JP2007176936A - Makeup cosmetic material - Google Patents
Makeup cosmetic material Download PDFInfo
- Publication number
- JP2007176936A JP2007176936A JP2006323612A JP2006323612A JP2007176936A JP 2007176936 A JP2007176936 A JP 2007176936A JP 2006323612 A JP2006323612 A JP 2006323612A JP 2006323612 A JP2006323612 A JP 2006323612A JP 2007176936 A JP2007176936 A JP 2007176936A
- Authority
- JP
- Japan
- Prior art keywords
- extract
- acid
- treatment
- oil
- ultramarine
- 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.)
- Pending
Links
- 239000002537 cosmetic Substances 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 49
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- 230000002209 hydrophobic effect Effects 0.000 claims 1
- 235000013799 ultramarine blue Nutrition 0.000 abstract description 12
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Landscapes
- Cosmetics (AREA)
- Glass Melting And Manufacturing (AREA)
Abstract
Description
本発明は、メイクアップ化粧料に関する。 The present invention relates to a makeup cosmetic.
水を含有する乳化型や顔料水分散型のメイクアップ化粧料において青色系の色調を調整するための顔料として、チタン酸コバルト、チタン酸リチウムコバルト、酸化コバルト、酸化アルミニウムコバルト、水酸化クロム、酸化クロム等が従来から用いられている。一方、そのような顔料として群青が使用される頻度は低い。 Cobalt titanate, lithium cobalt titanate, cobalt oxide, aluminum cobalt oxide, chromium hydroxide, oxidation as pigments to adjust the blue color tone in water-based emulsified and pigment-dispersed makeup cosmetics Chrome or the like has been used conventionally. On the other hand, ultramarine is used less frequently as such a pigment.
群青は赤みのある鮮明な青色を呈する無機顔料であり、アイシャドウ、マスカラ、アイライナー等のメイクアップ化粧料に魅力的な色調を付与できる。しかし、群青は酸に弱く、化粧料中に微量存在する酸と容易に反応して、硫化水素を発生しながら、変色や退色するという問題点があった。また、アルカリ性を呈する化粧料中においても、高温や、機械的せん断力によって硫化水素が発生することから、群青を含む化粧料は製造が困難であるとともに、製品の変臭の原因となる場合がある。そのため、群青は、水を含有するメイクアップ化粧料の着色剤としてあまり使用されてこなかった。 Ultramarine blue is an inorganic pigment exhibiting a clear reddish blue color, and can impart an attractive color tone to makeup cosmetics such as eye shadow, mascara, and eyeliner. However, ultramarine blue is weak against acid, and it easily reacts with an acid present in a trace amount in cosmetics to cause discoloration or fading while generating hydrogen sulfide. In addition, even in cosmetics exhibiting alkalinity, hydrogen sulfide is generated due to high temperature and mechanical shearing force, so cosmetics containing ultramarine are difficult to manufacture and may cause a product odor. is there. For this reason, ultramarine blue has not been used as a colorant for makeup cosmetics containing water.
このような群青の性質を改良するために、群青粒子の表面を亜鉛化合物で封鎖する方法が提案されている(特許文献1参照)。また、群青粒子の表面をシリコーン化合物で被覆処理することによって安定性を向上させる方法が提案されている(特許文献2参照)。これらの方法によって改良された群青は、変色や退色の度合いが未処理の群青より改善されているものの、その改善は十分ではなく、かつ無機顔料特有のざらついた塗布感はまったく改善されていない。
このような状況において、本発明の目的の1つは、水を含有するメイクアップ化粧料において、群青由来の優れた色調を有し、安定で、かつ、ざらつきのない塗布感を有するメイクアップ化粧料を提供することである。 In such a situation, one of the objects of the present invention is to make up makeup that has an excellent color tone derived from ultramarine blue and has a stable and non-textured feeling in makeup cosmetics containing water. Is to provide a fee.
上記目的を達成するため、鋭意研究を重ねた結果、本発明者らは、水を含有するメイクアップ化粧料において、群青をフレーク状ガラスに封じ込めた複合着色顔料と皮膜形成剤とを特定の割合で配合することによって、上記目的を達成できることを見出し、本発明を完成するに至った。 In order to achieve the above object, as a result of intensive research, the present inventors, in a makeup cosmetic containing water, have a specific ratio of a composite color pigment in which ultramarine blue is contained in flaky glass and a film forming agent. It was found that the above-mentioned object can be achieved by blending with, and the present invention was completed.
すなわち、本発明のメイクアップ化粧料は、(a)群青の粒子が内部に分散されたフレーク状ガラス0.01質量%〜30質量%と、(b)皮膜形成剤0.1質量%〜30質量%と、(c)水とを含有し、前記フレーク状ガラスは、平均厚さが0.1μm〜3μmの範囲にあり、平均粒径が1μm〜300μmの範囲にあり、平均アスペクト比が5〜300の範囲にある。 That is, the makeup cosmetic of the present invention comprises (a) 0.01% by mass to 30% by mass of flake glass in which ultramarine blue particles are dispersed, and (b) 0.1% by mass to 30% of a film forming agent. The flake glass contains a mass% and (c) water. The flake glass has an average thickness in the range of 0.1 μm to 3 μm, an average particle diameter in the range of 1 μm to 300 μm, and an average aspect ratio of 5 It is in the range of ~ 300.
本発明によれば、安定で、経時での変色や退色等がなく、滑らかな塗布感を有した水含有メイクアップ化粧料が得られる。 According to the present invention, a water-containing makeup cosmetic that is stable, has no discoloration or fading over time, and has a smooth coating feeling can be obtained.
以下、本発明の実施形態について説明する。 Hereinafter, embodiments of the present invention will be described.
[メイクアップ化粧料]
本発明のメイクアップ化粧料は、(a)群青の粒子が内部に分散されたフレーク状ガラス(以下、「フレーク状ガラス(A)という場合がある」)0.01質量%〜30質量%と、(b)皮膜形成剤0.1質量%〜30質量%と、(c)水とを含有する。フレーク状ガラス(A)は、平均厚さが0.1μm〜3μmの範囲にあり、平均粒径が1μm〜300μmの範囲にあり、平均アスペクト比が5〜300の範囲にある。
[Makeup cosmetics]
The makeup cosmetic of the present invention comprises (a) flake glass in which ultramarine blue particles are dispersed (hereinafter, may be referred to as “flake glass (A)”) 0.01 mass% to 30 mass%. (B) 0.1 mass%-30 mass% of film formation agents, and (c) water are contained. The flaky glass (A) has an average thickness in the range of 0.1 μm to 3 μm, an average particle size in the range of 1 μm to 300 μm, and an average aspect ratio in the range of 5 to 300.
この明細書において、「群青」には、天然産あるいは人工的に合成される、含硫黄・ナトリウム−アルミノシリケート(Na6Al6Si6O24Sx)として示される顔料が含まれる。硫黄の量などの違いによって、青、緑、紫、ピンクなどいろいろな色を呈する群青があるが、青色から青紫色のものが一般的である。色素名としては、CI77007、CI77013、Pigment Blue 29、Pigment Green 24、Pigment Violet 15などのものが示される。 In this specification, “ultraviolet” includes a pigment represented as sulfur-containing sodium-aluminosilicate (Na 6 Al 6 Si 6 O 24 S x ), which is naturally produced or artificially synthesized. There are ultramarine blues with various colors such as blue, green, purple, and pink depending on the amount of sulfur, but blue to blue-violet are common. Examples of the dye name include CI77007, CI77013, Pigment Blue 29, Pigment Green 24, Pigment Violet 15, and the like.
典型的なフレーク状ガラス(A)は、透明な金属酸化物の母材と、その内部に分散された群青粒子(群青顔料の粒子)とからなる。群青粒子はフレーク状ガラスの内部に分散されており、実質的にガラスの表面に露出していないため、群青粒子が濡れることによる色のくすみを抑制できる。また、フレーク状ガラス(A)は、その外形が鱗片状であることから、凝集しにくい、塗膜面に平行に配向して並びやすい、などの特徴があり、フレーク状ガラス(A)を含む化粧料は滑らかな塗布感を有する。 A typical flaky glass (A) comprises a transparent metal oxide base material and ultramarine particles (ultraviolet pigment particles) dispersed therein. Since the ultramarine particles are dispersed inside the flaky glass and are not substantially exposed on the surface of the glass, it is possible to suppress color dullness due to wetness of the ultramarine particles. In addition, since the outer shape of the flaky glass (A) is scaly, it has characteristics such as being less likely to aggregate and being easily aligned and aligned in parallel with the coating surface, and includes the flaky glass (A). The cosmetic has a smooth application feeling.
フレーク状ガラス(A)を構成する透明な金属酸化物としては、二酸化ケイ素、三二酸化アルミニウム、酸化ジルコニウム、酸化チタン等が好ましく用いられる。 As the transparent metal oxide constituting the flaky glass (A), silicon dioxide, aluminum sesquioxide, zirconium oxide, titanium oxide and the like are preferably used.
フレーク状ガラス(A)に使用される群青粒子の粒径は、通常、30〜3000nmの範囲にある。粒径が30nmより小さいと着色が弱く、粒径が3000nmより大きいと、フレーク状ガラスのなかにうまく入らず、群青が露出し、くすみや感触に対する効果が少なくなる。群青粒子の粒径は、好ましくは50〜2000nmの範囲である。 The particle size of the ultramarine particles used in the flaky glass (A) is usually in the range of 30 to 3000 nm. When the particle size is smaller than 30 nm, the coloring is weak, and when the particle size is larger than 3000 nm, the flake glass does not enter well, and ultramarine is exposed, and the effect on dullness and touch is reduced. The particle size of the ultramarine particles is preferably in the range of 50 to 2000 nm.
フレーク状ガラス(A)は、平均厚さが0.1〜3μmの範囲にあり、平均粒径が1〜300μmの範囲にあり、平均アスペクト比が5〜300の範囲にある。ここで、平均厚さは、以下のようにして求めた。まず、多数のフレーク状ガラスを走査型電子顕微鏡で観察し、観察した像のうち、撮影された面に対してフレーク状ガラスの平面がほぼ垂直に立っているものを特定し、必要に応じて高倍率で観察して、そのフレークの2つの平面の間の距離(平面に対しほぼ垂直な方向の長さ)を測定した。そして、2つの平面間の距離の測定値を、そのフレーク状ガラスの厚さとした。20個のフレーク状ガラスの厚さを測定し、その算術平均を平均厚さとした。なお、走査型電子顕微鏡には、日本電子株式会社製のJSM−T330Aを用い、長さの測定には、日本電子株式会社製のミクロンリーダーMCRを用いた。平均粒径とは、レーザー回折式粒度分布測定装置(マイクロトラックII、日機装製)を用いて測定したフレーク状ガラスの粒径の50%粒径D50である。平均アスペクト比とは、その平均粒径を、平均厚みで除した値である。 The flaky glass (A) has an average thickness in the range of 0.1 to 3 μm, an average particle diameter in the range of 1 to 300 μm, and an average aspect ratio in the range of 5 to 300. Here, the average thickness was determined as follows. First, observe a large number of flake glasses with a scanning electron microscope, and identify the images in which the plane of the flake glasses stands almost perpendicular to the imaged surface. Observed at high magnification, the distance between the two planes of the flakes (the length in a direction substantially perpendicular to the plane) was measured. And the measured value of the distance between two planes was made into the thickness of the flaky glass. The thickness of 20 pieces of flaky glass was measured, and the arithmetic average was defined as the average thickness. JSM-T330A manufactured by JEOL Ltd. was used for the scanning electron microscope, and a micron reader MCR manufactured by JEOL Ltd. was used for the length measurement. The average particle diameter is a 50% particle diameter D50 of the particle diameter of the flaky glass measured using a laser diffraction particle size distribution analyzer (Microtrack II, manufactured by Nikkiso). The average aspect ratio is a value obtained by dividing the average particle diameter by the average thickness.
フレーク状ガラスの平均厚さが0.1μm未満であると、製造が困難で、かつ、破砕され易いなどの問題が生じる。一方、平均厚さが3μmを超えると、ごろつき感など、化粧料の使用感が劣化する。フレーク状ガラスの平均粒径が1μm未満であると、フレーク状ガラスが凝集し易いため、むらとなりやすい。一方、平均粒径が300μmを超えると、フィラーとして配合する際にフレーク状ガラスが破砕され易く、また化粧料に配合した場合には、ごろつき感が生じるなどその使用感が劣化する。フレーク状ガラスの平均アスペクト比が5未満であると、球状粒子としての特徴が表れ始め、凝集を起こし易くなる。一方、平均アスペクト比が300を超えると、フィラーとして配合する際に破砕されて、粒径が不均一になり、むらが生じやすい。 If the average thickness of the flaky glass is less than 0.1 μm, problems such as difficulty in production and easy crushing occur. On the other hand, when the average thickness is more than 3 μm, the feeling of use of the cosmetics such as a feeling of looseness is deteriorated. If the average particle size of the flaky glass is less than 1 μm, the flaky glass is likely to be aggregated, which tends to cause unevenness. On the other hand, when the average particle size exceeds 300 μm, the flaky glass is easily crushed when blended as a filler, and when blended with a cosmetic, the feeling of use is deteriorated, for example, a feeling of slack is generated. When the average aspect ratio of the flaky glass is less than 5, characteristics as spherical particles begin to appear, and aggregation tends to occur. On the other hand, if the average aspect ratio exceeds 300, it is crushed when blended as a filler, the particle size becomes non-uniform, and unevenness tends to occur.
好ましくは、フレーク状ガラス(A)は、平均厚さが0.2〜2.5μmの範囲にあり、平均粒径が8〜300μmの範囲にあり、平均アスペクト比が8〜200の範囲にある。より好ましくは、フレーク状ガラス(A)は、平均厚さが0.5〜2.0μmの範囲にあり、平均粒径が8〜50μmの範囲にあり、平均アスペクト比が8〜50の範囲にある。 Preferably, the flaky glass (A) has an average thickness in the range of 0.2 to 2.5 μm, an average particle diameter in the range of 8 to 300 μm, and an average aspect ratio in the range of 8 to 200. . More preferably, the flaky glass (A) has an average thickness in the range of 0.5 to 2.0 μm, an average particle diameter in the range of 8 to 50 μm, and an average aspect ratio in the range of 8 to 50. is there.
フレーク状ガラス(A)に含まれる着色成分(たとえば群青)の含有率は、通常、5〜60質量%(以下、含有量に関して単に「%」と記載している場合は、「質量%」を意味する)の範囲にあることが好ましく、10〜50%の範囲にあることがより好ましい。着色成分の含有率が5%以下であると、色が薄く着色力が弱い。着色成分の含有率が60%以上であると、着色成分がフレーク状ガラスから露出したりフレーク状ガラス中で凝集したりし、くすみや感触に対する本発明の効果が少なくなる。 The content of the coloring component (for example, ultramarine) contained in the flaky glass (A) is usually 5 to 60% by mass (hereinafter referred to as “%” when the content is simply described as “%”). It is preferably in the range of 10 to 50%. When the content of the coloring component is 5% or less, the color is thin and the coloring power is weak. When the content of the coloring component is 60% or more, the coloring component is exposed from the flaky glass or aggregated in the flaky glass, and the effect of the present invention on dullness and feel is reduced.
フレーク状ガラス(A)の製造方法は特に限定されない。母材の金属酸化物を作製する方法として、たとえば、金属酸化物コロイド溶液を使用するコロイドプロセスによる方法や、金属アルコキシド等の金属化合物溶液を利用するいわゆるゾルゲル法による方法や、アルカリケイ酸溶液(水ガラスなど)を利用する方法、等を適用できる。たとえば、特開平1−9803号公報に記載の方法を適用してもよい。たとえば、ゾルゲル法を用いた、特開平1−9803号公報に記載の方法を適用してもよい。この方法では、金属化合物(たとえば金属アルコキシドや金属有機酸塩)の溶液または金属酸化物ゾルに、群青微粒子を分散させて混合液を作製する。この混合液を、基材の平滑な表面に塗布して塗膜を形成し、ついで塗膜を乾燥や反応などの処理によって薄片状とする。そして、平滑面から青色の薄片を剥離させる。このようにして、フレーク状のガラスが形成される。また、コロイドプロセスを用いた、特開2004−026614号公報に記載の方法を適用してもよい。この方法では、上記の金属酸化物ゾルの代わりに、金属酸化物のコロイド溶液が使用される。基材から剥離させた青色の薄片は、200〜800℃で焼成される。この薄片は、必要に応じて粉砕・分級され、任意の平均粒径の薄片とされる。 The manufacturing method of flake shaped glass (A) is not specifically limited. As a method for producing a metal oxide of a base material, for example, a method by a colloid process using a metal oxide colloid solution, a method by a so-called sol-gel method using a metal compound solution such as a metal alkoxide, an alkali silicate solution ( A method using water glass or the like can be applied. For example, the method described in JP-A-1-9803 may be applied. For example, a method described in JP-A-1-9803 using a sol-gel method may be applied. In this method, ultramarine fine particles are dispersed in a solution of a metal compound (for example, metal alkoxide or metal organic acid salt) or a metal oxide sol to prepare a mixed solution. This mixed solution is applied to the smooth surface of the substrate to form a coating film, and then the coating film is formed into a flake shape by a treatment such as drying or reaction. Then, the blue flakes are peeled off from the smooth surface. In this way, flaky glass is formed. Moreover, you may apply the method as described in Unexamined-Japanese-Patent No. 2004-026614 using a colloid process. In this method, a colloidal solution of metal oxide is used instead of the above metal oxide sol. The blue flakes peeled from the substrate are fired at 200 to 800 ° C. The flakes are pulverized and classified as necessary to obtain flakes having an arbitrary average particle diameter.
フレーク状ガラス(A)は、表面が疎水化処理されていることが好ましい。疎水化処理によって、フレーク状ガラス(A)の安定性や分散性が良好となる。 The surface of the flaky glass (A) is preferably hydrophobized. By the hydrophobizing treatment, the stability and dispersibility of the flaky glass (A) are improved.
疎水化処理としては公知の方法を用いることができる。例えば、フッ素化合物処理(パーフルオロアルキルリン酸エステル処理やパーフルオロアルキルシラン処理、パーフルオロポリエーテル処理、フルオロシリコーン処理、フッ素化シリコーン樹脂処理が好ましい)、シリコーン処理(メチルハイドロジェンポリシロキサン処理、ジメチルポリシロキサン処理、気相法テトラメチルテトラハイドロジェンシクロテトラシロキサン処理が好ましい)、シリコーン樹脂処理(トリメチルシロキシケイ酸処理が好ましい)、ペンダント処理(気相法シリコーン処理後にアルキル鎖などを付加する方法)、シランカップリング剤処理、チタンカップリング剤処理、シラン処理(アルキルシランやアルキルシラザン処理が好ましい)、親油性油剤処理、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(ステアリン酸やミリスチン酸塩が好ましい)、アミノ酸処理、プラズマ処理、メカノケミカル処理等を適用できる。これらは複数組み合わせてもよい。 A known method can be used as the hydrophobizing treatment. For example, fluorine compound treatment (perfluoroalkyl phosphate treatment, perfluoroalkylsilane treatment, perfluoropolyether treatment, fluorosilicone treatment, fluorinated silicone resin treatment is preferred), silicone treatment (methylhydrogenpolysiloxane treatment, dimethyl) Polysiloxane treatment, vapor phase tetramethyltetrahydrogencyclotetrasiloxane treatment is preferred), silicone resin treatment (trimethylsiloxysilicic acid treatment is preferred), pendant treatment (method of adding alkyl chains after vapor phase silicone treatment) , Silane coupling agent treatment, titanium coupling agent treatment, silane treatment (alkyl silane or alkylsilazane treatment is preferred), lipophilic oil agent treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal Soap treatment (stearic acid or myristic acid salts are preferred), an amino acid treatment, plasma treatment, can be applied mechanochemical treatment. A plurality of these may be combined.
特に、Nε−ラウロイル−L−リジン(味の素社製アミホープLL)などを用いたN−アシル化リジン処理や、オクチルトリアルコキシシランなどを用いたアルキルシラン処理などが好ましい。疎水化処理剤の量は、粉末100質量部に対し、0.5〜15質量部の範囲にあることが好ましい。また、シリコーン処理も好ましく、例えば、メチルハイドロジェンポリシロキサン(例:信越化学工業製KF99P)や、ジメチル基含有メチルハイドロジェンポリシロキサン(例:信越化学工業製KF9901、HRS−2)、環状メチルハイドロジェンポリシロキサン(例:信越化学工業製KF9902)による処理、およびその焼き付け処理を用いてもよい。 In particular, N-acylated lysine treatment using Nε-lauroyl-L-lysine (Ajinomoto AMIHOPE LL) or alkyl silane treatment using octyltrialkoxysilane or the like is preferable. The amount of the hydrophobizing agent is preferably in the range of 0.5 to 15 parts by mass with respect to 100 parts by mass of the powder. Silicone treatment is also preferable. For example, methyl hydrogen polysiloxane (eg, KF99P manufactured by Shin-Etsu Chemical), dimethyl group-containing methyl hydrogen polysiloxane (eg: KF 9901, HRS-2 manufactured by Shin-Etsu Chemical), cyclic methyl hydro A treatment with Genpolysiloxane (for example, KF9902 manufactured by Shin-Etsu Chemical Co., Ltd.) and its baking treatment may be used.
さらに、疎水化表面処理に先立って、シリカやアルミナ、ジルコニアといった無機酸化物によって粉体の表面を処理することも好ましい。 Furthermore, it is also preferable to treat the surface of the powder with an inorganic oxide such as silica, alumina or zirconia prior to the hydrophobizing surface treatment.
本発明に用いられる皮膜形成剤は、塗布することにより湿潤膜を形成し、その湿潤膜から溶剤が蒸発することにより硬化し、被膜を形成する物質である限り、特に限定されるものではない。皮膜形成剤は、化粧料に用いられるものであれば広く用いることができ、目的とする剤形にあわせ適宜選択することができる。例えば、アルギン酸塩、デオキシリボ核酸、微生物産生ポリマー、寒天、アラビアゴム、カゼイン、デキストリン、ペクチン、キサンタンガム、アルギン酸ナトリウム、α型澱粉、メチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース等のセルロース誘導体、ケラチン及びコラーゲンまたはその誘導体等の天然皮膜形成剤を用いることができる。また、ポリビニルアルコール、ポリビニルピロリドン、ポリアクリル酸、カルボキシビニルポリマー等のビニル系樹脂を用いることができる。また、塩化ビニリデン樹脂、アクリル系樹脂、スチレン−ブタジエンゴム、ニトリルゴム等の合成皮膜形成剤を挙げることができる。これらは、2種以上を組み合わせて用いてもよい。 The film-forming agent used in the present invention is not particularly limited as long as it is a substance that forms a wet film by coating and is cured by evaporation of the solvent from the wet film to form a film. The film forming agent can be widely used as long as it is used in cosmetics, and can be appropriately selected according to the intended dosage form. For example, alginate, deoxyribonucleic acid, microbial polymer, agar, gum arabic, casein, dextrin, pectin, xanthan gum, sodium alginate, alpha starch, cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, keratin and collagen or derivatives thereof Natural film forming agents such as these can be used. Further, vinyl resins such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, and carboxyvinyl polymer can be used. In addition, synthetic film forming agents such as vinylidene chloride resin, acrylic resin, styrene-butadiene rubber, and nitrile rubber can be exemplified. You may use these in combination of 2 or more type.
本発明の化粧料における皮膜形成剤の含有率は、0.1〜30%の範囲にある。含有率が0.1%未満であると、なめらかな塗布感が得られず、安定性の面からも好ましくない。 The content rate of the film formation agent in the cosmetics of this invention exists in the range of 0.1 to 30%. When the content is less than 0.1%, a smooth coating feeling cannot be obtained, which is not preferable from the viewpoint of stability.
皮膜形成剤であるビニル系樹脂としては、例えば、エイコセン,塩化ビニル,酢酸ビニル,スチレン,ネオデカン酸ビニル,ビニルアセタールジエチルアミノアセテート,ビニルアルコール,ビニルピロリドン,ビニルブチラール,ブタジエン,及びヘキサデセン等の1種以上の単量体から得られる重合体が挙げられる。具体的には、ポリ塩化ビニル、ポリ酢酸ビニル、ポリスチレン、ポリビニルアルコール、ポリビニルブチラール、ポリビニルアセタールジエチルアミノアセテート、エイコセン・ビニルピロリドン共重合体、スチレン・ビニルピロリドン共重合体、ビニルピロリドン・ヘキサデセン共重合体、酢酸ビニル・ビニルピロリドン共重合体等が挙げられる。 Examples of the vinyl resin that is a film forming agent include one or more of eicosene, vinyl chloride, vinyl acetate, styrene, vinyl neodecanoate, vinyl acetal diethylaminoacetate, vinyl alcohol, vinyl pyrrolidone, vinyl butyral, butadiene, and hexadecene. And a polymer obtained from the above monomer. Specifically, polyvinyl chloride, polyvinyl acetate, polystyrene, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal diethylaminoacetate, eicosene / vinyl pyrrolidone copolymer, styrene / vinyl pyrrolidone copolymer, vinyl pyrrolidone / hexadecene copolymer, And vinyl acetate / vinyl pyrrolidone copolymer.
皮膜形成剤であるアクリル系樹脂としては、例えば,アクリル酸とその誘導体,メタクリル酸とその誘導体,クロトン酸とその誘導体,アクリルアミド,アクリルアルキルアミド,アクリロニトリル,ジアセトンアクリルアミド,及びメタクリルアミドのグループから選ばれる1種以上の単量体から得られる重合体等が挙げられる。具体的には、ポリアクリル酸、ポリメタクリル酸アルキル、ポリアクリル酸アミド、アクリル酸アルキル共重合体、ポリメタクリル酸、ポリアクリル酸アルキル、アクリル酸アルキル・メタクリル酸アルキル共重合体、アクリル酸エチル・メタクリル酸メチル・メタクリル酸塩化トリメチルアンモニウムエチル共重合体、アクリル酸オクチルアミド・アクリル酸・アクリル酸アルキル共重合体、アクリル酸オクチルアミド・メタクリル酸・メタクリル酸アルキル共重合体、アクリル酸オクチルアミド・アクリル酸2−ヒドロキシプロピル・メタクリル酸ブチルアミノエチル共重合体、アクリル酸2−ヒドロキシエチル・アクリル酸2−メトキシエチル共重合体、アクリル酸・アクリル酸アミド・アクリル酸エチル共重合体、アクリル酸アルキル・メタクリル酸アルキル・ジアセトンアクリルアミド・メタクリル酸共重合体、アクリル酸ブチル・メタクリル酸2−ヒドロキシエチル共重合体、メタクリル酸・メタクリル酸アルキル共重合体、メタクリル酸アルキル共重合体、メタクロイルエチルジメチルベタイン・塩化メタクリロイルエチルトリメチルアンモニウム・メタクリル酸2−ヒドロキシエチル共重合体、メタクロイルエチルジメチルベタイン・塩化メタクリロイルエチルトリメチルアンモニウム・メタクリル酸メトキシポリエチレングリコール共重合体、N−メタクロイルオキシエチルN,N−ジメチルアンモニウムα−N酢酸ベタイン・メタクリル酸アルキル共重合体等を挙げることができる。 Examples of the acrylic resin that is a film forming agent are selected from the group consisting of acrylic acid and its derivatives, methacrylic acid and its derivatives, crotonic acid and its derivatives, acrylamide, acrylic alkylamide, acrylonitrile, diacetone acrylamide, and methacrylamide. And polymers obtained from one or more monomers. Specifically, polyacrylic acid, polyalkyl methacrylate, polyacrylic amide, alkyl acrylate copolymer, polymethacrylic acid, polyalkyl acrylate, alkyl acrylate / alkyl methacrylate copolymer, ethyl acrylate / Methyl methacrylate / methacrylic acid trimethylammonium ethyl copolymer, acrylic acid octylamide / acrylic acid / alkyl acrylate copolymer, acrylic acid octylamide / methacrylic acid / alkyl methacrylate copolymer, acrylic acid octylamide / acrylic 2-hydroxypropyl / butylaminoethyl methacrylate copolymer, 2-hydroxyethyl acrylate / 2-methoxyethyl acrylate copolymer, acrylic acid / acrylic acid amide / ethyl acrylate copolymer, alkyl acrylate Alkyl methacrylate / diacetone acrylamide / methacrylic acid copolymer, butyl acrylate / methacrylic acid 2-hydroxyethyl copolymer, methacrylic acid / alkyl methacrylate copolymer, alkyl methacrylate copolymer, methacryloylethyldimethyl Betaine / methacryloylethyltrimethylammonium chloride / 2-hydroxyethyl methacrylate copolymer, methacryloylethyldimethylbetaine / methacryloylethyltrimethylammonium chloride / methoxypolyethylene glycol methacrylate copolymer, N-methacryloyloxyethyl N, N-dimethyl Examples thereof include ammonium α-N betaine acetate / alkyl methacrylate copolymer.
皮膜形成剤であるアクリル系・ビニル系樹脂としては、例えば、アクリル酸アルキル・酢酸ビニル共重合体、アクリル酸アルキル・スチレン共重合体、アクリル酸ブチル・アクリロニトリル・スチレン共重合体、塩化ジメチルジアリルアンモニウム・アクリルアミド共重合体、クロトン酸・酢酸ビニル・ネオデカン酸ビニル共重合体、酢酸ビニル・クロトン酸共重合体、ビニルピロリドン・N,N−ジメチルアミノエチルメタクリル酸共重合体ジエチル硫酸塩、ブタジエン・アクリロニトリル共重合体、メタクリル酸アミド・スチレン共重合体、メタクリル酸アルキル・酢酸ビニル共重合体、メタクリル酸アルキル・スチレン共重合体等を挙げることができる。 Examples of acrylic / vinyl resins that are film forming agents include alkyl acrylate / vinyl acetate copolymers, alkyl acrylate / styrene copolymers, butyl acrylate / acrylonitrile / styrene copolymers, and dimethyldiallylammonium chloride. Acrylamide copolymer, Crotonic acid / vinyl acetate / Neodecanoic acid vinyl copolymer, Vinyl acetate / crotonic acid copolymer, Vinylpyrrolidone / N, N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate, butadiene / acrylonitrile Examples thereof include a copolymer, a methacrylamide / styrene copolymer, an alkyl methacrylate / vinyl acetate copolymer, and an alkyl methacrylate / styrene copolymer.
より具体的には、例えば、アクリル酸エチル・メタクリル酸エチル共重合体エマルジョン、アクリル酸エチル・メタクリル酸共重合体エマルジョン、アクリル酸エチル・メタクリル酸メチル共重合体エマルジョン、アクリル酸オクチル・酢酸ビニル共重合体エマルジョン、アクリル酸オクチル・スチレン共重合体エマルジョン、アクリル酸スチレン・メタクリル酸アンモニウム共重合体エマルジョン、ポリアクリル酸エチルエマルジョン、ポリメタクリル酸エチルエマルジョン等を挙げることができる。より具体的には、例えば、アクリル酸エステル/メタクリル酸エステル共重合体(プラスサイズ、互応化学社製)、酢酸ビニル/クロトン酸共重合体(レジン28−1310、NSC社製)、酢酸ビニル/クロトン酸/ビニルネオデカネート共重合体(28−2930、NSC社製)、メチルビニルエーテルマレイン酸ハーフエステル(ガントレッツES、ISP社製)、t−ブチルアクリレート/アクリル酸エチル/メタクリル酸共重合体(ルビマー、BASF社製)、ビニルピロリドン/ビニルアセテート/ビニルプロピオネート共重合体(ルビスコールVAP、BASF社製)、ビニルアセテート/クロトン酸共重合体(ルビセットCA、BASF社製)、ビニルアセテート/クロトン酸/ビニルピロリドン共重合体(ルビセットCAP、BASF社製)、ビニルピロリドン/アクリレート共重合体(ルビフレックス、BASF社製)、アクリレート/アクリルアミド共重合体(ウルトラホールド、BASF社製)、ビニルアセテート/ブチルマレアート/イソボルニルアクリラート共重合体(アドバンテージ、ISP社製)、アルキル変性カルボキシビニルポリマー(PEMULEN、B.F.Goodrich社製)などのアニオン性高分子化合物や、ジアルキルアミノエチルメタクリエート重合体の酢酸両性化物(ユカフォーマー、三菱化学社製)、アクリル酸オクチルアクリルアミド/アクリル酸ヒドロキシプロピル/メタクリル酸ブチルアミノエチル共重合体(AMPHOMER、NSC社製)などの両性高分子化合物や、ビニルピロリドン/ジメチルアミノエチルメタクリレートの4級化物(GAFQUAT、ISP社製)、メチルビニルイミダゾリウムクロリド/ビニルピロリドン共重合体(ルビコート、BASF社製)などのカチオン性高分子化合物や、ポリビニルピロリドン(ルビスコールK、BASF社製)、ビニルピロリドン/酢酸ビニル共重合体(ルビスコールVA、BASF社製)、ビニルピロリドン/ジメチルアミノエチルメタクリレート共重合体(コポリマー937、ISP社製)、ビニルカプロラクタム/ビニルピロリドン/ジメチルアミノエチルメタクレレート共重合体(コポリマーVC713、ISP社製)などのノニオン性高分子化合物などを用いることができる。 More specifically, for example, ethyl acrylate / ethyl methacrylate copolymer emulsion, ethyl acrylate / methacrylic acid copolymer emulsion, ethyl acrylate / methyl methacrylate copolymer emulsion, octyl acrylate / vinyl acetate copolymer. Examples thereof include a polymer emulsion, an octyl acrylate / styrene copolymer emulsion, a styrene acrylate / ammonium methacrylate copolymer emulsion, a polyethyl acrylate emulsion, and a polyethyl methacrylate emulsion. More specifically, for example, acrylic acid ester / methacrylic acid ester copolymer (plus size, manufactured by Kyoyo Chemical), vinyl acetate / crotonic acid copolymer (resin 28-1310, manufactured by NSC), vinyl acetate / Crotonic acid / vinyl neodecanate copolymer (28-2930, manufactured by NSC), methyl vinyl ether maleic acid half ester (Gantrez ES, manufactured by ISP), t-butyl acrylate / ethyl acrylate / methacrylic acid copolymer ( Rubymer, manufactured by BASF), vinylpyrrolidone / vinyl acetate / vinyl propionate copolymer (rubiscol VAP, manufactured by BASF), vinyl acetate / crotonic acid copolymer (ruby set CA, manufactured by BASF), vinyl acetate / Crotonic acid / vinyl pyrrolidone copolymer (Rubiset CA) , BASF), vinylpyrrolidone / acrylate copolymer (Rubiflex, BASF), acrylate / acrylamide copolymer (Ultrahold, BASF), vinyl acetate / butyl maleate / isobornyl acrylate Anionic polymer compounds such as polymers (Advantage, manufactured by ISP), alkyl-modified carboxyvinyl polymers (PEMULEN, manufactured by BF Goodrich), and acetic acid amphoteric compounds of dialkylaminoethyl methacrylate polymers (Yukaformer, Mitsubishi) Chemicals), amphoteric polymer compounds such as octyl acrylate / hydroxypropyl acrylate / butyl aminoethyl methacrylate copolymer (AMPHOMER, NSC), vinylpyrrolidone / dimethylaminoethyl Cationic polymer compounds such as quaternized methacrylate (GAFQUAT, ISP), methyl vinyl imidazolium chloride / vinyl pyrrolidone copolymer (ruby coat, BASF), polyvinyl pyrrolidone (Rubicol K, BASF) ), Vinylpyrrolidone / vinyl acetate copolymer (rubiscol VA, manufactured by BASF), vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer (copolymer 937, manufactured by ISP), vinylcaprolactam / vinylpyrrolidone / dimethylaminoethyl methacrylate Nonionic polymer compounds such as a rate copolymer (copolymer VC713, manufactured by ISP) can be used.
本発明の化粧料は、本発明の効果が得られる限り、上記成分以外の他の成分を含んでもよい。そのような他の成分としては、粉体類、油剤、界面活性剤、粘剤、防腐剤、香料、紫外線吸収剤(紫外線防御成分)、保湿剤、生理塩類、溶媒、酸化防止剤、生理活性成分、キレート剤、中和剤、pH調整剤、昆虫忌避剤等が挙げられる。 The cosmetic of the present invention may contain components other than the above components as long as the effects of the present invention are obtained. Such other components include powders, oils, surfactants, stickers, preservatives, fragrances, UV absorbers (UV protection components), moisturizers, physiological salts, solvents, antioxidants, physiological activities Ingredients, chelating agents, neutralizing agents, pH adjusting agents, insect repellents and the like can be mentioned.
他の成分である顔料としては、通常の化粧料に使用されるものを用いることができ、本発明の効果が得られる限り、その形状(球状、棒状、針状、板状、不定形状、鱗片状、紡錘状等)や粒子径(煙霧状、微粒子、顔料級等)、粒子構造(多孔質、無孔質等)は限定されない。顔料としては、例えば、無機粉体、有機粉体、界面活性剤金属塩粉体、有色顔料、パール顔料、金属粉末顔料、天然色素等が挙げられる。具体的には、無機粉体としては、顔料級酸化チタン、酸化ジルコニウム、顔料級酸化亜鉛、酸化セリウム、酸化マグネシウム、硫酸バリウム、硫酸カルシウム、硫酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、タルク、マイカ、カオリン、セリサイト、白雲母、合成雲母、金雲母、紅雲母、黒雲母、リチア雲母、ケイ酸、無水ケイ酸、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、ケイ酸カルシウム、ケイ酸バリウム、ケイ酸ストロンチウム、タングステン酸金属塩、ヒドロキシアパタイト、バーミキュライト、ハイジライト、ベントナイト、モンモリロナイト、ヘクトライト、ゼオライト、セラミックスパウダー、第二リン酸カルシウム、アルミナ、水酸化アルミニウム、窒化ホウ素、シリカ、微粒子酸化チタン、微粒子酸化亜鉛、微粒子酸化セリウム等が挙げられる。 As other pigments, those used in ordinary cosmetics can be used, and as long as the effects of the present invention are obtained, the shape (spherical, rod-like, needle-like, plate-like, irregular shape, scale piece) Shape, spindle shape, etc.), particle diameter (smoke, fine particles, pigment grade, etc.) and particle structure (porous, nonporous, etc.) are not limited. Examples of the pigment include inorganic powder, organic powder, surfactant metal salt powder, colored pigment, pearl pigment, metal powder pigment, and natural dye. Specifically, as inorganic powder, pigment grade titanium oxide, zirconium oxide, pigment grade zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin Sericite, muscovite, synthetic mica, phlogopite, saucite, biotite, lithia mica, silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, Strontium silicate, metal tungstate, hydroxyapatite, vermiculite, hydrite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, silica, fine Child titanium oxide, zinc oxide particles, fine particles of cerium oxide and the like.
有機粉体としては、ポリアミドパウダー、ポリエステルパウダー、ポリエチレンパウダー、ポリプロピレンパウダー、ポリスチレンパウダー、ポリウレタンパウダー、ベンゾグアナミンパウダー、ポリメチルベンゾグアナミンパウダー、ポリテトラフルオロエチレンパウダー、ポリメチルメタクリレートパウダー、セルロース、シルクパウダー、ナイロンパウダー、12ナイロン、6ナイロン、シリコーンパウダー、シリコーンゴムパウダー、シリコーンエラストマー球状粉体、スチレン・アクリル酸共重合体、ジビニルベンゼン・スチレン共重合体、ビニル樹脂、尿素樹脂、フェノール樹脂、フッ素樹脂、ケイ素樹脂、アクリル樹脂、メラミン樹脂、エポキシ樹脂、ポリカーボネイト樹脂、微結晶繊維粉体、デンプン末、ラウロイルリジン等が挙げられる。 Organic powders include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, polytetrafluoroethylene powder, polymethylmethacrylate powder, cellulose, silk powder, nylon powder , 12 nylon, 6 nylon, silicone powder, silicone rubber powder, silicone elastomer spherical powder, styrene / acrylic acid copolymer, divinylbenzene / styrene copolymer, vinyl resin, urea resin, phenol resin, fluorine resin, silicon resin , Acrylic resin, melamine resin, epoxy resin, polycarbonate resin, microcrystalline fiber powder, starch powder, lauroyl lysine And the like.
界面活性剤金属塩粉体(金属石鹸)としては、ステアリン酸亜鉛、ステアリン酸アルミニウム、ステアリン酸カルシウム、ステアリン酸マグネシウム、ミリスチン酸亜鉛、ミリスチン酸マグネシウム、セチルリン酸亜鉛、セチルリン酸カルシウム、セチルリン酸亜鉛ナトリウム等が挙げられる。 Surfactant metal salt powder (metal soap) includes zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetyl phosphate, calcium cetyl phosphate, zinc sodium cetyl phosphate, etc. Can be mentioned.
有色顔料としては、酸化鉄、水酸化鉄、チタン酸鉄の無機赤色顔料、γ−酸化鉄等の無機褐色系顔料、黄酸化鉄、黄土等の無機黄色系顔料、黒酸化鉄、カーボンブラック等の無機黒色顔料、マンガンバイオレット、コバルトバイオレット等の無機紫色顔料、水酸化クロム、酸化クロム、酸化コバルト、チタン酸コバルト等の無機緑色顔料、紺青等の無機青色系顔料、タール系色素をレーキ化したもの、天然色素をレーキ化したもの、及びこれらの粉体を複合化した合成樹脂粉体等が挙げられる。 As colored pigments, inorganic red pigments such as iron oxide, iron hydroxide and iron titanate, inorganic brown pigments such as γ-iron oxide, inorganic yellow pigments such as yellow iron oxide and loess, black iron oxide, carbon black, etc. Raked inorganic black pigments, inorganic purple pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate, inorganic blue pigments such as bitumen, and tar dyes And those obtained by lacquering natural pigments and synthetic resin powders obtained by combining these powders.
パール顔料としては、酸化チタン被覆雲母、酸化チタン被覆マイカ、オキシ塩化ビスマス、酸化チタン被覆オキシ塩化ビスマス、酸化チタン被覆タルク、魚鱗箔、酸化チタン被覆着色雲母等、特に干渉色を有する雲母チタン、酸化チタン被覆ガラス末、酸化チタン被覆合成金雲母等を用いるのが好適である。干渉色を有する雲母チタンの市販品の例としては、「Timiron Super Gold」や「Timiron Super Red」(以上、メルク社製)、「Flamenco Sparkle Blue」や「Flamenco Green」(以上、エンゲルハード社製)等を挙げることができる。酸化チタン被覆ガラス末の市販品の例としては、メタシャイン(登録商標)MC1080RB、メタシャイン(登録商標)MC1020RY、メタシャイン(登録商標)MC1080RRSI(以上、日本板硝子株式会社製)等を挙げることができる。酸化チタン被覆合成金雲母の市販品の例としては、プロミネンスBH、プロミネンスYB、プロミネンスRBX(以上、トピー工業社製)等を挙げることができる。また、干渉色を有する真珠光沢顔料である、「Xirona Magic Mauve」や「Xirona Caribbean Blue」(以上、メルク社製)、「Sicopearl Fantastico Pink」や「Sicopearl Fantastico Ruby」(以上、BASF社製)等も好適に用いられる。 Examples of pearl pigments include titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scale foil, and titanium oxide-coated colored mica. It is preferable to use titanium-coated glass powder, titanium oxide-coated synthetic phlogopite, and the like. Examples of commercially available products of titanium mica having an interference color include “Timiron Super Gold”, “Timiron Super Red” (Merck), “Flamenco Sparkle Blue” and “Flamenco Green” (hereinafter Engelhard) And the like. Examples of commercially available titanium oxide-coated glass powders include Metashine (registered trademark) MC1080RB, Metashine (registered trademark) MC1020RY, Metashine (registered trademark) MC1080RRSI (manufactured by Nippon Sheet Glass Co., Ltd.), and the like. it can. Examples of commercially available titanium oxide-coated synthetic phlogopite include Prominence BH, Prominence YB, Prominence RBX (manufactured by Topy Industries, Ltd.), and the like. Further, pearlescent pigments having interference colors, such as “Xirona Magic Mauve” and “Xirona Caribbean Blue” (manufactured by Merck Ltd.), “Sicopearl Fantastico Pink”, “Sicoparant Fantastico RubyF”, Are also preferably used.
タール色素としては、赤色3号、赤色104号、赤色106号、赤色201号、赤色202号、赤色204号、赤色205号、赤色220号、赤色226号、赤色227号、赤色228号、赤色230号、赤色401号、赤色505号、黄色4号、黄色5号、黄色202号、黄色203号、黄色204号、黄色401号、青色1号、青色2号、青色201号、青色404号、緑色3号、緑色201号、緑色204号、緑色205号、橙色201号、橙色203号、橙色204号、橙色206号、橙色207号等が挙げられる。天然色素としては、カルミン酸、ラッカイン酸、カルサミン、ブラジリン、クロシン等から選ばれる粉体が挙げられる。これらの粉体も、上記と同様に、本発明の効果を妨げない範囲で、粉体の複合化を行ったり、一般油剤、シリコーン油、フッ素化合物、界面活性剤等で処理したりしたものを使用してもよい。 As tar pigments, Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red 230, Red 401, Red 505, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Yellow 204, Yellow 401, Blue 1, Blue 2, Blue 201, Blue 404 , Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207 and the like. Examples of natural pigments include powders selected from carminic acid, laccaic acid, calsamine, bradylin, crocin and the like. In the same manner as described above, these powders may be combined with powders or treated with general oils, silicone oils, fluorine compounds, surfactants, etc., as long as the effects of the present invention are not impaired. May be used.
粉体類としては、感触の調整能力が高いという点で、球状粉末やシリコーンエラストマーが好ましい。特に、粒度の異なる粉体類を混合して使用することが好ましい。また、吸水性や吸油性を有する粉体を用いることによって、化粧持ちを改善できる。 As the powders, spherical powders and silicone elastomers are preferable from the viewpoint of high touch adjusting ability. In particular, it is preferable to use a mixture of powders having different particle sizes. Further, the use of a powder having water absorbency or oil absorbency can improve the longevity of the makeup.
油剤としては、例えば、アボガド油、アマニ油、アーモンド油、イボタロウ、エノ油、オリーブ油、カカオ脂、カポックロウ、カヤ油、カルナウバロウ、肝油、キャンデリラロウ、牛脂、牛脚脂、牛骨脂、硬化牛脂、キョウニン油、鯨ロウ、硬化油、小麦胚芽油、ゴマ油、コメ胚芽油、コメヌカ油、サトウキビロウ、サザンカ油、サフラワー油、シアバター、シナギリ油、シナモン油、ジョジョバロウ、セラックロウ、タートル油、大豆油、茶実油、ツバキ油、月見草油、トウモロコシ油、豚脂、ナタネ油、日本キリ油、ヌカロウ、胚芽油、馬脂、パーシック油、パーム油、パーム核油、ヒマシ油、硬化ヒマシ油、ヒマシ油脂肪酸メチルエステル、ヒマワリ油、ブドウ油、ベイベリーロウ、ホホバ油、マカデミアナッツ油、ミツロウ、ミンク油、綿実油、綿ロウ、モクロウ、モクロウ核油、モンタンロウ、ヤシ油、硬化ヤシ油、トリヤシ油脂肪酸グリセライド、羊脂、落花生油、ラノリン、液状ラノリン、還元ラノリン、ラノリンアルコール、硬質ラノリン、酢酸ラノリン、ラノリン脂肪酸イソプロピル、ラウリン酸ヘキシル、POEラノリンアルコールエーテル、POEラノリンアルコールアセテート、ラノリン脂肪酸ポリエチレングリコール、POE水素添加ラノリンアルコールエーテル、卵黄油等が挙げられる。 Oils include, for example, avocado oil, linseed oil, almond oil, ibotarou, eno oil, olive oil, cacao butter, kapok wax, kayak oil, carnauba wax, liver oil, candelilla wax, beef tallow, bovine tallow, beef bone fat, and cured beef tallow , Kyounin oil, whale wax, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugar cane wax, sasanqua oil, safflower oil, shea butter, cinnamon oil, cinnamon oil, jojo barr, shellac wax, turtle oil, Soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard, rapeseed oil, Japanese kiri oil, nukarou, germ oil, horse fat, persic oil, palm oil, palm kernel oil, castor oil, hydrogenated castor oil , Castor oil fatty acid methyl ester, sunflower oil, grape oil, bayberry wax, jojoba oil, macadamia nut oil, beeswax, mink , Cottonseed oil, cotton wax, owl, owl kernel oil, montan wax, coconut oil, hydrogenated coconut oil, tricoconut oil fatty acid glyceride, sheep oil, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, lanolin Examples include fatty acid isopropyl, hexyl laurate, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, and egg yolk oil.
また、配合可能な炭化水素油としては、オゾケライト、スクワラン、スクワレン、セレシン、パラフィン、パラフィンワックス、流動パラフィン、プリスタン、ポリイソブチレン、マイクロクリスタリンワックス、ワセリン等が挙げられる。高級脂肪酸としては、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、ウンデシレン酸、オレイン酸、リノール酸、リノレン酸、アラキドン酸、エイコサペンタエン酸(EPA)、ドコサヘキサエン酸(DHA)、イソステアリン酸、12−ヒドロキシステアリン酸等が挙げられる。高級アルコールとしては、ラウリルアルコール、ミリスチルアルコール、パルミチルアルコール、ステアリルアルコール、ベヘニルアルコール、ヘキサデシルアルコール、オレイルアルコール、イソステアリルアルコール、ヘキシルドデカノール、オクチルドデカノール、セトステアリルアルコール、2−デシルテトラデシノール、コレステロール、フィトステロール、POEコレステロールエーテル、モノステアリルグリセリンエーテル(バチルアルコール)、モノオレイルグリセリルエーテル(セラキルアルコール)等が挙げられる。エステル油としては、アジピン酸ジイソブチル、アジピン酸2−ヘキシルデシル、アジピン酸ジ−2−ヘプチルウンデシル、イソノナン酸イソノニル、モノイソステアリン酸N−アルキルグリコール、イソステアリン酸イソセチル、トリイソステアリン酸トリメチロールプロパン、ジ−2−エチルヘキサン酸エチレングリコール、2−エチルヘキサン酸セチル、トリ−2−エチルヘキサン酸トリメチロールプロパン、テトラ−2−エチルヘキサン酸ペンタエリスリトール、オクタン酸セチル、オクチルドデシルガムエステル、オレイン酸オレイル、オレイン酸オクチルドデシル、オレイン酸デシル、ジカプリン酸ネオペンチルグリコール、クエン酸トリエチル、コハク酸2−エチルヘキシル、酢酸アミル、酢酸エチル、酢酸ブチル、ステアリン酸イソセチル、ステアリン酸ブチル、セバシン酸ジイソプロピル、セバシン酸ジ−2−エチルヘキシル、乳酸セチル、乳酸ミリスチル、パルミチン酸イソプロピル、パルミチン酸2−エチルヘキシル、パルミチン酸2−ヘキシルデシル、パルミチン酸2−ヘプチルウンデシル、12−ヒドロキシステアリル酸コレステリル、ジペンタエリスリトール脂肪酸エステル、ミリスチン酸イソプロピル、ミリスチン酸オクチルドデシル、ミリスチン酸2−ヘキシルデシル、ミリスチン酸ミリスチル、ジメチルオクタン酸ヘキシルデシル、ラウリン酸エチル、ラウリン酸ヘキシル、N−ラウロイル−L−グルタミン酸−2−オクチルドデシルエステル、リンゴ酸ジイソステアリル等が挙げられる。グリセライド油としては、アセトグリセリル、トリイソオクタン酸グリセリル、トリ(カプリル・カプリン酸)グリセリン、トリイソステアリン酸グリセリル、トリイソパルミチン酸グリセリル、モノステアリン酸グリセリル、ジ−2−ヘプチルウンデカン酸グリセリル、トリミリスチン酸グリセリル、ミリスチン酸イソステアリン酸ジグリセリル、ダイマージリノール酸ジ(フィトステリル・イソステアリル・セチル・ステアリル・ベヘニル)等が挙げられる。 Examples of the hydrocarbon oil that can be blended include ozokerite, squalane, squalene, ceresin, paraffin, paraffin wax, liquid paraffin, pristane, polyisobutylene, microcrystalline wax, petrolatum and the like. As higher fatty acids, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid , 12-hydroxystearic acid and the like. As higher alcohols, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyl decanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, Examples include cholesterol, phytosterol, POE cholesterol ether, monostearyl glycerin ether (batyl alcohol), monooleyl glyceryl ether (ceracyl alcohol), and the like. The ester oils include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, isononyl isononanoate, N-alkyl glycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, di 2-ethylhexanoic acid ethylene glycol, 2-ethylhexanoic acid cetyl, tri-2-ethylhexanoic acid trimethylolpropane, tetra-2-ethylhexanoic acid pentaerythritol, octyl octoate, octyldodecyl gum ester, oleyl oleate, Octyldodecyl oleate, decyl oleate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, stearyl Isocetyl acid, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptyl undecyl palmitate, Cholesteryl 12-hydroxystearyl, dipentaerythritol fatty acid ester, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, N-lauroyl -L-glutamic acid-2-octyldodecyl ester, diisostearyl malate and the like. Examples of glyceride oils include acetoglyceryl, glyceryl triisooctanoate, glyceryl tri (capryl / capric acid), glyceryl triisostearate, glyceryl triisopalmitate, glyceryl monostearate, glyceryl di-2-heptylundecanoate, and trimyristic acid Examples thereof include glyceryl, diglyceryl myristate, diglyceryl dimerdilinoleate (phytosteryl, isostearyl, cetyl, stearyl, and behenyl).
また、別の形態の油剤としては、例えば、ジメチルポリシロキサン、メチルハイドロジェンポリシロキサン、メチルフェニルポリシロキサン、アルキル変性オルガノポリシロキサン、末端変性オルガノポリシロキサン、フッ素変性オルガノポリシロキサン、アミノ変性オルガノポリシロキサン、ポリエーテル変性シリコーン、パーフルオロアルキル・ポリオキシアルキレン共変性オルガノポリシロキサン、アクリル変性シリコーン、グリセリル変性シリコーン、ポリグリセリル変性シリコーン、糖変性シリコーン、シリコーンゲル、シリコーンRTVゴム等のシリコーン化合物、パーフルオロポリエーテル、フッ化ピッチ、フルオロカーボン、フルオロアルコール等のフッ素化合物が挙げられる。 Other forms of oil include, for example, dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, alkyl-modified organopolysiloxane, terminal-modified organopolysiloxane, fluorine-modified organopolysiloxane, amino-modified organopolysiloxane. , Polyether-modified silicone, perfluoroalkyl / polyoxyalkylene co-modified organopolysiloxane, acrylic-modified silicone, glyceryl-modified silicone, polyglyceryl-modified silicone, sugar-modified silicone, silicone gel, silicone RTV rubber and other silicone compounds, perfluoropolyether , Fluorine compounds such as fluorinated pitch, fluorocarbon, and fluoroalcohol.
紫外線防御成分としては、無機系と有機系の紫外線防御剤が挙げられる。無機系の例としては、一部顔料と重複するが、例えば、二酸化チタン、低次酸化チタン、酸化亜鉛、酸化セリウムなどの金属酸化物;水酸化鉄などの金属水酸化物;板状酸化鉄、アルミニウムフレークなどの金属フレーク類;炭化珪素などのセラミック類が挙げられる。このうち、金属酸化物微粒子および金属水酸化物微粒子から選ばれる少なくとも1種の微粒子であって、平均粒径が5〜100nmの範囲にある微粒子が特に好ましい。これらの微粒子は、公知の表面処理、例えばフッ素化合物処理(パーフルオロアルキルリン酸エステル処理やパーフルオロアルキルシラン処理、パーフルオロポリエーテル処理、フルオロシリコーン処理、フッ素化シリコーン樹脂処理が好ましい)、シリコーン処理(メチルハイドロジェンポリシロキサン処理、ジメチルポリシロキサン処理、気相法テトラメチルテトラハイドロジェンシクロテトラシロキサン処理が好ましい)、シリコーン樹脂処理(トリメチルシロキシケイ酸処理が好ましい)、ペンダント処理(気相法シリコーン処理後にアルキル鎖などを付加する方法)、シランカップリング剤処理、チタンカップリング剤処理、シラン処理(アルキルシランやアルキルシラザン処理が好ましい)、油剤処理、ポリアクリル酸処理、金属石鹸処理(ステアリン酸やミリスチン酸塩が好ましい)、アクリル樹脂処理、金属酸化物処理といった処理によって表面が処理されていることが好ましい。これらの処理を複数組み合わせて用いることも好ましい。例えば、酸化チタン微粒子の表面を酸化ケイ素やアルミナなどの金属酸化物で被覆した後、アルキルシランで表面処理することなどが挙げられる。表面処理剤の量は合計で、粉体100質量部に対し、0.1〜50質量部の範囲にあることが好ましい。 Examples of the UV protection component include inorganic and organic UV protection agents. Examples of inorganic materials partially overlap with pigments. For example, metal oxides such as titanium dioxide, low-order titanium oxide, zinc oxide and cerium oxide; metal hydroxides such as iron hydroxide; plate-like iron oxide And metal flakes such as aluminum flakes; ceramics such as silicon carbide. Among these, at least one kind of fine particles selected from metal oxide fine particles and metal hydroxide fine particles and having an average particle size in the range of 5 to 100 nm is particularly preferable. These fine particles are treated with known surface treatments such as fluorine compound treatment (perfluoroalkyl phosphate treatment, perfluoroalkylsilane treatment, perfluoropolyether treatment, fluorosilicone treatment, fluorinated silicone resin treatment), silicone treatment. (Methylhydrogenpolysiloxane treatment, dimethylpolysiloxane treatment, vapor phase tetramethyltetrahydrogencyclotetrasiloxane treatment is preferred), silicone resin treatment (trimethylsiloxysilicate treatment is preferred), pendant treatment (vapor phase silicone treatment) Method of adding alkyl chain later), silane coupling agent treatment, titanium coupling agent treatment, silane treatment (alkyl silane or alkylsilazane treatment is preferred), oil agent treatment, polyacrylic acid treatment, gold Soap treatment (stearic acid or myristic acid salts are preferred), acrylic resin treatment, it is preferable that is surface-treated by processes such metal oxide treatment. It is also preferable to use a combination of these treatments. For example, the surface of titanium oxide fine particles may be coated with a metal oxide such as silicon oxide or alumina and then surface treated with alkylsilane. The total amount of the surface treatment agent is preferably in the range of 0.1 to 50 parts by mass with respect to 100 parts by mass of the powder.
また、有機系紫外線防御剤としては、例えば、パラメトキシケイ皮酸2−エチルヘキシル(別名;パラメトキシケイ皮酸オクチル)、2−ヒドロキシ−4−メトキシベンゾフェノン、2−ヒドロキシ−4−メトキシベンゾフェノン−5−硫酸、2,2’−ジヒドロキシ−4−メトキシベンゾフェノン、p−メトキシハイドロケイ皮酸ジエタノールアミン塩、パラアミノ安息香酸(以後、PABAと略す)、エチルジヒドロキシプロピルPABA、グリセリルPABA、サリチル酸ホモメンチル、メチル−O−アミノベンゾエート、2−エチルヘキシル−2−シアノ−3,3−ジフェニルアクリレート、オクチルジメチルPABA、サリチル酸オクチル、2−フェニル−ベンズイミダゾール−5−硫酸、サリチル酸トリエタノールアミン、3−(4−メチルベンジリデン)カンフル、2,4−ジヒドロキシベンゾフェニン、2,2’,4,4’−テトラヒドロキシベンゾフェノン、2,2’−ジヒドロキシ−4,4’−ジメトキシベンゾフェノン、2−ヒドロキシ−4−N−オクトキシベンゾフェノン、4−イソプロピルジベンゾイルメタン、ブチルメトキシジベンゾイルメタン、オクチルトリアゾン、4−(3,4−ジメトキシフェニルメチレン)−2,5−ジオキソ−1−イミダゾリジンプロピオン酸2−エチルヘキシル、およびこれらの高分子誘導体、およびこれらのシラン誘導体等が挙げられる。 Examples of the organic ultraviolet protective agent include 2-methoxyhexyl paramethoxycinnamate (also known as octyl paramethoxycinnamate), 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5. -Sulfuric acid, 2,2'-dihydroxy-4-methoxybenzophenone, p-methoxyhydrocinnamic acid diethanolamine salt, paraaminobenzoic acid (hereinafter abbreviated as PABA), ethyldihydroxypropyl PABA, glyceryl PABA, homomenthyl salicylate, methyl-O -Aminobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, octyldimethyl PABA, octyl salicylate, 2-phenyl-benzimidazole-5-sulfate, triethanolamine salicylate, 3- 4-methylbenzylidene) camphor, 2,4-dihydroxybenzophenine, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4 -N-octoxybenzophenone, 4-isopropyldibenzoylmethane, butylmethoxydibenzoylmethane, octyltriazone, 4- (3,4-dimethoxyphenylmethylene) -2,5-dioxo-1-imidazolidinepropionic acid 2- Examples thereof include ethylhexyl, polymer derivatives thereof, and silane derivatives thereof.
また、有機系紫外線防御剤として、ポリマー粉末中に封止された有機系紫外線防御剤を用いることも可能である。ポリマー粉末は中空であってもよいし、中空でなくてもよい。ポリマー粉末の平均一次粒子径は、0.1〜50μmの範囲にあればよく、その粒度分布はブロードであってもよいしシャープであってもよい。ポリマーの種類としては、アクリル樹脂、メタクリル樹脂、スチレン樹脂、ポリウレタン樹脂、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、シリコーン樹脂、ナイロン、アクリルアミド樹脂等が挙げられる。これらのポリマー粉末中に、0.1〜30質量%の範囲の含有率で有機系紫外線防御剤を含有させた粉末が好ましい。特に好ましい粉末の一例は、UVA吸収剤である4−tert−ブチル−4’−メトキシジベンゾイルメタンを含有させた粉末である。 Moreover, it is also possible to use the organic ultraviolet protective agent sealed in the polymer powder as the organic ultraviolet protective agent. The polymer powder may be hollow or may not be hollow. The average primary particle size of the polymer powder may be in the range of 0.1 to 50 μm, and the particle size distribution may be broad or sharp. Examples of the polymer include acrylic resin, methacrylic resin, styrene resin, polyurethane resin, polyethylene, polypropylene, polyethylene terephthalate, silicone resin, nylon, and acrylamide resin. In these polymer powders, powders containing an organic ultraviolet protective agent at a content in the range of 0.1 to 30% by mass are preferable. An example of a particularly preferable powder is a powder containing 4-tert-butyl-4'-methoxydibenzoylmethane, which is a UVA absorber.
上記の紫外線防御成分のうち、酸化チタン微粒子、酸化亜鉛微粒子、パラメトキシケイ皮酸2−エチルヘキシル、ブチルメトキシジベンゾイルメタン、オキシベンゾンおよびベンゾフェノン系紫外線吸収剤からなる群より選ばれる少なくとも1種が好ましい。これらは、汎用されており、入手が容易で、かつ紫外線防御効果が高いという利点を有する。また、無機系の紫外線防御成分と有機系の紫外線防御成分とを併用してもよい。また、UV−Aに対応したものとUV−Bに対応したものを併用してもよい。 Among the above-mentioned ultraviolet protection components, at least one selected from the group consisting of titanium oxide fine particles, zinc oxide fine particles, 2-ethylhexyl paramethoxycinnamate, butylmethoxydibenzoylmethane, oxybenzone and benzophenone-based ultraviolet absorbers is preferable. These are widely used, have an advantage that they are easily available and have a high UV protection effect. Further, an inorganic ultraviolet protection component and an organic ultraviolet protection component may be used in combination. Moreover, you may use together the thing corresponding to UV-A, and the thing corresponding to UV-B.
また、保湿剤としては、例えば、エチレングリコール、プロピレングリコール、ブチレングリコール、ジエチレングリコール、ジプロピレングリコール、グリセリン、ジグリセリン、ソルビトール、マルビトール、トレハロース、ラフィノース、キシリトール、マンニトール、ヒアルロン酸およびその塩、トレハロース誘導体、ラフィノース誘導体、ポリエチレングリコール、ポリグリセリン等のグリコール類、多価アルコール類および多糖類等が挙げられる。これらは単独で使用してもよいし、2種以上を混合して使用してもよい。 Examples of the humectant include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, glycerin, diglycerin, sorbitol, malbitol, trehalose, raffinose, xylitol, mannitol, hyaluronic acid and salts thereof, trehalose derivatives, Examples include raffinose derivatives, glycols such as polyethylene glycol and polyglycerin, polyhydric alcohols and polysaccharides. These may be used singly or in combination of two or more.
生理活性成分とは、皮膚に塗布した場合に皮膚に何らかの生理活性を与える物質である。本発明の化粧料は、生理活性成分を1種または2種以上含むことが好ましい。生理活性成分としては、例えば、美白成分、抗炎症剤、老化防止剤、紫外線防御剤、スリミング剤、ひきしめ剤、抗酸化剤、発毛剤、育毛剤、保湿剤、血行促進剤、抗菌剤、殺菌剤、乾燥剤、冷感剤、温感剤、ビタミン類、アミノ酸、創傷治癒促進剤、刺激緩和剤、鎮痛剤、細胞賦活剤、酵素成分等が挙げられる。その中でも、天然の成分、たとえば、植物抽出成分、海藻抽出成分、生薬成分が好ましい。 A physiologically active ingredient is a substance that imparts some physiological activity to the skin when applied to the skin. The cosmetic of the present invention preferably contains one or more physiologically active ingredients. Examples of physiologically active ingredients include whitening ingredients, anti-inflammatory agents, anti-aging agents, UV protection agents, slimming agents, tanning agents, antioxidants, hair growth agents, hair restorers, moisturizers, blood circulation promoters, antibacterial agents, Examples include bactericides, desiccants, cooling agents, warming agents, vitamins, amino acids, wound healing promoters, irritation relaxation agents, analgesics, cell activators, enzyme components, and the like. Of these, natural ingredients such as plant extract ingredients, seaweed extract ingredients, and herbal medicine ingredients are preferred.
天然の成分としては、例えば、アシタバエキス、アボガドエキス、アマチャエキス、アルテアエキス、アルニカエキス、アロエエキス、アンズエキス、アンズ核エキス、イチョウエキス、ウイキョウエキス、ウコンエキス、ウーロン茶エキス、エイジツエキス、エチナシ葉エキス、オウゴンエキス、オウバクエキス、オウレンエキス、オオムギエキス、オトギリソウエキス、オドリコソウエキス、オランダカラシエキス、オレンジエキス、海水乾燥物、海藻エキス、加水分解エラスチン、加水分解コムギ末、加水分解シルク、カモミラエキス、カロットエキス、カワラヨモギエキス、甘草エキス、カルカデエキス、カキョクエキス、キウイエキス、キナエキス、キューカンバーエキス、グアノシン、クチナシエキス、クマザサエキス、クララエキス、クルミエキス、グレープフルーツエキス、クレマティスエキス、クロレラエキス、クワエキス、ゲンチアナエキス、紅茶エキス、酵母エキス、ゴボウエキス、コメヌカ発酵エキス、コメ胚芽油、コンフリーエキス、コラーゲン、コケモモエキス、サイシンエキス、サイコエキス、サイタイ抽出液、サルビアエキス、サボンソウエキス、ササエキス、サンザシエキス、サンショウエキス、シイタケエキス、ジオウエキス、シコンエキス、シソエキス、シナノキエキス、シモツケソウエキス、シャクヤクエキス、ショウブ根エキス、シラカバエキス、スギナエキス、セイヨウキズタエキス、セイヨウサンザシエキス、セイヨウニワトコエキス、セイヨウノコギリソウエキス、セイヨウハッカエキス、セージエキス、ゼニアオイエキス、センキュウエキス、センブリエキス、ダイズエキス、タイソウエキス、タイムエキス、茶エキス、チョウジエキス、チガヤエキス、チンピエキス、トウキエキス、トウキンセンカエキス、トウニンエキス、トウヒエキス、ドクダミエキス、トマトエキス、納豆エキス、ニンジンエキス、ニンニクエキス、ノバラエキス、ハイビスカスエキス、バクモンドウエキス、ハスエキス、パセリエキス、蜂蜜、ハマメリスエキス、パリエタリアエキス、ヒキオコシエキス、ビサボロール、ビワエキス、フキタンポポエキス、フキノトウエキス、ブクリョウエキス、ブッチャーブルームエキス、ブドウエキス、プロポリス、ヘチマエキス、ベニバナエキス、ペパーミントエキス、ボダイジュエキス、ボタンエキス、ホップエキス、マツエキス、マロニエエキス、ミズバショウエキス、ムクロジエキス、メリッサエキス、モモエキス、ヤグルマギクエキス、ユーカリエキス、ユキノシタエキス、ユズエキス、ヨクイニンエキス、ヨモギエキス、ラベンダーエキス、リンゴエキス、レタスエキス、レモンエキス、レンゲソウエキス、ローズエキス、ローズマリーエキス、ローマカミツレエキス、ローヤルゼリーエキス等を挙げることができる。 Examples of natural ingredients include Ashitaba extract, Avocado extract, Achacha extract, Altea extract, Arnica extract, Aloe extract, Apricot extract, Apricot extract, Ginkgo biloba extract, Fennel extract, Turmeric extract, Oolong tea extract, Ages extract, Echinashi leaf Extract, Ogon extract, Oat extract, Oen extract, Barley extract, Hypericum extract, Odrianthus extract, Dutch mustard extract, Orange extract, Seawater dried product, Seaweed extract, Hydrolyzed elastin, Hydrolyzed wheat powder, Hydrolyzed silk, Chamomile extract, Carrot extract, Kawara mugwort extract, licorice extract, calcade extract, oyster extract, kiwi extract, kina extract, cucumber extract, guanosine, gardenia extract, kumazasa extract, clara Kiss, walnut extract, grapefruit extract, clematis extract, chlorella extract, mulberry extract, gentian extract, tea extract, yeast extract, burdock extract, fermented rice bran extract, rice germ oil, comfrey extract, collagen, bilberry extract, saicin extract, psycho extract Extract Kizuta extract, hawthorn extract, elderberry extract, yarrow extract, mint extract, sage extract, mallow extract, Cucumber extract, assembly extract, soybean extract, peanut extract, thyme extract, tea extract, clove extract, chigaya extract, chimpi extract, touki extract, toshinsen extract, tonin extract, spruce extract, dokudami extract, tomato extract, natto extract, carrot extract, garlic extract , Novara extract, hibiscus extract, bacmond extract, lotus extract, parsley extract, honey, hamamelis extract, parietalia extract, toad extract, bisabolol, loquat extract, dandelion extract, fukinotou extract, bukkuri extract, butcher bloom extract, grape extract, propolis, Loofah extract, safflower extract, peppermint extract, bodaiju extract, button extract, hop extract, pine extract, maronier extract , Citrus extract, Mulberry extract, Melissa extract, Peach extract, Cornflower extract, Eucalyptus extract, Yukinoshita extract, Yuzu extract, Yakuinin extract, Artemisia extract, Lavender extract, Apple extract, Lettuce extract, Lemon extract, Astragalus extract, Rose extract, Rosemary extract , Roman chamomile extract, royal jelly extract and the like.
本発明のメイクアップ化粧料としては、例えば、ファンデーション、アイシャドウ、白粉、チーク、コンシーラー等を挙げることができる。化粧料に含まれる水の形態は、特に限定されず、抱水形態であってもよいし、油中水型の乳化形態であってもよいし、水中油型の乳化形態であってもよいし、粘土鉱物やゲル化剤等による乳化形態であってもよい。 Examples of the makeup cosmetic of the present invention include foundation, eye shadow, white powder, teak, concealer and the like. The form of water contained in the cosmetic is not particularly limited, and may be a hydrated form, a water-in-oil emulsified form, or an oil-in-water emulsified form. However, an emulsified form using a clay mineral or a gelling agent may be used.
次に、実施例によって本発明を更に詳細に説明するが、本発明は以下の実施例に限定されない。尚、表中の数値は含有量(質量%)を表わす。各実施例で採用した評価方法を、以下に説明する。 EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to a following example. In addition, the numerical value in a table | surface represents content (mass%). The evaluation methods employed in each example are described below.
[経時安定性の評価方法]
調製したメイクアップ化粧料を密閉ガラス容器に入れた後、45℃の恒温槽に6ヶ月間放置した。6ヶ月経過後、30℃に一晩置いたあとの臭気を評価者10名によって評価した。硫化水素臭がすると答えた人数を数え、下記の評価基準に従って安定性を評価した。硫化水素臭がすると答えた人数が多いほど安定性が悪いという評価になる。
硫化水素臭がすると答えた人数が7人以上: ×
硫化水素臭がすると答えた人数が4〜6人: △
硫化水素臭がすると答えた人数が1〜3人: ○
硫化水素臭がすると答えた人数が0人: ◎
[使用特性の評価方法]
女性評価者20名によって、塗布したときの使用特性(なめらかなのびの良さ)について下記の評価基準に従って評価した。
良いと答えた人数が18人以上: ◎
良いと答えた人数が14〜17人:○
良いと答えた人数が7〜13人: △
良いと答えた人数が6人以下: ×
以下の製造方法によって、5種類のシリカフレーク(フレーク状ガラス(A))を作製した。以下の製造例1〜5では、二酸化ケイ素(シリカ)のゾル溶液として、日本化学工業株式会社製の「シリカドール30」(粒径20nm、水分散)を用いた。また、群青の粒子として、第一化成工業株式会社製の「CB−80」(粒径200nm)を用いた。
[Method for evaluating stability over time]
The prepared makeup cosmetic was placed in a sealed glass container and then left in a thermostatic bath at 45 ° C. for 6 months. After 6 months, the odor after leaving overnight at 30 ° C. was evaluated by 10 evaluators. The number of people who answered that they had a hydrogen sulfide odor was counted, and the stability was evaluated according to the following evaluation criteria. The more people who answered that they had a hydrogen sulfide odor, the worse the stability.
More than 7 people answered that they had a hydrogen sulfide odor: ×
4-6 people who answered that they had a hydrogen sulfide odor: △
1 to 3 people responded that they had a hydrogen sulfide odor: ○
The number of people who answered that they had a hydrogen sulfide odor was 0: ◎
[Method for evaluating usage characteristics]
Twenty female evaluators evaluated the use characteristics (smoothness and goodness) when applied according to the following evaluation criteria.
More than 18 people answered good: ◎
14-17 people who answered good: ○
7-13 people answered that it was good: △
Less than 6 people answered good: ×
Five types of silica flakes (flaked glass (A)) were produced by the following production method. In the following Production Examples 1 to 5, “Silica Dole 30” (particle size 20 nm, water dispersion) manufactured by Nippon Chemical Industry Co., Ltd. was used as a sol solution of silicon dioxide (silica). Moreover, “CB-80” (particle size: 200 nm) manufactured by Daiichi Kasei Kogyo Co., Ltd. was used as ultramarine particles.
[製造例1](群青内包シリカフレークの製造)
シリカ中の群青の含有率が15質量%となるように、シリカのゾル溶液141g(ゾル溶液中のシリカ分42g)を攪拌しながら、群青の粒子7.5gを加え、さらに純水178gを加えて混合し、公知のホモジナイザー分散機を使用して10分間分散させ、群青含有シリカゾルを作製した。この時、シリカゾルのpHが8〜10のアルカリ性であることを確認した。
[Production Example 1] (Production of ultramarine inclusion silica flakes)
While stirring 141 g of silica sol solution (42 g of silica in the sol solution), 7.5 g of ultramarine particles were added, and 178 g of pure water was further added so that the content of ultramarine in silica was 15% by mass. The mixture was dispersed for 10 minutes using a known homogenizer disperser to prepare ultramarine-containing silica sol. At this time, it was confirmed that the silica sol had an alkaline pH of 8-10.
このシリカゾルに、水溶性物質であるトレハロース(分子量342)を5.0g添加し、公知のホモジナイザー分散機を使用して、さらに30分間分散させた。次に、このゾル溶液を25℃で18時間静置した。次に、ゾル溶液を、幅10cmのポリエチレンテレフタレートフィルム(PETフィルム)にバーコーターを用いて、乾燥後の厚さが0.7μmになるように塗布した。このフィルムを120℃の乾燥炉に3分間入れ、フィルム上のゾル溶液を乾燥させた。そして、このフィルムを乾燥炉から取り出し、室温まで冷却した。このとき、薄膜はPETフィルム表面に均一に付着していた。 To this silica sol, 5.0 g of trehalose (molecular weight 342), which is a water-soluble substance, was added and dispersed for another 30 minutes using a known homogenizer disperser. Next, this sol solution was allowed to stand at 25 ° C. for 18 hours. Next, the sol solution was applied to a polyethylene terephthalate film (PET film) having a width of 10 cm using a bar coater so that the thickness after drying was 0.7 μm. This film was placed in a drying oven at 120 ° C. for 3 minutes to dry the sol solution on the film. And this film was taken out from the drying furnace and cooled to room temperature. At this time, the thin film was uniformly attached to the surface of the PET film.
このフィルムに室温の水を噴霧しながら、薄膜が形成されている面に、市販のバインダークリップで挟んだフェルトを押し付けつつ、フィルムだけを引っ張ってスライドさせた。これによって、フィルム表面から薄膜が剥離して薄片が生じた。この薄片を回収し、120℃で1時間乾燥させた後、400℃で5時間焼成を行った。これによって、群青微粒子が内部に分散された、シリカからなる薄片を得た。この薄片を、公知の装置を用いて粉砕・分級して、平均粒径30μm、平均厚さ0.7μm、平均アスペクト比43のフレーク状ガラス(A)を得た。 While spraying room temperature water on the film, the film sandwiched between commercially available binder clips was pressed against the surface on which the thin film was formed, and only the film was pulled and slid. As a result, the thin film was peeled off from the film surface, and a flake was generated. The flakes were collected and dried at 120 ° C. for 1 hour, and then fired at 400 ° C. for 5 hours. Thus, a flake made of silica in which ultramarine fine particles were dispersed was obtained. The flakes were pulverized and classified using a known apparatus to obtain flaky glass (A) having an average particle diameter of 30 μm, an average thickness of 0.7 μm, and an average aspect ratio of 43.
[製造例2](群青内包シリカフレークの製造)
シリカ中の群青の含有率が30質量%となるように、シリカのゾル溶液154g(ゾル溶液中のシリカ分46g)を攪拌しながら、群青の粒子18gを加えて、さらに純水178gを加えて混合し、公知のホモジナイザー分散機を使用して10分間分散させ、群青含有シリカゾルを作製した。この時、シリカゾルのpHが8〜10のアルカリ性であることを確認した。
[Production Example 2] (Production of ultramarine inclusion silica flakes)
While stirring 154 g of silica sol solution (46 g of silica in the sol solution), 18 g of ultramarine particles were added, and 178 g of pure water was further added so that the content of ultramarine in silica was 30% by mass. The mixture was mixed and dispersed for 10 minutes using a known homogenizer disperser to prepare an ultramarine-containing silica sol. At this time, it was confirmed that the silica sol had an alkaline pH of 8-10.
このシリカゾルに、水溶性物質であるトレハロース(分子量342)を6.0g添加し、さらに30分間公知のホモジナイザー分散機を使用して分散させた。次に、このゾル溶液を25℃で18時間静置した。次に、ゾル溶液を幅10cmのPETフィルムにバーコーターを用いて、乾燥後の厚さが1.0μmになるように塗布し、そのフィルムを120℃の乾燥炉に3分間入れ、フィルム上のゾル溶液を乾燥させた。そして、このフィルムを乾燥炉から取り出し、室温まで冷却した。このとき、薄膜はPETフィルム表面に均一に付着していた。 To this silica sol, 6.0 g of trehalose (molecular weight 342), which is a water-soluble substance, was added and further dispersed for 30 minutes using a known homogenizer disperser. Next, this sol solution was allowed to stand at 25 ° C. for 18 hours. Next, the sol solution was applied to a PET film having a width of 10 cm using a bar coater so that the thickness after drying was 1.0 μm, and the film was placed in a drying oven at 120 ° C. for 3 minutes. The sol solution was dried. And this film was taken out from the drying furnace and cooled to room temperature. At this time, the thin film was uniformly attached to the surface of the PET film.
このフィルムに室温の水を噴霧しながら、薄膜が形成されている面に、市販のバインダークリップで挟んだフェルトを押し付けつつ、フィルムだけを引っ張ってスライドさせた。これによって、フィルム表面から薄膜が剥離して薄片が生じた。剥離した薄片を回収し、120℃で1時間乾燥させた後、400℃で5時間焼成を行った。これによって、群青微粒子が内部に分散された、シリカからなる薄片を得た。この薄片を公知の装置を用いて粉砕・分級して、平均粒径10μm、平均厚さ1.0μm、平均アスペクト比10のフレーク状ガラス(A)を得た。 While spraying room temperature water on the film, the film sandwiched between commercially available binder clips was pressed against the surface on which the thin film was formed, and only the film was pulled and slid. As a result, the thin film was peeled off from the film surface, and a flake was generated. The peeled flakes were collected and dried at 120 ° C. for 1 hour, and then fired at 400 ° C. for 5 hours. Thus, a flake made of silica in which ultramarine fine particles were dispersed was obtained. The flakes were pulverized and classified using a known apparatus to obtain flaky glass (A) having an average particle diameter of 10 μm, an average thickness of 1.0 μm, and an average aspect ratio of 10.
[製造例3](群青内包シリカフレークの製造)
シリカ中の群青の含有率が45質量%となるように、シリカのゾル溶液141g(ゾル溶液中のシリカ分42g)を攪拌しながら、群青の粒子34gを加え、さらに純水178gを加えて混合し、公知のホモジナイザー分散機を使用して10分間分散させ、群青含有シリカゾルを作製した。この時、群青含有シリカゾルのpHが8〜10のアルカリ性であることを確認した。
[Production Example 3] (Production of ultramarine inclusion silica flakes)
While stirring 141 g of silica sol solution (42 g of silica in the sol solution), 34 g of ultramarine particles were added, and 178 g of pure water was further added and mixed so that the content of ultramarine in silica was 45% by mass. Then, the mixture was dispersed for 10 minutes using a known homogenizer disperser to prepare an ultramarine-containing silica sol. At this time, it was confirmed that the pH of the ultramarine-containing silica sol was alkaline of 8-10.
このシリカゾルに、水溶性物質であるトレハロース(分子量342)を7.6g添加し、さらに30分間公知のホモジナイザー分散機を使用して分散させた。さらに、このゾル溶液を25℃で18時間静置した。このゾル溶液を幅10cmのPETフィルムにバーコーターを用いて、乾燥後の厚さが1.8μmになるように塗布し、そのフィルムを120℃の乾燥炉に3分間入れ、ゾル溶液を乾燥させた。そして、このフィルムを乾燥炉から取り出し、室温まで冷却した。このとき、薄膜はPETフィルム表面に均一に付着していた。 To this silica sol, 7.6 g of water-soluble substance trehalose (molecular weight 342) was added, and further dispersed for 30 minutes using a known homogenizer disperser. Further, this sol solution was allowed to stand at 25 ° C. for 18 hours. This sol solution was applied to a PET film having a width of 10 cm using a bar coater so that the thickness after drying was 1.8 μm, and the film was placed in a drying oven at 120 ° C. for 3 minutes to dry the sol solution. It was. And this film was taken out from the drying furnace and cooled to room temperature. At this time, the thin film was uniformly attached to the surface of the PET film.
このフィルムに室温の水を噴霧しながら、薄膜が形成されている面に、市販のバインダークリップで挟んだフェルトを押し付けつつ、フィルムだけを引っ張ってスライドさせた。これによって、フィルム表面から薄膜が剥離して薄片が生じた。剥離した薄片を回収し、120℃で1時間乾燥させた後、400℃で5時間焼成を行った。これにより群青微粒子が内部に分散された、シリカからなる薄片を得た。この薄片を公知の装置を用いて分級して、平均粒径30μm、平均厚さ1.8μm、平均アスペクト比16のフレーク状ガラス(A)を得た。 While spraying room temperature water on the film, the film sandwiched between commercially available binder clips was pressed against the surface on which the thin film was formed, and only the film was pulled and slid. As a result, the thin film was peeled off from the film surface, and a flake was generated. The peeled flakes were collected and dried at 120 ° C. for 1 hour, and then fired at 400 ° C. for 5 hours. As a result, flakes made of silica in which ultramarine fine particles were dispersed were obtained. The flakes were classified using a known apparatus to obtain flaky glass (A) having an average particle diameter of 30 μm, an average thickness of 1.8 μm, and an average aspect ratio of 16.
[製造例4](シリコーン処理された群青内包シリカフレークの製造)
製造例2で得られた群青内包シリカフレークに対し、メチルハイドロジェンポリシロキサン(信越化学工業社製KF−9901)を用いて、被覆量が3質量%となるように乾式被覆処理を行った。
[Production Example 4] (Production of silicone-treated ultramarine inclusion silica flakes)
The ultramarine encapsulated silica flakes obtained in Production Example 2 were subjected to a dry coating treatment using methyl hydrogen polysiloxane (KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd.) so that the coating amount was 3% by mass.
[製造例5](N−ラウロイル−L−リジンで処理された群青内包シリカフレークの製造)
6mol/L塩酸12質量部と水600質量部との混合溶液に、製造例2で得られた群青内包シリカフレーク63質量部を加え、超音波を併用したモーター攪拌を30分間行い、分散させた。一方、5mol/L水酸化ナトリウム12.5質量部と水90質量部との混合溶液にN−ラウロイル−L−リジン(味の素社製、アミホープLL)7質量部を溶解させた溶液を用意し、モーター攪拌の上記溶液中に滴下した。pHメーターによって溶液のpHを確認し、中和を完了させた後、メチルフェニルポリシロキサン(粘度200cs)2質量部を入れ、超音波を併用したモーター攪拌を3分間行った。次に、溶液を減圧ろ過し、さらに水洗した後、塩分計にて塩化ナトリウムが充分に除去されていることを確認した。得られた粉体を金属バットに移し、80℃に設定した送風乾燥機にて12時間乾燥を行った後、120℃で滅菌を行った。そして、乾燥によって凝集している粉体を、ミキサーを用いて粉砕・解砕し、N−アシル化リジンで処理された群青内包シリカフレークを得た。
[Production Example 5] (Production of ultramarine encapsulated silica flakes treated with N-lauroyl-L-lysine)
63 parts by mass of ultramarine inclusion silica flakes obtained in Production Example 2 was added to a mixed solution of 12 parts by mass of 6 mol / L hydrochloric acid and 600 parts by mass of water, and the mixture was dispersed by carrying out motor stirring using ultrasonic waves for 30 minutes. . On the other hand, a solution prepared by dissolving 7 parts by mass of N-lauroyl-L-lysine (Ajinomoto Co., Amihope LL) in a mixed solution of 12.5 parts by mass of 5 mol / L sodium hydroxide and 90 parts by mass of water was prepared. It was dripped in the said solution of motor stirring. After confirming the pH of the solution with a pH meter and completing neutralization, 2 parts by mass of methylphenylpolysiloxane (viscosity 200 cs) was added, and motor agitation using ultrasonic waves was performed for 3 minutes. Next, the solution was filtered under reduced pressure and further washed with water, and it was confirmed that sodium chloride was sufficiently removed with a salinometer. The obtained powder was transferred to a metal vat, dried for 12 hours in a blow dryer set at 80 ° C., and then sterilized at 120 ° C. And the powder aggregated by drying was grind | pulverized and pulverized using the mixer, and the ultramarine inclusion silica flake processed with N-acylated lysine was obtained.
[実施例1〜4、比較例1〜2](アイシャドウ)
以下の表1の成分を含有する水型(水中油型、顔料分散型)および表2の成分を含有する油中水型アイシャドウを、常法によって調製した(実施例1〜7および比較例1〜4)。得られたアイシャドウについて、上記試験方法によって使用特性および経時安定性を評価した。評価結果を、表1および表2に記載する。なお、以下の表に示す成分において、皮膜形成剤には、☆印を付す。
[Examples 1-4, Comparative Examples 1-2] (Eyeshadow)
Water types (oil-in-water type, pigment dispersion type) containing the components shown in Table 1 below and water-in-oil eye shadows containing the components shown in Table 2 were prepared by conventional methods (Examples 1 to 7 and Comparative Examples). 1-4). The obtained eye shadow was evaluated for use characteristics and stability over time by the above test methods. The evaluation results are shown in Tables 1 and 2. In addition, in the component shown in the following table | surfaces, * is attached | subjected to a film formation agent.
なお、表1および表2において、フレーク状ガラス(A)は、製造例2、4または5で製造されたシリカフレークである。また、皮膜形成剤は、ヒドロキシエチルセルロース、アクリル酸アルキル共重合体エマルジョン、ポリビニルアルコール、トリメチルシロキシケイ酸、フルオロシリケートである。 In Tables 1 and 2, the flaky glass (A) is the silica flake produced in Production Example 2, 4 or 5. The film forming agent is hydroxyethyl cellulose, alkyl acrylate copolymer emulsion, polyvinyl alcohol, trimethylsiloxysilicic acid, or fluorosilicate.
[応用例]
上記製造例1〜5で製造されたフレーク状ガラス(A)を用いて、常法によって、以下のメイクアップ化粧料を調製した。いずれの応用例の化粧料も、経時安定性が良好であり、滑らかな塗布感を有していた。
[Application example]
The following makeup cosmetics were prepared by a conventional method using the flaky glass (A) produced in Production Examples 1 to 5. The cosmetics of any application examples had good temporal stability and a smooth coating feeling.
[応用例1〜3](マスカラ)
以下の表3の成分を含有するマスカラを作製した。
[Application Examples 1 to 3] (Mascara)
A mascara containing the components in Table 3 below was prepared.
[応用例4〜6](マスカラ)
以下の表4の成分を含有するマスカラを作製した。
[Application Examples 4 to 6] (Mascara)
A mascara containing the components in Table 4 below was prepared.
[応用例7](アイライナー)
以下の表5の成分を含有するアイライナーを作製した。
[Application Example 7] (Eyeliner)
An eyeliner containing the components shown in Table 5 below was prepared.
[応用例8および9](アイシャドウ)
以下の表6の成分を含有するアイシャドウを作製した。
[Application Examples 8 and 9] (Eyeshadow)
Eye shadows containing the components in Table 6 below were prepared.
[応用例10および11](アイシャドウ)
以下の表7の成分を含有するアイシャドウを作製した。
[Application Examples 10 and 11] (Eye Shadow)
Eye shadows containing the components in Table 7 below were prepared.
[応用例12および13](アイシャドウ)
以下の表8の成分を含有するアイシャドウを作製した。
[Application Examples 12 and 13] (Eyeshadow)
Eye shadows containing the components in Table 8 below were prepared.
[応用例14](ファンデーション)
以下の表9の成分を含有するファンデーションを作製した。
[Application Example 14] (Foundation)
A foundation containing the components in Table 9 below was prepared.
[応用例15](ファンデーション)
以下の表10の成分を含有するファンデーションを作製した。
[Application Example 15] (Foundation)
A foundation containing the components in Table 10 below was prepared.
[応用例16](口紅)
以下の表11の成分を含有する口紅を作製した。
[Application Example 16] (lipstick)
Lipsticks containing the ingredients in Table 11 below were prepared.
以上、本発明の実施形態について例を挙げて説明したが、本発明は上記実施形態および実施例に限定されず、本発明の技術的思想に基づいて他の実施形態に適用できる。 The embodiments of the present invention have been described above with examples. However, the present invention is not limited to the above-described embodiments and examples, and can be applied to other embodiments based on the technical idea of the present invention.
本発明は、水を含有するメイクアップ化粧料に適用できる。 The present invention can be applied to makeup cosmetics containing water.
Claims (2)
前記フレーク状ガラスは、平均厚さが0.1μm〜3μmの範囲にあり、平均粒径が1μm〜300μmの範囲にあり、平均アスペクト比が5〜300の範囲にあるメイクアップ化粧料。 (A) containing 0.01% to 30% by mass of flaky glass in which ultramarine particles are dispersed, (b) 0.1% to 30% by mass of a film-forming agent, and (c) water. And
The flaky glass is a makeup cosmetic having an average thickness in the range of 0.1 μm to 3 μm, an average particle diameter in the range of 1 μm to 300 μm, and an average aspect ratio in the range of 5 to 300.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2009155209A (en) * | 2007-12-25 | 2009-07-16 | Pola Chem Ind Inc | Oil-in-water type emulsion composition and method for producing the same |
JP2016069347A (en) * | 2014-09-30 | 2016-05-09 | 小林製薬株式会社 | Liquid external composition |
JP2017008009A (en) * | 2015-06-25 | 2017-01-12 | 花王株式会社 | Oil-in-water type emulsion composition |
JP2020070259A (en) * | 2018-10-31 | 2020-05-07 | 株式会社トキワ | Water-based liquid cosmetics |
WO2022091873A1 (en) * | 2020-10-26 | 2022-05-05 | 株式会社 資生堂 | Powder-containing composition |
JPWO2024166690A1 (en) * | 2023-02-07 | 2024-08-15 |
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JP2009155209A (en) * | 2007-12-25 | 2009-07-16 | Pola Chem Ind Inc | Oil-in-water type emulsion composition and method for producing the same |
JP2016069347A (en) * | 2014-09-30 | 2016-05-09 | 小林製薬株式会社 | Liquid external composition |
JP2017008009A (en) * | 2015-06-25 | 2017-01-12 | 花王株式会社 | Oil-in-water type emulsion composition |
JP7448987B2 (en) | 2018-10-31 | 2024-03-13 | 株式会社トキワ | water-based liquid cosmetics |
CN111110591A (en) * | 2018-10-31 | 2020-05-08 | 株式会社常盘 | Water-based liquid cosmetics |
JP7182259B2 (en) | 2018-10-31 | 2022-12-02 | 株式会社トキワ | water-based liquid cosmetics |
JP2023001376A (en) * | 2018-10-31 | 2023-01-04 | 株式会社トキワ | water-based liquid cosmetics |
CN111110591B (en) * | 2018-10-31 | 2023-10-03 | 株式会社常盘 | Aqueous liquid cosmetic |
JP2020070259A (en) * | 2018-10-31 | 2020-05-07 | 株式会社トキワ | Water-based liquid cosmetics |
WO2022091873A1 (en) * | 2020-10-26 | 2022-05-05 | 株式会社 資生堂 | Powder-containing composition |
WO2022091872A1 (en) * | 2020-10-26 | 2022-05-05 | 株式会社 資生堂 | Powder-containing composition |
WO2022091871A1 (en) * | 2020-10-26 | 2022-05-05 | 株式会社 資生堂 | Aqueous composition |
WO2022091874A1 (en) * | 2020-10-26 | 2022-05-05 | 株式会社 資生堂 | Aqueous composition |
JPWO2024166690A1 (en) * | 2023-02-07 | 2024-08-15 | ||
WO2024166690A1 (en) * | 2023-02-07 | 2024-08-15 | Dic株式会社 | Pigment composition and production method for pigment composition |
JP7697595B2 (en) | 2023-02-07 | 2025-06-24 | Dic株式会社 | Pigment composition and method for producing the same |
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