JP4820164B2 - Oil-in-water emulsified cosmetic - Google Patents

Description

  The present invention relates to an oil-in-water emulsified cosmetic, and particularly relates to an oil-in-water emulsified cosmetic that is easy to use and does not easily lose its makeup over time.

Oil-in-water emulsified cosmetics have a high evaluation because they are fresh and have a good feeling of use. Generally, since the outer phase is water, an emulsifier (high HLB) is used as a surfactant. Therefore, the decorative film after application has a problem that it has poor water resistance and causes makeup loss over time.
In order to solve these problems, a water-soluble polysaccharide derivative (polymer emulsifier) is used, a small amount (content 0.01 to 1.9% by weight) of a hydrophobic emulsifier (HLB is 7 or less) and a hydrophobic powder. By combining these, cosmetics excellent in water resistance while being oil-in-water emulsified cosmetics have been proposed. (See Patent Document 1).
However, in such an emulsified cosmetic, if the water resistance of the cosmetic film is improved, the cosmetic film floats due to moisture below the cosmetic film when sweat is secreted over time, so that the cosmetic collapse is sufficiently prevented. There was a problem that could not.

JP 2003-73226 A

  An object of the present invention is to provide an oil-in-water emulsified cosmetic material that has a good feeling of use and does not easily lose its makeup over time.

The present inventors have found that the above-mentioned problems can be solved by combining a water-soluble alkyl-substituted polysaccharide derivative having a specific structure, a porous spherical powder, and a hydrophobic nonionic surfactant.
That is, the present invention contains (A) a water-soluble alkyl-substituted polysaccharide derivative, (B) an oil agent, (C) a porous spherical powder, (D) a nonionic surfactant having an HLB of 7 or less, and (E) water. An oil-in-water emulsified cosmetic, wherein the content of component (A) is 0.1 to 1% by mass, the content of component (B) is 10 to 50% by mass, and the content of component (C) is 0.00. 05 to 20% by mass, and the content of component (D) is 0.01 to 5% by mass, and component (A) is a part of or all of the hydrogen atoms of the hydroxyl group of the polysaccharide or derivative thereof. The oil-in-water emulsified cosmetics are substituted with the groups (a) and (b), and the ratio of the number of the substituents (a) to the substituents (b) is 1: 1000 to 100: 1. It is.
(A) an alkyl glyceryl ether group having a linear or branched alkyl group having 10 to 40 carbon atoms and / or an alkenyl glyceryl ether group having a linear or branched alkenyl group having 10 to 40 carbon atoms (b) a hydroxyl group Optionally substituted sulfoalkyl group having 1 to 5 carbon atoms or salt thereof

  The oil-in-water emulsified cosmetic of the present invention absorbs sebum and sweat with a well-dispersed powder, has a good feeling of use, and does not easily lose its makeup over time.

Component (A) of the present invention is a water-soluble alkyl-substituted polysaccharide derivative having a polysaccharide or a derivative thereof as a basic skeleton, and a part or all of the hydrogen atoms of the hydroxyl group are represented by the following substituent (a) and substituent: (B) is substituted. The substituent (a) is an alkyl glyceryl ether group having a linear or branched alkyl group having 10 to 40 carbon atoms and / or an alkenyl glyceryl ether group having a linear or branched alkenyl group having 10 to 40 carbon atoms. Yes, the substituent (b) is a C1-C5 sulfoalkyl group which may be substituted with a hydroxyl group or a salt thereof.
In addition, water solubility means what melt | dissolves 0.001 mass% or more in water at 25 degreeC here.

  Specific examples of the substituent (a) include 2-hydroxy-3-alkoxypropyl group, 2-alkoxy-1- (hydroxymethyl) ethyl group, 2-hydroxy-3-alkenyloxypropyl group, 2-alkenyloxy- Examples include 1- (hydroxymethyl) ethyl groups, and these groups may be substituted with a hydrogen atom of a hydroxyl group of a hydroxyethyl group or a hydroxypropyl group bonded to a polysaccharide molecule. The alkyl group or alkenyl group having 10 to 40 carbon atoms substituted on these glyceryl ether groups is preferably a linear or branched alkyl group or alkenyl group having 12 to 36 carbon atoms, particularly 16 to 24 carbon atoms, and emulsifying. From the viewpoint of storage stability of the cosmetic, an alkyl group, particularly a linear alkyl group is preferred. In addition, when the substituent (a) has a hydroxyl group, the hydroxyl group may be further substituted with another substituent (a) or (b).

  Specific examples of the substituent (b) include 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfo-2-hydroxypropyl group, 2-sulfo-1- (hydroxymethyl) ethyl group and the like. , All or a part thereof may be a salt with an alkali metal such as Na or K, an alkaline earth metal such as Ca or Mg, an organic cation group such as amines, or an ammonium ion. In addition, when the substituent (b) has a hydroxyl group, the hydroxyl group may be further substituted with another substituent (a) or (b).

  The degree of substitution of the substituent (a) is preferably 0.001 to 1, particularly 0.002 to 0.5, more preferably 0.003 to 0.1 per constituent monosaccharide residue, and the substituent (b) The substitution degree is preferably 0.01 to 2.5, particularly 0.02 to 2, and more preferably 0.1 to 1.5 per constituent monosaccharide residue. The ratio of the number of substituents (a) to substituents (b) is preferably 1: 1000 to 100: 1, particularly 1: 500 to 10: 1, and more preferably 1: 300 to 10: 1. In the water-soluble alkyl-substituted polysaccharide derivative, the substituents (a) and (b) are not necessarily present in the same repeating unit of the polysaccharide or its derivative, and when viewed as a whole molecule The substituents (a) and (b) may be introduced. The degree of substitution is preferably within the above range on average.

  In addition, the polysaccharide that is the basic skeleton of the water-soluble alkyl-substituted polysaccharide derivative of component (A) or a derivative thereof includes cellulose, guar gum, starch, hydroxyethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch , Ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl starch, hydroxyethyl methylcellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methylcellulose, hydroxypropyl methyl guar gum, hydroxypropyl methyl starch, etc. Among them, cellulose, hydroxyethyl cellulose, Chill cellulose, ethyl cellulose, hydroxypropyl cellulose are preferred. Further, the substituents such as methyl group, ethyl group, hydroxyethyl group, hydroxypropyl group and the like of these polysaccharides may be substituted with a single substituent or may be substituted with a plurality of substituents. The substitution degree per constituent monosaccharide residue is preferably 0.1 to 10, particularly 0.5 to 5. The weight average molecular weight of these polysaccharides or derivatives thereof is in the range of 10,000 to 10,000,000, preferably 100,000 to 5,000,000, particularly preferably 300,000 to 2,000,000.

  The component (A) water-soluble alkyl-substituted polysaccharide derivative of the present invention is partially hydrophobized (introduction of the substituent (a)) or sulfonation (substitution having a sulfonic acid group) of the hydroxyl group of the polysaccharide or its derivative. After the introduction of the group (b), it can be produced by sulfonating or hydrophobizing all or some of the remaining hydroxyl groups, or simultaneously hydrophobizing and sulfonating.

  Substituents (a) and (b) in the polysaccharide derivative are substituted not only with the hydroxyl group of the polysaccharide or its derivative used as a raw material, but also with the hydroxyl group of other substituent (a) or substituent (b). In some cases, such substitution may occur in a superimposed manner. That is, in addition to the compound in which only the hydrogen atom of the hydroxyl group of the polysaccharide or derivative thereof is substituted with the substituents (a) and (b), when the sulfonation is carried out after the hydrophobization, the substituent (a) is further substituted. The group (a) or (b) may be substituted, and the substituent (b) may be further substituted with the substituent (b). In the case of hydrophobization after sulfonation, the substituent (a) is further substituted with the substituent (a), and the substituent (b) is further substituted with the substituent (b) or (a). May be included. Further, when the hydrophobization and sulfonation are performed simultaneously, the substituent (a) or (b) is further substituted on the substituent (a), and the substituent (a) or (b) is further substituted on the substituent (b). ) May be included, and further, substitution to other substituents may be included. In the present invention, any of such polysaccharide derivatives can be used.

  The water-soluble alkyl-substituted polysaccharide derivative of component (A) can be used singly or in combination of two or more, and is preferably blended in an amount of 0.1 to 1% by weight, particularly 0.3 to 0, in the total composition. It is preferable to blend 5 mass%. Within these ranges, the component (B) oil agent and the component (C) porous spherical powder can be uniformly dispersed, and sufficient emulsifiability is obtained, and the feeling in use is also preferable.

  Next, as the component (B) used in the present invention, liquid, semi-solid and solid synthetic and natural oils generally used in cosmetics, for example, volatile isoparaffin, non-volatile liquid paraffin, squalane Hydrocarbon oil such as petrolatum; ester oil such as isotridecyl isononanoate, neopentyl glycol dicaprate, glyceryl monoisostearate, glyceryl monomyristate; vegetable oils such as olive oil and soybean oil; animal oils such as beeswax and lanolin Higher alcohols such as cetyl alcohol and stearyl alcohol; silicone oils such as volatile cyclic silicone, dimethylpolysiloxane and non-volatile dimethylpolysiloxane; fluorine-modified silicone, polyether-modified silicone, alkyl-modified silicone, amino-modified silicone, It may include fluorine oil such as perfluoropolyether; alkoxy-modified silicones, carboxy-modified silicone, modified silicone oil such as methacryl-modified silicone. Volatile oils and non-volatile oils can be used as a mixture, but it is preferable that there are more volatile oils than non-volatile oils, and that the oil is a volatile oil. It is preferable from the point.

  The oil agent of a component (B) can be used individually by 1 type or in combination of 2 or more types, The content is 10-50 mass% in the whole composition, Preferably it is the range of 20-40 mass%. Within this range, the feeling of use is excellent.

Next, the component (C) used in the present invention is a porous spherical powder. In general, in order to improve water resistance, the surface of the porous powder is subjected to a hydrophobic treatment, but in the present invention, the porous spherical powder is not subjected to a hydrophobic treatment such as a silicone treatment or a fluorine treatment. It is preferable. Hydrophobic treatment of the powder improves the longevity of the makeup, but reduces the action of absorbing sebum and sweat and deteriorates the feeling of use over time.
Furthermore, the porous spherical powder in the present invention preferably has a water absorption capacity of 50 mL / 100 g or more. Here, the water absorption capacity refers to that measured by the following method.
<Measurement method of water absorption ability>
It is a value measured according to the two-blade mixing method of the mechanical method (JIS K6221-1982), and is measured using an oil absorption measuring device S-410 (manufactured by Frontex Corporation). In the measurement method, the torque was calculated from the torsion angle of the torsion bar corresponding to the mixing torque when water was dripped onto the powder at 4 mL / min, and the dripping amount of 70% torque of the maximum torque was defined as the water absorption capacity.

The component (C) of the present invention has an action of absorbing sebum and sweat, and suppresses the lift of the makeup film due to sweat, which is a feature of the present invention, and makes it possible to prevent makeup collapse.
The component (C) of the present invention is spherical and includes a substantially spherical form. Use feeling can be improved by being spherical. In the present invention, the porous powder is dispersed in the oil phase, thereby making it possible to maintain a makeup without deteriorating the action of absorbing sebum and sweat.

Specific examples of the porous spherical powder include polyamide, polyacrylate, polymethacrylate, styrene-divinylbenzene copolymer, styrene-stearyl methacrylate-divinylbenzene copolymer, organic porous powder such as cellulose; calcium silicate, silicic acid Silicate metal salts such as aluminum and barium silicate; Carbonate salts such as calcium carbonate and cobalt carbonate; Tungstic metal salts such as calcium tungstate; Metal oxides such as cobalt oxide, α-iron oxide and hydrated iron oxide Silica (including silica gel); hydroxyapatite; lanolin powder and the like.
Among these porous spherical powders, porous silica having a water absorption capacity of 50 to 200 mL / 100 g is preferable.

  The porous spherical powder preferably has an average particle size of 3 to 20 μm, more preferably 5 to 15 μm, and particularly preferably 10 to 15 μm. When the porous spherical powder has an average particle size of 3 μm or more, good spreading is obtained when it is used as a skin cosmetic, and when the average particle size is 20 μm or less, there is no stain and it is good. Moreover, it is preferable that the average pore diameter of the pores in one powder particle is 50 A or more.

  The porous spherical powder of component (C) can be used alone or in combination of two or more, and its content is 0.05 to 20% by mass, preferably 0.1 to 0.1% in the total composition. It is 10 mass%, More preferably, it is the range of 1-5 mass%. If it is within this range, it is possible to sufficiently absorb sebum and sweat, and the feeling of use is also excellent.

Next, the component (D) used in the present invention is a nonionic surfactant having an HLB of 7 or less. By using a nonionic surfactant having an HLB of 7 or less, water resistance is imparted to the oil-in-water emulsified cosmetic of the present invention. Here, the HLB of the nonionic surfactant is calculated by the following Kawakami equation (1).
HLB value = 7 + 11.7 log (Mw / Mo) (1)
Mo: Molecular weight of lipophilic group Mw: Molecular weight of hydrophilic group

  Furthermore, from the viewpoint of water resistance of the coating film after the oil-in-water emulsified cosmetic of the present invention is applied to the skin, the component (D) particularly preferably has an HLB of 5 or less.

  Specific examples of the component (D) include glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbit sorbitan fatty acid ester, polyoxyethylene castor oil, Examples thereof include polyoxyethylene hydrogenated castor oil, ethylene glycol fatty acid ester, polyethylene glycol fatty acid ester, alkyl glyceryl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether fatty acid ester, and silicone surfactant.

  Among these, glycerin fatty acid ester, alkyl glyceryl ether, ethylene glycol mono fatty acid ester, polyethylene glycol mono fatty acid ester and the like are preferable, and α-monoalkyl glyceryl ether of alkyl glyceryl ether is particularly preferable.

  In the present invention, the content of component (D) is in the range of 0.01 to 5% by mass, preferably 0.5 to 5% by mass, more preferably 2.1 to 4% by mass in the total composition. A combination of more than one species can also be used. Within this range, the emulsion type does not phase-invert from the oil-in-water type to the water-in-oil type, and becomes an emulsion of fine emulsified particles, providing sufficient skin familiarity and does not feel sticky during application. .

The water of the component (E) used in the present invention is not particularly limited as long as it is used in ordinary cosmetics. For example, purified water, ion exchange water, natural water, mineral water, etc. Any of them can be used.
The amount of water of component (E) varies depending on the type of skin cosmetic and is not particularly limited, but is substantially 1 to 85% by mass, particularly 10 to 60% by mass, and further 30 to 60% by mass in the total composition. Is preferred.

The particle diameter of the emulsified particles in the oil-in-water emulsified cosmetic of the present invention is preferably 1 to 5 μm. When the particle size of the emulsified particles is within this range, the oil droplets become smaller and the specific surface area of the oil droplets becomes larger. Therefore, when applying the oil-in-water emulsified cosmetic to the skin, The number of contact points can be increased, and the oil agent is not repelled in the water of the outer phase. Therefore, it can be applied to the skin quickly.
Further, when the particle size of the emulsified particles is within the above range, the stability is high even at a high temperature of 40 ° C. or higher. From the above points and easy production, the particle size of the emulsified particles is more preferably in the range of 3 to 5 μm.

  In the oil-in-water emulsified cosmetic of the present invention, in addition to the above components (A) to (E), components usually used as cosmetics, for example, surfactants other than components (A) and (D); various alcohols Humectants such as 1,3-butylene glycol, polyethylene glycol, glycerin; film forming agents; organic ultraviolet absorbers such as paraaminobenzoic acid, octylcinnamate, benzophenone; powders such as titanium oxide, mica, silica; Agents; thickeners; chelating agents; pH adjusters; preservatives; medicinal ingredients; pigments;

  The oil-in-water emulsified cosmetic of the present invention is preferably used as a skin cosmetic, and can be suitably used as a makeup base such as a foundation, a lotion, a milky lotion, a moisturizing cosmetic liquid or a cream.

Production Example 1
(A) Water-soluble alkyl-substituted polysaccharide derivative (1) In a 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser, a hydroxy compound having a weight average molecular weight of about 800,000 and a hydroxyethyl group substitution degree of 1.8 A slurry solution was prepared by adding 50 g of ethyl cellulose (HEC-QP4400, manufactured by Union Carbide), 400 g of 88% isopropyl alcohol and 3.5 g of 48% aqueous sodium hydroxide, and the mixture was stirred at room temperature for 30 minutes in a nitrogen atmosphere. To this was added 5.4 g of stearyl glycidyl ether, and the mixture was reacted at 80 ° C. for 8 hours for hydrophobicity. After completion of the hydrophobic reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 500 g of 80% acetone (20% water) and then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for one day to obtain 49.4 g of a hydrophobized hydroxyethyl cellulose derivative.

(2) In a 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube, 10.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in (1), 80.0 g of isopropyl alcohol and 48% sodium hydroxide A slurry solution was prepared by charging 0.33 g of an aqueous solution, and stirred at room temperature for 30 minutes under a nitrogen stream. A mixed solution consisting of 6.4 g of sodium 3-chloro-2-hydroxypropanesulfonate, 2.7 g of 48% aqueous sodium hydroxide and 20.0 g of water was added to the reaction solution, and sulfonation was performed at 50 ° C. for 9 hours. After completion of the reaction, the reaction solution was neutralized with acetic acid and the product was filtered off. The product was washed three times with 500 g of 80% acetone (20% water) and then twice with 500 g of acetone, and then dried under reduced pressure at 70 ° C. for one day to replace with stearyl glyceryl ether groups and sulfo-2-hydroxypropyl groups. 7.2 g of a water-soluble alkyl-substituted polysaccharide derivative was obtained.

  The water-soluble alkyl-substituted polysaccharide derivative thus obtained has a substitution degree of (a) 3-stearyl glyceryl ether group of 0.030, (b) substitution degree of 3-sulfo-2-hydroxypropyl group of 0.15, and hydrophobicity The ratio of the number of part substituents (a) to hydrophilic part substituents (b) was 1: 5.

Evaluation Method (1) Dispersibility The oil-in-water emulsified cosmetics produced in each Example and Comparative Example were placed in a glass bottle and allowed to stand at room temperature for 1 day, and then evaluated with the naked eye. The evaluation criteria are as follows.
5: Good.
3: Slight aggregation / sedimentation is observed.
1: Aggregation and sedimentation are clearly observed.
(2) Feeling of use 10 expert panelists evaluated the "feeling of use" when the oil-in-water emulsified cosmetics produced in each of the examples and comparative examples were applied to the face with fingers. The percentage of people who were good was expressed as a percentage.
(3) Presence or absence of stickiness after 3 hours Ten expert panelists applied the oil-in-water emulsified cosmetics produced in each Example and Comparative Example to their faces with their fingers, and sensory evaluation of “stickiness” after 3 hours The percentage of people who were “not sticky” was expressed as a percentage.
(4) Makeup after 3 hours Ten expert panelists apply the oil-in-water emulsified cosmetics produced in each of the Examples and Comparative Examples to their faces with their fingers, and sensory evaluation of "makeup breaks" after 3 hours The percentage of the number of people who did not lose their makeup was expressed as a percentage.
(5) Familiarity to the skin at the time of application Ten professional panelists applied the oil-in-water emulsified cosmetics produced in each Example and Comparative Example to the face with their fingers and rubbed them with their fingers until they were familiarized. The average number of times was evaluated (rounded down).

Examples 1-4 and Comparative Examples 1-5
Among the components shown in Table 1, component (A) water-soluble alkyl-substituted polysaccharide derivative (produced in Production Example 1) is dissolved in purified water, and other aqueous phase components are added and mixed to obtain aqueous solution A. It was. The powder shown in Table 1 was added in advance to the oil phase component and strongly dispersed using a disper to obtain dispersion B. The aqueous solution A was transferred to an azimuth mixer, and while the high-speed stirring at 5000 rpm was performed at room temperature, the dispersion B was slowly added and stirred for 30 minutes to obtain an oil-in-water emulsion cosmetic. The results evaluated by the above method are shown in Table 1.

* 1 Water-soluble alkyl-substituted polysaccharide derivative; (A) Water-soluble alkyl-substituted polysaccharide derivative synthesized in Production Example 1 * 2 Hydroxyethyl cellulose; Union Carbide “HEC-QP4400”
* 3 Carboxyvinyl polymer; “Carbopol 941” manufactured by Goodrich
* 4 Porous spherical powder; spherical porous silica (water absorption capacity: 168 ml / 100 g average particle size 12 μm)
* 5 Hydrophobic porous spherical powder; fluorine-treated spherical porous silica (water absorption capacity: 34 mL / 100 g, average particle size 12 μm)
* 6 Appropriate amount; added so that pH was 6.

  The oil-in-water emulsified cosmetic of the present invention is preferably used as a skin cosmetic, and can be suitably used as a makeup base such as a foundation, a lotion, a milky lotion, a moisturizing cosmetic liquid or a cream. The oil-in-water emulsified cosmetic of the present invention has good dispersibility of powder, good usability, and does not easily lose its makeup over time.

Claims (4)

(A) a water-soluble alkyl-substituted polysaccharide derivative, (B) an oil agent, (C) a porous spherical powder having a water absorption capacity of 50 mL / 100 g or more , (D) a nonionic surfactant having an HLB of 7 or less, and (E) An oil-in-water emulsified cosmetic containing water, wherein the content of component (A) is 0.1 to 1% by mass, the content of component (B) is 10 to 50% by mass, and the content of component (C) The amount is 0.05 to 20% by mass, the content of component (D) is 0.01 to 5% by mass, and component (A) is a part of the hydrogen atom of the hydroxyl group of the polysaccharide or derivative thereof, or All are substituted with the following groups (a) and (b), and the ratio of the number of the substituents (a) to the substituents (b) is 1: 1000 to 100: 1. .
(A) an alkyl glyceryl ether group having a linear or branched alkyl group having 10 to 40 carbon atoms and / or an alkenyl glyceryl ether group having a linear or branched alkenyl group having 10 to 40 carbon atoms (b) a hydroxyl group Optionally substituted sulfoalkyl group having 1 to 5 carbon atoms or salt thereof   The degree of substitution of the substituent (a) is 0.001-1 per constituent monosaccharide residue, and the degree of substitution of the substituent (b) is 0.01-2.5 per constituent monosaccharide residue. Item 2. The oil-in-water emulsified cosmetic according to Item 1.   The oil-in-water emulsified cosmetic according to claim 1 or 2, wherein the component (C) has an average particle size of 3 to 20 µm.   The oil-in-water emulsified cosmetic according to any one of claims 1 to 3, wherein the component (C) is porous silica having a water absorption capacity of 50 to 200 mL / 100 g.