JP2018131393A - Aqueous make-up cosmetic - Google Patents
Aqueous make-up cosmetic Download PDFInfo
- Publication number
- JP2018131393A JP2018131393A JP2017024495A JP2017024495A JP2018131393A JP 2018131393 A JP2018131393 A JP 2018131393A JP 2017024495 A JP2017024495 A JP 2017024495A JP 2017024495 A JP2017024495 A JP 2017024495A JP 2018131393 A JP2018131393 A JP 2018131393A
- Authority
- JP
- Japan
- Prior art keywords
- component
- water
- cosmetic
- aqueous
- makeup
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
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- 235000014593 oils and fats Nutrition 0.000 description 1
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- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000008133 orange flower water Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- 229960001173 oxybenzone Drugs 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- BPHQIXJDBIHMLT-UHFFFAOYSA-N perfluorodecane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BPHQIXJDBIHMLT-UHFFFAOYSA-N 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000008132 rose water Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- XLUBVTJUEUUZMR-UHFFFAOYSA-B silicon(4+);tetraphosphate Chemical compound [Si+4].[Si+4].[Si+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XLUBVTJUEUUZMR-UHFFFAOYSA-B 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- AOBORMOPSGHCAX-DGHZZKTQSA-N tocofersolan Chemical compound OCCOC(=O)CCC(=O)OC1=C(C)C(C)=C2O[C@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C AOBORMOPSGHCAX-DGHZZKTQSA-N 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- SVETUDAIEHYIKZ-IUPFWZBJSA-N tris[(z)-octadec-9-enyl] phosphate Chemical compound CCCCCCCC\C=C/CCCCCCCCOP(=O)(OCCCCCCCC\C=C/CCCCCCCC)OCCCCCCCC\C=C/CCCCCCCC SVETUDAIEHYIKZ-IUPFWZBJSA-N 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
Landscapes
- Cosmetics (AREA)
Abstract
Description
本発明は、メイクアップ化粧料に関し、更に詳しくは、水溶性多糖類とシリコーンリン酸トリエステルと水と光輝性粉体を含有することにより、均一な化粧膜で、光輝性粉体の光沢感、化粧持続性に優れ、光輝性粉体が物理的接触に対して剥離しづらい(二次付着レス効果)水性メイクアップ化粧料に関するものである。 The present invention relates to a makeup cosmetic, and more specifically, by containing a water-soluble polysaccharide, a silicone phosphate triester, water, and a glitter powder, the gloss feeling of the glitter powder in a uniform cosmetic film. The present invention relates to a water-based makeup cosmetic that is excellent in makeup persistence and that the glittering powder is difficult to peel off due to physical contact (less effect of secondary adhesion).
メイクアップ化粧料は、まぶたや頬に塗布し、陰影を付けたり、化粧効果を演出するためにパールの光沢感が高いものが求められている。水と水性のゲル化剤を用いてゲルを形成した基剤に光輝性粉体を含有した水性メイクアップ化粧料は、透明感のある光沢感、水々しさを演出することができ、市場で好まれている。水性メイクアップ化粧料は、水性のゲル化剤、粉体、水等からなり、化粧料として求められる使用感、及び機能性を向上させるために、剤型や成分の検討が行われてきた。 Makeup cosmetics are required to have a high pearly luster for application to the eyelids and cheeks, shading, and producing a cosmetic effect. Aqueous makeup cosmetics containing glitter powder in a base formed with a gel using water and an aqueous gelling agent can produce a glossy and watery feeling with transparency. Is preferred. Aqueous makeup cosmetics are composed of an aqueous gelling agent, powder, water, etc., and in order to improve the feeling of use and functionality required for cosmetics, studies have been made on dosage forms and ingredients.
例えば、パール粉体の光沢感を得るためにジェランガムやアクリル酸アルキル共重合体ポリマーエマルション等の水性の増粘・ゲル化剤とパール光沢粉体を用いる技術(特許文献1)や化粧膜の均一性を高めるためにジェランガムとグリセリンを用いる技術(特許文献2)、パール光沢粉体の化粧持続性と均一な化粧膜を得るために特定の含フッ素共重合体を用いる技術(特許文献3)などが検討されてきた。 For example, in order to obtain glossiness of pearl powder, a technique (Patent Document 1) using a water-based thickening / gelling agent such as gellan gum or an alkyl acrylate copolymer polymer emulsion and pearly luster powder, or a uniform cosmetic film Technology that uses gellan gum and glycerin to enhance the properties (Patent Document 2), Technology that uses a specific fluorine-containing copolymer to obtain a makeup film with a pearly luster powder and a uniform cosmetic film (Patent Document 3), etc. Has been studied.
しかしながら、こうした化粧料は水系であるために化粧持ちに欠ける傾向があり、特に粒径が大きい光輝性粉体は、汗と共に剥がれ落ちたり、指などに触れた際に剥離したり、アイシャドウであればまばたきの際に転写したりするなど化粧持ちに満足できるものではなかった。また、ジェランガムとグリセリンを含有する技術(特許文献2)では、水系への分散性がよく、均一な化粧膜は得られるが、汗に弱く、満足のいく化粧持ちが得られていなかった。特定の含フッ素共重合体を含有する技術(特許文献3)では、柔軟で均一な化粧膜が得られ、光輝性粉体の持ちは良くなるもの、物理的接触に対する耐転写性(二次付着レス効果)については十分な効果が得られていなかった。 However, since these cosmetics are water-based, they tend to lack makeup, especially glittering powders with large particle sizes are peeled off with sweat, peeled off when touched with fingers, and eyeshadows. It wasn't satisfactory for a long-lasting makeup, such as transferring it when blinking. Moreover, in the technique (patent document 2) containing gellan gum and glycerin, the dispersibility to an aqueous system is good, and a uniform makeup film is obtained, but it is weak against sweat and a satisfactory makeup cannot be obtained. With the technology (Patent Document 3) containing a specific fluorine-containing copolymer, a flexible and uniform decorative film can be obtained, and the durability of the glittering powder can be improved. Transfer resistance against physical contact (secondary adhesion) A sufficient effect was not obtained for the “less effect”.
上記実情に鑑み、本発明は、均一な化粧膜で、光輝性粉体の光沢感、化粧持続性に優れ、光輝性粉体が物理的接触に対して剥離しづらい(二次付着レス効果)水性メイクアップ化粧料を提供することを課題とする。 In view of the above circumstances, the present invention is a uniform decorative film, excellent in glossiness and makeup durability of the glitter powder, and the glitter powder is difficult to peel off against physical contact (secondary adhesion-less effect). It is an object to provide an aqueous makeup cosmetic.
本発明者らは、水溶性多糖類を用いた水々しい感触の水性メイクアップ化粧料に、肌への親和性が高く、タック性の低い成分を含有することで化粧持ち効果を高めることができると考え、種々の成分の含有検討を行ったところ、特定のシリコーンリン酸トリエステルを含有することで、肌への密着性が高く、かつ表面のべたつき(タック性)が少ないため、物理的な接触ではがれにくい化粧膜ができることを見出し、本発明を完成させた。 The inventors of the present invention can enhance the long-lasting effect by including an ingredient having a high affinity for the skin and a low tackiness in an aqueous makeup cosmetic using a water-soluble polysaccharide. As a result of examining the inclusion of various components, the inclusion of a specific silicone phosphate triester has high adhesion to the skin and is less sticky to the surface (tackiness). The present invention has been completed by finding that a decorative film that does not easily peel off by simple contact can be produced.
すなわち、本発明は、次の成分(A)〜(D);
(A)水溶性多糖類
(B)式(1)
(C)水
(D)光輝性粉体
を含有する水性メイクアップ化粧料を提供するものである。
That is, the present invention provides the following components (A) to (D);
(A) Water-soluble polysaccharide (B) Formula (1)
前記成分(B)の含有量が0.05〜10質量%である前記水性メイクアップ化粧料を提供するものである。 The water-based makeup cosmetic is provided with a content of the component (B) of 0.05 to 10% by mass.
前記成分(A)の含有量が0.1〜5質量%である前記水性メイクアップ化粧料を提供するものである。 The water-based makeup cosmetics having a content of the component (A) of 0.1 to 5% by mass are provided.
前記成分(D)の含有量が0.1〜60質量%である前記水性メイクアップ化粧料を提供するものである。 The water-based makeup cosmetics having a content of the component (D) of 0.1 to 60% by mass are provided.
前記成分(A)と前記成分(B)の含有質量比が、(A)/(B)=0.1〜10である前記水性メイクアップ化粧料を提供するものである。 Provided is the aqueous makeup cosmetic wherein the mass ratio of the component (A) and the component (B) is (A) / (B) = 0.1-10.
前記成分(B)と前記成分(D)の含有質量比が、(B)/(D)=0.01〜0.5である前記水性メイクアップ化粧料を提供するものである。 The content makeup ratio of the said component (B) and the said component (D) provides the said water-based makeup cosmetics whose (B) / (D) = 0.01-0.5.
前記成分(A)の水溶性多糖類がジェランガムである前記水性メイクアップ化粧料を提供するものである。 The water-based makeup cosmetics in which the water-soluble polysaccharide of the component (A) is gellan gum are provided.
本発明は、均一な化粧膜で、光輝性粉体の光沢感、化粧持続性に優れ、光輝性粉体が物理的接触に対して剥離しづらい(二次付着レス効果)水性メイクアップ化粧料を提供するものである。 The present invention is a uniform cosmetic film, excellent in glossiness and makeup durability of the glitter powder, and the glitter powder is difficult to peel off against physical contact (secondary adhesion-less effect). Is to provide.
以下本発明を詳細に説明する。なお、本明細書において、「〜」はその前後の数値を含む範囲を意味するものとする。 The present invention will be described in detail below. In the present specification, “to” means a range including numerical values before and after.
本発明に用いられる成分(A)水溶性多糖類は、水で膨潤させることで、弾力のあるゲルを形成する多糖類である。水溶性多糖類には、ジェランガム、ペクチン、カンテン末、アルギン酸、カラギーナン、ヒアルロン酸等や、それらの塩類が挙げられ、これらを1種又は2種以上を組み合わせて用いることができる。特に、ジェランガムがタック性が低く、二次付着レス効果を発現しやすいため好ましい。ジェランガムには脱アシル型ジェランガムやネイティブ型ジェランガムがあり、どちらも好適に使用することができる。市販品としては、ケルコゲル、ケルコゲル LT100、ケルコゲル HM(以上、大日本住友製薬社製)、ゲニュペクチンLM−104AS−J(CPケルコ社製)、伊那寒天 UP−37CS(伊那食品工業社製)、キミカアルギンI3−150(キミカ社製)等が挙げられ、これらの1種又は2種以上を組み合わせて用いることもできる。 The component (A) water-soluble polysaccharide used in the present invention is a polysaccharide that forms an elastic gel by swelling with water. Examples of water-soluble polysaccharides include gellan gum, pectin, agar powder, alginic acid, carrageenan, hyaluronic acid, and salts thereof, and these can be used alone or in combination of two or more. In particular, gellan gum is preferable because it has low tackiness and easily develops a secondary adhesion-less effect. Gellan gum includes deacylated gellan gum and native gellan gum, both of which can be suitably used. Commercially available products include Kelcogel, Kelcogel LT100, Kelcogel HM (manufactured by Dainippon Sumitomo Pharma Co., Ltd.), Genipectin LM-104AS-J (CP Kelco), Inagar Agar UP-37CS (Ina Food Industry Co., Ltd.), Kimika Argin I3-150 (manufactured by Kimika Co., Ltd.) and the like can be mentioned, and these can be used alone or in combination.
本発明に用いられる成分(A)の含有量は、特に限定されないが、均一な化粧膜と光輝性粉体の光沢感が良好なゲルを形成することができる等の観点から0.1〜5質量%(以下、単に「%」とする)であるとが好ましく、より好ましくは0.2〜2%である。 The content of the component (A) used in the present invention is not particularly limited, but it is 0.1 to 5 from the viewpoint of being able to form a uniform decorative film and a gel with good glossiness of the glittering powder. The content is preferably mass% (hereinafter simply referred to as “%”), more preferably 0.2 to 2%.
本発明における成分(B)のシリコーンリン酸トリエステルは、下記一般式(1) The silicone phosphate triester of component (B) in the present invention is represented by the following general formula (1)
式中、各R1は、それぞれ独立して、炭素数1〜4のアルキル基を表し、Rは−O−及び−CO−から選ばれる少なくとも1種を有していても良い炭素数2〜7の2価の炭化水素基を表し、nは5〜40のいずれかの整数を表す。
In the formula, each R 1 independently represents an alkyl group having 1 to 4 carbon atoms, and R may have at least one selected from —O— and —CO—. In which n represents an integer of 5 to 40.
R1における「炭素数1〜4のアルキル基」としては、メチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、s−ブチル基、i−ブチル基、t−ブチル基が挙げられる。R1としては、これらのうち、メチル基が好ましい。
Rにおける「−O−及び−CO−から選ばれる少なくとも1種を有していても良い炭素数2〜7の2価の炭化水素基」の「炭素数2〜7の2価の炭化水素基」としては、エチレン鎖、プロピレン鎖、メチルエチレン鎖、ブチレン鎖、1,2−ジメチルエチレン鎖、ペンチレン鎖、1−メチルブチレン鎖、2−メチルブチレン鎖、ヘキシレン鎖、ヘプチレン鎖等が挙げられる。
Examples of the “alkyl group having 1 to 4 carbon atoms” in R1 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, and t-butyl group. Is mentioned. Of these, methyl is preferred as R1.
“Divalent hydrocarbon group having 2 to 7 carbon atoms” of “Divalent hydrocarbon group having 2 to 7 carbon atoms which may have at least one selected from —O— and —CO—” in R Examples of "" include ethylene chain, propylene chain, methylethylene chain, butylene chain, 1,2-dimethylethylene chain, pentylene chain, 1-methylbutylene chain, 2-methylbutylene chain, hexylene chain, heptylene chain and the like.
「−O−及び−CO−から選ばれる少なくとも1種を有している炭素数2〜7の2価の炭化水素基」としては、−O−又は−CO−を1又は2以上有していて良く、たとえば、−CH2−O−(CH2)2−、−(CH2)2−O−(CH2)2−、−(CH2)3−O−(CH2)2−、−(CH2)4−O−(CH2)2−、−(CH2)2−O(CH2)2−O−(CH2)2−、−(CH2)2−O−(CH2)4−、−(CH2)2−O−(CH2)5−、−(CH2)3−O−CH2−、−CH2−CO−(CH2)2−、−(CH2)2−CO−(CH2)2−、−(CH2)3−CO−(CH2)2−、−(CH2)4−CO−(CH2)2−、−(CH2)2−CO−(CH2)4−、−(CH2)2−CO−(CH2)5−、−(CH2)3−CO−CH2−等が挙げられる。
「−O−及び−CO−から選ばれる少なくとも1種を有していても良い炭素数2〜7の2価の炭化水素基」としては、これらのうち、−(CH2)3O(CH2)2−が好ましい。
The “C2-C7 divalent hydrocarbon group having at least one selected from —O— and —CO—” has one or more of —O— or —CO—. For example, -CH2-O- (CH2) 2-,-(CH2) 2-O- (CH2) 2-,-(CH2) 3-O- (CH2) 2-,-(CH2) 4- O- (CH2) 2-,-(CH2) 2-O (CH2) 2-O- (CH2) 2-,-(CH2) 2-O- (CH2) 4-,-(CH2) 2-O- (CH2) 5-,-(CH2) 3-O-CH2-, -CH2-CO- (CH2) 2-,-(CH2) 2-CO- (CH2) 2-,-(CH2) 3-CO- (CH2) 2-,-(CH2) 4-CO- (CH2) 2-,-(CH2) 2-CO- (CH2) 4-,-(CH2) 2-CO- (CH2) -, - (CH2) 3-CO-CH2-, and the like.
Among these, “(C 2) 2 divalent hydrocarbon group optionally having at least one selected from —O— and —CO—” is — (CH 2) 3 O (CH 2) 2. -Is preferred.
具体的に、シリコーンリン酸トリエステルとしては、例えば、以下のものが挙げられる。ただし、nは5〜40のいずれかの整数である。これらは、1種単独でも、2種以上の混合物でも使用できる。 Specific examples of silicone phosphate triesters include the following. However, n is an integer in any one of 5-40. These can be used singly or in a mixture of two or more.
本発明のシリコーンリン酸トリエステルは、たとえば、以下の反応式に示される方法により製造することができる(特開2011−173852号公報を参照)。 The silicone phosphate triester of the present invention can be produced, for example, by the method shown in the following reaction formula (refer to JP2011-173852A).
式(IV)で表される片末端カルビノール変性シリコーンと式(V)で表されるオキシ塩化リンとを、溶媒中で塩基の存在化で反応させる。
上記反応を行う際に使用する溶媒としては、テトラヒドロフラン、ジメチルスルホキシド、N,N−ジメチルホルムアミド、アセトン、ジエチルエーテル、アセトニトリル等の極性溶媒等が使用できる。
塩基としては、ジエチルアミン、トリエチルアミン等のアルキルアミン類、ピペラジン、イミダゾールなどの複素環状アミン類、ベンジルトリエチルアンモニウムクロライド、メチルトリオクチルアンモニウムクロライド等の4級アンモニウム塩類、n−ブチルリチウム、リチウムジイソプロピルアミド等の有機金属類等が使用できる。
反応温度は、通常、25℃〜50℃程度であり、反応時間は、シリコーン鎖長によっても異なるが、通常、2時間〜20時間程度である。
One-terminal carbinol-modified silicone represented by the formula (IV) is reacted with phosphorus oxychloride represented by the formula (V) in the presence of a base in a solvent.
As a solvent used in carrying out the above reaction, polar solvents such as tetrahydrofuran, dimethyl sulfoxide, N, N-dimethylformamide, acetone, diethyl ether and acetonitrile can be used.
Examples of the base include alkylamines such as diethylamine and triethylamine, heterocyclic amines such as piperazine and imidazole, quaternary ammonium salts such as benzyltriethylammonium chloride and methyltrioctylammonium chloride, n-butyllithium, lithium diisopropylamide and the like. Organic metals can be used.
The reaction temperature is usually about 25 ° C. to 50 ° C., and the reaction time is usually about 2 hours to 20 hours, although it varies depending on the silicone chain length.
上記反応により、式(I)で表されるシリコーンリン酸トリエステルが得られるが、副生物として、以下の式(II)で表されるシリコーンリン酸ジエステル、以下の式(III)で表されるシリコーンリン酸モノエステルなどが生じる。 By the above reaction, a silicone phosphate triester represented by the formula (I) is obtained. As a by-product, a silicone phosphate diester represented by the following formula (II), represented by the following formula (III): Silicon phosphate monoester is produced.
これら副生物が存在したままシリコーンリン酸エステル混合物として使用することもできるが、通常の方法により、生成物を精製して、実質的に式(I)で表されるシリコーンリン酸トリエステルのみとして使用してもよい。 Although these by-products can be used as a silicone phosphate ester mixture, the product is purified by a conventional method to obtain substantially only the silicone phosphate triester represented by the formula (I). May be used.
本発明において、式(I)で表されるシリコーンリン酸トリエステル、式(II)で表されるシリコーンリン酸ジエステル及び、式(III)で表されるシリコーンリン酸モノエステルの含有質量比は、式(I)で表されるシリコーンリン酸トリエステルが効果を奏する限り特に限定されないが、シリコーンリン酸エステル混合物の合計100部に対して、好ましくは、式(I)で表されるシリコーンリン酸トリエステルが60〜100質量部、式(II)で表されるシリコーンリン酸ジエステルが0〜35質量部、及び、式(III)で表されるシリコーンリン酸モノエステルが0〜5質量部である。 In the present invention, the content mass ratio of the silicone phosphate triester represented by the formula (I), the silicone phosphate diester represented by the formula (II), and the silicone phosphate monoester represented by the formula (III) is Although the silicone phosphate triester represented by the formula (I) is not particularly limited as long as it has an effect, the silicone phosphate represented by the formula (I) is preferably used with respect to a total of 100 parts of the silicone phosphate ester mixture. 60 to 100 parts by mass of the acid triester, 0 to 35 parts by mass of the silicone phosphoric diester represented by the formula (II), and 0 to 5 parts by mass of the silicone phosphoric monoester represented by the formula (III) It is.
本発明に用いられる、成分(B)のシリコーンリン酸トリエステルの含有量は、特に限定されないが、化粧料基材、特に光輝性粉体の肌への密着性が高まると共に、表面のタック性が抑えられ、二次付着レス効果に優れる等の観点から0.05〜10%が好ましく、0.1〜10%がより好ましく、0.5〜10%が特に好ましい。 The content of the silicone phosphate triester of component (B) used in the present invention is not particularly limited, but the adhesiveness of the cosmetic base material, particularly the glitter powder, to the skin is increased and the surface tackiness is increased. Is preferably 0.05 to 10%, more preferably 0.1 to 10%, and particularly preferably 0.5 to 10% from the viewpoint of being excellent in the secondary adhesion-less effect.
本発明に用いられる成分(C)の水は、特に限定されないが、常水、精製水、温泉水、深層水、ラベンダー水、ローズ水、オレンジフラワー水等が挙げられ、1種又は2種以上を用いることができる。 The water of component (C) used in the present invention is not particularly limited, and examples thereof include ordinary water, purified water, hot spring water, deep water, lavender water, rose water, orange flower water, and the like. Can be used.
本発明における成分(C)の含有量は、特に限定されないが、本発明の効果がより優れる等の観点から30〜90%が好ましく、40〜90%であることがより好ましい。 Although content of the component (C) in this invention is not specifically limited, From a viewpoint that the effect of this invention is more excellent, 30 to 90% is preferable and it is more preferable that it is 40 to 90%.
本発明に用いられる成分(D)の光輝性粉体は、化粧料に通常使用される光輝性粉体であれば、特に限定されず、例えば、マイカ、セリサイト、合成マイカ、合成セリサイト、ケイ酸アルミニウム、ケイ酸マグネシウム、ケイ酸アルミニウムマグネシウム、劈開タルク、板状無水ケイ酸、板状酸化アルミニウム、板状カオリン、板状窒化硼素、板状酸化チタン、板状セルロース等の体質粉体、雲母チタン、オキシ塩化ビスマス、有機顔料処理雲母チタン、二酸化チタン被覆雲母、二酸化チタン被覆合成金雲母、二酸化チタン被覆オキシ塩化ビスマス、酸化鉄雲母チタン、紺青処理雲母チタン、カルミン処理雲母チタン、魚鱗箔、二酸化チタン被覆ガラス末、ポリエチレンテレフタレート・アルミニウム・エポキシ積層末、ポリエチレンテレフタレート・ポリオレフィン積層フィルム末、ポリエチレンテレフタレート・ポリメチルメタクリレート積層フィルム末等の樹脂積層末等の光輝性粉体等が挙げられ、これらの1種又は2種以上を組み合わせて用いることができる。これらの中でも、マイカ、合成マイカ、ガラス末を母体とする光輝性粉体が光沢が良く好ましい。なお、これらの成分(D)は、フッ素系化合物、シリコーン系化合物、金属石鹸、レシチン、水素添加レシチン、コラーゲン、炭化水素、高級脂肪酸、高級アルコール、エステル、ワックス、ロウ、界面活性剤等の1種又は2種以上を用いて表面処理を施してあっても良い。 The glitter powder of component (D) used in the present invention is not particularly limited as long as it is a glitter powder commonly used in cosmetics. For example, mica, sericite, synthetic mica, synthetic sericite, Body powders such as aluminum silicate, magnesium silicate, magnesium aluminum silicate, cleaved talc, plate-like anhydrous silicic acid, plate-like aluminum oxide, plate-like kaolin, plate-like boron nitride, plate-like titanium oxide, plate-like cellulose, Mica titanium, bismuth oxychloride, organic pigment-treated mica titanium, titanium dioxide coated mica, titanium dioxide coated synthetic phlogopite, titanium dioxide coated bismuth oxychloride, iron oxide mica titanium, bituminized mica titanium, carmine treated mica titanium, fish scale foil, Titanium dioxide coated glass powder, polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terf Rate polyolefin laminated film powder, bright powders of the resin laminate powder such as powder of polyethylene terephthalate polymethyl methacrylate laminated film and the like, may be used in combination of two or more thereof. Among these, glittering powders based on mica, synthetic mica, and glass powder are preferable because of their good gloss. These components (D) are 1 compound such as fluorine compound, silicone compound, metal soap, lecithin, hydrogenated lecithin, collagen, hydrocarbon, higher fatty acid, higher alcohol, ester, wax, wax, surfactant, etc. You may surface-treat using seed | species or 2 or more types.
本発明に用いられる成分(D)の平均粒径は、特に限定されないが、艶高さにより優れる等の観点から、20〜400μmのものを用いることが好ましく、30〜200μmのものを用いることがより好ましい。また、アスペクト比は、30以上であることが好ましく、50以上であることがより好ましい。なお、本発明において平均粒径とは、レーザー回折・散乱式粒度分布測定装置を用い、水中分散状態で測定された粉体の幅と長さの装置上の平均値(積算体積50%の平均粒径値)をいう。 The average particle diameter of the component (D) used in the present invention is not particularly limited, but is preferably 20 to 400 μm, more preferably 30 to 200 μm from the standpoint of superior glossiness. More preferred. Further, the aspect ratio is preferably 30 or more, and more preferably 50 or more. In the present invention, the average particle diameter means an average value (average of 50% integrated volume) of powder width and length measured in a dispersion state in water using a laser diffraction / scattering particle size distribution measuring apparatus. Particle size value).
成分(D)の含有量としては、特に限定されないが、十分な化粧効果が得られ、水々しく光沢感が高い化粧膜が得られる等の観点から、0.1〜60%が好ましく、5〜40%がより好ましい。 The content of the component (D) is not particularly limited, but is preferably 0.1 to 60% from the viewpoint that a sufficient cosmetic effect is obtained and a decorative film having a watery and high gloss feeling is obtained. -40% is more preferable.
本発明における成分(D)は撥水撥油処理されたものを含んでいると、更に化粧持続性の点で好ましく、化粧料の安定性の面からもよい。撥水撥油処理は、パーフルオロアルキルリン酸エステルジエタノールアミン塩、パーフルオロオクチルトリエトキシシラン等が挙げられる。撥水撥油処理されたものを含む場合、その含有量は成分(D)中に15%以上であるのが好ましく、30%以上であるとより好ましい。 The component (D) in the present invention preferably contains a water- and oil-repellent treated product from the viewpoint of makeup sustainability, and may be from the viewpoint of cosmetic stability. Examples of the water / oil repellent treatment include perfluoroalkyl phosphate diethanolamine salt and perfluorooctyltriethoxysilane. When the water- and oil-repellent-treated product is included, the content thereof is preferably 15% or more in the component (D), and more preferably 30% or more.
本発明における成分(A)と成分(B)の含有質量比は、特に限定されないが、均一な化粧膜と二次付着レス効果により優れる等の観点から、(A)/(B)=0.1〜10であることが好ましく、0.15〜5であることがより好ましい。 The content ratio by mass of the component (A) and the component (B) in the present invention is not particularly limited, but (A) / (B) = 0. It is preferable that it is 1-10, and it is more preferable that it is 0.15-5.
また、本発明における成分(B)と成分(D)の含有質量比は、特に限定されないが、光輝性粉体の光沢感と二次付着レス効果により優れる等の観点から、(B)/(D)=0.01〜0.5であることが好ましく、0.02〜0.3であることがより好ましい。 In addition, the mass ratio of the component (B) and the component (D) in the present invention is not particularly limited, but from the viewpoint of being excellent in the glossiness of the glittering powder and the secondary adhesion-less effect, (B) / ( D) = 0.01 to 0.5 is preferable, and 0.02 to 0.3 is more preferable.
本発明の水性メイクアップ化粧料は、上記の成分(A)〜(D)の他に、本発明の効果を妨げない範囲で、通常化粧料に使用される成分、油性成分、粉体、粉体分散や感触調整としての界面活性剤、皮膜形成剤、水性成分、紫外線吸収剤、保湿剤、褪色防止剤、酸化防止剤、消泡剤、美容成分、防腐剤、香料などを本発明の効果を損なわない範囲で適宜含有することができる。 In addition to the above components (A) to (D), the aqueous makeup cosmetic of the present invention includes components, oily components, powders and powders that are usually used in cosmetics as long as the effects of the present invention are not hindered. The effects of the present invention include surfactants, film forming agents, aqueous components, UV absorbers, moisturizers, anti-fading agents, antioxidants, antifoaming agents, cosmetic ingredients, preservatives, and fragrances for body dispersion and feel adjustment. Can be appropriately contained within a range not impairing the above.
油性成分としては、動物油、植物油、合成油等の起源、及び、固形油、半固形油、液体油等の性状を問わず、炭化水素類、油脂類、ロウ類、硬化油類、エステル油類、脂肪酸類、高級アルコール類、シリコーン油類、フッ素系油類、ラノリン誘導体類、油性ゲル化剤類、油溶性樹脂、揮発性油剤等が挙げられる。
具体的には、流動パラフィン、スクワラン、ワセリン、パラフィンワックス、セレシンワックス、マイクロクリスタリンワックス、エチレンプロピレンコポリマー、モンタンワックス、フィッシャトロプスワックス等の炭化水素類、モクロウ、オリーブ油、ヒマシ油、ミンク油、マカデミアンナッツ油等の油脂類、ミツロウ、カルナウバワックス、キャンデリラワックス、ゲイロウ等のロウ類、ホホバ油、セチルイソオクタネート、ミリスチン酸イソプロピル、パルミチン酸イソプロピル、ミリスチン酸オクチルドデシル、トリオクタン酸グリセリル、ジイソステアリン酸ポリグリセリル、トリイソステアリン酸ジグリセリル、トリベヘン酸グリセリル、リンゴ酸ジイソステアリル、ジオクタン酸ネオペンチルグリコール、コレステロール脂肪酸エステル、N−ラウロイル−L−グルタミン酸ジ(コレステリル・ベヘニル・オクチルドデシル)等のエステル類、ステアリルアルコール、セチルアルコール、ラウリルアルコール、オレイルアルコール、イソステアリルアルコール、ベヘニルアルコール等の高級アルコール類、メチルフェニルポリシロキサン、フッ素変性オルガノポリシロキサン等のシリコーン類、パーフルオロデカン、パーフルオロオクタン、パーフルオロポリエーテル等のフッ素系油剤類、ラノリン、酢酸ラノリン、ラノリン脂肪酸イソプロピル、ラノリンアルコール等のラノリン誘導体、オクタン酸デキストリン、ラウリン酸デキストリン、パルミチン酸デキストリン、ミリスチン酸デキストリン、ステアリン酸デキストリン、ベヘニン酸デキストリン、ヤシ油脂肪酸デキストリン、(パルミチン酸/オクタン酸)デキストリン、蔗糖脂肪酸エステル、デンプン脂肪酸エステル、12−ヒドロキシステアリン酸、ステアリン酸カルシウム等の油性ゲル化剤類、水添ロジン酸ペンタエリスリチル、特定のアクリル酸アルキルメチルポリシロキサンエステル等の油溶性樹脂、軽質流動イソパラフィン、イソドデカン等の炭化水素油、デカメチルシクロペンタシロキサン、オクタメチルシクロテトラシロキサン、メチルトリメチコン、低重合度ジメチルポリシロキサン等のシリコーン類等の揮発性油剤等が挙げられる。
Oily components include hydrocarbons, oils and fats, waxes, hardened oils, ester oils, regardless of the origin, such as animal oils, vegetable oils, synthetic oils, and solid oils, semisolid oils, liquid oils, etc. , Fatty acids, higher alcohols, silicone oils, fluorine oils, lanolin derivatives, oily gelling agents, oil-soluble resins, volatile oils and the like.
Specifically, hydrocarbons such as liquid paraffin, squalane, petrolatum, paraffin wax, ceresin wax, microcrystalline wax, ethylene propylene copolymer, montan wax, fisher trops wax, molasses, olive oil, castor oil, mink oil, macadamia Oils such as peanut oil, beeswax, carnauba wax, candelilla wax, waxes such as gay wax, jojoba oil, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, diisostearate Polyglyceryl acid, diglyceryl triisostearate, glyceryl tribehenate, diisostearyl malate, neopentyl glycol dioctanoate, cholesterol fat Acid esters, esters such as N-lauroyl-L-glutamate di (cholesteryl, behenyl, octyldodecyl), stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol and other higher alcohols, methylphenyl poly Silicones such as siloxane and fluorine-modified organopolysiloxane, fluorinated oils such as perfluorodecane, perfluorooctane and perfluoropolyether, lanolin, lanolin acetate, lanolin fatty acid isopropyl, lanolin derivatives such as lanolin alcohol, dextrin octoate , Dextrin laurate, dextrin palmitate, dextrin myristate, dextrin stearate, dextrin behenate, coconut oil Fatty acid dextrin, (palmitic acid / octanoic acid) dextrin, sucrose fatty acid ester, starch fatty acid ester, 12-hydroxystearic acid, calcium stearate and other oily gelling agents, hydrogenated rosin acid pentaerythrityl, specific alkyl acrylate Volatilization of oil-soluble resins such as methylpolysiloxane esters, hydrocarbon oils such as light liquid isoparaffin and isododecane, silicones such as decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, methyltrimethicone, and low polymerization degree dimethylpolysiloxane Oily agents and the like.
成分(D)以外の粉体としては、紡錘状、針状、繊維状、球状等の形状、煙霧状、微粒子、顔料級などの粒子径、多孔質、無孔質等の粒子構造等により特に限定されず、無機粉体類、複合粉体類、等が挙げられる。具体的には、酸化アルミニウム、酸化マグネシウム、酸化ジルコニウム、炭酸マグネシウム、炭酸カルシウム、タルク、カオリン、シリカ、炭化珪素等の無機粉体類、ステアリン酸マグネシウム、ステアリン酸亜鉛、N−アシルリジン、ナイロン等の有機粉体類、酸化チタン、酸化亜鉛、酸化セリウム、硫酸バリウム等の白色無機顔料、酸化鉄、カーボンブラック、酸化クロム、水酸化クロム、紺青、群青、ベンガラ等の有色無機顔料、赤色201号、赤色202号、赤色205号、赤色226号、赤色228号、橙色203号、橙色204号、青色404号、黄色401号等の有機顔料粉体、赤色3号、赤色104号、赤色106号、橙色205号、黄色4号、黄色5号、緑色3号、青色1号等のジルコニウム、バリウム又はアルミニウムレーキ等の有機顔料粉体あるいは更にアルミニウム粉、金粉、銀粉等の金属粉体等が挙げられ、これらを1種又は2種以上を用いることができる。また、これら粉体は1種又は2種以上の複合化したものを用いても良く、フッ素化合物、シリコーン系油剤、金属石ケン、界面活性剤、油脂、炭化水素等を用いて公知の方法により表面処理してあっても良い。 The powders other than the component (D) are particularly in the form of spindles, needles, fibers, spheres, etc., fumes, fine particles, particle sizes such as pigment grades, porous, non-porous particle structures, etc. Without being limited, inorganic powders, composite powders and the like can be mentioned. Specifically, inorganic powders such as aluminum oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, talc, kaolin, silica, silicon carbide, magnesium stearate, zinc stearate, N-acyl lysine, nylon, etc. Organic powders, white inorganic pigments such as titanium oxide, zinc oxide, cerium oxide and barium sulfate, colored inorganic pigments such as iron oxide, carbon black, chromium oxide, chromium hydroxide, bitumen, ultramarine blue, red rose, red 201, Organic pigment powder such as red 202, red 205, red 226, red 228, orange 203, orange 204, blue 404, yellow 401, red 3, red 104, red 106, Zirconium, barium or aluminum such as orange 205, yellow 4, yellow 5, green 3, blue 1 Organic pigment powders or even aluminum powder over key such as gold powder, include metal powders such as silver, it can be used more than those one or. In addition, these powders may be used singly or in combination of two or more, and by a known method using a fluorine compound, a silicone-based oil agent, a metal soap, a surfactant, fats and oils, etc. It may be surface-treated.
粉体の分散性向上を目的で含有される界面活性剤としては、化粧料一般に用いられている界面活性剤であればいずれのものも使用でき、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、両性界面活性剤等が挙げられる。例えば、グリセリン脂肪酸エステル及びそのアルキレングリコール付加物、ポリグリセリン脂肪酸エステル及びそのアルキレングリコール付加物、ソルビタン脂肪酸エステル及びそのアルキレングリコール付加物、蔗糖脂肪酸エステル、ポリオキシエチレン硬化ヒマシ油、ポリオキシアルキレンアルキル共変性オルガノポリシロキサン、ポリエーテル変性オルガノポリシロキサン、レシチン等が挙げられる。 As the surfactant contained for the purpose of improving the dispersibility of the powder, any surfactant that is generally used in cosmetics can be used. Nonionic surfactants and anionic surfactants can be used. , Cationic surfactants, amphoteric surfactants and the like. For example, glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol adduct, sucrose fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene alkyl co-modified Examples thereof include organopolysiloxane, polyether-modified organopolysiloxane, and lecithin.
皮膜形成剤としては、アクリル酸アルキル重合体、メタクリル酸アルキル重合体、メタクリル酸アルキル共重合体等が挙げられる。 Examples of the film forming agent include alkyl acrylate polymers, alkyl methacrylate polymers, and alkyl methacrylate copolymers.
水性成分としては、水に可溶な成分であれば何れでもよく、例えば、エチルアルコール、ブチルアルコール等の低級アルコール、プロピレングリコール、1,3−ブチレングリコール、ジプロピレングリコール、ポリエチレングリコール等のグリコール類、グリセリン、ジグリセリン、ポリグリセリン等のグリセロール類等が挙げられる。 The aqueous component may be any component that is soluble in water, for example, lower alcohols such as ethyl alcohol and butyl alcohol, glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol, and polyethylene glycol. Glycerols such as glycerin, diglycerin and polyglycerin.
水溶性高分子としては、カルボキシビニルポリマー、アルキル付加カルボキシビニルポリマー、ポリアクリル酸ナトリウム等の合成系のものを挙げることができる。タンパク質、コラーゲン、エラスチン、ケラチン等の他の保湿剤を含有する事もできる。 Examples of the water-soluble polymer include synthetic compounds such as carboxyvinyl polymer, alkyl-added carboxyvinyl polymer, and sodium polyacrylate. Other moisturizing agents such as protein, collagen, elastin, keratin and the like can also be contained.
紫外線吸収剤としては、例えばベンゾフェノン系、PABA系、ケイ皮酸系、サリチル酸系、4−tert−ブチル−4’−メトキシジベンゾイルメタン、オキシベンゾン等、保湿剤としては、例えばタンパク質、ムコ多糖、コラーゲン、エラスチン、ケラチン等、酸化防止剤としては、例えばα−トコフェロール、アスコルビン酸等、美容成分としては、例えばビタミン類、消炎剤、生薬等、防腐剤としては、例えばパラオキシ安息香酸エステル、フェノキシエタノール、1,2―ペンタンジオール等が挙げられる。 Examples of ultraviolet absorbers include benzophenone-based, PABA-based, cinnamic acid-based, salicylic acid-based, 4-tert-butyl-4'-methoxydibenzoylmethane, and oxybenzone. Examples of humectants include protein, mucopolysaccharide, and collagen. , Elastin, keratin, etc., antioxidants such as α-tocopherol, ascorbic acid, etc., cosmetic ingredients such as vitamins, anti-inflammatory agents, herbal medicines, etc., antiseptics such as paraoxybenzoic acid esters, phenoxyethanol, 1 , 2-pentanediol and the like.
本発明の水性メイクアップ化粧料は、特に限定されないが、アイカラー、フェイスカラー、チークカラー、アイライナーなどに応用でき、形状としては、固型、クリーム状、ゲル状、液状等が挙げられるが、中でも粘度50,000mm2/s以上の流動性のあるものから流動性を有しない固型のゲル状が好ましい。外観は、透明、半透明、不透明それぞれの化粧料として使用することができる。 The aqueous makeup cosmetic of the present invention is not particularly limited, but can be applied to eye color, face color, cheek color, eyeliner and the like, and examples of the shape include solid, cream, gel, and liquid. Among them, a solid gel shape having no fluidity is preferred from one having a viscosity of 50,000 mm 2 / s or more. Appearance can be used as transparent, translucent and opaque cosmetics.
本発明の水性メイクアップ化粧料は、成分(C)の水を連続相とする化粧料であり、特に限定されないが、油性成分の含有量が50%未満であることが好ましく、30%未満であることがより好ましく、本発明の効果がより発揮される点から、10%未満であることがより好ましい。剤型としては、特に限定されないが、水中油型や、乳化工程のない水性型が挙げられる。これらの中でも、本発明の効果がより顕著に発揮される点から、油性成分の含有量が1%未満である水性型であることが特に好ましい。 The aqueous makeup cosmetic of the present invention is a cosmetic having water as the component (C) as a continuous phase, and is not particularly limited. However, the content of the oily component is preferably less than 50%, and less than 30%. More preferably, it is more preferably less than 10% from the viewpoint that the effect of the present invention is more exerted. Although it does not specifically limit as a dosage form, The oil-in-water type | mold and the aqueous type | mold without an emulsification process are mentioned. Among these, the aqueous type in which the content of the oil component is less than 1% is particularly preferable from the viewpoint that the effects of the present invention are more remarkably exhibited.
以下に実施例をあげて本発明を詳細に説明する。尚、これらは本発明を何ら限定するものではない。 Hereinafter, the present invention will be described in detail with reference to examples. Note that these do not limit the present invention.
本発明における成分(B)のシリコーンリン酸トリエステルの合成例を以下に示す。
[合成例1]
カルビノール変性シリコーン(式2)を265g、テトラヒドロフラン136gを混合し、−40℃に冷却した。リチウムジイソプロピルアミド(LDA)(1mol/THF溶液)200mlを滴下し、90分反応させた後、オキシ塩化リン(式1)7.8gを添加し、1時間反応させた。25℃まで温度を上げさらに2時間熟成させた後、濃塩酸42gを加え反応を終了させた。メタノールで洗浄し溶媒を留去することにより、シリコーンリン酸トリエステルを含む混合物を得た。得られた混合物の組成比は、31P−NMR測定により、トリエステル体である式(I)が92%、ジエステル体である式(II)が1%、その他ポリリン酸を含む副生成物が7%であった。
A synthesis example of the silicone phosphate triester of component (B) in the present invention is shown below.
[Synthesis Example 1]
265 g of carbinol-modified silicone (formula 2) and 136 g of tetrahydrofuran were mixed and cooled to -40 ° C. After adding 200 ml of lithium diisopropylamide (LDA) (1 mol / THF solution) dropwise and reacting for 90 minutes, 7.8 g of phosphorus oxychloride (formula 1) was added and allowed to react for 1 hour. After raising the temperature to 25 ° C. and further aging for 2 hours, 42 g of concentrated hydrochloric acid was added to terminate the reaction. The mixture containing silicone phosphate triester was obtained by washing with methanol and distilling off the solvent. The composition ratio of the obtained mixture was determined by 31P-NMR measurement to be 92% for the formula (I) as the triester, 1% for the formula (II) as the diester, and 7% by-product containing polyphosphoric acid. %Met.
[処方例]
上記製造実施例において製造されたシリコーンリン酸トリエステルを含む混合物を、以下の処方において使用した。したがって、以下の実施例において例えば「合成例1の生成物」とは、合成例1において得られたシリコーンリン酸トリエステルを含む混合物を意味する。
[Prescription example]
The mixture containing the silicone phosphate triester produced in the above production example was used in the following formulation. Therefore, in the following examples, for example, “product of Synthesis Example 1” means a mixture containing the silicone phosphate triester obtained in Synthesis Example 1.
実施例1〜8及び比較例1〜5:アイカラー(水性ゲル状)
表1に示す処方のアイカラーを調製し、a.化粧膜の均一性、b.パールの光沢感、c.化粧持続性、d.二次付着レス効果について下記の方法により評価した。結果を表1に示す。
Examples 1 to 8 and Comparative Examples 1 to 5: Eye color (aqueous gel)
Prepare eye colors of the formulation shown in Table 1, a. Uniformity of decorative film, b. Pearl luster, c. Makeup persistence, d. The secondary adhesion-less effect was evaluated by the following method. The results are shown in Table 1.
A.成分(1)〜(5)を成分(20)の一部で均一に加温膨潤する。
B.Aに(6)〜(19)、(20)の残部を加え均一に混合する。
C.Bを容器に充填しアイカラー(水性ゲル状)を得た。
A. The components (1) to (5) are uniformly heated and swollen with a part of the component (20).
B. Add the remainder of (6) to (19) and (20) to A and mix uniformly.
C. B was filled in a container to obtain an eye color (aqueous gel).
(評価方法)
下記評価項目について各々下記方法により評価を行った。
(評価項目)
a.化粧膜の均一性
b.パールの光沢感
c. 化粧持続性
a〜cの項目について、各試料について専門パネル20名による使用テストを行った。パネル各人が実施例1〜8及び比較例1〜5の各アイカラーを指で使用し、下記絶対評価基準にて7段階に評価し評点をつけ、各試料についてパネル全員の評点合計からその平均値を算出し、下記判定基準により判定した。アイカラー使用後に化粧膜が均一に塗れているか、パールの光沢感が高いか、それぞれa.化粧膜の均一性、b.パールの光沢感、として評価した。化粧持続性については、各試料を塗布し、パネルに通常の生活をしてもらった後、6時間後に涙や汗などで化粧膜がくずれていないかを評価した。
(Evaluation method)
The following evaluation items were evaluated by the following methods.
(Evaluation item)
a. Uniformity of decorative film b. Glossiness of pearl c. Makeup persistence For each of the items a to c, a use test was conducted by 20 professional panels for each sample. Each panel person uses each eye color of Examples 1 to 8 and Comparative Examples 1 to 5 with a finger, evaluates it according to the following absolute evaluation criteria in 7 levels, and gives a score from the total score of all panel members The average value was calculated and judged according to the following criteria. Whether the cosmetic film is applied evenly after the eye color is used, and whether the gloss of pearl is high, a. Uniformity of decorative film, b. The glossiness of pearl was evaluated. For makeup persistence, each sample was applied, and after having a normal life on the panel, it was evaluated whether the makeup film was broken by tears or sweat after 6 hours.
絶対評価基準
(評点):(評価)
6 :非常に良い
5 :良い
4 :やや良い
3 :普通
2 :やや悪い
1 :悪い
0 :非常に悪い
Absolute Evaluation Criteria (Score): (Evaluation)
6: Very good 5: Good 4: Somewhat good 3: Normal 2: Somewhat bad 1: Bad 0: Very bad
判定基準
(判定):(評点の平均点)
◎ :5点以上
○ :3.5点以上〜5点未満
△ :2点以上〜3.5点未満
× :2点未満
Judgment criteria (judgment): (average score)
◎: 5 points or more ○: 3.5 points or more to less than 5 points △: 2 points or more to less than 3.5 points ×: Less than 2 points
d.二次付着レス効果
各試料0.2gを人工皮革A(ビューラックス社製)に2cm四方に指で塗り広げ、3分間乾燥させた後に、別の人工皮革Bを50gwtの荷重で10秒間押し付け、引きはがした際の耐転写性(二次付着レス効果)を色差計(CM−700d、コニカミノルタ社製)を用いて人工皮革Bの転写前後の色調差ΔEを算出して評価し、下記の判断基準により判定した。
判定基準
(判定): (評価)
◎ : ΔE<1.0
○ : 1.0≦ΔE<3.0
△ : 3.0≦ΔE<5.0
× : 5.0<ΔE
d. Secondary adhesion-less effect 0.2 g of each sample was applied to artificial leather A (manufactured by Beaulux) with 2 cm square fingers and dried for 3 minutes, and then another artificial leather B was pressed with a load of 50 gwt for 10 seconds. Transfer resistance (secondary adhesion-less effect) at the time of peeling was evaluated by calculating a color difference ΔE before and after transfer of the artificial leather B using a color difference meter (CM-700d, manufactured by Konica Minolta Co., Ltd.). Judgment was made according to the criteria.
Judgment criteria (judgment): (Evaluation)
: ΔE <1.0
○: 1.0 ≦ ΔE <3.0
Δ: 3.0 ≦ ΔE <5.0
×: 5.0 <ΔE
表1の結果から明らかな如く、本発明の実施例1〜8の水性アイカラーは、比較例1〜5に比べ、化粧膜の均一性、パールの光沢感、化粧持続性、ニ次付着レス効果の全てにおいて優れたものであった。これに対して、成分(A)のかわりに、水性のゲル化剤である、カルボキシビニルポリマーを含有した比較例1は、パールの光沢が十分ではなく、肌への密着感に劣るため、化粧膜が均一でなく化粧持持続性や二次付着レス効果が悪いものであった。成分(B)を含有していない比較例2、成分(B)のかわりに、ジメチコンを含有している比較例3及び、リン酸トリオレイルを含有している比較例4は、分散性が悪いために化粧膜が均一でなく、肌への密着感に劣るために二次付着レス効果も十分ではなかった。酢酸ビニル共重合体エマルションを含有している比較例5は、化粧料の肌への付着性は向上するものの、表面のタック性も同時に上がるため二次付着レス効果が悪いものであった。
As is clear from the results in Table 1, the aqueous eye colors of Examples 1 to 8 of the present invention were more uniform than the Comparative Examples 1 to 5, the uniformity of the cosmetic film, the pearly luster, the makeup persistence, and the secondary adhesion less. It was excellent in all of the effects. On the other hand, Comparative Example 1 containing a carboxyvinyl polymer, which is an aqueous gelling agent, instead of component (A) is not sufficient in pearl luster and has a poor adhesion to the skin. The film was not uniform, and the makeup persistence and secondary adhesion-less effect were poor. Comparative Example 2 containing no component (B), Comparative Example 3 containing dimethicone instead of Component (B), and Comparative Example 4 containing trioleyl phosphate have poor dispersibility. Therefore, the makeup film is not uniform and the adhesion to the skin is inferior, so the secondary adhesion-less effect is not sufficient. In Comparative Example 5 containing the vinyl acetate copolymer emulsion, although the adhesion of the cosmetic to the skin was improved, the surface tackiness was also increased, and the secondary adhesion-less effect was poor.
実施例9 頬紅(水性固型ゲル状)
(成分) (%)
1.脱アシル型ジェランガム 0.6
2.水 残量
3.トリエタノールアミン 0.1
4.EDTA−2Na 0.05
5.ジブチレングリコール 15
6.レシチン 0.2
7.ポリオキシエチレンソルビタンモノオレート 0.15
8.タルク 2
9.パーフルオロオクチルトリエトキシシラン5%処理黄酸化鉄 0.2
10.パーフルオロオクチルトリエトキシシラン5%処理黒酸化鉄 0.02
11.パーフルオロオクチルトリエトキシシラン5%処理ベンガラ 0.1
12.パーフルオロアルキルリン酸エステルジエタノールアミン塩5%処理
酸化チタン 0.05
13.合成金雲母※9 14
14.パーフルオロアルキルリン酸エステルジエタノールアミン塩3%処理
酸化チタン被覆マイカ※10 10
15.シリコーン2%処理酸化チタン被覆合成金雲母※11 1
16.合成例1の生成物 2
※9:PDM−10L(トピー工業社製)
※10:FLAMENCO RED 420C(BASF社製)にパーフルオロアルキルリン酸エステルジエタノールアミン塩を3%処理したもの
※11:HELIOS R100S(S)(トピー工業社製)
(製造方法)
A.成分(1)を成分(2)の一部で均一に膨潤する。
B.成分(3)〜(12)を均一に分散する。
C.AにBと成分(13)〜(16)を加え均一に混合する。
D.Cを容器に充填し頬紅(水性ゲル状)を得た。
本実施例6の頬紅は、化粧膜の均一性、パールの光沢感、化粧持続性、ニ次付着レス効果の全てにおいて優れたものであった。
Example 9 Blusher (aqueous solid gel)
(Ingredient) (%)
1. Deacylated gellan gum 0.6
2. Water remaining amount 3. Triethanolamine 0.1
4). EDTA-2Na 0.05
5. Dibutylene glycol 15
6). Lecithin 0.2
7). Polyoxyethylene sorbitan monooleate 0.15
8). Talc 2
9. Perfluorooctyltriethoxysilane 5% treated yellow iron oxide 0.2
10. Perfluorooctyltriethoxysilane 5% black iron oxide 0.02
11. Perfluorooctyltriethoxysilane 5% treated bengara 0.1
12 Perfluoroalkyl phosphate diethanolamine 5% treated Titanium oxide 0.05
13. Synthetic phlogopite * 9 14
14 Perfluoroalkyl phosphate diethanolamine salt 3% treatment Titanium oxide coated mica * 10 10
15. Silicone 2% treated titanium oxide coated synthetic phlogopite * 11 1
16. Product of Synthesis Example 1 2
* 9: PDM-10L (Topy Industries, Ltd.)
* 10: FLAMENCO RED 420C (manufactured by BASF) treated with 3% perfluoroalkyl phosphate diethanolamine salt * 11: HELIOS R100S (S) (manufactured by Topy Industries)
(Production method)
A. Ingredient (1) is uniformly swollen with part of ingredient (2).
B. Ingredients (3) to (12) are uniformly dispersed.
C. Add B and components (13) to (16) to A and mix uniformly.
D. C was filled into a container to obtain blusher (aqueous gel).
The blusher of Example 6 was excellent in all of the uniformity of the cosmetic film, the glossiness of the pearl, the makeup persistence, and the effect of preventing secondary adhesion.
実施例10 ファンデーション(水中油型固型ゲル状)
(成分) (%)
1.ペクチン※12 0.5
2.精製水 残量
3.L−アルギニン 0.1
4.EDTA−2Na 0.05
5.塩化カルシウム 0.03
6.フェノキシエタノール 0.3
7.1,3−ブチレングリコール 15
8.ポリオキシエチレンポリオキシプロピレングリコール※13 0.3
9.ポリオキシエチレンアルキルエーテルリン酸ナトリウム 0.3
10.ジメチルポリシロキサン2%処理タルク 3.5
11.ジメチルポリシロキサン2%処理黄酸化鉄 1.5
12.ジメチルポリシロキサン2%処理黒酸化鉄 0.1
13.ジメチルポリシロキサン2%処理ベンガラ 0.1
14.ジメチルポリシロキサン2%処理板状酸化チタン 7
15.ジメチルポリシロキサン2%処理雲母チタン※14 10
16.合成例1の生成物 0.5
17.モノステアリン酸グリセリン 1.5
18.セタノール 1.5
19.流動パラフィン 1
20.スクワラン 2
21.トリオクタン酸グリセリル 3
22.ジペンタエリトリットテトラ12−ヒドロキシステアリン酸
セスキステアリン酸ヘミロジンエステル 0.5
23.ジメチルポリシロキサン(20CS) 0.5
24.アクリル酸アルキル・スチレン共重合体エマルション※15 3
※12:GENUペクチン LM−104AS−J(三晶社製)
※13:ユニルーブ70DP−950B(日本油脂社製)
※14:チミロンスーパーゴールド(MERCK社製)にジメチルポリシロキサンを2%処理したもの
※15:ヨドゾールGH41F(アグゾノーベル社製)
(製造方法)
A.成分(1)を成分(2)にて均一に膨潤する。
B.成分(3)〜(16)を均一に分散する。
C.成分(17)〜(23)を70℃で加熱溶解する。
D.A、Bを混合し、そこにCを加えて乳化する。
E.Dに成分(24)を添加し混合する。
F.Eを加温溶解し、容器に充填した後、室温まで冷却して、ゲル状ファンデーションを得た。
本実施例6のゲル状ファンデーションは、化粧膜の均一性、化粧持続性、ニ次付着レス効果の全てにおいて優れたものであった。
Example 10 Foundation (oil-in-water solid gel)
(Ingredient) (%)
1. Pectin * 12 0.5
2. 2. Purified water remaining amount L-Arginine 0.1
4). EDTA-2Na 0.05
5. Calcium chloride 0.03
6). Phenoxyethanol 0.3
7.1,3-Butylene glycol 15
8). Polyoxyethylene polyoxypropylene glycol * 13 0.3
9. Sodium polyoxyethylene alkyl ether phosphate 0.3
10. Dimethylpolysiloxane 2% treated talc 3.5
11. Dimethylpolysiloxane 2% treated yellow iron oxide 1.5
12 Dimethylpolysiloxane 2% black iron oxide 0.1
13. Dimethylpolysiloxane 2% treated bengara 0.1
14 Dimethylpolysiloxane 2% treated plate-like titanium oxide 7
15. Dimethylpolysiloxane 2% treated mica titanium * 14 10
16. Product of Synthesis Example 1 0.5
17. Glycerol monostearate 1.5
18. Cetanol 1.5
19. Liquid paraffin 1
20. Squalane 2
21. Glyceryl trioctanoate 3
22. Dipentaerythritol tetra 12-hydroxystearic acid sesquistearic acid hemirosin ester 0.5
23. Dimethylpolysiloxane (20CS) 0.5
24. Alkyl acrylate / styrene copolymer emulsion * 15 3
* 12: GENU pectin LM-104AS-J (manufactured by Sankisha)
* 13: Unilube 70DP-950B (Nippon Yushi Co., Ltd.)
* 14: Timilon Super Gold (MERCK) treated with 2% dimethylpolysiloxane * 15: Iodosol GH41F (Axon Nobel)
(Production method)
A. Ingredient (1) is uniformly swollen with ingredient (2).
B. Ingredients (3) to (16) are uniformly dispersed.
C. Components (17) to (23) are dissolved by heating at 70 ° C.
D. A and B are mixed, and C is added thereto to emulsify.
E. Add component (24) to D and mix.
F. E was heated and dissolved, filled into a container, and then cooled to room temperature to obtain a gel-like foundation.
The gel-like foundation of Example 6 was excellent in all of the uniformity of the cosmetic film, makeup persistence, and secondary adhesion-less effect.
実施例11 下地(水中油型クリーム状))
(成分) (%)
1.寒天※2 0.3
2.ローカストビーンガム 0.1
3.キサンタンガム 0.1
4.1,2−ペンチレングリコール 5
5.1,3−ブチレングリコール 5
6.精製水 残量
7.2−アミノ−2−メチル−1−プロパノール 0.3
8.EDTA−2Na 0.05
9.合成例1の生成物 0.1
10.パラオキシ安息香酸メチル 0.1
11.ポリオキシエチレンアルキルエーテルリン酸ナトリウム 0.3
12.ジメチルポリシロキサン2%処理タルク 3.5
13.ジメチルポリシロキサン2%処理黄酸化鉄 1.5
14.ジメチルポリシロキサン2%処理黒酸化鉄 0.1
15.ジメチルポリシロキサン2%処理ベンガラ 0.1
16.ジメチルポリシロキサン2%処理板状酸化チタン 7
17.ベンガラ被覆雲母チタン※16 7
18.モノステアリン酸ポリグリセリル 1.5
19.セタノール 1.5
20.ポリオキシエチレン(60)硬化ひまし油 1
21.スクワラン 3
22.トリオクタン酸グリセリル 5
23.モノステアリン酸グリセリル 0.5
24.ジメチルポリシロキサン(100CS) 0.5
25.ワセリン 0.5
※16CLOISONNE ROUGE FLAMBE(BASF社製)
(製造方法)
A.成分(1)〜(3)、(7)〜(11)を成分(4)、(5)、(6)の一部で均一に膨潤する。
B.成分(18)〜(25)を70℃で加熱溶解する。
C.成分(6)の残部に成分(12)〜(17)を均一に分散する。
D.CにBを添加して乳化する。
E.DにA、成分(6)を添加し混合する。
F.Eを容器に溶融充填した後、室温まで冷却して、ゲル状下地を得た。
本実施例7のゲル状下地は、化粧膜の均一性、パールの光沢感、化粧持続性、ニ次付着レス効果の全てにおいて優れたものであった。
Example 11 Base (oil-in-water cream))
(Ingredient) (%)
1. Agar * 2 0.3
2. Locust bean gum 0.1
3. Xanthan gum 0.1
4. 1,2-pentylene glycol 5
5.1,3-Butylene glycol 5
6). Purified water Residual amount 7. 2-Amino-2-methyl-1-propanol 0.3
8). EDTA-2Na 0.05
9. Product of Synthesis Example 1 0.1
10. Methyl paraoxybenzoate 0.1
11. Sodium polyoxyethylene alkyl ether phosphate 0.3
12 Dimethylpolysiloxane 2% treated talc 3.5
13. Dimethylpolysiloxane 2% treated yellow iron oxide 1.5
14 Dimethylpolysiloxane 2% black iron oxide 0.1
15. Dimethylpolysiloxane 2% treated bengara 0.1
16. Dimethylpolysiloxane 2% treated plate-like titanium oxide 7
17. Bengala-coated mica titanium * 16 7
18. Polyglyceryl monostearate 1.5
19. Cetanol 1.5
20. Polyoxyethylene (60) hydrogenated castor oil 1
21. Squalane 3
22. Glyceryl trioctanoate 5
23. Glyceryl monostearate 0.5
24. Dimethylpolysiloxane (100CS) 0.5
25. Vaseline 0.5
* 16CLOISNE ROUGE FLAMBE (BASF)
(Production method)
A. Components (1) to (3) and (7) to (11) are uniformly swollen with a part of components (4), (5), and (6).
B. Components (18) to (25) are dissolved by heating at 70 ° C.
C. Components (12) to (17) are uniformly dispersed in the remainder of component (6).
D. B is added to C and emulsified.
E. Add A and component (6) to D and mix.
F. After E was melt-filled in the container, it was cooled to room temperature to obtain a gel-like substrate.
The gel-like substrate of Example 7 was excellent in all of the uniformity of the decorative film, the glossiness of pearl, the makeup durability, and the effect of preventing secondary adhesion.
実施例12 アイライナー(水性液状)
(成分) (%)
1.ネイティブジェランガム※1 0.1
2.精製水 残量
3.EDTA−2Na 0.05
4.トリエタノールアミン 0.1
5.1,3−ブチレングリコール 15
6.レシチン 0.2
7.ポリオキシエチレンソルビタンモノオレート 0.15
8.セリサイト 2
9.板状セルロース 2
10.パーフルオロオクチルトリエトキシシラン3%処理黒酸化鉄 5
11.酸化チタン被覆ホウケイ酸※17 5
12.黒酸化鉄被覆マイカ※18 20
13.合成例1の生成物 10
※17:メタシャインMT1080RS(日本板硝子社製)
※18:COLORONA MICA BLACK(メルク社製)
(製造方法)
A.成分(1)を成分(2)で均一に膨潤する。
B.成分(3)〜(10)を均一に分散する。
C.AにBと成分(11)〜(13)を加え均一に混合する。
D.Cを容器に充填しアイライナー(水性ゲル状)を得た。
本実施例8のアイライナーは、化粧膜の均一性、パールの光沢感、化粧持続性、ニ次付着レス効果の全てにおいて優れたものであった。
Example 12 Eyeliner (aqueous liquid)
(Ingredient) (%)
1. Native gellan gum * 1 0.1
2. 2. Purified water remaining amount EDTA-2Na 0.05
4). Triethanolamine 0.1
5.1,3-Butylene glycol 15
6). Lecithin 0.2
7). Polyoxyethylene sorbitan monooleate 0.15
8). Sericite 2
9. Plate cellulose 2
10. Perfluorooctyltriethoxysilane 3% treated black iron oxide 5
11. Titanium oxide coated borosilicate * 17 5
12 Black iron oxide coated mica * 18 20
13. Product of Synthesis Example 1 10
* 17: Metashine MT1080RS (manufactured by Nippon Sheet Glass Co., Ltd.)
* 18: COLORONA MICA BLACK (Merck)
(Production method)
A. Ingredient (1) is uniformly swollen with ingredient (2).
B. Ingredients (3) to (10) are uniformly dispersed.
C. Add B and components (11) to (13) to A and mix uniformly.
D. C was filled into a container to obtain an eyeliner (aqueous gel).
The eyeliner of Example 8 was excellent in all of the uniformity of the decorative film, the glossiness of the pearl, the makeup persistence, and the secondary adhesion-less effect.
Claims (7)
(A)水溶性多糖類
(B)式(1)
(C)水
(D)光輝性粉体
を含有する水性メイクアップ化粧料。 The following components (A) to (D);
(A) Water-soluble polysaccharide (B) Formula (1)
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JP2021080231A (en) * | 2019-11-22 | 2021-05-27 | 株式会社ノエビア | Topical skin preparation |
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JP2021080231A (en) * | 2019-11-22 | 2021-05-27 | 株式会社ノエビア | Topical skin preparation |
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