hydrocarbon group having 7 to 9 carbon atoms.)
本発明の水中油型乳化化粧料は、経時安定性に優れ、高い紫外線防御効果を有する。更に、塗布時には肌へののびが良く、べたつき感を抑えた良好な使用感を有し、実使用においても高い紫外線防御効果が期待される。 The oil-in-water emulsified cosmetic of the present invention is excellent in stability over time and has a high ultraviolet protection effect. Furthermore, it spreads well on the skin during application, has a good feeling of use with reduced stickiness, and is expected to have a high UV protection effect even in actual use.
本発明に用いられる（Ａ）無水ヘキシトールのジ脂肪酸エステルは、下記一般式（１）で表される化合物である。 The difatty acid ester of (A) anhydrous hexitol used in the present invention is a compound represented by the following general formula (1).
（式中、Ｒ1及びＲ2は、同一又は異なって、炭素数７〜９の飽和又は不飽和の直鎖又は分岐の炭化水素基を示す。） (In the formula, R 1 and R 2 are the same or different and represent a saturated or unsaturated linear or branched hydrocarbon group having 7 to 9 carbon atoms.)
一般式（１）中のＲ1及びＲ2は、同一又は異なって、炭素数７〜９の飽和又は不飽和の直鎖又は分岐の炭化水素基である。Ｒ1及びＲ2は、同一の炭化水素基であることが好ましい。また、炭素数７〜９の飽和又は不飽和の直鎖又は分岐の炭化水素基のうち、経時安定性、使用感の点で炭素数７〜９の直鎖又は分岐のアルキル基が好ましく、さらに炭素数７〜９の直鎖アルキル基がより好ましい。具体的には、Ｒ1及びＲ2はヘプチル基、オクチル基又はノニル基が好ましい。これらのうち、油溶性紫外線吸収剤との相溶性の良さ（経時安定性）、油溶性紫外線吸収剤のべたつき感を低減させる点から、ヘプチル基であることがより好ましい。一般式（１）中の無水ヘキシトール部分はイソソルビド(isosobide)、イソマンニド（isomannide）及びイソイジド（isoidide）から選択される１種であるが、好ましくはイソソルビド又はイソマンニドであり、より好ましくはイソソルビドである。 R < 1 > and R < 2 > in General formula (1) are the same or different, and are a C7-C9 saturated or unsaturated linear or branched hydrocarbon group. R 1 and R 2 are preferably the same hydrocarbon group. Of the saturated or unsaturated linear or branched hydrocarbon groups having 7 to 9 carbon atoms, linear or branched alkyl groups having 7 to 9 carbon atoms are preferable in terms of stability over time and feeling of use. A linear alkyl group having 7 to 9 carbon atoms is more preferable. Specifically, R 1 and R 2 are preferably a heptyl group, an octyl group or a nonyl group. Among these, a heptyl group is more preferable from the viewpoints of good compatibility with oil-soluble UV absorbers (stability over time) and reduction in stickiness of oil-soluble UV absorbers. The anhydrous hexitol moiety in the general formula (1) is one selected from isosorbide, isomannide and isoidide, preferably isosorbide or isomannide, and more preferably isosorbide.
無水ヘキシトールのジ脂肪酸エステルは、本願実施例記載の合成方法など、公知のエステル合成方法によって合成することができる。 The difatty acid ester of anhydrous hexitol can be synthesized by a known ester synthesis method such as the synthesis method described in Examples of the present application.
（Ａ）無水ヘキシトールのジ脂肪酸エステルの本発明の化粧料総量に対する含有量は、経時安定性の点、使用感の点、成分（Ｃ）との併用による紫外線防御効果向上作用の点から、０．３質量％以上が好ましく、０．５質量％以上がより好ましく、０．８質量％以上がさらに好ましく、２質量％以上がさらに好ましい。また、１５質量％以下が好ましく、１０質量％以下がより好ましく、６．５質量％以下がさらに好ましい。具体的な範囲としては、０．３〜１５質量％が好ましく、０．５〜１０質量％が好ましく、０．８〜８質量％がより好ましく、２〜６．５質量％がさらに好ましい。 (A) The content of the difatty acid ester of anhydrous hexitol relative to the total amount of the cosmetic of the present invention is 0 from the viewpoint of the stability over time, the feeling of use, and the effect of improving the UV protection effect when used in combination with the component (C). .3% by mass or more is preferable, 0.5% by mass or more is more preferable, 0.8% by mass or more is more preferable, and 2% by mass or more is more preferable. Moreover, 15 mass% or less is preferable, 10 mass% or less is more preferable, and 6.5 mass% or less is further more preferable. As a specific range, 0.3-15 mass% is preferable, 0.5-10 mass% is preferable, 0.8-8 mass% is more preferable, 2-6.5 mass% is further more preferable.
本発明で用いられる（Ｂ）水溶性高分子としては、化粧品原料として一般的に用いられるものであれば特に限定されないが、ポリアクリルアミド、アクリルアミドコポリマーが好適に用いられる。ここで、アクリルアミドコポリマーとしては、アクリルアミド及び／又はアクリロイルジメチルタウリンを構成単位として含むコポリマーが挙げられる。 The water-soluble polymer (B) used in the present invention is not particularly limited as long as it is generally used as a cosmetic raw material, but polyacrylamide and acrylamide copolymer are preferably used. Here, examples of the acrylamide copolymer include a copolymer containing acrylamide and / or acryloyldimethyltaurine as a structural unit.
アクリルアミド及び／又はアクリロイルジメチルタウリンを構成単位として含むコポリマーとしては、アクリル酸ヒドロキシエチルとアクロイルジメチルタウリン塩との共重合体、アクリル酸塩とアクリロイルジメチルタウリン塩との共重合体、アクリルアミドとアクリル酸塩との共重合体、アクリル酸とアクリル酸アミドとアクリル酸塩とアクリロイルジメチルタウリン塩の共重合体等を挙げることができる。 Examples of the copolymer containing acrylamide and / or acryloyldimethyltaurine as a structural unit include a copolymer of hydroxyethyl acrylate and acryloyldimethyltaurine, a copolymer of acrylate and acryloyldimethyltaurine, acrylamide and acrylic acid. Examples thereof include a copolymer with a salt, a copolymer of acrylic acid, an acrylic amide, an acrylate, and an acryloyldimethyltaurine salt.
これらの成分は市販されており、ポリアクリルアミドとしては、SEPIGEL 305（ポリアクリルアミド、水添ポリイソブテン（または(C13,14)イソパラフィン）、ラウレス-7、水）；アクリル酸ヒドロキシエチルとアクロイルジメチルタウリン塩との共重合体としては、SEPINOV EMT 10（（アクリル酸ヒドロキシエチル/アクリロイルジメチルタウリンNa）コポリマー）、SIMULGEL NS（（アクリル酸ヒドロキシエチル/アクリロイルジメチルタウリンNa）コポリマー、スクワラン、ポリソルベート 60、水）、SIMULGEL FL（（アクリル酸ヒドロキシエチル/アクリロイルジメチルタウリンNa）コポリマー、イソヘキサデカン、ポリソルベート60、水）、SEPIPLUS S（（アクリル酸ヒドロキシエチル/アクリロイルジメチルタウリンNa）コポリマー、ポリイソブテン、PEG-7トリメチロールプロパンヤシ油アルキルエーテル、水）；アクリル酸塩とアクリロイルジメチルタウリン塩との共重合体としては、SIMULGEL EG（（アクリル酸Na/アクリロイルジメチルタウリンNa）コポリマー、イソヘキサデカン、ポリソルベート 80、水）；アクリルアミドとアクリル酸塩との共重合体としては、SEPIPLUS 265（（アクリルアミド/アクリル酸アンモニウム）コポリマー、ポリイソブテン、ポリソルベート20、水）；アクリル酸とアクリル酸アミドとアクリル酸塩とアクリロイルジメチルタウリン塩の共重合体としては、SEPIPLUS 400（ポリアクリレート−13、ポリイソブテン、ポリソルベート20、水）が挙げられる。 These components are commercially available. As polyacrylamide, SEPIGEL 305 (polyacrylamide, hydrogenated polyisobutene (or (C13,14) isoparaffin), laureth-7, water); hydroxyethyl acrylate and acroyldimethyltaurine salt SEPINOV EMT 10 ((hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer), SIMULGEL NS ((hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer, squalane, polysorbate 60, water), SIMULGEL FL ((hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer, isohexadecane, polysorbate 60, water), SEPIPLUS S ((hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer, polyisobutene, PEG-7 trimethyl Propane coconut oil alkyl ether, water); as a copolymer of acrylate and acryloyldimethyltaurine salt, SIMULGEL EG ((Na acrylate / acryloyldimethyltaurine Na) copolymer, isohexadecane, polysorbate 80, water); As a copolymer with acrylate, SEPIPLUS 265 ((acrylamide / ammonium acrylate) copolymer, polyisobutene, polysorbate 20, water); copolymer of acrylic acid, acrylamide, acrylate, and acryloyldimethyltaurate SEPIPLUS 400 (polyacrylate-13, polyisobutene, polysorbate 20, water).
これらのうち好ましくは、アクリル酸塩とアクリロイルジメチルタウリン塩との共重合体が挙げられ、特に好ましくは、（アクリル酸Na/アクリロイルジメチルタウリンNa）コポリマーが挙げられる。これらの（Ｂ）成分は、１種又は２種以上を用いることができる。 Among these, a copolymer of an acrylate and an acryloyldimethyltaurine salt is preferable, and a (acrylic acid Na / acryloyldimethyltaurine Na) copolymer is particularly preferable. These (B) components can use 1 type (s) or 2 or more types.
（Ｂ）成分の含有量は、本発明の化粧料総量に対して、塗布時の伸ばしやすさの点で、０．１質量％以上が好ましく、０．２質量％以上がより好ましく、また２質量％以下が好ましく、１．４質量％以下がより好ましい。具体的な範囲としては、０．１〜２質量％であるのが好ましく、０．２〜１．４質量％であるのがより好ましい。（Ｂ）成分の含有量は、有効成分の含有量である。 The content of the component (B) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, with respect to the total amount of the cosmetic of the present invention, in terms of easiness of elongation at the time of application. % By mass or less is preferable, and 1.4% by mass or less is more preferable. As a specific range, it is preferable that it is 0.1-2 mass%, and it is more preferable that it is 0.2-1.4 mass%. (B) Content of a component is content of an active ingredient.
本発明で用いられる（Ｃ）疎水化処理紫外線散乱剤の紫外線散乱剤としては、紫外線を散乱する効果が高い点から、酸化亜鉛、酸化チタン及び酸化セリウムから選択される１種又は２種以上が好ましい。また、これらの紫外線散乱剤は＋２価以上の微量元素を含有させることができ、鉄、ジルコニウム、カルシウム、マンガン、マグネシウム、イットリウム等の金属を、単独又は２種以上を適宜組み合わせて、前記紫外線散乱剤に含有させることができる。 As the ultraviolet scattering agent of the (C) hydrophobized ultraviolet scattering agent used in the present invention, one or two or more selected from zinc oxide, titanium oxide and cerium oxide are used because of the high effect of scattering ultraviolet rays. preferable. Further, these ultraviolet scattering agents can contain +2 or more trace elements, and metals such as iron, zirconium, calcium, manganese, magnesium and yttrium can be used alone or in combination of two or more, and the ultraviolet scattering can be performed. It can be contained in the agent.
本発明に用いられる紫外線散乱剤の平均粒子径は、凝集防止の点から０．０１μｍ以上が好ましく、０．０１２μｍ以上がより好ましく、０．０１５μｍ以上がさらに好ましい。また、組成物の透明性を確保する点から、１μｍ以下が好ましく、０．２μｍ以下がより好ましく、０．１μｍ以下がさらに好ましい。具体的な平均粒子径としては、０．０１〜１μｍの範囲が好ましく、より好適には０．０１２〜０．２μｍ、さらに好適には０．０１５〜０．１μｍである。なお、平均粒子径は、レーザー回折／散乱法により測定される。 The average particle diameter of the ultraviolet scattering agent used in the present invention is preferably 0.01 μm or more, more preferably 0.012 μm or more, and further preferably 0.015 μm or more from the viewpoint of preventing aggregation. Moreover, from the point which ensures the transparency of a composition, 1 micrometer or less is preferable, 0.2 micrometer or less is more preferable, and 0.1 micrometer or less is further more preferable. As a specific average particle diameter, the range of 0.01-1 micrometer is preferable, More preferably, it is 0.012-0.2 micrometer, More preferably, it is 0.015-0.1 micrometer. The average particle diameter is measured by a laser diffraction / scattering method.
本発明で用いる紫外線散乱剤の形状としては、球状、棒状、紡錘状、針状、板状、不定形状等が挙げられるが、平均粒子径が前記範囲にあれば任意の形状のものを使用することができる。 Examples of the shape of the ultraviolet scattering agent used in the present invention include a spherical shape, a rod shape, a spindle shape, a needle shape, a plate shape, and an indefinite shape, and any shape having an average particle diameter within the above range is used. be able to.
微粒子酸化亜鉛粉末としては、例えばＦＩＮＥＸ−２５、ＦＩＮＥＸ−５０、ＦＩＮＥＸ−７５（堺化学社製）、ＭＺ５００シリーズ、ＭＺ７００シリーズ（テイカ社製）、ＺｎＯ−３５０（住友大阪セメント社製）などが市販されている。微粒子酸化チタン粉末としては、ＴＴＯ−５５シリーズ、ＴＴＯ−５１シリーズ（石原産業社製）、ＪＲシリーズ、ＪＡシリーズ（テイカ社製）などが市販されている。また、微粒子酸化セリウムとしては、ニッキ社又はセイミケミカル社から販売される高純度セリウムが含まれる。このうち、微粒子酸化亜鉛粉末又は微粒子酸化チタン粉末を用いることが好ましい。 As fine particle zinc oxide powder, for example, FINEX-25, FINEX-50, FINEX-75 (manufactured by Sakai Chemical Co., Ltd.), MZ500 series, MZ700 series (manufactured by Teika), ZnO-350 (manufactured by Sumitomo Osaka Cement Co., Ltd.) and the like are commercially available. Has been. As the fine particle titanium oxide powder, TTO-55 series, TTO-51 series (Ishihara Sangyo Co., Ltd.), JR series, JA series (Taika Co., Ltd.) and the like are commercially available. The fine cerium oxide includes high-purity cerium sold by Nikki or Seimi Chemical. Among these, it is preferable to use fine particle zinc oxide powder or fine particle titanium oxide powder.
前記紫外線散乱剤への疎水化処理としては、特に限定されず、種々の表面処理、例えば、フッ素化合物処理、シリコーン処理、シリコーン樹脂処理、ペンダント型シリコーン処理、シランカップリング剤処理、チタンカップリング剤処理、油剤処理、Ｎ−アシル化リジン処理、ポリアクリル酸処理、金属石鹸処理、アミノ酸処理、無機化合物処理、プラズマ処理、メカノケミカル処理、シラン化合物又はシラザン化合物等が挙げられる。 The hydrophobizing treatment to the ultraviolet scattering agent is not particularly limited, and various surface treatments such as fluorine compound treatment, silicone treatment, silicone resin treatment, pendant type silicone treatment, silane coupling agent treatment, titanium coupling agent. Treatment, oil treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, silane compound or silazane compound and the like can be mentioned.
これらの疎水化処理のうち、シリコーン処理、シリコーン樹脂処理、ペンダント型シリコーン処理、シランカップリング処理、シラン化合物処理、シラザン化合物処理等のケイ素化合物処理が好ましく、例えば、シリコーン又はシリコーン樹脂を用いた表面処理、メチルハイドロジェンポリシロキサン又は下記式（２）のメチルハイドロジェンポリシロキサン・ジメチルポリシロキサン共重合体の表面処理剤を用いた処理、シラン化合物又はシラザン化合物の表面処理剤を用いた処理がより好ましい。特に好ましくはシリコーン又はシリコーン樹脂を用いた表面処理、メチルハイドロジェンポリシロキサンを用いた表面処理である。 Among these hydrophobizing treatments, silicon compound treatments such as silicone treatment, silicone resin treatment, pendant type silicone treatment, silane coupling treatment, silane compound treatment, silazane compound treatment, etc. are preferable. For example, surface using silicone or silicone resin Treatment, treatment using a surface treatment agent of methylhydrogenpolysiloxane or methylhydrogenpolysiloxane / dimethylpolysiloxane copolymer of the following formula (2), treatment using a surface treatment agent of a silane compound or silazane compound is more preferable. Particularly preferred is a surface treatment using silicone or a silicone resin, or a surface treatment using methylhydrogenpolysiloxane.
（ｍ、ｎは整数、１≦ｍ＋ｎ≦６０） (M and n are integers, 1 ≦ m + n ≦ 60)
前記シリコーン又はシリコーン樹脂を用いた表面処理としては、特許第３１８７４４０号公報に記載されるように、酸化亜鉛粉末等の金属酸化物をオルガノポリシロキサン類及びシリコーン樹脂よりなるシリコーン化合物（但し、シラン化合物を除く）の少なくとも１種で非気相状態で被覆した後、酸素含有雰囲気中で６００〜９５０℃の温度で焼成することにより、酸化珪素で金属酸化物表面を被覆する方法が挙げられる。 As the surface treatment using the silicone or the silicone resin, as described in Japanese Patent No. 3187440, a metal compound such as zinc oxide powder is converted into a silicone compound comprising an organopolysiloxane and a silicone resin (however, a silane compound) And a method in which the surface of the metal oxide is coated with silicon oxide by firing at a temperature of 600 to 950 ° C. in an oxygen-containing atmosphere.
前記シラン化合物又はシラザン化合物としては、炭素数１〜２０のアルキル基若しくはフルオロアルキル基を有し、無機酸化物と反応性を有するシラン化合物又はシラザン化合物が好ましく、具体的には下記一般式（３）で示されるシラン化合物又は一般式（４）で示されるシラザン化合物であり、これらを１種又は２種以上用いることができる。 As the silane compound or silazane compound, a silane compound or silazane compound having an alkyl group or fluoroalkyl group having 1 to 20 carbon atoms and having reactivity with an inorganic oxide is preferable. Specifically, the following general formula (3 ) Or a silazane compound represented by the general formula (4), and one or more of them can be used.
（ｐは０又は１の整数であり、Ｒ3は炭素数１〜２０のアルキル基又はフルオロアルキル基（直鎖であっても分岐鎖であっても構わない）を示し、Ｒ4は炭素数１〜６のアルキル基を示し、Ｘはハロゲン原子又はアルコキシ基を示す。） (P is an integer of 0 or 1, R 3 represents an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group (which may be linear or branched), and R 4 is carbon number. 1 to 6 alkyl groups, and X represents a halogen atom or an alkoxy group.)
（Ｒ5〜Ｒ10は炭素数１〜２０のアルキル基又はフルオロアルキル基（直鎖であっても分岐鎖であっても構わない）を示し、同一又は異なっていても良い。） (R 5 to R 10 represent an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group (which may be linear or branched) and may be the same or different.)
具体的なシラン化合物としては、ヘキシルトリメトキシシラン、オクチルトリメトキシシラン、デシルトリメトキシシラン、オクタデシルトリメトキシシラン、オクチルトリエトキシシラン、トリフルオロプロピルトリメトキシシラン、ヘプタデカフルオロデシルトリメトキシシラン等が挙げられる。これらのうち好ましくはオクチルトリエトキシシラン、オクチルトリメトキシシランである。シラザン化合物の好ましい例としては、ヘキサメチルジシラザン、オクチルジシラザンが挙げられる。これらのうちより好ましくは、オクチルトリエトキシシラン、オクチルトリメトキシシラン及びヘキサメチルジシラザンから選択される１種又は２種以上であり、さらに好ましくはオクチルトリエトキシシラン及び／又はオクチルトリメトキシシランである。当該シラン化合物又はシラザン化合物は処理が均一にできやすく、かつ供給が容易でコスト的に安価である特徴があり、さらにこれらの化合物で表面処理した（Ｃ）微粒子紫外線散乱剤を配合した化粧料は分散性等の特性が優れているので好ましい。 Specific silane compounds include hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, octyltriethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, and the like. It is done. Of these, octyltriethoxysilane and octyltrimethoxysilane are preferable. Preferable examples of the silazane compound include hexamethyldisilazane and octyldisilazane. Of these, more preferably one or more selected from octyltriethoxysilane, octyltrimethoxysilane and hexamethyldisilazane, and more preferably octyltriethoxysilane and / or octyltrimethoxysilane. . The silane compound or silazane compound is characterized in that it can be uniformly treated, is easy to supply, and is inexpensive in cost. Further, a cosmetic containing (C) a fine particle ultraviolet scattering agent surface-treated with these compounds It is preferable because of excellent properties such as dispersibility.
前記シラン化合物又はシラザン化合物での処理方法としては、ｎ−ヘキサン、シクロヘキサン、低級アルコール等の有機溶媒中でシラン化合物又はシラザン化合物と酸化亜鉛粉末等の金属酸化物（紫外線散乱剤）とを混合し、場合により微粉砕した後、有機溶媒を加熱や減圧により除去し、好ましくは８０〜２５０℃で加熱処理する方法等で、シラン化合物又はシラザン化合物を酸化亜鉛等の金属酸化物（紫外線散乱剤）の表面で反応性基にて化学反応させる方法が挙げられる。 As a treatment method using the silane compound or silazane compound, a silane compound or silazane compound and a metal oxide (ultraviolet scattering agent) such as zinc oxide powder are mixed in an organic solvent such as n-hexane, cyclohexane or lower alcohol. In some cases, after finely pulverizing, the organic solvent is removed by heating or reduced pressure, and preferably a metal oxide such as zinc oxide (ultraviolet scattering agent) such as zinc oxide or the like by heat treatment at 80 to 250 ° C. And a method of chemically reacting with a reactive group on the surface of the substrate.
また、特開２００７−３２６９０２号公報に記載されるように、紫外線散乱剤を特定のポリシロキサン化合物を被覆処理した後に、アルキルアルコキシシランを水中にて表面処理する方法も挙げられる。 In addition, as described in JP-A-2007-326902, a method in which an alkylalkoxysilane is surface-treated in water after a specific polysiloxane compound is coated with an ultraviolet scattering agent.
紫外線散乱剤への表面処理剤の被覆量は、用いられる紫外線散乱剤の総量に対して、３質量％以上が好ましく、５質量％以上がより好ましく、また１５質量％以下が好ましく、１０質量％以下がより好ましい。具体的な範囲としては、３〜１５質量％であるのが好ましく、より好ましくは５〜１０質量％である。当該範囲内であれば、これら粉末表面に表面処理剤が均一に被覆され、酸化亜鉛等粉末表面で表面処理剤が凝集や、析出することがない。（Ｃ）成分は、１種又は２種以上を用いることができる。 The coating amount of the surface treatment agent on the ultraviolet scattering agent is preferably 3% by mass or more, more preferably 5% by mass or more, and preferably 15% by mass or less, based on the total amount of the ultraviolet scattering agent used. The following is more preferable. As a specific range, it is preferable that it is 3-15 mass%, More preferably, it is 5-10 mass%. Within this range, the surface treatment agent is uniformly coated on the powder surface, and the surface treatment agent does not aggregate or precipitate on the powder surface such as zinc oxide. (C) A component can use 1 type (s) or 2 or more types.
本発明で用いる（Ｃ）疎水化処理紫外線散乱剤は、本発明の化粧料の総量に対して、１質量％以上含有するのが好ましく、３質量％以上含有するのがより好ましく、５質量％以上含有するのがさらに好ましく、また２０質量％以下含有するのが好ましく、１８質量％以下含有するのがより好ましく、１５質量％以下含有するのがより好ましい。具体的な範囲としては、１〜２０質量％含有することが好ましく、さらに３〜１８質量％が好ましく、さらに好適には５〜１５質量％である。当該範囲内であれば、紫外線防御効果、粉末の分散性が良好で、経日安定性という問題も生じない。 The (C) hydrophobized UV scatterer used in the present invention is preferably contained in an amount of 1% by mass or more, more preferably 3% by mass or more, more preferably 5% by mass with respect to the total amount of the cosmetic of the present invention. More preferably, the content is more preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 15% by mass or less. As a specific range, it is preferable to contain 1-20 mass%, 3-18 mass% is more preferable, More preferably, it is 5-15 mass%. If it is in the said range, the ultraviolet-ray protective effect, the dispersibility of powder will be favorable, and the problem of aging stability will not arise.
（Ｃ）疎水化処理紫外線散乱剤中には、疎水化処理微粒子酸化亜鉛粉末を６０質量％以上含有することが、ＵＶＡ防御能の向上、高温安定性の改善に繋がるため好ましい。 (C) It is preferable to contain 60% by mass or more of the hydrophobized fine particle zinc oxide powder in the hydrophobized UV scatterer because it leads to an improvement in UVA protection ability and an improvement in high-temperature stability.
本発明の水中油型乳化化粧料においては、優れた紫外線防御効果を得るためには、（Ｃ）成分と（Ａ）成分の含有質量比（（Ｃ）／（Ａ））が０．５〜１５であることが必要である。また良好な使用感触を得る点から、（（Ｃ）／（Ａ））は、０．５以上が好ましく、０．６以上がより好ましく、また１０以下が好ましく、７．５以下がより好ましく、５以下がさらに好ましく、４以下がさらに好ましい。（（Ｃ）／（Ａ））の具体的な範囲としては、０．５〜１０が好ましく、０．５〜７．５がより好ましく、０．５〜５がさらに好ましく、０．６〜４がさらに好ましい。 In the oil-in-water emulsified cosmetic of the present invention, in order to obtain an excellent ultraviolet protection effect, the mass ratio ((C) / (A)) of the component (C) to the component (A) is 0.5 to It is necessary to be 15. Further, from the viewpoint of obtaining a good feeling of use, ((C) / (A)) is preferably 0.5 or more, more preferably 0.6 or more, and preferably 10 or less, more preferably 7.5 or less, 5 or less is more preferable, and 4 or less is more preferable. The specific range of ((C) / (A)) is preferably 0.5 to 10, more preferably 0.5 to 7.5, still more preferably 0.5 to 5, and 0.6 to 4 Is more preferable.
本発明ではさらに、（Ｄ）成分として油溶性の有機紫外線吸収剤を含有することが好ましい。（Ｄ）成分は一般的に感触が重く、ベタツキ感が強い油剤であるが、（Ａ）成分と併用することで、感触の低下を抑えつつ、紫外線防御効果を高めることが可能である。 In the present invention, it is further preferable to contain an oil-soluble organic ultraviolet absorber as the component (D). The component (D) is generally an oil that has a heavy feel and a strong stickiness, but when used in combination with the component (A), it is possible to enhance the UV protection effect while suppressing a decrease in feel.
油溶性の有機紫外線吸収剤としては、パラメトキシケイ皮酸２−エチルヘキシル、パラメトキシケイ皮酸２−エトキシエチル、パラメトキシケイ皮酸イソプロピル・ジイソプロピルケイ皮酸エステル混合物、トリメトキシケイ皮酸メチルビス(トリメチルシロキシ)シリルイソペンチル、パラジメチルアミノ安息香酸アミル、パラジメチルアミノ安息香酸２−エチルヘキシル、サリチル酸エチレングリコール、サリチル酸２−エチルヘキシル、サリチル酸ベンジル、サリチル酸ホモメンチル、オクトクリレン、ジメチコジエチルベンザルマロネート、ジメトキシベンジリデンジオキソイミダゾリジンプロピオン酸２−エチルヘキシル、ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシルエステル、２，４−ビス｛［４−（２−エチルヘキシルオキシ）−２−ヒドロキシ］−フェニル｝−６−（４−メトキシフェニル）−１，３，５−トリアジン、２，４，６−トリス［４−（２−エチルヘキシルオキシカルボニル）アニリノ］−１，３，５−トリアジン、４−ｔｅｒｔ−ブチル−４’−メトキシジベンゾイルメタン等が挙げられる。これらのうち、パラメトキシケイ皮酸２−エチルヘキシル、サリチル酸２−エチルヘキシル、サリチル酸ホモメンチル、オクトクリレン、ジメチコジエチルベンザルマロネート、ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシルエステル、２，４−ビス｛［４−（２−エチルヘキシルオキシ）−２−ヒドロキシ］−フェニル｝−６−（４−メトキシフェニル）−１，３，５−トリアジン、２，４，６−トリス［４−（２−エチルヘキシルオキシカルボニル）アニリノ］−１，３，５−トリアジン、４−ｔｅｒｔ−ブチル−４’−メトキシジベンゾイルメタンが好ましく、紫外線防御効果を高める点から、より好ましくはパラメトキシケイ皮酸２−エチルヘキシル、オクトクリレン、ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシルエステル、２，４−ビス｛［４−（２−エチルヘキシルオキシ）−２−ヒドロキシ］−フェニル｝−６−（４−メトキシフェニル）−１，３，５−トリアジン、２，４，６−トリス［４−（２−エチルヘキシルオキシカルボニル）アニリノ］−１，３，５−トリアジン、４−ｔｅｒｔ−ブチル−４’−メトキシジベンゾイルメタンであり、さらに好ましくはパラメトキシケイ皮酸２−エチルヘキシル、ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシルエステル、２，４−ビス｛［４−（２−エチルヘキシルオキシ）−２−ヒドロキシ］−フェニル｝−６−（４−メトキシフェニル）−１，３，５−トリアジン、２，４，６−トリス［４−（２−エチルヘキシルオキシカルボニル）アニリノ］−１，３，５−トリアジンである。（Ｄ）成分は１種又は２種以上を用いることができる。 Examples of the oil-soluble organic ultraviolet absorber include 2-methoxyhexyl paramethoxycinnamate, 2-ethoxyethyl paramethoxycinnamate, isopropyl dimethoxycinnamate / diisopropyl cinnamate ester, methyl bis (trimethoxycinnamate) Trimethylsiloxy) silylisopentyl, amyl paradimethylaminobenzoate, 2-ethylhexyl paradimethylaminobenzoate, ethylene glycol salicylate, 2-ethylhexyl salicylate, benzyl salicylate, homomenthyl salicylate, octocrylene, dimethicodiethylbenzalmalonate, dimethoxybenzylidene Dioxoimidazolidinepropionic acid 2-ethylhexyl, diethylaminohydroxybenzoylbenzoic acid hexyl ester, 2,4-bis {[4- (2-ethylhexyl Oxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1, 3,5-triazine, 4-tert-butyl-4′-methoxydibenzoylmethane and the like can be mentioned. Among these, 2-methoxyhexyl paramethoxycinnamate, 2-ethylhexyl salicylate, homomenthyl salicylate, octocrylene, dimethicodiethylbenzalmalonate, diethylaminohydroxybenzoylbenzoic acid hexyl ester, 2,4-bis {[4- (2 -Ethylhexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino]- 1,3,5-triazine and 4-tert-butyl-4′-methoxydibenzoylmethane are preferable, and 2-ethylhexyl paramethoxycinnamate, octocrylene, diethylaminohydroxybenzoylbenzoate are more preferable from the viewpoint of enhancing the UV protection effect. Acid hex Ester, 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, 4-tert-butyl-4′-methoxydibenzoylmethane, more preferably 2-ethylhexyl paramethoxycinnamate, diethylamino Hydroxybenzoylbenzoic acid hexyl ester, 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, 2, 4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine. (D) A component can use 1 type (s) or 2 or more types.
紫外線防御効果と良好な感触を維持する点から、（Ｄ）成分の本発明化粧料総量に対する含有量は、０．１質量％以上が好ましく、１質量％以上がより好ましく、３質量％以上がさらに好ましい。また、２０質量％以下が好ましく、１５質量％以下がより好ましい。具体的な範囲としては、０．１〜２０質量％が好ましく、１〜１５質量％がより好ましく、３〜１５質量％がより好ましい。 From the point of maintaining the UV protection effect and good feel, the content of the component (D) with respect to the total amount of the cosmetic of the present invention is preferably 0.1% by mass or more, more preferably 1% by mass or more, and more preferably 3% by mass or more. Further preferred. Moreover, 20 mass% or less is preferable, and 15 mass% or less is more preferable. As a specific range, 0.1-20 mass% is preferable, 1-15 mass% is more preferable, and 3-15 mass% is more preferable.
本発明の水中油型乳化化粧料には、使用感、経時安定性を調整する目的で、界面活性剤を含有させることができる。界面活性剤としては、特に制限されず、非イオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤、天然系界面活性剤、ポリエーテル変性シリコーン、シロキサン誘導体等のシリコーン含有界面活性剤、パーフルオロアルキル基を含有する界面活性剤等のいずれでも用いることができ、これらを１種又は２種以上用いることができる。 The oil-in-water emulsion cosmetic of the present invention may contain a surfactant for the purpose of adjusting the feeling of use and stability over time. The surfactant is not particularly limited, and includes nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, natural surfactants, polyether-modified silicones, siloxane derivatives, and the like. Any of a silicone-containing surfactant, a surfactant containing a perfluoroalkyl group, and the like can be used, and one or more of these can be used.
これらの界面活性剤のうち、非イオン性界面活性剤、ポリエーテル変性シリコーン、シリコーン含有界面活性剤が好ましく、具体的には、モノイソソテアリン酸ソルビタン、ジメチコンコポリオール、ポリオキシエチレン硬化ヒマシ油（４０ＥＯ）、ポリオキシエチレンヒマシ油（４０ＥＯ)、モノラウリン酸ポリオキシエチレンソルビタン（２０ＥＯ）、モノステアリン酸ポリオキシエチレン（２０ＥＯ）、オレイン酸ポリオキシエチレンソルビタン（２０ＥＯ）、ポリオキシエチレン（７）ラウリルエーテル、PEG-7トリメチロールプロパンヤシ油アルキルエーテル等が挙げられる。 Of these surfactants, nonionic surfactants, polyether-modified silicones, and silicone-containing surfactants are preferred. Specifically, sorbitan monoisosotearate, dimethicone copolyol, polyoxyethylene hydrogenated castor oil (40EO), polyoxyethylene castor oil (40EO), polyoxyethylene sorbitan monolaurate (20EO), polyoxyethylene monostearate (20EO), polyoxyethylene sorbitan oleate (20EO), polyoxyethylene (7) lauryl And ether, PEG-7 trimethylolpropane coconut oil alkyl ether, and the like.
本発明の水中油型乳化化粧料では、上記界面活性剤を併用しなくとも使用感、経時安定性が良好であり、多量に界面活性剤を配合すると、界面活性剤に由来するべたつき感が生じてしまうことがあるため、界面活性剤の好ましい含有量は化粧料総量に対して、０〜３質量％であり、さらに好ましくは０〜１．５質量％である。 In the oil-in-water emulsified cosmetic of the present invention, the feeling of use and stability over time are good without using the above surfactants in combination, and when a large amount of the surfactant is added, a sticky feeling derived from the surfactant occurs. Therefore, the preferable content of the surfactant is 0 to 3% by mass, and more preferably 0 to 1.5% by mass with respect to the total amount of the cosmetic.
本発明の水中油型乳化化粧料において、水の含有量は経時安定性に優れた水中油型乳化組成物を形成する点から、本発明化粧料総量に対して、好ましくは４０〜７５質量％であり、より好ましくは４５〜７０質量％である。 In the oil-in-water emulsified cosmetic of the present invention, the water content is preferably 40 to 75% by mass with respect to the total amount of the cosmetic of the present invention from the viewpoint of forming an oil-in-water emulsified composition having excellent temporal stability. More preferably, it is 45-70 mass%.
また、本発明の水中油型乳化化粧料には、上記成分の他に、目的に応じて本発明の効果を損なわない範囲内で、高級アルコール類、脂肪酸類、エステル類、ステロール類、ステロール脂肪酸エステル類、炭化水素類、油脂類、シリコーンオイル、保湿剤、本発明の（Ａ）成分以外の水溶性高分子、植物エキス、ビタミン類、酸化防止剤、防菌防腐剤、消炎剤、昆虫忌避剤、生理活性成分、塩類、キレート剤、中和剤、ｐＨ調整剤、香料等を配合することができる。 The oil-in-water emulsified cosmetic of the present invention includes, in addition to the above components, higher alcohols, fatty acids, esters, sterols, sterol fatty acids within the range not impairing the effects of the present invention depending on the purpose. Esters, hydrocarbons, fats and oils, silicone oils, moisturizers, water-soluble polymers other than the component (A) of the present invention, plant extracts, vitamins, antioxidants, antibacterial preservatives, anti-inflammatory agents, insect repellents Agents, physiologically active ingredients, salts, chelating agents, neutralizing agents, pH adjusters, fragrances and the like can be blended.
本発明の水中油型乳化化粧料は、シャンプー、リンス、コンディショナーなどの毛髪化粧料、洗顔料、クレンジング化粧料、日焼け止め化粧料、パック、マッサージ化粧料などの皮膚化粧料として好適に利用できる。これらのうち、特に日焼け止め化粧料（化粧水、クリーム、乳液、美容液等）、サンタン、化粧下地化粧料、紫外線防御能を有するファンデーション等に適用するのが好ましい。 The oil-in-water emulsified cosmetic of the present invention can be suitably used as hair cosmetics such as shampoos, rinses and conditioners, facial cleansers, cleansing cosmetics, sunscreen cosmetics, packs and massage cosmetics. Among these, it is particularly preferable to apply to sunscreen cosmetics (skin lotion, cream, milky lotion, beauty serum, etc.), suntan, cosmetic base cosmetics, foundations having UV protection ability, and the like.
上述の実施形態に関し、本発明はさらに以下の実施態様の組成物を開示する。 In relation to the above-described embodiments, the present invention further discloses compositions of the following embodiments.
＜１＞下記の（Ａ）〜（Ｃ）成分を含有し、（Ｃ）成分と（Ａ）成分の含有質量比（（Ｃ）／（Ａ））が０．５〜１５である水中油型乳化化粧料。
（Ａ）下記一般式（１）で表される無水ヘキシトールのジ脂肪酸エステル、
（Ｂ）水溶性高分子、
（Ｃ）疎水化処理紫外線散乱剤
<1> Oil-in-water type containing the following components (A) to (C) and having a mass ratio of (C) component to (A) component ((C) / (A)) of 0.5 to 15 Emulsified cosmetic.
(A) difatty acid ester of anhydrous hexitol represented by the following general formula (1),
(B) a water-soluble polymer,
(C) Hydrophobized UV scattering agent
（式中、Ｒ1及びＲ2は、同一又は異なって、炭素数７〜９の飽和又は不飽和の直鎖又は分岐の炭化水素基示す。） (In the formula, R 1 and R 2 are the same or different and represent a saturated or unsaturated linear or branched hydrocarbon group having 7 to 9 carbon atoms.)
＜２＞一般式（１）中、Ｒ1及びＲ2が炭素数７〜９の直鎖又は分岐のアルキル基であり、好ましくは炭素数７〜９の直鎖アルキル基である＜１＞の水中油型乳化化粧料。
＜３＞（Ａ）成分の含有量が、化粧料総量に対し、好ましくは０．３質量％以上、より好ましくは０．５質量％以上、さらに好ましくは０．８質量％以上、さらに好ましくは２質量％以上であり、また好ましくは１５質量％以下、より好ましくは１０質量％以下、さらに好ましくは６．５質量％以下である＜１＞又は＜２＞の水中油型乳化化粧料。
＜４＞（Ａ）成分の含有量が、化粧料総量に対し、好ましくは０．３〜１５質量％、より好ましくは０．５〜１０質量％、さらに好ましくは０．８〜８質量％、さらに好ましくは２〜６．５質量％である＜１＞〜＜３＞のいずれかの水中油型乳化化粧料。
＜５＞（Ｂ）成分が、ポリアクリルアミド及びアクリルアミドコポリマーから選ばれる１種又は２種以上であり、好ましくはアクリルアミドコポリマーが、アクリルアミド及び／又はアクリロイルジメチルタウリンを構成単位として含むコポリマーである＜１＞〜＜４＞のいずれかの水中油型乳化化粧料。
＜６＞アクリルアミド及び／又はアクリロイルジメチルタウリンを構成単位として含むコポリマーが、アクリル酸ヒドロキシエチルとアクロイルジメチルタウリン塩との共重合体、アクリル酸塩とアクリロイルジメチルタウリン塩との共重合体、アクリルアミドとアクリル酸塩との共重合体、及びアクリル酸とアクリル酸アミドとアクリル酸塩とアクリロイルジメチルタウリン塩の共重合体から選ばれる１種又は２種以上である＜５＞の水中油型乳化化粧料。
＜７＞（Ｂ）成分の含有量が、化粧料総量に対して、好ましくは０．１質量％以上、より好ましくは０．２質量％以上であり、また好ましくは２質量％以下、より好ましくは１．４質量％以下である＜１＞〜＜６＞のいずれかの水中油型乳化化粧料。
＜８＞（Ｂ）成分の含有量が、化粧料総量に対して、好ましくは０．１〜２質量％、より好ましくは０．２〜１．４質量％である＜１＞〜＜７＞のいずれかの水中油型乳化化粧料。
＜９＞（Ｃ）成分の紫外線散乱剤が、酸化亜鉛、酸化チタン及び酸化セリウムから選ばれる１種又は２種以上の金属酸化物である＜１＞〜＜８＞のいずれかの水中油型乳化化粧料。
＜10＞（Ｃ）成分の紫外線散乱剤の平均粒子径が、好ましくは０．０１μｍ以上、より好ましくは０．０１２μｍ以上、さらに好ましくは０．０１５μｍ以上であり、また好ましくは１μｍ以下、より好ましくは０．２μｍ以下、さらに好ましくは０．１μｍ以下である＜１＞〜＜９＞のいずれかの水中油型乳化化粧料。
＜11＞（Ｃ）成分の紫外線散乱剤の平均粒子径が、好ましくは０．０１〜１μｍ、より好ましくは０．０１２〜０．２μｍ、さらに好ましくは０．０１５〜０．１μｍである＜１＞〜＜１０＞のいずれかの水中油型乳化化粧料。
＜12＞（Ｃ）成分の紫外線散乱剤の疎水化処理が、好ましくはフッ素化合物処理、シリコーン処理、シリコーン樹脂処理、ペンダント型シリコーン処理、シランカップリング剤処理、チタンカップリング剤処理、油剤処理、Ｎ−アシル化リジン処理、ポリアクリル酸処理、金属石鹸処理、アミノ酸処理、無機化合物処理、プラズマ処理、メカノケミカル処理、シラン化合物又はシラザン化合物処理であり；より好ましくはケイ素化合物処理であり、より好ましくはシリコーン処理、シリコーン樹脂処理、ペンダント型シリコーン処理、シランカップリング処理、シラン化合物処理、シラザン化合物処理である＜１＞〜＜１１＞のいずれかの水中油型乳化化粧料。
＜13＞（Ｃ）成分の紫外線散乱剤の表面処理が、好ましくはシリコーン又はシリコーン樹脂を用いた表面処理、メチルハイドロジェンポリシロキサン又は下記式（２）のメチルハイドロジェンポリシロキサン・ジメチルポリシロキサン共重合体の表面処理剤を用いた処理、シラン化合物又はシラザン化合物の表面処理剤を用いた処理であり、より好ましくはシリコーン又はシリコーン樹脂を用いた表面処理、メチルハイドロジェンポリシロキサンを用いた表面処理である＜１＞〜＜１２＞のいずれかの水中油型乳化化粧料。
<2> In the general formula (1), R 1 and R 2 are linear or branched alkyl groups having 7 to 9 carbon atoms, preferably linear alkyl groups having 7 to 9 carbon atoms. Oil-in-water emulsified cosmetic.
<3> The content of the component (A) is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, further preferably, relative to the total amount of the cosmetic. <1> or <2> oil-in-water emulsified cosmetic, which is 2% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 6.5% by mass or less.
<4> The content of the component (A) is preferably 0.3 to 15% by mass, more preferably 0.5 to 10% by mass, further preferably 0.8 to 8% by mass, based on the total amount of the cosmetic. More preferably, the oil-in-water emulsified cosmetic according to any one of <1> to <3>, which is 2 to 6.5% by mass.
<5> The component (B) is one or more selected from polyacrylamide and acrylamide copolymer, and preferably the acrylamide copolymer is a copolymer containing acrylamide and / or acryloyldimethyltaurine as a structural unit <1> The oil-in-water emulsified cosmetic according to any one of ~ <4>.
<6> A copolymer containing acrylamide and / or acryloyldimethyltaurine as a constituent unit is a copolymer of hydroxyethyl acrylate and acryloyldimethyltaurine, a copolymer of acrylate and acryloyldimethyltaurine, acrylamide, <5> oil-in-water emulsified cosmetic, which is one or more selected from a copolymer with an acrylate, and a copolymer of acrylic acid, an acrylic amide, an acrylate, and an acryloyldimethyltaurine salt .
<7> The content of the component (B) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 2% by mass or less, more preferably based on the total amount of the cosmetic. Is an oil-in-water emulsified cosmetic according to any one of <1> to <6>, which is 1.4% by mass or less.
<8> The content of the component (B) is preferably 0.1 to 2% by mass, more preferably 0.2 to 1.4% by mass with respect to the total amount of the cosmetic, <1> to <7>. Any of oil-in-water emulsified cosmetics.
<9> The oil-in-water type of any one of <1> to <8>, wherein the ultraviolet scattering agent of component (C) is one or more metal oxides selected from zinc oxide, titanium oxide, and cerium oxide Emulsified cosmetic.
<10> The average particle size of the component (C) ultraviolet scattering agent is preferably 0.01 μm or more, more preferably 0.012 μm or more, further preferably 0.015 μm or more, and preferably 1 μm or less, more preferably Is an oil-in-water emulsified cosmetic according to any one of <1> to <9>, which is 0.2 μm or less, more preferably 0.1 μm or less.
<11> The average particle size of the ultraviolet scattering agent as the component (C) is preferably 0.01 to 1 μm, more preferably 0.012 to 0.2 μm, and still more preferably 0.015 to 0.1 μm. >-<10> Oil-in-water emulsified cosmetics.
<12> The hydrophobic treatment of the ultraviolet scattering agent of the component (C) is preferably a fluorine compound treatment, a silicone treatment, a silicone resin treatment, a pendant silicone treatment, a silane coupling agent treatment, a titanium coupling agent treatment, an oil agent treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, silane compound or silazane compound treatment; more preferred is silicon compound treatment, more preferred Is an oil-in-water emulsion cosmetic according to any one of <1> to <11>, which is a silicone treatment, a silicone resin treatment, a pendant silicone treatment, a silane coupling treatment, a silane compound treatment, and a silazane compound treatment.
<13> The surface treatment of the ultraviolet scattering agent of component (C) is preferably a surface treatment using silicone or silicone resin, methylhydrogenpolysiloxane or methylhydrogenpolysiloxane / dimethylpolysiloxane of the following formula (2) Treatment using a polymer surface treatment agent, treatment using a silane compound or silazane compound surface treatment agent, more preferably surface treatment using silicone or silicone resin, surface treatment using methylhydrogenpolysiloxane The oil-in-water emulsified cosmetic according to any one of <1> to <12>.
（ｍ、ｎは整数、１≦ｍ＋ｎ≦６０）
＜14＞（Ｃ）成分における紫外線散乱剤への表面処理剤の被覆量が、好ましくは３質量％以上、より好ましくは５質量％以上であり、また好ましくは１５質量％以下、より好ましくは１０質量％以下である＜１＞〜＜１３＞のいずれかの水中油型乳化化粧料。
＜15＞（Ｃ）成分における紫外線散乱剤への表面処理剤の被覆量が、好ましくは３〜１５質量％、より好ましくは５〜１０質量％である＜１＞〜＜１４＞のいずれかの水中油型乳化化粧料。
＜16＞（Ｃ）成分の含有量が、化粧料総量に対して、１質量％以上、より好ましくは３質量％以上、より好ましくは５質量％以上であり、また好ましくは２０質量％以下、より好ましくは１８質量％以下、さらに好ましくは１５質量％以下である＜１＞〜＜１５＞のいずれかの水中油型乳化化粧料。
＜17＞（Ｃ）成分の含有量が、化粧料総量に対して、好ましくは１〜２０質量％、より好ましくは３〜１８質量％、より好ましくは５〜１５質量％である＜１＞〜＜１６＞のいずれかの水中油型乳化化粧料。
＜18＞（Ｃ）成分と（Ａ）成分の含有質量比（（Ｃ）／（Ａ））が、０．５〜１５であり、０．５以上が好ましく、０．６以上がより好ましく、また１０以下が好ましく、７．５以下がより好ましく、５以下がさらに好ましく、４以下がさらに好ましい＜１＞〜＜１７＞のいずれかの水中油型乳化化粧料。
＜19＞（（Ｃ）／（Ａ））が、好ましくは０．５〜１０、より好ましくは０．５〜７．５、さらに好ましくは０．５〜５、さらに好ましくは０．６〜４である＜１＞〜＜１８＞のいずれかの水中油型乳化化粧料。
＜20＞さらに（Ｄ）油溶性の有機紫外線吸収剤を含有する＜１＞〜＜１９＞のいずれかの水中油型乳化化粧料。
＜21＞（Ｄ）成分が、パラメトキシケイ皮酸２−エチルヘキシル、パラメトキシケイ皮酸２−エトキシエチル、パラメトキシケイ皮酸イソプロピル・ジイソプロピルケイ皮酸エステル混合物、トリメトキシケイ皮酸メチルビス(トリメチルシロキシ)シリルイソペンチル、パラジメチルアミノ安息香酸アミル、パラジメチルアミノ安息香酸２−エチルヘキシル、サリチル酸エチレングリコール、サリチル酸２−エチルヘキシル、サリチル酸ベンジル、サリチル酸ホモメンチル、オクトクリレン、ジメチコジエチルベンザルマロネート、ジメトキシベンジリデンジオキソイミダゾリジンプロピオン酸２−エチルヘキシル、ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシルエステル、２，４−ビス｛［４−（２−エチルヘキシルオキシ）−２−ヒドロキシ］−フェニル｝−６−（４−メトキシフェニル）−１，３，５−トリアジン、２，４，６−トリス［４−（２−エチルヘキシルオキシカルボニル）アニリノ］−１，３，５−トリアジン、及び４−ｔｅｒｔ−ブチル−４’−メトキシジベンゾイルメタンから選ばれる１種又は２種以上であり；より好ましくはパラメトキシケイ皮酸２−エチルヘキシル、サリチル酸２−エチルヘキシル、サリチル酸ホモメンチル、オクトクリレン、ジメチコジエチルベンザルマロネート、ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシルエステル、２，４−ビス｛［４−（２−エチルヘキシルオキシ）−２−ヒドロキシ］−フェニル｝−６−（４−メトキシフェニル）−１，３，５−トリアジン、２，４，６−トリス［４−（２−エチルヘキシルオキシカルボニル）アニリノ］−１，３，５−トリアジン、及び４−ｔｅｒｔ−ブチル−４’−メトキシジベンゾイルメタンから選ばれる１種又は２種以上であり；さらに好ましくはパラメトキシケイ皮酸２−エチルヘキシル、オクトクリレン、ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシルエステル、２，４−ビス｛［４−（２−エチルヘキシルオキシ）−２−ヒドロキシ］−フェニル｝−６−（４−メトキシフェニル）−１，３，５−トリアジン、２，４，６−トリス［４−（２−エチルヘキシルオキシカルボニル）アニリノ］−１，３，５−トリアジン、４−ｔｅｒｔ−ブチル−４’−メトキシジベンゾイルメタンから選ばれる１種又は２種以上である＜２０＞の水中油型乳化化粧料。
＜22＞（Ｄ）成分の含有量が、化粧料総量に対して、好ましくは０．１質量％以上、好ましくは１質量％以上、より好ましくは３質量％以上であり、また、好ましくは２０質量％以下、より好ましくは１５質量％以下である＜２０＞又は＜２１＞の水中油型乳化化粧料。
＜23＞（Ｄ）成分の含有量が、化粧料総量に対して、好ましくは０．１〜２０質量％、より好ましくは１〜１５質量％、さらに好ましくは３〜１５質量％である＜２０＞〜＜２２＞のいずれかの水中油型乳化化粧料。
＜24＞さらに界面活性剤を０〜３質量％、好ましくは０〜１．５質量％含有する＜１＞〜＜２３＞のいずれかの水中油型乳化化粧料。
＜25＞水の含有量が、化粧料総量に対して、好ましくは４０〜７５質量％、より好ましくは４５〜７０質量％である＜１＞〜＜２４＞のいずれかの水中油型乳化化粧料。
＜26＞日焼け止め化粧料である＜１＞〜＜２５＞のいずれかの水中油型乳化化粧料。
＜27＞一般式（１）中の無水ヘキシトール部分がイソソルビド(isosobide)、イソマンニド（isomannide）及びイソイジド（isoidide）から選択される１種であり、好ましくはイソソルビド又はイソマンニドであり、より好ましくはイソソルビドである＜１＞〜＜２６＞のいずれかの水中油型乳化化粧料。
(M and n are integers, 1 ≦ m + n ≦ 60)
The coating amount of the surface treatment agent on the ultraviolet scattering agent in <14> (C) component is preferably 3% by mass or more, more preferably 5% by mass or more, and preferably 15% by mass or less, more preferably 10%. The oil-in-water emulsified cosmetic according to any one of <1> to <13>, which is not more than mass%.
<15> The coating amount of the surface treatment agent on the ultraviolet scattering agent in the component (C) is preferably 3 to 15% by mass, more preferably 5 to 10% by mass, and any one of <1> to <14> Oil-in-water emulsified cosmetic.
<16> The content of the component (C) is 1% by mass or more, more preferably 3% by mass or more, more preferably 5% by mass or more, and preferably 20% by mass or less, based on the total amount of the cosmetic. The oil-in-water emulsified cosmetic according to any one of <1> to <15>, more preferably 18% by mass or less, and still more preferably 15% by mass or less.
<17> The content of the component (C) is preferably 1 to 20% by mass, more preferably 3 to 18% by mass, and more preferably 5 to 15% by mass with respect to the total amount of the cosmetic <1> to <16> The oil-in-water emulsified cosmetic according to any one of the above.
<18> The mass ratio of the component (C) to the component (A) ((C) / (A)) is 0.5 to 15, preferably 0.5 or more, more preferably 0.6 or more, Moreover, 10 or less are preferable, 7.5 or less are more preferable, 5 or less are more preferable, and 4 or less are further more preferable, The oil-in-water type emulsion cosmetic in any one of <1>-<17>.
<19> ((C) / (A)) is preferably 0.5 to 10, more preferably 0.5 to 7.5, still more preferably 0.5 to 5, and still more preferably 0.6 to 4. <1> to <18>, wherein the oil-in-water emulsified cosmetic composition is any one of the following.
<20> The oil-in-water emulsified cosmetic according to any one of <1> to <19>, further comprising (D) an oil-soluble organic ultraviolet absorber.
<21> (D) component is 2-methoxyhexyl paramethoxycinnamate, 2-ethoxyethyl paramethoxycinnamate, isopropyl dimethoxycinnamate / diisopropyl cinnamate ester mixture, methyl bis (trimethyl trimethoxycinnamate) Siloxy) silylisopentyl, amyl paradimethylaminobenzoate, 2-ethylhexyl paradimethylaminobenzoate, ethylene glycol salicylate, 2-ethylhexyl salicylate, benzyl salicylate, homomenthyl salicylate, octocrylene, dimethicodiethylbenzalmalonate, dimethoxybenzylidene diene Oxoimidazolidinepropionic acid 2-ethylhexyl, diethylaminohydroxybenzoylbenzoic acid hexyl ester, 2,4-bis {[4- (2-ethylhexyloxy) -2- Hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine , And 4-tert-butyl-4′-methoxydibenzoylmethane; more preferably 2-ethylhexyl paramethoxycinnamate, 2-ethylhexyl salicylate, homomenthyl salicylate, octocrylene, dimethyl Codiethylbenzalmalonate, diethylaminohydroxybenzoylbenzoic acid hexyl ester, 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine, 2,4,6-tris [4- (2-ethylhexyl Loxycarbonyl) anilino] -1,3,5-triazine, and 4-tert-butyl-4′-methoxydibenzoylmethane; more preferably paramethoxycinnamic acid 2 -Ethylhexyl, octocrylene, diethylaminohydroxybenzoylbenzoic acid hexyl ester, 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3 One selected from 5-triazine, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, 4-tert-butyl-4′-methoxydibenzoylmethane Or <20> oil-in-water type emulsified cosmetics which are 2 or more types.
<22> The content of the component (D) is preferably 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 20%, based on the total amount of the cosmetic. The <20> or <21> oil-in-water emulsified cosmetic, which is not more than mass%, more preferably not more than 15 mass%.
<23> The content of the component (D) is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and further preferably 3 to 15% by mass with respect to the total amount of the cosmetic <20 The oil-in-water emulsified cosmetic composition according to any one of> to <22>.
<24> The oil-in-water emulsion cosmetic according to any one of <1> to <23>, further comprising 0 to 3% by mass, preferably 0 to 1.5% by mass of a surfactant.
<25> The oil-in-water emulsion makeup according to any one of <1> to <24>, wherein the content of water is preferably 40 to 75% by mass, more preferably 45 to 70% by mass, based on the total amount of the cosmetic. Fee.
<26> The oil-in-water emulsified cosmetic according to any one of <1> to <25>, which is a sunscreen cosmetic.
<27> The anhydrous hexitol moiety in the general formula (1) is one selected from isosorbide, isomannide and isoidide, preferably isosorbide or isomannide, more preferably isosorbide. The oil-in-water emulsified cosmetic according to any one of <1> to <26>.
以下、実施例及び比較例にて本発明を詳細に説明するが、本発明はこれらに限定されるものではない。なお、無水ヘキシトールのジ脂肪酸エステルとして以下の実施例では、下記のジカプリル酸イソソルビドを使用した。 Hereinafter, although an example and a comparative example explain the present invention in detail, the present invention is not limited to these. The following dicaprylic acid isosorbide was used as a difatty acid ester of anhydrous hexitol in the following examples.
ジカプリル酸イソソルビドの合成
３００ｍｌフラスコに、イソソルビド（東京化成工業社製）１４．６ｇを入れ、無水テトラヒドロフラン１００ｍｌに溶解させた。さらにピリジン（関東化学社製）を１６ｇ加えて、均一な溶液とした。反応溶液を氷浴において冷却しながら、カプロン酸クロライド（東京化成工業社製）２７ｇをゆっくりと滴下した。滴下終了後、室温にもどし２４時間撹拌を行った。反応終了をTLCにて確認した後、１N塩酸を用いて中和し、酢酸エチルを添加して有機層を得た。無水硫酸マグネシウムで脱水した後、減圧下にて溶媒を留去して、粗生成物を約２５ｇ得た。シリカゲルカラムクロマトグラフィー（移動相：酢酸エチル／ヘキサン＝１：９）を用いて精製し、無色油状物質20gを得た。NMRを測定し、既知の報告と同等であることを確認した。
Synthesis of dicaprylic acid isosorbide 14.6 g of isosorbide (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a 300 ml flask and dissolved in 100 ml of anhydrous tetrahydrofuran. Further, 16 g of pyridine (manufactured by Kanto Chemical Co., Inc.) was added to obtain a uniform solution. While cooling the reaction solution in an ice bath, 27 g of caproic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added dropwise. After completion of dropping, the mixture was returned to room temperature and stirred for 24 hours. The completion of the reaction was confirmed by TLC, neutralized with 1N hydrochloric acid, and ethyl acetate was added to obtain an organic layer. After dehydration with anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain about 25 g of a crude product. Purification using silica gel column chromatography (mobile phase: ethyl acetate / hexane = 1: 9) gave 20 g of a colorless oil. NMR was measured and confirmed to be equivalent to a known report.
実施例１〜１４、比較例１〜１１
表１〜３に示した処方に従い水中油型乳化化粧料を常法により調製した。これらを用いて、下記に示した（１）ＵＶ防御能評価試験、（２）乳化状態確認試験、（３）経時安定性試験、（４）使用感試験を実施した。結果を表１〜３に併せて示す。
Examples 1 to 14 and Comparative Examples 1 to 11
Oil-in-water emulsified cosmetics were prepared by a conventional method according to the formulations shown in Tables 1 to 3. Using these, the following (1) UV protection ability evaluation test, (2) emulsification state confirmation test, (3) stability test over time, and (4) usability test were performed. A result is combined with Tables 1-3 and shown.
（１）ＵＶ防御能評価試験
石英ガラス板上に表１〜３に示した各試料を２ｍｇ／ｃｍ2になるように均一に塗布し、１５分間自然乾燥させた。その後、試料塗布した石英ガラス板に一定の距離（１０mm）から紫外線を照射した。その際の透過紫外線をＳＰＦアナライザー（Ｏｐｔｏｍｅｔｉｃｅｓ社）で２９０〜４００ｎｍの範囲で石英ガラス板上の１０箇所以上において検出し、平均化したスペクトルを得て、ＳＰＦ値を算出した。
(1) UV protection ability evaluation test Each sample shown in Tables 1 to 3 was uniformly applied on a quartz glass plate so as to be 2 mg / cm 2 , and was naturally dried for 15 minutes. Thereafter, the quartz glass plate coated with the sample was irradiated with ultraviolet rays from a certain distance (10 mm). Transmitted ultraviolet rays at that time were detected at 10 or more locations on the quartz glass plate within a range of 290 to 400 nm with an SPF analyzer (Optometics), and an averaged spectrum was obtained to calculate an SPF value.
〔ＵＶ防御効果の向上評価〕
ＵＶ防御能向上率（％）＝（試料を測定したＳＰＦ値）／（比較例１の試料を測定したSPF値）×１００
[Improvement of UV protection effect]
UV protection capacity improvement rate (%) = (SPF value measured for sample) / (SPF value measured for sample of Comparative Example 1) × 100
〔ＵＶ防御能向上率の評価基準〕
◎：１６０％以上
○：１３５％以上１６０％未満
△：１１０％以上１３５％未満
×：１１０％未満
[Evaluation criteria for UV protection ability improvement rate]
◎: 160% or more ○: 135% or more and less than 160% △: 110% or more and less than 135% ×: less than 110%
（２）乳化状態
製造直後の水中油型乳化化粧料の顕微鏡観察を行い、下記の基準により評価を行った。
〔乳化状態判定基準〕
○：内相（油相）に粉体が入り込み、略球形のきれいな乳化粒子が形成されている
△：内相に粉体が入り込んでいるが、乳化粒子形状・大きさが不均一となっている
×：粉体が外相（水相）に漏れ出している又は乳化粒子を形成していない
(2) Emulsified state Microscopic observation of the oil-in-water emulsified cosmetic immediately after production was performed, and evaluation was performed according to the following criteria.
[Emulsification condition criteria]
○: The powder enters the inner phase (oil phase), and substantially spherical emulsified particles are formed. Δ: The powder enters the inner phase, but the shape and size of the emulsified particles are not uniform. X: The powder leaks into the outer phase (aqueous phase) or does not form emulsified particles
（３）経時安定性試験
表１〜３に示した水中油型乳化化粧料を４５℃の恒温槽で３月間保存、及び−１０℃で１月間保存し、その後、外観を目視により評価した。
〔粘度変化判定基準〕
○：変化なし又は若干の粘度変化が見られる
△：明らかな粘度変化又は外観の変化が見られる
×：明らかな形状の変化（ゲル化している、分離している又は結晶の析出が見られる）
(3) Stability test over time The oil-in-water emulsified cosmetics shown in Tables 1 to 3 were stored in a 45 ° C. thermostatic bath for 3 months and stored at −10 ° C. for 1 month, and then the appearance was visually evaluated.
[Criteria for viscosity change]
○: No change or slight change in viscosity Δ: Clear change in viscosity or change in appearance is observed ×: Clear change in shape (gelled, separated, or precipitated crystals)
（４）使用感試験
上記（３）経時安定性試験（４５℃、３月間）後の表１〜３に示した水中油型乳化化粧料を専門パネラー１５名に使用してもらった。塗布時の使用感として、「塗布時のきしみ感のなさ」、「塗布後のべたつき感のなさ」、「塗布時の伸びの良さ」に関して、以下の評価基準及び判定基準に基づき、評価と判定を行った。なお、経時安定性試験において、分離しているものは評価していない。
（評価基準：塗布時のきしみ感のなさ）
５：専門パネラー１３名以上が塗布時にきしみ感がないと認めた。
４：専門パネラー１０名以上１３名未満が塗布時にきしみ感がないと認めた。
３：専門パネラー７名以上１０名未満が塗布時にきしみ感がないと認めた。
２：専門パネラー４名以上７名未満が塗布時にきしみ感がないと認めた。
１：専門パネラー４名未満が塗布時にきしみ感がないと認めた。
(4) Usability test 15 professional panelists used the oil-in-water emulsified cosmetics shown in Tables 1 to 3 after the above (3) stability test over time (45 ° C., 3 months). Regarding the feeling of use at the time of application, with regard to “no squeaking feeling at the time of application”, “no stickiness after application”, and “goodness of elongation at the time of application”, evaluation and determination are based on the following evaluation criteria and judgment criteria Went. In the time stability test, the separated ones are not evaluated.
(Evaluation criteria: No squeaky feeling during application)
5: More than 13 professional panelists recognized that there was no squeaky feeling during application.
4: More than 10 professional panelists recognized that there was no squeaky feeling during application.
3: 7 or more professional panelists recognized that there was no squeaky feeling at the time of application.
2: 4 or more and less than 7 professional panelists recognized that there was no squeaky feeling at the time of application.
1: Less than 4 professional panelists recognized that there was no squeaky feeling during application.
（評価基準：塗布後のべたつき感のなさ）
５：専門パネラー１３名以上が塗布後にべたつき感がないと認めた。
４：専門パネラー１０名以上１３名未満が塗布後にべたつき感がないと認めた。
３：専門パネラー７名以上１０名未満が塗布後にべたつき感がないと認めた。
２：専門パネラー４名以上１０名未満が塗布後にべたつき感がないと認めた。
１：専門パネラー４名未満が塗布後にべたつき感がないと認めた。
(Evaluation criteria: No stickiness after application)
5: More than 13 professional panelists recognized that there was no stickiness after application.
4: More than 10 professional panelists recognized that there was no stickiness after application.
3: 7 or more professional panelists recognized that there was no stickiness after application.
2: 4 or more professional panelists recognized that there was no stickiness after application.
1: Less than 4 professional panelists recognized that there was no stickiness after application.
（評価基準：塗布時の伸びの良さ）
５：専門パネラー１３名以上が塗布時に伸びが良いと認めた。
４：専門パネラー１０名以上１３名未満が塗布時に伸びが良いと認めた。
３：専門パネラー７名以上１０名未満が塗布時に伸びが良いと認めた。
２：専門パネラー４名以上７名未満が塗布時に伸びが良いと認めた。
１：専門パネラー４名未満が塗布時に伸びが良いと認めた。
(Evaluation criteria: Good elongation during application)
5: More than 13 professional panelists recognized that the elongation was good at the time of application.
4: More than 10 professional panelists recognized that the elongation was good at the time of application.
3: 7 or more professional panelists and less than 10 recognized that elongation was good at the time of application.
2: Special panelists 4 or more and less than 7 recognized good elongation at the time of application.
1: Less than 4 professional panelists recognized that the elongation was good at the time of application.
本実施例、比較例及び処方例で用いた疎水化処理粉末は下記のものを用いた。 The following hydrophobized powders used in the examples, comparative examples, and formulation examples were used.
（製造例１ シリコーン表面処理微粒子酸化亜鉛粉末の製造）
平均一次粒子径が１６ｎｍの微粒子酸化亜鉛88重量部とジメチルポリシロキサン（２０ｃＳｔ、信越化学工業社製）１２重量部をトルエン中に投入しよく撹拌した後、トルエンを減圧下に加熱して除去した。得られた粉体をアトマイザーを用いて粉砕した。次いで高温加熱炉を用いて空気中で、８００℃で２時間焼成処理を行い、シリコーン表面処理微粒子酸化亜鉛粉末を得た。
(Production Example 1 Production of Silicone Surface-treated Fine Zinc Oxide Powder)
After 88 parts by weight of fine zinc oxide having an average primary particle size of 16 nm and 12 parts by weight of dimethylpolysiloxane (20 cSt, manufactured by Shin-Etsu Chemical Co., Ltd.) were put into toluene and stirred well, the toluene was removed by heating under reduced pressure. . The obtained powder was pulverized using an atomizer. Subsequently, a baking treatment was performed at 800 ° C. for 2 hours in air using a high-temperature heating furnace to obtain a silicone surface-treated fine particle zinc oxide powder.
（製造例２ シリコーン処理酸化亜鉛粉末の製造）
微粒子酸化亜鉛粉末（略球状、平均粒子径０．０２μｍ）９３質量部とメチルハイドロジェンポリシロキサン（ＫＦ−９９Ｐ、信越化学工業社製）７質量部とイソプロピルアルコールからなるスラリーを作成し、よく攪拌・粉砕した後、溶媒を減圧下に加熱留去し、空気中１５０℃で４時間加熱処理を行い、メチルハイドロジェンポリシロキサン表面処理微粒子酸化亜鉛粉末を得た。
(Production Example 2 Production of silicone-treated zinc oxide powder)
A slurry composed of 93 parts by mass of fine zinc oxide powder (substantially spherical, average particle size 0.02 μm), 7 parts by mass of methyl hydrogen polysiloxane (KF-99P, manufactured by Shin-Etsu Chemical Co., Ltd.) and isopropyl alcohol is prepared and stirred well. After pulverization, the solvent was removed by heating under reduced pressure, and heat treatment was performed in air at 150 ° C. for 4 hours to obtain methyl hydrogen polysiloxane surface-treated fine particle zinc oxide powder.
（製造例３ シリコーン処理酸化チタン粉末の製造）
微粒子酸化チタン粉末（略球状、平均粒子径０．０１７μｍ）９５質量部とメチルハイドロジェンポリシロキサン（ＫＦ−９９Ｐ、信越化学工業社製）５質量部とイソプロピルアルコールからなるスラリーを作成し、よく攪拌・粉砕した後、溶媒を減圧下に加熱留去し、空気中１６０℃で４時間加熱処理を行い、メチルハイドロジェンポリシロキサン表面処理微粒子酸化チタン粉末を得た。
(Production Example 3 Production of silicone-treated titanium oxide powder)
A slurry composed of 95 parts by mass of fine particle titanium oxide powder (substantially spherical, average particle size 0.017 μm), 5 parts by mass of methyl hydrogen polysiloxane (KF-99P, manufactured by Shin-Etsu Chemical Co., Ltd.) and isopropyl alcohol is prepared and stirred well. After pulverization, the solvent was removed by heating under reduced pressure, and a heat treatment was performed in air at 160 ° C. for 4 hours to obtain methylhydrogenpolysiloxane surface-treated fine particle titanium oxide powder.
（製造例４ アルキルシラン表面処理微粒子酸化亜鉛粉末の製造）
微粒子酸化亜鉛粉末（略球状、平均粒子径０．０２μｍ）９３質量部とオクチルトリエトキシシラン７質量部と、トルエンからなるスラリーを作成し、ビーズミル（シンマルエンタープライゼス社製ダイノミル）を用いて粉砕・解砕を行った。次いで、トルエンを減圧下に加熱留去した後、送風気流型乾燥機を用いて１５０℃にて４時間加熱処理し、オクチルトリエトキシシラン処理微粒子酸化亜鉛粉末を得た。
(Production Example 4 Production of alkylsilane surface-treated fine zinc oxide powder)
A slurry composed of 93 parts by mass of fine zinc oxide powder (substantially spherical, average particle size 0.02 μm), 7 parts by mass of octyltriethoxysilane, and toluene was prepared and pulverized using a bead mill (Dynomill manufactured by Shinmaru Enterprises).・ We disintegrated. Next, toluene was distilled off by heating under reduced pressure, followed by heat treatment at 150 ° C. for 4 hours using an air blast dryer to obtain octyltriethoxysilane-treated fine particle zinc oxide powder.
表１〜３の結果から、本発明の化粧料は、比較例と比べて、ＵＶ防御能、経時安定性に優れ、更に使用感にも優れるものであることは明らかである。なお、試験結果において「−」となっている試料は、安定性が悪く、評価していないものを表している。
（Ａ）成分を含有しない比較例１、２及び９は、安定な水中油型乳化物を得ることができなかった。一方、（Ａ）成分単独では紫外線吸収能をほとんど示さないにもかかわらず、（Ｂ）成分及び（Ｃ）成分に加えて（Ａ）成分を配合することにより、（Ｃ）成分の紫外線防御効果が顕著に向上したことは予想外であった。また、（（Ｃ）／（Ａ））を０．５〜１５の範囲に調整することにより、紫外線防御能が向上し、経時安定性だけでなく、使用感も良好となった。
From the results shown in Tables 1 to 3, it is clear that the cosmetic of the present invention is superior in UV protection ability and stability over time, and also excellent in usability compared with the comparative example. In addition, the sample which becomes "-" in a test result represents the thing which is not stable and is not evaluated.
In Comparative Examples 1, 2, and 9 containing no component (A), a stable oil-in-water emulsion could not be obtained. On the other hand, although the component (A) alone exhibits almost no ultraviolet absorbing ability, the component (A) is added to the components (B) and (C), so that the ultraviolet protective effect of the component (C) is obtained. It was unexpected that there was a significant improvement. Moreover, by adjusting ((C) / (A)) to the range of 0.5-15, the ultraviolet-ray protective ability improved and not only the temporal stability but the usability | use_condition became favorable.
以下に本発明の乳化化粧料の処方例を挙げる。 Examples of emulsified cosmetics according to the present invention will be given below.
処方例１〜３ （化粧下地）
下記組成の水中油型乳化化粧料（化粧下地）を作製し評価したところ、紫外線防御効果、使用感、保存安定性の全ての点において優れていた。
Formulation examples 1 to 3 (makeup base)
When an oil-in-water emulsified cosmetic composition (makeup base) having the following composition was prepared and evaluated, it was excellent in all points of UV protection effect, feeling of use, and storage stability.
尚、上記の処方例において使用した香料の組成は表５に示す。 In addition, the composition of the fragrance | flavor used in said formulation example is shown in Table 5.
本発明によれば、紫外線防御効果に優れ、経時安定性が良好でかつ、使用感の良好な水中油型乳化化粧料が提供できる。 According to the present invention, it is possible to provide an oil-in-water emulsified cosmetic that has an excellent ultraviolet protection effect, good temporal stability, and good usability.
Claims (9)
（Ａ）下記一般式（１）で表される無水ヘキシトールのジ脂肪酸エステル、
（Ｂ）水溶性高分子、
（Ｃ）疎水化処理紫外線散乱剤
(A) difatty acid ester of anhydrous hexitol represented by the following general formula (1),
(B) a water-soluble polymer,
(C) Hydrophobized UV scattering agent
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