CN102727392A - Emulsified composition - Google Patents
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Abstract
本发明涉及一种乳化组合物的制造方法,所述制造方法具有:将以下的成分(A)、(B)、(C)、(D)以及含有(F1)的水相I混合,接着乳化并冷却的工序1;然后,进一步混合以下的成分(E)以及含有(F2)的水相II的工序2,(A)由以下的通式(1)表示的化合物0.001~10质量%,Z1为在甘油、失水山梨糖醇、山梨糖醇或蔗糖残基上具有2个以上的羟基的结构,Y1为酯键或醚键,R为C14~22的烃基,n为1~4的数;(B)选自C14~22的高级醇以及甾醇类中的1种以上的化合物0.001~10质量%;(C)由通式(2)表示的化合物0.001~15质量%,R1为C4~30的烃基,Z为亚甲基、次甲基或O,X1、X2和X3为H、OH或乙酰氧基,X4为H、乙酰基或甘油基,r2和R3为H、OH、羟甲基或乙酰氧甲基,R4为C5~60的烃基,r5为H、C1~30的烃基;(D)阴离子表面活性剂0.00025~10质量%;(F1)水;(E)选自烷基改性聚丙烯酸类乙烯基聚合物以及烷基改性多糖类聚合物中的水溶性高分子0.001~6质量%;(F2)水。The present invention relates to a method for producing an emulsified composition comprising: mixing the following components (A), (B), (C), (D) and an aqueous phase I containing (F1), followed by emulsification and cooling step 1; then, further mixing the following component (E) and step 2 of the aqueous phase II containing (F2), (A) 0.001 to 10% by mass of a compound represented by the following general formula (1), Z 1 is a structure having two or more hydroxyl groups on glycerol, sorbitan, sorbitol or sucrose residues, Y 1 is an ester bond or an ether bond, R is a C14-22 hydrocarbon group, and n is 1-22 The number of 4; (B) 0.001 to 10 mass % of one or more compounds selected from C14 to 22 higher alcohols and sterols; (C) 0.001 to 15 mass % of compounds represented by general formula (2), R 1 is a C4-30 hydrocarbon group, Z is methylene, methine or O, X 1 , X 2 and X 3 are H, OH or acetoxy, X 4 is H, acetyl or glyceryl, r 2 and R3 are H, OH, hydroxymethyl or acetoxymethyl, R4 is a C5-60 hydrocarbon group, r5 is H, a C1-30 hydrocarbon group; (D) anionic surfactant 0.00025-10% by mass ; (F1) water; (E) 0.001 to 6% by mass of water-soluble polymers selected from alkyl-modified polyacrylic vinyl polymers and alkyl-modified polysaccharide polymers; (F2) water.
Description
技术领域 technical field
本发明涉及乳化组合物。The present invention relates to emulsified compositions.
背景技术 Background technique
在皮肤最外层的角质层中存在充塞角质层细胞和其间隙的细胞间脂质。其大半为α-凝胶结构,对于皮肤,通过抑制来自外部的物质的侵入、由内部的水分蒸发的同时,还保持其自身的水分,从而具有保持皮肤柔软性和光滑的外观的功能。In the stratum corneum, the outermost layer of the skin, there are intercellular lipids that fill the stratum corneum cells and their spaces. Most of it has an α-gel structure, and for the skin, it has the function of keeping the skin soft and smooth by preventing the intrusion of substances from the outside and evaporating the water from the inside while retaining its own moisture.
通常,已知由于细胞间脂质、特别是神经酰胺的减少,会引发不优选的肌肤状态,从而考虑以外用补充神经酰胺的做法涉及改善肌肤机能的降低。In general, it is known that the reduction of intercellular lipids, especially ceramide, leads to undesirable skin conditions, and it is considered that external ceramide supplementation involves improvement of the decrease in skin function.
然而,由于神经酰胺高熔点并且结晶性高,难以配合于外用剂等中,因而,对稳定地配合神经酰胺进行了各种探讨。However, since ceramide has a high melting point and high crystallinity, it is difficult to incorporate it into external preparations and the like. Therefore, various studies have been made on stably incorporating ceramide.
例如,在专利文献1中记载了以特定的比例组合神经酰胺、甘油单脂肪酸酯、高级醇的乳化组合物能抑制神经酰胺的结晶析出,形成容易保持水分的α-凝胶结构,从而保湿效果高。For example, in Patent Document 1, it is described that an emulsified composition combining ceramide, glycerol monofatty acid ester, and higher alcohol in a specific ratio can inhibit the crystallization of ceramide and form an α-gel structure that is easy to retain moisture, thereby moisturizing The effect is high.
另外,还探讨了通过进一步组合特定的糖醇或2单糖或3单糖,从而可以进一步提高α-凝胶的水分保持能力,使水分长时间残留于皮肤上来改善皮肤的状态(专利文献2、专利文献3)。In addition, it has also been considered that by further combining specific sugar alcohols or 2-monosaccharides or 3-monosaccharides, the water retention capacity of the α-gel can be further improved, and the water can be left on the skin for a long time to improve the condition of the skin (Patent Document 2 , Patent Document 3).
然而,这些组合物虽然形成α-凝胶结构,但是由于以低粘度难以涂布于皮肤上,因而,即使形成了具有保湿效果的皮膜,其皮膜较脆,不能均匀地覆盖皮肤,从而也难以发挥充分的水分保持能力。However, although these compositions form an α-gel structure, they are difficult to apply to the skin due to their low viscosity. Therefore, even if a film with a moisturizing effect is formed, the film is fragile and cannot cover the skin uniformly, making it difficult to apply it on the skin. Exhibit sufficient moisture retention.
另外,因为皮膜欠缺柔软性以及弹性,所以涂布后肌肤有特有的粗糙感·不光滑感,从而得不到良好的使用触感。此外,还有涂布后外观欠缺光滑、得不到肌肤的外观提高效果的问题。In addition, since the film lacks flexibility and elasticity, the skin has a characteristic roughness and roughness after application, and a good touch cannot be obtained. In addition, there was a problem that the appearance after application was not smooth, and the effect of improving the appearance of the skin could not be obtained.
现有技术文献prior art literature
专利文献patent documents
专利文献1:日本特开2007-22997号公报Patent Document 1: Japanese Patent Laid-Open No. 2007-22997
专利文献2:日本特开2011-32265号公报Patent Document 2: Japanese Unexamined Patent Publication No. 2011-32265
专利文献3:日本特开2011-32266号公报Patent Document 3: Japanese Patent Laid-Open No. 2011-32266
发明内容 Contents of the invention
本发明提供一种乳化组合物的制造方法,所述制造方法具有:将以下的成分(A)、(B)、(C)、(D)以及含有(F1)的水相I混合,接着乳化并冷却的工序1;然后,进一步混合以下的成分(E)以及含有(F2)的水相II的工序2,The present invention provides a method for producing an emulsified composition comprising: mixing the following components (A), (B), (C), and (D) and an aqueous phase I containing (F1), followed by emulsification And the operation 1 of cooling; Then, the operation 2 of further mixing the following ingredients (E) and the aqueous phase II containing (F2),
(A)由以下的通式(1)表示的化合物0.001~10质量%,(A) 0.001 to 10% by mass of a compound represented by the following general formula (1),
(式中,Z1表示在甘油、失水山梨糖醇、山梨糖醇或蔗糖残基上具有2个以上的羟基的结构,Y1表示酯键或醚键,R表示碳原子数为14~22的烃基,n表示1~4的数。)(In the formula, Z 1 represents a structure with more than 2 hydroxyl groups on glycerol, sorbitan, sorbitol or sucrose residues, Y 1 represents an ester bond or an ether bond, R represents a carbon atom number of 14 to 22 hydrocarbon group, n represents the number of 1 to 4.)
(B)选自碳原子数为14~22的高级醇以及甾醇类中的1种以上的化合物0.001~10质量%;(B) 0.001 to 10% by mass of one or more compounds selected from higher alcohols and sterols with 14 to 22 carbon atoms;
(C)由通式(2)表示的化合物0.001~15质量%;(C) 0.001 to 15% by mass of the compound represented by the general formula (2);
(式中,R1表示被羟基、羰基或氨基取代或不取代的碳原子数为4~30的直链、支链或环状的饱和或不饱和烃基;Z表示亚甲基、次甲基或氧原子;X1、X2和X3分别独立地表示氢原子、羟基或乙酰氧基;X4表示氢原子、乙酰基或甘油基,或与相邻的氧原子一起形成桥氧基(但是,当Z为次甲基时X1和X2的任意一个为氢原子而另一个不存在,当X4形成桥氧基时X3不存在。);R2和R3分别独立地表示氢原子、羟基、羟甲基或乙酰氧甲基;R4表示被羟基、羰基或氨基取代或不取代的主链上具有或不具有醚键、酯键或酰胺键的碳原子数为5~60的直链、支链或环状的饱和或不饱和的烃基;R5表示氢原子,或表示具有或不具有选自羟基、羟基烷氧基、烷氧基以及乙酰氧基中的取代基的总碳原子数为1~30的直链或支链的饱和或不饱和的烃基;虚线部分表示可以是不饱和键。)(wherein, R 1 represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group with 4 to 30 carbon atoms substituted or unsubstituted by hydroxyl, carbonyl or amino; Z represents methylene, methine or an oxygen atom; X 1 , X 2 and X 3 independently represent a hydrogen atom, a hydroxyl group or an acetoxy group; X 4 represent a hydrogen atom, an acetyl group or a glyceryl group, or form a bridging oxygen group together with an adjacent oxygen atom ( However, when Z is a methine group, any one of X 1 and X 2 is a hydrogen atom and the other does not exist, and X 3 does not exist when X 4 forms a bridging oxygen group.); R 2 and R 3 independently represent Hydrogen atom, hydroxyl group, hydroxymethyl group or acetoxymethyl group; R 4 represents the number of carbon atoms with or without ether bond, ester bond or amide bond on the main chain substituted or unsubstituted by hydroxyl group, carbonyl group or amino group, and the number of carbon atoms is from 5 to 60 linear, branched or cyclic saturated or unsaturated hydrocarbon groups; R 5 represents a hydrogen atom, or represents with or without a substituent selected from hydroxyl, hydroxyalkoxy, alkoxy and acetoxy A straight-chain or branched saturated or unsaturated hydrocarbon group with a total carbon number of 1 to 30; the dotted line indicates that it may be an unsaturated bond.)
(D)阴离子表面活性剂0.00025~10质量%;(D) 0.00025% to 10% by mass of anionic surfactant;
(F1)水;(F1) water;
(E)选自烷基改性聚丙烯酸类乙烯基聚合物以及烷基改性多糖类聚合物中的水溶性高分子0.001~6质量%;(E) 0.001-6% by mass of water-soluble polymers selected from alkyl-modified polyacrylic vinyl polymers and alkyl-modified polysaccharide polymers;
(F2)水。(F2) Water.
另外,本发明提供一种乳化组合物,其含有以下的成分(A)、(B)、(C)、(D)、(E)以及(F),In addition, the present invention provides an emulsified composition containing the following components (A), (B), (C), (D), (E) and (F),
(A)单山嵛酸甘油酯或单十六烷基甘油醚0.001~10质量%;(A) 0.001% to 10% by mass of glyceryl monobehenate or monocetyl glyceryl ether;
(B)十六醇或硬脂醇0.001~10质量%;(B) 0.001% to 10% by mass of cetyl alcohol or stearyl alcohol;
(C)由通式(3)或通式(4)表示的神经酰胺类0.001~15质量%,(C) 0.001 to 15% by mass of ceramides represented by general formula (3) or general formula (4),
(式中,R11表示被羟基取代或不取代的碳原子数为7~19的直链、支链或环状的饱和或不饱和的烃基;Z1表示亚甲基或次甲基;X5、X6和X7分别独立地表示氢原子、羟基或乙酰氧基;X8表示氢原子,或与相邻的氧原子一起形成桥氧基(但是,当Z1为次甲基时,X5和X6的任意一个为氢原子而另一个不存在;当X8形成桥氧基时,X7不存在。);R12表示羟甲基或乙酰氧甲基;R13表示氢原子,或表示碳原子数为1~4的烷基;R14表示被羟基取代或不取代的碳原子数为5~30的直链、支链或环状的饱和或不饱和的烃基,或表示在该烷基的ω末端上以酯键结合被羟基取代或不取代的碳原子数为8~22的直链或支链的饱和或不饱和的脂肪酸而成的基团;虚线部分表示可以是不饱和键。)(wherein, R 11 represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group with 7 to 19 carbon atoms substituted or unsubstituted by hydroxyl; Z 1 represents methylene or methine; X 5 , X 6 and X 7 independently represent a hydrogen atom, hydroxyl or acetoxy group; X 8 represents a hydrogen atom, or forms a bridging oxygen group together with an adjacent oxygen atom (however, when Z 1 is a methine group, Any one of X 5 and X 6 is a hydrogen atom and the other does not exist; when X 8 forms a bridging oxygen group, X 7 does not exist.); R 12 represents a hydroxymethyl or acetoxymethyl group; R 13 represents a hydrogen atom , or represent an alkyl group with 1 to 4 carbon atoms; R 14 represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group with 5 to 30 carbon atoms substituted or unsubstituted by a hydroxyl group, or represents The omega end of the alkyl group is formed by ester-bonding a linear or branched saturated or unsaturated fatty acid with 8 to 22 carbon atoms substituted or unsubstituted by a hydroxyl group; the dotted line indicates that it can be unsaturated bonds.)
(式中,R15表示被羟基取代或不取代的碳原子数为10~22的直链、支链或环状的饱和或不饱和的烃基;X9表示氢原子、乙酰基或甘油基;R16表示被羟基或氨基取代或不取代的碳原子数为5~22的直链、支链或环状的饱和或不饱和的烃基,或表示在该烃基的ω末端上以酯键结合被羟基取代或不取代的碳原子数为8~22的直链或支链的饱和或不饱和的脂肪酸而成的基团;R17表示氢原子,或表示被羟基、羟基烷氧基、烷氧基或乙酰氧基取代或不取代的总碳原子数为1~30的烷基。)(wherein, R 15 represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group with 10-22 carbon atoms substituted or unsubstituted by hydroxyl; X 9 represents a hydrogen atom, acetyl group or glycerol group; R 16 represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group with 5 to 22 carbon atoms substituted or unsubstituted by hydroxyl or amino group, or represents an ester bond at the ω terminal of the hydrocarbon group to be Hydroxyl-substituted or unsubstituted straight-chain or branched chain saturated or unsaturated fatty acids with 8 to 22 carbon atoms; R 17 represents a hydrogen atom, or represents a group formed by hydroxyl, hydroxyalkoxy, or alkoxy An alkyl group with a total carbon number of 1 to 30 substituted or unsubstituted by a group or an acetoxy group.)
(D)硬脂酰基谷氨酸盐、硬脂酰基甲基牛磺酸盐或聚氧乙烯硬脂基醚磷酸盐0.00025~10质量%;(D) 0.00025% to 10% by mass of stearyl glutamate, stearyl methyl taurate or polyoxyethylene stearyl ether phosphate;
(E)(丙烯酸/丙烯酸烷基酯(C10-30))共聚物、(丙烯酸烷基酯/甲基丙烯酸硬脂醇聚醚-20)共聚物、月桂醇聚醚-13PG羟乙基纤维素或硬脂氧基PG羟乙基纤维素磺酸钠0.001~6质量%;(E) (Acrylic acid/Alkyl Acrylate (C10-30)) Copolymer, (Alkyl Acrylate/Steareth Methacrylate-20) Copolymer, Laureth-13PG Hydroxyethyl Cellulose Or 0.001% to 6% by mass of sodium stearyloxy PG hydroxyethyl cellulose sulfonate;
(F)水。(F) water.
发明的效果The effect of the invention
本发明的乳化组合物由于能够得到高粘度且弹性的液性,涂布膜具有柔软性以及弹性,因而可以均匀地覆盖肌肤,提高水分保持能力,并使肌肤触感光滑,外观也光滑。Since the emulsified composition of the present invention can obtain a high-viscosity and elastic liquid, and the coating film has softness and elasticity, it can evenly cover the skin, improve the moisture retention capacity, and make the skin smooth to the touch and smooth in appearance.
具体实施方式 Detailed ways
本发明涉及一种乳化组合物,其涂布膜具有柔软性以及弹性,能够均匀地覆盖肌肤,提高水分保持能力,并使肌肤触感光滑,外观也光滑。The present invention relates to an emulsified composition, the coating film of which has softness and elasticity, can evenly cover the skin, improves the moisture retention capacity, and makes the skin smooth to the touch and smooth in appearance.
本发明者们发现,对于提高水分保持能力而设计的α-凝胶,通过组合特定的水溶性高分子,可以得到由于能得到高粘度且弹性的液性,涂布膜具有柔软性以及弹性,因而能够均匀地覆盖肌肤,提高水分保持能力,并且能使肌肤触感光滑,外观也光滑的乳化组合物。The inventors of the present invention have found that the α-gel designed to improve the water retention ability can be obtained by combining specific water-soluble polymers, because it can obtain high viscosity and elastic liquid properties, and the coating film has flexibility and elasticity. Therefore, it is an emulsified composition that can evenly cover the skin, improve the moisture retention capacity, and make the skin feel smooth and smooth.
本发明中使用的成分(A)为由上述通式(1)表示的化合物。Component (A) used in the present invention is a compound represented by the above general formula (1).
式中,作为由R表示的碳原子数为14~22的烃基,优选为直链烃基,例如可以列举肉豆蔻基、棕榈基、硬脂基、山嵛基等直链烷基;棕榈酰基、油基等。In the formula, as the hydrocarbon group having 14 to 22 carbon atoms represented by R, it is preferably a straight-chain hydrocarbon group, for example, straight-chain alkyl groups such as myristyl, palmityl, stearyl, behenyl, etc.; palmitoyl, Oil base etc.
作为由通式(1)表示的化合物,可以列举甘油单脂肪酸酯、失水山梨糖醇单脂肪酸酯、失水山梨糖醇二脂肪酸酯、山梨糖醇单脂肪酸酯、山梨糖醇二脂肪酸酯、蔗糖单脂肪酸酯、甘油单烷基醚等。Examples of the compound represented by the general formula (1) include glycerol monofatty acid ester, sorbitan monofatty acid ester, sorbitan difatty acid ester, sorbitol monofatty acid ester, sorbitol Di fatty acid ester, sucrose mono fatty acid ester, glycerin monoalkyl ether, etc.
作为成分(A),优选甘油单脂肪酸酯、失水山梨糖醇单脂肪酸酯、甘油单烷基醚。其中,优选单棕榈酸甘油酯、单硬脂酸甘油酯、单山嵛酸甘油酯、失水山梨糖醇单硬脂酸酯、单十六烷基甘油醚、单硬脂基甘油醚,此外,从提高后述片层状皮膜的形成性、保水性的观点出发,更优选单山嵛酸甘油酯或单十六烷基甘油醚。As component (A), glycerol monofatty acid ester, sorbitan monofatty acid ester, and glycerin monoalkyl ether are preferable. Among them, glyceryl monopalmitate, glyceryl monostearate, glyceryl monobehenate, sorbitan monostearate, monocetyl glyceryl ether, and monostearyl glyceryl ether are preferred. Among them, glyceryl monobehenate or monocetylglyceryl ether is more preferable from the viewpoint of improving the formation property of the lamellar film described later and the water retention property.
成分(A)可以使用1种以上的化合物,在全部组成中含有0.001~10质量%,优选含有0.05~7质量%、更优选含有0.25~3质量%。如果在该范围内的话,则将本发明的乳化组合物涂布于皮肤上后,可以在干燥过程中在皮肤表面形成后述的成分(B)~(E)构成的脂质层和水分层交替排列的片层状皮膜。因为该结果提高了可用于保持层间水分的水分保持能力,因此优选。还因为涂布膜的使用触感也变得良好,因此优选。Component (A) can use one or more types of compounds, and it contains 0.001-10 mass % in the whole composition, Preferably it contains 0.05-7 mass %, More preferably, it contains 0.25-3 mass %. Within this range, after the emulsified composition of the present invention is applied to the skin, a lipid layer composed of components (B) to (E) described later and moisture can be formed on the skin surface during the drying process. Lamellar film with alternating layers. This result is preferable because the moisture retention capacity which can be used to retain moisture between layers is improved. It is also preferable because the feeling of use of the coating film becomes favorable.
在本发明所使用的成分(B)中,高级醇为碳原子数为14~22、优选碳原子数为16~18的高级醇。例如,可以列举肉豆蔻醇、十六醇、硬脂醇、山嵛醇等。In the component (B) used in the present invention, the higher alcohol is a higher alcohol having 14 to 22 carbon atoms, preferably 16 to 18 carbon atoms. For example, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, etc. are mentioned.
其中,优选十六醇、硬脂醇,更优选十六醇。Among them, cetyl alcohol and stearyl alcohol are preferred, and cetyl alcohol is more preferred.
另外,在成分(B)中,作为甾醇,可以列举胆甾醇、植物甾醇。植物甾醇是β-谷甾醇、菜油甾醇、豆甾醇、菜籽甾醇等植物甾醇的总称,其组成没有限定。Moreover, in a component (B), cholesterol and a phytosterol are mentioned as a sterol. Phytosterol is a general term for phytosterols such as β-sitosterol, campesterol, stigmasterol, and brassicasterol, and its composition is not limited.
成分(B)可以使用1种以上,在全部组成中含有0.001~10质量%,优选含有0.05~7质量%、更优选含有0.1~3质量%。如果在范围内的话,则将本发明的乳化组合物涂布于皮肤后,可以在干燥过程中在皮肤表面形成上述成分(A)以及后述成分(C)~(E)构成的脂质层和水分层交替排列的片层状皮膜。因为该结果提高了可保持层间水分的水分闭塞性,因此优选。还因为涂布后也提高了肌肤的外观,因此优选。Component (B) can be used in 1 or more types, and it contains 0.001-10 mass % in the whole composition, Preferably it contains 0.05-7 mass %, More preferably, it contains 0.1-3 mass %. If it is within the range, after the emulsified composition of the present invention is applied to the skin, a lipid layer composed of the above-mentioned component (A) and the following components (C) to (E) can be formed on the skin surface during drying. Lamellar membranes arranged alternately with water layers. This result is preferable because the moisture blocking property capable of retaining interlayer moisture is improved. It is also preferable because it improves the appearance of the skin after application.
本发明中使用的成分(C)的神经酰胺类是以上述通式(2)表示的化合物。The ceramides of the component (C) used in the present invention are compounds represented by the above general formula (2).
式中,R1是可以被羟基、羰基或氨基取代的碳原子数为4~30、优选为可以被羟基取代的碳原子数为7~22的直链、支链或环状的饱和或不饱和的烃基或氢原子。In the formula, R1 is a straight chain, branched or cyclic saturated or unsaturated compound having 4 to 30 carbon atoms that may be substituted by hydroxyl, carbonyl or amino, preferably 7 to 22 carbon atoms that may be substituted by hydroxyl. Saturated hydrocarbon groups or hydrogen atoms.
Z表示亚甲基、次甲基或氧原子中的任意一种。Z represents any one of a methylene group, a methine group or an oxygen atom.
X1、X2和X3分别独立地表示氢原子、羟基或乙酰氧基。优选X1、X2和X3中的0~1个为羟基、其余的为氧原子。当Z为次甲基时,X1和X2的任意一个仅为氢原子,而另一个不存在。另外,X4优选为氢原子或甘油基。X 1 , X 2 and X 3 each independently represent a hydrogen atom, a hydroxyl group or an acetoxy group. Preferably, 0 to 1 of X 1 , X 2 and X 3 is a hydroxyl group, and the rest are oxygen atoms. When Z is a methine group, any one of X1 and X2 is only a hydrogen atom, and the other is absent. In addition, X 4 is preferably a hydrogen atom or a glyceryl group.
R2和R3表示氢原子、羟基、羟甲基或乙酰氧甲基,优选R2为氢原子或羟甲基,优选R3为氢原子。R 2 and R 3 represent a hydrogen atom, a hydroxyl group, a hydroxymethyl group or an acetoxymethyl group, preferably R 2 is a hydrogen atom or a hydroxymethyl group, and preferably R 3 is a hydrogen atom.
R4表示可以被羟基、羧基或氨基取代的、并且可以在主链上具有醚键、酯键或酰胺键的碳原子数为5~60的直链、支链或环状的饱和或不饱和的烃基。优选可以列举,可以被羟基或氨基取代的碳原子数为5~35的直链、支链或环状的饱和或不饱和的烃基,或在该烃基的ω位上以酯键结合或以酰胺键结合可以被羟基取代的碳原子数为8~22的直链、支链或环状的饱和或不饱和的脂肪酸的基团。作为结合的脂肪酸,优选异硬脂酸、12-羟基硬脂酸或亚油酸。R 4 represents a straight-chain, branched or cyclic saturated or unsaturated compound with 5 to 60 carbon atoms that may be substituted by hydroxyl, carboxyl or amino and may have an ether bond, ester bond or amide bond on the main chain. the hydrocarbon group. Preferable examples include linear, branched or cyclic saturated or unsaturated hydrocarbon groups with 5 to 35 carbon atoms that may be substituted by hydroxyl or amino groups, or bonded with an ester bond or amide at the ω position of the hydrocarbon group. A group bonded to a linear, branched or cyclic saturated or unsaturated fatty acid with 8 to 22 carbon atoms which may be substituted by a hydroxyl group. As bound fatty acid, preference is given to isostearic acid, 12-hydroxystearic acid or linoleic acid.
R5表示氢原子,或是也可以具有选自羟基、羟基烷氧基、烷氧基以及乙酰氧基的取代基的总碳原子数为1~30的直链或支链的饱和或不饱和的烃基。当R1为氢原子、Z为氧原子时,R5为总碳原子数为10~30的烃基。另外,当R1为烃基时,R5为总碳原子数为1~8的烃基。其中,优选氢原子或也可以被选自羟基以及羟基烷氧基、烷氧基中的1~3个取代的总碳原子数为1~8的烃基。在此,作为羟基烷氧基以及烷氧基,优选碳原子数为1~7的基团。R 5 represents a hydrogen atom, or a linear or branched saturated or unsaturated group with a total carbon number of 1 to 30 that may also have a substituent selected from hydroxyl, hydroxyalkoxy, alkoxy and acetoxy the hydrocarbon group. When R1 is a hydrogen atom and Z is an oxygen atom, R5 is a hydrocarbon group with 10 to 30 carbon atoms in total. In addition, when R 1 is a hydrocarbon group, R 5 is a hydrocarbon group with 1 to 8 carbon atoms in total. Among them, a hydrogen atom or a hydrocarbon group having 1 to 8 total carbon atoms which may be substituted by 1 to 3 selected from hydroxyl, hydroxyalkoxy, and alkoxy is preferable. Here, as the hydroxyalkoxy group and the alkoxy group, a group having 1 to 7 carbon atoms is preferable.
作为由通式(2)表示的化合物,优选由以下的通式(3)或(4)表示的神经酰胺类。As the compound represented by the general formula (2), ceramides represented by the following general formula (3) or (4) are preferable.
(I)由通式(3)表示的化合物可以是来自天然的神经酰胺类或相同结构的合成物。(I) The compound represented by the general formula (3) may be a natural ceramide or a synthetic compound having the same structure.
(式中,R11表示可以被羟基取代的碳原子数为7~19的直链、支链或环状的饱和或不饱和的烃基;Z1表示亚甲基或次甲基;X5、X6和X7分别独立地表示氢原子、羟基或乙酰氧基;X8表示氢原子,或与相邻的氧原子一起形成桥氧基(但是,当Z1为次甲基时,X5和X6的任意一个为氢原子而另一个不存在;当X8形成桥氧基时,X7不存在。);R12表示羟甲基或乙酰氧甲基;R13表示氢原子,或表示碳原子数为1~4的烷基;R14表示可以被羟基取代的碳原子数为5~30的直链、支链或环状的饱和或不饱和的烃基,或表示在该烷基的ω末端上以酯键结合可以被羟基取代的碳原子数为8~22的直链或支链的饱和或不饱和的脂肪酸而成的基团;虚线部分表示可以是不饱和键。)(In the formula, R 11 represents a straight chain, branched chain or cyclic saturated or unsaturated hydrocarbon group with 7 to 19 carbon atoms that can be substituted by a hydroxyl group; Z 1 represents a methylene or methine group; X 5 , X 6 and X 7 independently represent a hydrogen atom, hydroxyl or acetoxy; X 8 represents a hydrogen atom, or forms a bridging oxygen group with an adjacent oxygen atom (however, when Z 1 is a methine group, X 5 and any one of X6 is a hydrogen atom and the other does not exist; when X8 forms a bridging oxygen group, X7 does not exist.); R12 represents a hydroxymethyl or acetoxymethyl group; R13 represents a hydrogen atom, or Represents an alkyl group with 1 to 4 carbon atoms; R 14 represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group with a carbon number of 5 to 30 that may be substituted by a hydroxyl group, or The omega end of the α-terminal is ester-bonded to a straight-chain or branched saturated or unsaturated fatty acid with 8 to 22 carbon atoms that can be substituted by a hydroxyl group; the dotted line indicates that it may be an unsaturated bond.)
优选可以列举R11为碳原子数为7~19、更优选碳原子数为13~15的直链烷基,R14为可以被羟基取代的碳原子数为9~27的直链烷基或以酯键结合亚油酸的碳原子数为9~27的直链烷基的化合物。另外,优选X8表示氢原子,或与氧原子一起形成桥氧基。此外,作为R14,优选二十三烷基、1-羟基十五烷基、1-羟基二十三烷基、十七烷基、1-羟基十一烷基、ω位上以酯键结合亚油酸的二十九烷基。Preferably, R11 is a straight-chain alkyl group with 7 to 19 carbon atoms, more preferably 13 to 15 carbon atoms, R14 is a straight-chain alkyl group with 9 to 27 carbon atoms that may be substituted by a hydroxyl group, or A compound in which a linear alkyl group having 9 to 27 carbon atoms is bonded to linoleic acid through an ester bond. In addition, it is preferable that X8 represents a hydrogen atom, or forms a bridging oxygen group together with an oxygen atom. In addition, as R 14 , tricosyl, 1-hydroxypentadecyl, 1-hydroxytricosyl, heptadecyl, 1-hydroxyundecyl, and an ester bond at the ω position are preferable. The nonacosyl group of linoleic acid.
作为天然型神经酰胺的具体例子,可以列举鞘氨醇、二氢鞘氨醇、植物鞘氨醇或鞘氨二烯醇(Sphingadienine)被酰胺化了的神经酰胺类型1~7(例如,J.Lipid Res.,24:759(1983)的图2、以及J.Lipid.Res.,35:2069(1994)的图4记载的猪和人的神经酰胺类)。Specific examples of natural ceramides include ceramide types 1 to 7 in which sphingosine, dihydrosphingosine, phytosphingosine, or sphingadienine (Sphingadienine) has been amidated (for example, J. Lipid Res., 24: 759 (1983) Figure 2, and J. Lipid. Res., 35: 2069 (1994) Figure 4 described porcine and human ceramides).
进一步,还包含这些的N-烷基体(例如,N-甲基体)。Furthermore, these N-alkyl forms (eg, N-methyl forms) are also included.
这些神经酰胺类可以使用天然型(D(-)体)的光学活性体,也可以使用非天然型(L(+)体)的光学活性体,还可以使用天然型和非天然型的混合物。上述化合物的相对构型可以是天然型的构型、也可以是除此以外的非天然型的构型,另外,也可以是这些的混合物。其中,优选CERAMIDE 1、CERAMIDE2、CERAMIDE3、CERAMIDE5、CERAMIDE6II的化合物(以上、INCI、第8版)以及由下式表示的物质。These ceramides may be optically active in natural type (D(-) form), optically active in non-natural type (L(+) form), or a mixture of natural and non-natural types. The relative configuration of the above-mentioned compounds may be a natural configuration, a non-natural configuration, or a mixture of these. Among them, compounds of CERAMIDE 1, CERAMIDE 2, CERAMIDE 3, CERAMIDE 5, and CERAMIDE 6II (above, INCI, 8th edition) and substances represented by the following formula are preferable.
这些可以是来自天然的提取物以及合成物的任意一种,可以使用市售的产品。These may be either natural extracts or synthetic compounds, and commercially available products may be used.
作为这样的天然型神经酰胺的市售品,可以列举Ceramide I、CeramideIII、CeramideIIIA、CeramideIIIB、CeramideIIIC、CeramideVI(以上,Cosmo Farm公司)、Ceramide TIC-001(高砂香料公司)、CERAMIDE II(Quest International公司)、DS-CeramideVI、DS-CLA-Phytoceramide、C6-Phytoceramide、DS-ceramide Y3S(DOOSAN公司)、CERAMIDE 2(Sederma公司)。Commercially available products of such natural ceramides include Ceramide I, CeramideIII, CeramideIIIA, CeramideIIIB, CeramideIIIC, CeramideVI (above, Cosmo Farm Co.), Ceramide TIC-001 (Takasago Fragrance Co.), CERAMIDE II (Quest International Inc. ), DS-CeramideVI, DS-CLA-Phytoceramide, C6-Phytoceramide, DS-ceramide Y3S (DOOSAN Company), CERAMIDE 2 (Sederma Company).
(II)由通式(4)表示的凝似型神经酰胺(pseudo-ceramide)。(II) A pseudo-ceramide represented by the general formula (4).
(式中,R15表示可以被羟基取代的碳原子数为10~22的直链、支链或环状的饱和或不饱和的烃基或氢原子;X9表示氢原子、乙酰基或甘油基;R16表示可以被羟基或氨基取代的碳原子数为5~22的直链、支链或环状的饱和或不饱和的烃基,或表示在该烃基的ω末端上以酯键结合可以被羟基取代的碳原子数为8~22的直链或支链的饱和或不饱和的脂肪酸而成的基团;R17表示氢原子,或表示可以被羟基、羟基烷氧基、烷氧基或乙酰氧基取代的总碳原子数为1~30的烷基。)(In the formula, R 15 represents a straight chain, branched chain or cyclic saturated or unsaturated hydrocarbon group or hydrogen atom with a carbon number of 10 to 22 that can be substituted by a hydroxyl group; X 9 represents a hydrogen atom, acetyl group or glyceryl group ; R 16 represents a straight chain, branched or cyclic saturated or unsaturated hydrocarbon group with 5 to 22 carbon atoms that can be substituted by hydroxyl or amino group, or represents an ester bond at the ω end of the hydrocarbon group that can be A group formed by a straight-chain or branched saturated or unsaturated fatty acid with 8 to 22 carbon atoms substituted by a hydroxyl group; R 17 represents a hydrogen atom, or represents a group that can be replaced by a hydroxyl group, a hydroxyalkoxy group, an alkoxy group or An alkyl group with a total carbon number of 1 to 30 substituted by an acetoxy group.)
作为R16,优选壬基、十三烷基、十五烷基、ω位上以酯键结合亚油酸的十一烷基、ω位上以酯键结合亚油酸的十五烷基、ω位上以酯键结合12-羟基硬脂酸的十五烷基、ω位上以酰胺键结合甲基支链异硬脂酸的十一烷基。R 16 is preferably nonyl, tridecyl, pentadecyl, undecyl in which linoleic acid is bonded to the ω position through an ester bond, pentadecyl in which linoleic acid is bonded to the ω position through an ester bond, The pentadecyl group of 12-hydroxystearic acid is bonded to the ω position by an ester bond, and the undecyl group of methyl branched isostearic acid is bonded to the ω position by an amide bond.
在R15为氢原子的情况下,R17优选为可以被羟基、羟基烷氧基、烷氧基或乙酰氧基取代的总碳原子数为10~30、优选总碳原子数为12~20的烷基;在R15为可以被羟基取代的碳原子数为10~22的直链、支链或环状的饱和或不饱和的烃基的情况下,R17优选表示氢原子,或表示可以被羟基、羟基烷氧基、烷氧基或乙酰氧基取代的总碳原子数为1~8的烷基。作为R17的羟基烷氧基或烷氧基,优选碳原子数为1~7。When R 15 is a hydrogen atom, R 17 is preferably 10 to 30 total carbon atoms that may be substituted by hydroxyl, hydroxyalkoxy, alkoxy or acetoxy, preferably 12 to 20 total carbon atoms. An alkyl group; when R 15 is a linear, branched or cyclic saturated or unsaturated hydrocarbon group with 10 to 22 carbon atoms that can be substituted by a hydroxyl group, R 17 preferably represents a hydrogen atom, or represents that it can be An alkyl group having 1 to 8 carbon atoms in total substituted by hydroxy, hydroxyalkoxy, alkoxy or acetoxy. The hydroxyalkoxy or alkoxy group of R 17 preferably has 1 to 7 carbon atoms.
作为通式(4),优选R15为十六烷基、X9为氢原子、R16为十五烷基、R17为羟乙基的化合物;R15为十六烷基、X9为氢原子、R16为壬基、R17为羟乙基的化合物;或R15为十六烷基、X9为甘油基、R16为十三烷基、R17为3-甲氧基丙基的凝似型神经酰胺类,更优选通式(4)的R15为十六烷基、X9为氢原子、R16为十五烷基、R17为羟乙基的化合物(N-(十六烷氧基羟丙基)-N-羟乙基十六酰胺)。As general formula (4), preferably R 15 is hexadecyl, X 9 is a hydrogen atom, R 16 is pentadecyl, R 17 is a compound of hydroxyethyl; R 15 is hexadecyl, X 9 is Hydrogen atom, R 16 is nonyl, R 17 is hydroxyethyl; or R 15 is hexadecyl, X 9 is glyceryl, R 16 is tridecyl, R 17 is 3-methoxypropane The condensate-like ceramides of the group , more preferably the compound ( N- (Hexadecyloxyhydroxypropyl)-N-Hydroxyethylhexadecanoamide).
成分(C)的化合物可以使用1种以上,在全部组成中含有0.001~15质量%,优选含有0.05~7质量%、更优选含有0.5~5质量%。如果在范围内的话,则将本发明的乳化组合物涂布于皮肤上后,在干燥过程中可以在皮肤表面形成上述成分(A)、(B)以及后述成分(D)~(E)构成的脂质层和水分层交替排列的片层状皮膜。该结果可以保持层间水分。另外,在本发明的乳化组合物中以及涂布干燥后形成的片层状皮膜中,成分(C)没有结晶化。因为该结果可以使成分(C)高渗透于皮肤中,因此优选。进而,因为涉及涂布后肌肤外观提高·使用触感提高,因此优选。The compound of component (C) can use 1 or more types, It contains 0.001-15 mass % in the whole composition, Preferably it contains 0.05-7 mass %, More preferably, it contains 0.5-5 mass %. If it is within the range, the above-mentioned components (A), (B) and the following components (D) to (E) can be formed on the skin surface during the drying process after the emulsified composition of the present invention is applied to the skin. A lamellar membrane consisting of lipid layers and water layers alternately arranged. As a result, interlayer moisture can be maintained. In addition, in the emulsified composition of the present invention and in the lamellar film formed after coating and drying, the component (C) was not crystallized. As a result, the component (C) can be highly permeated into the skin, which is preferable. Furthermore, it is preferable because it leads to an improvement in the appearance of the skin after application and an improvement in the feeling of use.
作为本发明中使用的成分(D)的阴离子表面活性剂,例如可以列举月桂酸钠、棕榈酸钾、硬脂酸精氨酸等碳原子数为12~24的脂肪酸盐;月桂基硫酸钠、月桂基硫酸钾等烷基硫酸酯盐;聚氧乙烯月桂基硫酸酯三乙醇胺等烷基醚硫酸酯盐;月桂酰基肌氨酸钠等N-酰基肌氨酸盐;N-硬脂酰基-N-甲基牛磺酸钠、N-肉豆蔻酰基-N-甲基牛磺酸钠等脂肪酸酰胺磺酸盐;单硬脂基磷酸钠等烷基磷酸盐;聚氧乙烯油基醚磷酸钠、聚氧乙烯硬脂基醚磷酸钠等聚氧乙烯烷基醚磷酸盐;二-2-乙基己基磺基琥珀酸钠等长链磺基琥珀酸盐;N-月桂酰基谷氨酸单钠、N-硬脂酰基-L-谷氨酸钠、N-硬脂酰基-L-谷氨酸精氨酸、N-硬脂酰基谷氨酸钠、N-肉豆蔻酰基-L-谷氨酸钠等长链N-酰基谷氨酸盐等。Examples of the anionic surfactant used in the present invention as component (D) include fatty acid salts having 12 to 24 carbon atoms such as sodium laurate, potassium palmitate, and arginine stearate; sodium lauryl sulfate , Potassium lauryl sulfate and other alkyl sulfate salts; Polyoxyethylene lauryl sulfate triethanolamine and other alkyl ether sulfate salts; N-acyl sarcosinates such as sodium lauryl sarcosinate; N-stearyl- Fatty acid amide sulfonates such as sodium N-methyl taurate and sodium N-myristoyl-N-methyl taurate; alkyl phosphates such as sodium monostearyl phosphate; sodium polyoxyethylene oleyl ether phosphate Polyoxyethylene alkyl ether phosphates, such as sodium polyoxyethylene stearyl ether phosphate; long-chain sulfosuccinates such as di-2-ethylhexyl sodium sulfosuccinate; monosodium N-lauroyl glutamate , Sodium N-Stearyl-L-Glutamate, Arginine N-Stearyl-L-Glutamate, Sodium N-Stearyl Glutamate, N-Myristoyl-L-Glutamate Sodium and other long chain N-acyl glutamate, etc.
其中,优选碳原子数为12~24的脂肪酸盐、烷基脂肪酸酯盐、烷基醚硫酸酯盐、脂肪酸酰胺磺酸盐、烷基磷酸盐、聚氧乙烯烷基醚磷酸盐、长链N-酰基谷氨酸盐。Among them, fatty acid salts, alkyl fatty acid ester salts, alkyl ether sulfate ester salts, fatty acid amide sulfonates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl ether phosphates, long Chain N-acyl glutamate.
其中,优选硬脂酰基谷氨酸盐、硬脂酰基甲基牛磺酸盐、聚氧乙烯硬脂基醚磷酸盐,进一步优选硬脂酰基谷氨酸盐、硬脂酰基甲基牛磺酸盐,更优选硬脂酰基谷氨酸盐。Among them, stearoyl glutamate, stearoyl methyl taurate, polyoxyethylene stearyl ether phosphate are preferred, stearoyl glutamate and stearoyl methyl taurate are more preferred. , more preferably stearoyl glutamate.
作为成分(D)的盐,优选选自钠盐、钾盐、碱性氨基酸盐、铵中的1种以上,从表现出乳化组合物的粘度的观点出发,优选选自钠盐、精氨酸盐中的1种以上。The salt of component (D) is preferably at least one selected from sodium salts, potassium salts, basic amino acid salts, and ammonium, and is preferably selected from sodium salts and arginine from the viewpoint of expressing the viscosity of the emulsified composition. One or more types of salt.
成分(D)可以作为酸来配合,也可以用碱中和而作为盐来含有。该情况下中和成分(D)的碱优选选自碱性氨基酸、氢氧化钠、氢氧化钾、三乙醇胺、氢氧化钙中的1种或2种以上,碱性氨基酸优选选自精氨酸、赖氨酸、组氨酸中的1种或2种以上。作为中和成分(D)的碱,从表现乳化组合物的粘度的观点出发,优选选自精氨酸、氢氧化钠中的1种或2种,从使用感的观点出发,更优选精氨酸。Component (D) may be blended as an acid, or may be contained as a salt after being neutralized with an alkali. In this case, the base to neutralize the component (D) is preferably one or more selected from basic amino acids, sodium hydroxide, potassium hydroxide, triethanolamine, and calcium hydroxide, and the basic amino acids are preferably selected from arginine , lysine, and histidine, or one or more of them. The base for neutralizing the component (D) is preferably one or two selected from arginine and sodium hydroxide from the viewpoint of expressing the viscosity of the emulsified composition, and more preferably arginine from the viewpoint of usability. acid.
成分(D)可以使用1种以上,在全部组成中含有0.00025~10质量%,优选含有0.05~2质量%、更优选含有0.1~1质量%。如果在该范围内的话,则可以乳化成分(A)~(C)。此外,将本发明的乳化组合物涂布于皮肤后,可以在干燥过程中在皮肤表面形成成分(A)~(D)以及成分(E)构成的脂质层和水分层交替排列的片层状皮膜。该结果因为可以保持层间水分,对提高水分保持能力有用,所以优选。Component (D) can be used in 1 or more types, and it contains 0.00025-10 mass % in the whole composition, Preferably it contains 0.05-2 mass %, More preferably, it contains 0.1-1 mass %. Components (A) to (C) can be emulsified within this range. In addition, after the emulsified composition of the present invention is applied to the skin, a sheet in which lipid layers and water layers composed of components (A) to (D) and component (E) are alternately arranged can be formed on the skin surface during the drying process. Lamellar membrane. This result is preferable because interlayer moisture can be retained and is useful for improving the moisture retention capacity.
本发明中使用的成分(E)是选自烷基改性聚丙烯酸类聚合物以及烷基改性多糖类聚合物中的水溶性高分子。Component (E) used in the present invention is a water-soluble polymer selected from alkyl-modified polyacrylic polymers and alkyl-modified polysaccharide polymers.
例如,可以列举丙烯酸烷基酯共聚物、(甲基)丙烯酸/(甲基)丙烯酸烷基酯共聚物、丙烯酸烷基酯·甲基丙烯酸烷基酯·聚氧乙烯硬脂基醚共聚物、多糖衍生物等。Examples include alkyl acrylate copolymers, (meth)acrylic acid/alkyl (meth)acrylate copolymers, alkyl acrylate/alkyl methacrylate/polyoxyethylene stearyl ether copolymers, polysaccharide derivatives, etc.
更具体来说,优选(丙烯酸/丙烯酸烷基酯(C10-30))共聚物、(丙烯酸烷基酯/甲基丙烯酸硬脂醇聚醚-20)共聚物、月桂醇聚醚-13PG羟乙基纤维素、硬脂氧基PG羟乙基纤维素磺酸钠等。More specifically, (acrylic acid/alkyl acrylate (C10-30)) copolymer, (alkyl acrylate/steareth-20 methacrylate) copolymer, laureth-13PG hydroxyethyl Base cellulose, sodium stearyloxy PG hydroxyethyl cellulose sulfonate, etc.
作为市售品,例如,作为丙烯酸烷基酯聚合物,可以列举ACULYN33(The Dow Chemical Company);作为(甲基)丙烯酸/(甲基)丙烯酸烷基酯共聚物,可以列举PEMULEN TR-1、PEMULEN TR-2、Carbopol ETD2020(以上,Lubrizol Advanced Materials,Inc.)等。另外,作为丙烯酸烷基酯·甲基丙烯酸烷基酯·聚氧乙烯硬脂基醚共聚物,可以列举ACULYN 22(The Dow Chemical Company)等。作为多糖衍生物,可以列举SPS-S-SA、SOFCARE EP-S(以上,花王公司)、NatrosolPlus(Hercules-Aqualon)等。As a commercial product, for example, ACULYN33 (The Dow Chemical Company) can be mentioned as an alkyl acrylate polymer; PEMULEN TR-1, PEMULEN TR-1, PEMULEN TR-2, Carbopol ETD2020 (above, Lubrizol Advanced Materials, Inc.), etc. In addition, examples of the alkyl acrylate/alkyl methacrylate/polyoxyethylene stearyl ether copolymer include ACULYN 22 (The Dow Chemical Company) and the like. Examples of polysaccharide derivatives include SPS-S-SA, SOFCARE EP-S (above, Kao Corporation), Natrosol Plus (Hercules-Aqualon) and the like.
成分(E)可以使用1种以上,在全部组成中含有0.001~6质量%,优选含有0.05~5质量%、更优选含有0.1~3质量%。如果在该范围内的话,则可以提高本发明的乳化组合物的保存稳定性。此外,可以抑制由成分(A)~(D)构成的脂质混合物的结晶化。其结果,在涂布本发明的乳化组合物之后,可以在干燥过程中赋予形成于皮肤表面的片层状皮膜柔软性。因为其结果对水分保持能力/提高使用触感/涂布后提高肌肤外观有用,因此优选。One or more types of component (E) can be used, and it contains 0.001-6 mass % in the whole composition, Preferably it contains 0.05-5 mass %, More preferably, it contains 0.1-3 mass %. When it exists in this range, the storage stability of the emulsified composition of this invention can be improved. In addition, crystallization of the lipid mixture composed of components (A) to (D) can be suppressed. As a result, after application of the emulsified composition of the present invention, flexibility can be imparted to the lamellar film formed on the skin surface during the drying process. As a result, it is useful for moisture retention ability/improvement of feel/improvement of skin appearance after application, and is therefore preferable.
在本发明中,成分(F)的水可以作为各成分的余量,在全部组成中优选含有49~85质量%、更优选含有55~80质量%。In the present invention, the water of the component (F) may be contained as the balance of each component, and it is preferably contained in an amount of 49 to 85% by mass, and more preferably contained in an amount of 55 to 80% by mass in the entire composition.
在本发明中,从得到高粘度且弹性的液性的观点出发,成分(A)、(B)、(C)、(D)以及(E)的质量比例优选为,(E)/((A)+(B)+(C))=0.0025~50、更优选为0.01~3、特别优选为0.1~1.5。其结果在涂布于皮肤上时,可以感觉到高涂布感、赋予良好的使用感。In the present invention, from the viewpoint of obtaining high-viscosity and elastic liquid, the mass ratio of components (A), (B), (C), (D) and (E) is preferably (E)/(( A)+(B)+(C)) = 0.0025 to 50, more preferably 0.01 to 3, particularly preferably 0.1 to 1.5. As a result, when applied to the skin, a high coating feeling can be felt and a good usability can be provided.
另外,为了得到具有柔软性以及弹性的皮膜,优选(E)/(D)=0.025~100、更优选为0.14~7.5、特别优选为1.2~6。In addition, in order to obtain a film having flexibility and elasticity, (E)/(D)=0.025-100 is preferable, 0.14-7.5 is more preferable, and 1.2-6 is especially preferable.
在本发明中,更优选组合上述成分的各自优选的成分以及优选的含量。In the present invention, it is more preferable to combine the respective preferred components and preferred contents of the above components.
此外,在本发明的乳化组合物中,优选:成分(A)为单山嵛酸甘油酯或单十六烷基甘油醚,成分(B)为十六醇或硬脂醇,成分(C)为由通式(1)表示的化合物,成分(D)为硬脂酰基谷氨酸盐、硬脂酰基甲基牛磺酸盐或聚氧乙烯硬脂基醚磷酸盐,成分(E)为(丙烯酸/丙烯酸烷基酯(C10-30))共聚物、(丙烯酸烷基酯/甲基丙烯酸硬脂醇聚醚-20)共聚物、月桂醇聚醚-13PG羟乙基纤维素或硬脂氧基PG羟乙基纤维素磺酸钠,成分(F)为水。In addition, in the emulsified composition of the present invention, preferably: component (A) is glyceryl monobehenate or monocetyl glyceryl ether, component (B) is cetyl alcohol or stearyl alcohol, component (C) It is a compound represented by the general formula (1), the component (D) is stearoyl glutamate, stearyl methyl taurate or polyoxyethylene stearyl ether phosphate, and the component (E) is ( Acrylic acid/Alkyl Acrylate (C10-30)) Copolymer, (Alkyl Acrylate/Steareth-20) Copolymer, Laureth-13PG Hydroxyethylcellulose or Stearyl Oxygen Sodium PG hydroxyethyl cellulose sulfonate, component (F) is water.
此外,在本发明的乳化组合物中,优选:成分(A)为单山嵛酸甘油酯,成分(B)为十六醇,成分(C)为由通式(1)表示的化合物,成分(D)为硬脂酰基谷氨酸盐,成分(E)为(丙烯酸/丙烯酸烷基酯(C10-30))共聚物、(丙烯酸烷基酯/甲基丙烯酸硬脂醇聚醚-20)共聚物、月桂醇聚醚-13PG羟乙基纤维素或硬脂氧基PG羟乙基纤维素磺酸钠,成分(F)为水。In addition, in the emulsified composition of the present invention, it is preferable that the component (A) is glyceryl monobehenate, the component (B) is cetyl alcohol, the component (C) is a compound represented by the general formula (1), and the component (D) is stearyl glutamate, component (E) is (acrylic acid/alkyl acrylate (C10-30)) copolymer, (alkyl acrylate/steareth-20 methacrylate) Copolymer, laureth-13PG hydroxyethylcellulose or sodium stearyl PG hydroxyethylcellulose sulfonate, ingredient (F) is water.
在本发明中,由成分(A)~(D)形成乳化物的脂质。如果将这些进行干燥,则会引起结晶化,形成硬且脆的皮膜,从而不能得到保湿性高的皮膜。然而,通过进一步含有成分(E),可以抑制脂质的结晶化,从而大量含有水分,形成脂质层和水层交替排列的片层状的柔软的皮膜。特别是,如果使用十六醇为成分(B),则可以增加皮膜的柔软性,提高肌肤的外观以及触感的光滑。进而,可以提供用于制造皮肤涂布剂的本发明的乳化组合物的用途、用于制造皮肤水分保持剂的本发明的乳化组合物的用途、以及用于制造对皮肤的涂布膜形成剂的本发明的乳化组合物的用途。In this invention, the lipid which forms an emulsion from components (A)-(D). If these are dried, crystallization will occur and a hard and brittle film will be formed, so that a film with high moisture retention cannot be obtained. However, by further containing the component (E), the crystallization of the lipid can be suppressed, and a large amount of water can be contained to form a lamellar soft film in which lipid layers and water layers are alternately arranged. In particular, when cetyl alcohol is used as the component (B), the flexibility of the film can be increased, and the appearance and smoothness of the skin can be improved. Furthermore, the use of the emulsified composition of the present invention for producing a skin coating agent, the use of the emulsified composition of the present invention for producing a skin moisturizing agent, and the production of a coating film-forming agent for skin can be provided Use of the emulsified composition of the present invention.
本发明的乳化组合物还可以含有成分(B)以及(C)以外的油性成分。例如,可以列举液体石蜡、角鲨烷、凡士林等烃油;鲸蜡基二甲基丁基醚、乙二醇二辛基醚、甘油基单油基醚等醚油;肉豆蔻酸十八烷基酯、棕榈酸异丙酯、硬脂酸丁酯、己二酸二-2-乙基己酯、二癸酸新戊二醇酯、三辛酸甘油酯(trioctanoin)等酯油;硬脂酸、山嵛酸、异肉豆蔻酸等高级脂肪酸;橄榄油等植物油;二甲基聚硅氧烷、环状二甲基聚硅氧烷、甲基苯基聚硅氧烷、氨基改性硅酮、羧基改性硅酮、醇改性硅酮、烷基改性硅酮、聚醚改性硅酮、氟改性硅酮等硅油;全氟烷基乙基磷酸、全氟烷基聚氧乙烯磷酸、全氟聚醚、聚四氟乙烯等氟类油等。这些油性成分优选在全部组成中含有0~20质量%。The emulsified composition of the present invention may contain oily components other than components (B) and (C). Examples include hydrocarbon oils such as liquid paraffin, squalane, and petrolatum; ether oils such as cetyl dimethyl butyl ether, ethylene glycol dioctyl ether, and glyceryl monooleyl ether; octadecyl myristate; ester oils such as isopropyl palmitate, butyl stearate, di-2-ethylhexyl adipate, neopentyl glycol dicaprate, and trioctanoin; stearic acid , behenic acid, isomyristic acid and other higher fatty acids; olive oil and other vegetable oils; dimethyl polysiloxane, cyclic dimethyl polysiloxane, methylphenyl polysiloxane, amino-modified silicone , Carboxyl-modified silicone, alcohol-modified silicone, alkyl-modified silicone, polyether-modified silicone, fluorine-modified silicone and other silicone oils; perfluoroalkyl ethyl phosphoric acid, perfluoroalkyl polyoxyethylene Phosphoric acid, perfluoropolyether, polytetrafluoroethylene and other fluorine oils, etc. These oily components are preferably contained in an amount of 0 to 20% by mass in the entire composition.
另外,本发明的乳化组合物可以含有通常化妆品中使用的有效成分和添加剂,例如抗坏血酸、烟酸酰胺、烟酸等水溶性维生素类;黄柏提取物、甘草提取物、芦荟提取物、问荆提取物、茶提取物、黄瓜提取物、丁香提取物、胡萝卜提取物、金缕梅提取液、胎盘提取物、海藻提取物、七叶树提取物、柚子提取物、罗汉柏提取物、蜂王浆提取物、桉树提取物、罗汉柏提取液等动·植物提取液;氢氧化钾、氢氧化钠、三乙醇胺、碳酸钠等碱;柠檬酸、酒石酸、乳酸、磷酸、琥珀酸、己二酸等酸等。In addition, the emulsified composition of the present invention may contain active ingredients and additives commonly used in cosmetics, such as water-soluble vitamins such as ascorbic acid, niacinamide, and niacin; Extract, Tea Extract, Cucumber Extract, Clove Extract, Carrot Extract, Witch Hazel Extract, Placenta Extract, Seaweed Extract, Horse Chestnut Extract, Grapefruit Extract, Podocarpus Extract, Royal Jelly Extract , eucalyptus extract, Luo Hanbo extract and other animal and plant extracts; potassium hydroxide, sodium hydroxide, triethanolamine, sodium carbonate and other alkalis; citric acid, tartaric acid, lactic acid, phosphoric acid, succinic acid, adipic acid and other acids, etc. .
本发明的乳化组合物的制造方法优选具有:将成分(A)~(D)以及含有成分(F)的一部分(F1)的水相I混合,接着乳化并冷却的工序1;然后,进一步混合成分(E)以及含有成分(F)的剩余部分(F2)的水相成分(水相II)的工序。因为根据该方法,通过在形成α-凝胶结构之后使聚合物相互作用,从而可以得到在较广的温度范围内稳定性优异的乳化物,所以优选。The method for producing the emulsified composition of the present invention preferably comprises: mixing the components (A) to (D) and the aqueous phase I containing a part (F1) of the component (F), followed by emulsification and cooling step 1; and then further mixing The process of component (E) and the water phase component (water phase II) containing the remainder (F2) of component (F). According to this method, an emulsion excellent in stability over a wide temperature range can be obtained by causing the polymers to interact after forming an α-gel structure, and it is preferable.
工序1是使α-凝胶结构形成的工序,优选选自以下的工序1A、1B、1C以及1D的4个制造工序中的工序。从制造性的观点出发,优选从具备将未中和的成分(D)用碱来中和的工序的工序1A以及工序1C中选择的工序;从表现粘度的观点出发,优选从在油相中混合成分(D)的工序1A以及工序1B中选择的工序。如上所述,工序1优选具备从工序1A、工序1B以及工序1C中选择的工序,更优选具备工序1A或工序1B,进一步优选具备工序1A。Step 1 is a step of forming an α-gel structure, and is preferably a step selected from the following four production steps of Steps 1A, 1B, 1C, and 1D. From the standpoint of manufacturability, it is preferable to select from Step 1A and Step 1C which include a step of neutralizing the unneutralized component (D) with an alkali; A step selected from step 1A and step 1B of mixing the component (D). As described above, step 1 preferably includes a step selected from step 1A, step 1B, and step 1C, more preferably includes step 1A or step 1B, and even more preferably includes step 1A.
工序1A:是具有得到含有成分(A)、(B)、(C)以及未中和的成分(D)的油相的混合成分的工序;和在该油相中混合含有成分(F)的一部分(F1)以及碱的水相I,接着乳化并冷却的工序。Step 1A: is a step of obtaining a mixed component of an oil phase containing components (A), (B), (C) and an unneutralized component (D); and mixing components containing component (F) in the oil phase A portion (F1) and the aqueous phase I of the base, followed by emulsification and cooling.
工序1B:是具有得到含有成分(A)、(B)、(C)以及成分(D)的盐的油相的混合成分的工序;和在该油相中混合含有成分(F)的一部分(F1)的水相I,接着乳化并冷却的工序。Step 1B: is a step of mixing ingredients with an oil phase containing ingredients (A), (B), (C) and a salt of ingredient (D); and mixing a part of the oil phase containing ingredient (F) ( The aqueous phase I of F1) is followed by emulsification and cooling.
工序1C:是具有得到含有成分(A)、(B)以及(C)的油相的混合成分的工序;和在该油相中混合含有未中和的成分(D)、成分(F)的一部分(F1)以及碱的水相I,接着乳化并冷却的工序。Step 1C: a step of obtaining a mixed component of an oil phase containing components (A), (B) and (C); and mixing unneutralized component (D) and component (F) in the oil phase A portion (F1) and the aqueous phase I of the base, followed by emulsification and cooling.
工序1D:是具有得到含有成分(A)、(B)以及(C)的油相的混合成分的工序;和在该油相中混合含有成分(D)的盐以及成分(F)的一部分(F1)的水相I,接着乳化并冷却的工序。Step 1D: is a step of obtaining a mixed component of an oil phase containing components (A), (B) and (C); and mixing a salt containing component (D) and a part of component (F) in the oil phase ( The aqueous phase I of F1) is followed by emulsification and cooling.
在这些方法中,将成分(F)的水分为(F1)和(F2)来添加·混合,其质量比例优选为(F1)/(F2)=0.1~9、更优选为0.25~4。In these methods, the water of component (F) is added and mixed as (F1) and (F2), and the mass ratio thereof is preferably (F1)/(F2)=0.1-9, more preferably 0.25-4.
得到的乳化组合物是α-凝胶(α型结晶),抑制结晶(γ型结晶)的析出。α-凝胶可以通过X射线进行结构分析来确认。α型结构的特征在于,是六方晶系,亲油基相对于亲水基层面垂直取向,在Bragg角21~23°附近出现一个尖锐的衍射峰。The obtained emulsified composition is an α-gel (α-type crystal), and precipitation of crystals (γ-type crystal) is suppressed. The α-gel can be confirmed by X-ray structural analysis. The characteristic of the α-type structure is that it is a hexagonal crystal system, the lipophilic group is vertically oriented relative to the hydrophilic group, and a sharp diffraction peak appears near the Bragg angle of 21-23°.
另外,乳化组合物在25℃下的粘度优选为10~8000dPa·s、进一步优选为500~1500dPa·s、更优选为1500~5000dPa·s。本发明的乳化组合物通过组合上述成分,这样可以得到高粘度且弹性的液性。In addition, the viscosity of the emulsified composition at 25° C. is preferably 10 to 8000 dPa·s, more preferably 500 to 1500 dPa·s, and still more preferably 1500 to 5000 dPa·s. The emulsified composition of the present invention can obtain a highly viscous and elastic liquid by combining the above-mentioned components.
另外,在本发明中,粘度是在25℃下通过B8R型旋转粘度计(转子C或D、5r/min、测定1分钟)来测得的。In addition, in the present invention, the viscosity is measured at 25° C. with a B8R type rotational viscometer (spindle C or D, 5 r/min, measurement for 1 minute).
另外,得到的乳化组合物是水包油型乳化组合物,优选作为例如化妆水、乳液、乳脂、凝胶等化妆品或皮肤外用剂。关于上述实施方式,本发明进一步公开以下的乳化组合物的使用方法、用途。In addition, the obtained emulsified composition is an oil-in-water emulsified composition, and is preferably used as cosmetics such as lotion, emulsion, cream, and gel, or external skin preparations. Regarding the above-mentioned embodiment, the present invention further discloses the usage method and application of the following emulsified composition.
含有成分(A)、(B)、(C)、(D)、(E)以及(F)的乳化组合物在用于制造对皮肤的涂布膜形成剂中的用途。Use of an emulsified composition containing components (A), (B), (C), (D), (E) and (F) for producing a coating film-forming agent for skin.
含有成分(A)、(B)、(C)、(D)、(E)以及(F)的乳化组合物在用于制造皮肤外用剂中的用途。Use of an emulsified composition containing components (A), (B), (C), (D), (E) and (F) for the production of an external preparation for skin.
含有成分(A)、(B)、(C)、(D)、(E)以及(F)的对皮肤的涂布膜形成用水包油型乳化组合物。The application film to the skin containing the components (A), (B), (C), (D), (E) and (F) forms an oil-in-water emulsion composition.
实施例Example
实施例1~10以及比较例1~7Examples 1-10 and Comparative Examples 1-7
制造表1以及表2所示组成的水包油型乳化组合物,进行粘度以及残留水分量的测定的同时,对皮膜,通过SAXS进行片层结构的确认以及通过SEM进行表面状态的观察。另外,感官评价湿润的持续性、涂布后的肌肤的触感以及外观。结果一并表示于表1以及表2中。The oil-in-water emulsion compositions with the compositions shown in Table 1 and Table 2 were produced, and the viscosity and residual water content were measured. The lamellar structure of the film was confirmed by SAXS and the surface state was observed by SEM. In addition, the durability of moisture, the touch and appearance of the skin after application were sensory evaluated. The results are shown in Table 1 and Table 2 together.
(制造方法)(Manufacturing method)
在80~90℃下将第I相的成分加热混合,在螺旋桨搅拌下(300rpm)在其中加入加热至80~90℃的第II相的成分,用乳化均质机(homomixer)以7000rpm、10分钟的条件一边施加剪切,一边进行乳化,形成α-凝胶。慢慢冷却至25℃之后,加入第III相的成分,得到水包油型乳化组合物。Heat and mix the ingredients of the first phase at 80-90°C, add the ingredients of the second phase heated to 80-90°C under propeller stirring (300rpm), and use an emulsifying homogenizer (homomixer) at 7000rpm, 10 Minutes of emulsification while applying shear to form α-gel. After slowly cooling to 25° C., the ingredients of Phase III were added to obtain an oil-in-water emulsion composition.
(评价方法)(Evaluation method)
(1)粘度:(1) Viscosity:
在25℃下,通过B8R型旋转粘度计(转子C或D、5r/min、测定1分钟)进行测定。Measured at 25° C. with a B8R-type rotational viscometer (spindle C or D, 5 r/min, measurement for 1 minute).
(2)残留水分量:(2) Residual moisture content:
在6×6cm的金属浅盘中以一定厚度均匀地扩展1g水包油型乳化组合物,在20℃、湿度40%的恒温恒湿下,对相对于时间的质量变化作图。由于经时形成片层皮膜,其后质量变化变得极小。求得质量一定的24小时后的残留水分量,用以下的式子求得制剂中相对于固体成分的水分量。在固体成分中含有成分(A)~(E)的全部成分。1 g of the oil-in-water emulsion composition was uniformly spread to a certain thickness in a metal tray of 6×6 cm, and the mass change with respect to time was plotted at 20° C. and a constant temperature and humidity of 40%. Since the lamellar film is formed over time, the change in mass thereafter becomes extremely small. The amount of residual moisture after 24 hours with a constant mass was obtained, and the amount of moisture relative to the solid content in the formulation was obtained by the following formula. All components of components (A)-(E) are contained in solid content.
(3)通过SAXS的片层结构的确认:(3) Confirmation of the sheet structure by SAXS:
在人造皮革PRARE(注册商标)上以0.001g/cm2均匀地铺展水包油型乳化组合物,使之干燥1天后,以Nano-viewer、30分钟照射,在照相机长度(camera length)649.5mm、2θ=0.2~5°的范围内来测定皮膜表面的状态。Spread the oil-in-water emulsion composition evenly on the artificial leather PRARE (registered trademark) at 0.001g/cm 2 , let it dry for 1 day, and use Nano-viewer, After irradiating for 30 minutes, the state of the film surface was measured in the range of camera length (camera length) 649.5 mm, 2θ=0.2 to 5°.
(4)通过SEM的皮膜表面状态的观察:(4) Observation of the surface state of the film by SEM:
在人造皮革PRARE(注册商标)上以0.001g/cm2均匀地铺展水包油型乳化组合物,使之干燥1天后,通过SEM(扫描电子显微镜)以倍率50倍来观察皮膜表面的状态。结果由以下的基准表示。The oil-in-water emulsion composition was evenly spread on the artificial leather PRARE (registered trademark) at 0.001 g/cm 2 , dried for 1 day, and the state of the surface of the film was observed by SEM (scanning electron microscope) at a magnification of 50 times. The results are shown by the following benchmarks.
○:皮丘·皮沟的边界部分光滑。◯: The boundary portion of Pichu and Pigou is smooth.
△:皮丘·皮沟的边界部分有卷缩。△: There is crimping at the boundary portion of Pichu and Pigou.
×:没有形成皮膜。x: No film was formed.
(5)湿润的持续性、涂布后的肌肤的触感(光滑)以及外观(外观光滑):(5) Persistence of moisture, touch (smoothness) and appearance (smooth appearance) of the skin after application:
12名专门评价小组成员将0.4~0.6g各水包油型乳化组合物涂布于脸上后立刻感官评价“肌肤的触感光滑”以及“肌肤的外观光滑”、涂布10小时经过后再感官评价“湿润的持续性”。用评价为“良好”的专门评价小组成员的人数来表示结果。12 panelists applied 0.4 to 0.6 g of each oil-in-water emulsion composition on the face and immediately sensory evaluated "the touch of the skin is smooth" and "the appearance of the skin is smooth", and after 10 hours after application, the sensory evaluation The "persistence of moisture" was evaluated. The results are expressed in terms of the number of panelists rated as "good".
实施例11~29以及比较例8~9Examples 11-29 and Comparative Examples 8-9
与实施例1~10同样地制造表3~表6所示组成的水包油型乳化组合物,进行粘度以及残留水分量的测定的同时,对皮膜通过SAXS进行片层结构的确认以及通过SEM进行表面状态的观察。另外,评价湿润的持续性、涂布后的肌肤的触感以及外观。结果一并表示于表3~表6中。In the same manner as in Examples 1 to 10, oil-in-water emulsion compositions with the compositions shown in Tables 3 to 6 were produced, and the viscosity and residual water content were measured, and the lamellar structure of the film was confirmed by SAXS and by SEM. Observation of the surface state is carried out. In addition, the durability of moisture, the touch and appearance of the skin after application were evaluated. The results are shown in Table 3 to Table 6 together.
[表3][table 3]
[表4][Table 4]
[表5][table 5]
[表6][Table 6]
实施例1、30~32Embodiment 1, 30-32
与实施例1~10同样地制造表7所示组成的水包油型乳化组合物,进行粘度以及残留水分量的测定的同时,对皮膜通过SAXS进行片层结构的确认以及通过SEM进行表面状态的观察。另外,评价湿润的持续性、涂布后的肌肤的触感以及外观。结果一并表示于表7中。An oil-in-water emulsion composition with the composition shown in Table 7 was produced in the same manner as in Examples 1 to 10, and the viscosity and residual moisture were measured, and the lamellar structure of the film was confirmed by SAXS and the surface state by SEM. observation. In addition, the durability of moisture, the touch and appearance of the skin after application were evaluated. The results are shown in Table 7 together.
[表7][Table 7]
实施例1、30通过制造工序1A来制造,实施例31通过制造工序1C来制造,实施例32通过制造工序1D来制造。通过在油相中配合未中和的成分(D)的制造工序1A来制造的实施例1以及实施例30,涂布后的肌肤触感的光滑性的评价高,确认抑制神经酰胺结晶析出的片层结构,得到保湿效果高的结果,并且得到高粘度。Examples 1 and 30 were manufactured by manufacturing process 1A, Example 31 was manufactured by manufacturing process 1C, and Example 32 was manufactured by manufacturing process 1D. In Example 1 and Example 30 produced by the production process 1A of blending the unneutralized component (D) into the oil phase, the evaluation of the smoothness of the skin touch after application was high, and the sheet that suppressed the precipitation of ceramide crystals was confirmed Layer structure, high moisturizing effect is obtained, and high viscosity is obtained.
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