JP2013056943A - Water-in-oil emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-in-oil emulsion composition compounded with a large amount of a silicone oil which is excellent in emulsion stability and improved in stickiness.SOLUTION: The water-in-oil emulsion composition is obtained by compounding: (A) a specific N-long-chain acyl neutral amino acid ester; (B) a silicone oil; and (C) water.

Description

  The present invention relates to a water-in-oil emulsion composition containing a specific N-long chain acyl neutral amino acid ester, silicone oil, water, and a cosmetic containing a water-in-oil emulsion composition.

  Water-in-oil emulsified cosmetics have the advantages of protecting the skin and imparting flexibility because the outer phase is oily. On the other hand, when stored at high temperatures, the system becomes unstable and water droplets coalesce and phase separation. There is a problem that it causes a stickiness when it is applied to the skin because the external phase is oil. It has been common knowledge to eliminate the sticky feeling by adding a high amount of silicone oil, but it is extremely difficult to emulsify the silicone oil itself, and various attempts have been made to stabilize the emulsion.

  Patent Document 1 and Patent Document 2 disclose a water-in-oil emulsion composition containing a specific emulsifier and containing a specific emulsifier in order to obtain an excellent water-in-oil emulsion composition. Yes. However, the emulsifiers that can be used for preparing the water-in-oil emulsion composition are extremely limited, and it is necessary to add a high amount of a surfactant.

  Patent Document 3 discloses a technique for stabilizing a water-in-oil emulsion composition using a clay mineral obtained by treatment with a quaternary ammonium salt. Patent Document 4 discloses that an extremely stable water-in-oil emulsion composition can be obtained when an organically modified clay mineral obtained by treatment with an N-long chain acyl acidic amino acid ester and a quaternary ammonium salt is contained. Is disclosed. However, there is no example of highly blending silicone oil as the oil phase, and when silicone oil is blended in a high amount, an emulsion composition cannot be obtained.

  On the other hand, Patent Document 5 discloses an N-long chain acyl neutral amino acid ester. However, even though it is known as a highly safe oil-based raw material, the knowledge that it has emulsifying ability has never been known.

  A water-in-oil emulsified composition with a high silicone oil blend, which has excellent emulsification stability and improved stickiness, has been highly desired.

JP 2006-169130 A JP 2006-306868 A JP 61-129033 A JP-A-8-20529 Japanese Patent No. 3802288

  An object of the present invention is to provide a water-in-oil emulsion composition with high silicone oil blending, which has excellent emulsion stability and improved stickiness.

  As a result of intensive studies to solve the above problems, the present inventor has solved the problem by blending (A) N-long chain acyl neutral amino acid ester, (B) silicone oil, and (C) water. We found what we could do and completed the invention.

That is, the present invention includes the following aspects.
[1] (A) N-long-chain acyl neutral amino acid ester represented by the following general formula (I) (B) containing silicone oil, (C) water, and the outer phase being (B) silicone oil A water-in-oil emulsion composition characterized by the above. (However, in the general formula (I), R ¹ represents a branched or straight chain alkyl group or alkenyl group having 5 to 21 carbon atoms, and R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ³ represents a hydrogen atom, a methyl group or an ethyl group, a branched or straight chain alkyl group having 3 to 4 carbon atoms, or a hydroxymethyl or hydroxyethyl group, and R ⁴ has 1 to 34 carbon atoms. A branched or straight chain alkyl group or alkenyl group, or an alcohol residue of sterol, and n represents an integer of 0 to 2.)

[2] The weight ratio of the component (A) and the component (B) is 4:96 to 90:10, and the weight of the component (C) is 0.1 to 94.6% with respect to the composition. The water-in-oil emulsion composition according to claim 1.
[3] The neutral amino acid of component (A) is one or more selected from glycine, alanine, N-methyl-β-alanine, threonine, and sarcosine. The water-in-oil type emulsion composition in any one of -2.
[4] The component (A) is one or two selected from N-myristoyl-N-methyl-β-alanine phytosteryl and N-myristoyl-N-methyl-β-alanine decyltetradecyl. A water-in-oil emulsion composition characterized by the above.
[5] The water-in-oil emulsion composition according to any one of claims 1 to 4, wherein the component (B) is a cyclic silicone oil.
[6] A cosmetic comprising the water-in-oil emulsion composition according to any one of claims 1 to 5.

  By blending a specific N-long chain acyl neutral amino acid ester, silicone oil and water, it has become possible to provide a water-in-oil emulsion composition having excellent emulsification stability and improved stickiness. .

  The component (A) used in the present invention is an N-long chain acyl neutral amino acid ester represented by the following general formula (I).

However, in the general formula (I), R ¹ represents a branched or straight chain alkyl group or alkenyl group having 5 to 21 carbon elements, and R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. , R ³ represents a hydrogen atom, a methyl group or an ethyl group, a branched or straight chain alkyl group having 3 to 4 carbon atoms, or a hydroxymethyl or hydroxyethyl group, and R ⁴ represents a branched chain having 1 to 34 carbon atoms. A chain or straight chain alkyl group or alkenyl group, or an alcohol residue of a sterol, and n represents an integer of 0 to 2.

  The N-long chain acyl neutral amino acid ester which is the component (A) used in the present invention can be easily obtained by known methods such as Japanese Patent No. 2990624 and Japanese Patent No. 3802288. Specifically, a method of esterifying alcohol or sterol after the Schotten-Baumann reaction between a neutral amino acid and a fatty acid halide is widely known.

  As the neutral amino acid of component (A), glycine, alanine, N-methyl-β-alanine, threonine, sarcosine, β-alanine, phenylalanine, proline, valine, leucine, isoleucine, serine, hydroxyproline, aminobutyric acid, aminocapron Acid or the like can be used. These amino acids may be L-form, D-form or DL-form. One of these may be used, or two or more selected from the above group may be mixed and used. N-methyl-β-alanine is preferable from the viewpoint of stability and good usability of the material after esterification.

  As the acyl group of component (A), a linear or branched one derived from a saturated or unsaturated fatty acid having 8 to 22 carbon atoms can be used. For example, as the fatty acid, caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, isostearic acid, palmitic acid, oleic acid, linoleic acid, behenic acid, coconut oil fatty acid, palm fatty acid, hardened beef tallow fatty acid, etc. It is done. One of these may be used, or two or more selected from the above group may be mixed and used. In particular, lauric acid, myristic acid, and palm fatty acid are preferable, and myristic acid is particularly preferable from the viewpoint of obtaining a stable water-in-oil emulsion composition.

As the hydrocarbon group (R ⁴ ) constituting the alcohol moiety of the N-long chain acyl neutral amino acid ester of component (A), a branched or straight chain alkyl group having 1 to 34 carbon elements or a straight chain alkyl group or alkenyl group, Sterols can be used. For example, methanol, ethanol, propanol, isopropanol, butanol, t-butanol, isobutanol, 3-methyl-1-butanol, 2-methyl-1-butanol, fusel oil, pentanol, hexanol, cyclohexanol, octanol, 2- Ethylhexanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, aralkyl alcohol, behenyl alcohol, jojoba alcohol, 2-hexadecyl alcohol, 2-octyldodecanol, isostearyl alcohol, decyl Tetradecanol, tetradecyl octadecanol, cholesterol, dihydrocholesterol, sitosterol, campesterol Stigmasterol, it may be mentioned those derived phytosterols, and lanosterol. Among these, preferred are isostearyl alcohol, decyltetradecanol, tetradecyloctadecanol, behenyl alcohol, phytosterol, cholesterol and sitosterol, and particularly preferred are decyltetradecanol and phytosterol. Of these, one type may be used, or two or more types selected from the above counties may be mixed and used. These may be animal-derived, plant-derived, or synthetic.

  Although there is no restriction | limiting in particular as a component (B) silicone oil, The solid or liquid silicone oil normally used for cosmetics can be used. Specifically, methylpolysiloxane, highly polymerized methylpolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, polyoxyethylene / methylpolysiloxane copolymer, cross-linked methylpolysiloxane Polysiloxanes such as siloxane and cross-linked methylphenyl polysiloxane; modified silicones such as polyether-modified silicone, fatty acid-modified silicone, acrylic-modified silicone, fluorine-modified silicone, amino-modified silicone, and alkyl-modified silicone; decamethyltetrasiloxane, octamethylcyclo Tetrasiloxane, octamethylcyclopentasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, methylcyclopolysiloxane Cyclic silicones etc., and the like. One of these may be used, or two or more selected from the above group may be mixed and used. From the viewpoint that a stable water-in-oil emulsion composition can be easily obtained regardless of other conditions, liquid silicone is preferable, cyclic silicone is more preferable, decamethyltetrasiloxane, octamethylcyclotetrasiloxane, octamethylcyclopentasiloxane. Decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and methylcyclopolysiloxane are more preferable, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane are still more preferable, and decamethylcyclopentasiloxane is particularly preferable.

  The water which is the component (C) used in the present invention is not particularly limited as long as it is of a purity that is generally used for cleaning agents and cosmetics. Specifically, ion exchange water, well water, natural water, ground water, city water, hard water, soft water, and the like can be used. One of these may be used, or two or more selected from the above group may be mixed and used. Ion exchange water is preferred from the viewpoint of storage stability and hygiene of the product of the present invention.

  The weight ratio of the component (A) and the component (B) used in the present invention is not particularly limited as long as it forms a water-in-oil emulsion composition, but is preferably 4:96 to 90:10. When the amount of the component (A) is less than 4, a sufficient emulsified state may not be obtained and phase separation may occur, and when the amount of the component (A) exceeds 90, fluidity may be deteriorated. From the viewpoint of obtaining a stable water-in-oil emulsion composition, 5:95 to 80:20 is more preferable, and 6:94 to 75:25 is still more preferable.

  The weight of the component (C) used in the present invention is not particularly limited as long as it forms a water-in-oil emulsion composition, but with respect to the total weight of (A), (B) and (C). 0.1 to 94.6% by weight is preferable. When the weight of the component (C) is less than 0.1% by weight, it may be difficult to form an emulsified composition. When the weight is more than 94.6%, water separation may occur. From the viewpoint of obtaining a stable water-in-oil emulsion composition, 0.5 to 90% is more preferable, and 1.0 to 80% is particularly preferable.

  The water-in-oil emulsion composition of the present invention can be used as cosmetics such as sunscreen creams, moisturizing creams, makeup removers, liquid foundations, and foundation creams.

  The water-in-oil emulsified composition of the present invention includes various optional components used in normal cosmetics, quasi drugs, etc. in addition to the above-described essential components, such as hydrocarbons, higher fatty acid esters, animal and vegetable oils and fats, and fluorine-based emulsions. Oily components such as oil, powders such as organic pigments and inorganic pigments, water-soluble polymers, aqueous components such as alcohols, surfactants, ultraviolet absorbers, moisturizers, antioxidants, cosmetic ingredients, preservatives, A fragrance | flavor etc. can be suitably mix | blended to such an extent that the effect of this invention is not inhibited.

  As the oil component, in addition to silicone oil, which is an essential component, solid oil, semi-solid oil, liquid oil, volatile oil, and the like that are generally used in cosmetics can be used. Examples include hydrocarbons, fats and oils, waxes, hardened oils, esters, fatty acids, higher alcohols, fluorine oils, lipophilic surfactants, and the like. These may be animal oil, vegetable oil, mineral oil, or synthetic oil. Specifically, solid paraffin wax, microcrystalline wax, carnauba wax, ceresin wax, beeswax, wood wax, spermaceti, polyethylene wax, liquid paraffin, squalane, polybutene, polyisobutene, petrolatum, olive oil, castor oil, jojoba oil, macadamian nut Oil, rosin acid pentaerythritol ester, dipentaerythritol fatty acid ester, cholesterol fatty acid ester, phytosterol fatty acid ester, lanolin, isopropyl myristate, isopropyl palmitate, cetyl 2-ethylhexanoate, octyldodecyl myristate, glyceryl trioctanoate, Diglyceryl polyisostearate, stearic acid, lauric acid, myristic acid, behenic acid, isostearic acid, oleic acid, cetyl al Lumpur, stearyl alcohol, lauryl alcohol, isostearyl alcohol, oleyl alcohol, perfluorooctane, perfluoro decane, perfluoro polyether, glyceryl monostearate, include sorbitan tristearate, and the like.

  The powder is not limited to a shape as long as it is a powder generally used in cosmetics, and any of a spherical shape, a plate shape, a needle shape, and the like can be used. For example, inorganic powders include talc, kaolin, mica, synthetic mica, sericite, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, magnesium aluminum silicate, anhydrous silicic acid, silicon carbide, barium sulfate, bentonite , Smectite, Titanium oxide, Zinc oxide, Magnesium oxide, Aluminum oxide, Bengala, Yellow iron oxide, Black iron oxide, Titanium oxide, Chromium oxide, Conger, Ultramarine, Iron oxide mica, Iron oxide mica titanium, Mica titanium, Bismuth oxychloride Examples of organic powders include nylon powder, polyethylene powder, polystyrene powder, methyl methacrylate powder, polytetrafluoroethylene powder, wool powder, silk powder, crystalline cellulose, tar dyes, and lake dyes thereof. Those complexed one or more of these powders and the like. Furthermore, what surface-treated using 1 type (s) or 2 or more types, such as a fluorine compound, a silicone type oil agent, metal soap, wax, fats and oils, and a hydrocarbon, can also be used.

  The aqueous component can be used without particular limitation as long as it is a water-soluble component generally used in cosmetics. For example, glycerols such as glycerin, diglycerin and polyglycerin, glycols such as propylene glycol, dipropylene glycol, butylene glycol and polyethylene glycol, saccharides such as sorbitol, sucrose and maltitol, guar gum, gum arabic, carrageenan and alginic acid Sodium, chondroitin sodium sulfate, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxyvinyl polymer, polyvinyl alcohol, polyvinylpyrrolidone, alkylated carboxyvinyl polymer, water-soluble polymer such as sodium polyacrylate, sodium chloride, magnesium chloride, sodium lactate, Salts such as sodium pyrrolidonecarboxylate, zinc pyrrolidonecarboxylate, rose, lemon, la Plant extracts such as Nda like.

  Examples of the surfactant include an anionic surfactant, an N-long chain acyl amino acid salt, an N-long chain acyl acidic amino acid salt such as an N-long chain acyl glutamate and an N-long chain acyl aspartate, N-long chain acyl glycine salt, N-long chain acyl alanine salt, N-long chain acyl neutral amino acid salt such as N-long chain acyl threonine salt, N-long chain fatty acid acyl-N-methyl taurine salt, alkyl Examples thereof include sulfates and their alkylene oxide adducts, fatty acid amide ether sulfates, metal salts and weak base salts of fatty acids, sulfosuccinic acid surfactants, and alkyl phosphates. Examples of amphoteric surfactants include betaine type surfactants such as alkylbetaines, alkylamide betaines, aminopropionates, and carboxybetaines, aminocarboxylic acid type surfactants, imidazoline type surfactants, and the like. As cationic surfactants, aliphatic amine salts such as alkyl ammonium chloride and dialkyl ammonium chloride, aromatic quaternary ammonium salts such as quaternary ammonium salts and benzalkonium salts, fatty acid acyl arginine esters, alkyloxyhydroxypropyl arginine Examples include salts. Nonionic surfactants include glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, propylene glycol fatty acid ester and its alkylene glycol adduct, butylene glycol fatty acid ester and its alkylene glycol adduct, Sorbitol fatty acid ester and its alkylene glycol adduct, polyalkylene glycol fatty acid ester, sucrose fatty acid ester, glycerin alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene hydrogenated castor oil, lanolin alkylene glycol addition Thing etc. are mentioned.

  Examples of ultraviolet absorbers include organic substances (photoprotective filters) that are liquid or crystalline at room temperature, absorb ultraviolet rays, and release the absorbed energy as longer wavelength radiation (for example, heat). is there. The UV-B filter can be oil-soluble or water-soluble. Examples of the oil-soluble substance include 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof such as 3- (4-methylbenzylidene) -camphor; 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) -Benzoic acid-2-ethylhexyl ester, 4- (dimethylamino) -benzoic acid-2-octyl ester, and 4- (dimethylamino) -benzoic acid amyl ester; cinnamic acid ester, preferably 4-methoxycinnamic acid-2 -Ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid-2-ethylhexyl ester [Octocrylene]; salicylic acid ester, preferably salicylic acid 2-ethylhexyl ester, salicylic acid-4-isopropylbenzyl ester, salicylic acid homomenthyl ester; benzophenone derivatives, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2 ' -Dihydroxy-4-methoxybenzophenone; benzalmalonic acid ester, preferably 4-methoxybenzalmalonic acid di-2-ethylhexyl ester; triazine derivatives such as 2,4,6-trianilino- (p-carbo-2'-ethyl- 1′-hexyloxy) -1,3,5-triazine, and octyl triazone, or dioctyl butamide triazone [Uvasorb® HEB]; propane-1,3-dione, such as 1- (4-t − Butylphenyl) -3- (4'-methoxyphenyl) - propane-1,3-dione; Ketotorishikuro (5.2.1.0) decane derivatives. Suitable water-soluble substances are, for example, 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucamonium salts; sulfonic acid of benzophenone Derivatives, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; sulfonic acid derivatives of 3-benzylidene camphor, such as 4- (2-oxo-3-bornylidenemethyl) -benzenesulfonic acid and Examples include 2-methyl-5- (2-oxo-3-bornylidene) -sulfonic acid and salts thereof. Conventional UV-A filters are inter alia as benzoylmethane derivatives, for example 1- (4′-t-butylphenyl) -3- (4′-methoxyphenyl) -propane-1,3-dione, 4-t-butyl. -4′-methoxydibenzoylmethane (Parsol (registered trademark) 1789) or 1-phenyl-3- (4′-isopropylphenyl) -propane-1,3-dione, and enamine compounds.

  Examples of the humectant include mucopolysaccharide, collagen, peptide, keratin and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following Example.

Examples 1 to 24 and Comparative Examples 1 to 12:
The water-in-oil type emulsion composition (Examples 1-24, Comparative Examples 1-12) which consists of a compounding composition of the following Tables 1-5 was prepared. (A) N-myristoyl-N-methyl-β-alanine phytosteryl and N-myristoyl-N-methyl-β-alanine decyltetradecyl as (N) long-chain acyl neutral amino acid ester, (B) silicone As the oil, dodecamethylcyclohexasiloxane (DC246, Toray Dow Corning Silicone Co., Ltd.) was used.

(Evaluation of storage stability of water-in-oil emulsion composition)
Immediately after the preparation, the phase state after 2 weeks and 4 weeks at 40 ° C. was visually observed, and the stability was evaluated according to the following criteria.
A: Phase separation was not observed after 4 weeks of storage at 40 ° C. ○: Phase separation was observed after 4 weeks of storage at 40 ° C. Δ: Phase separation was observed after 2 weeks of storage at 40 ° C. ×: Phase immediately after preparation at 25 ° C. Separation was observed

(Evaluation of feeling of use of water-in-oil emulsion composition)
The feeling of use when the prepared water-in-oil emulsion composition was applied to the skin was subjected to sensory evaluation by three specialized panelists and evaluated based on the following evaluation criteria. The average value of the three evaluation points was calculated, 0 or more and less than 1 point was evaluated as x, 1 or more and less than 2 points was evaluated as Δ, 2 or more and less than 3 points as ◯, and 3 or more and 4 points or less as ◎.
4 points: Very smooth and good water-in-oil emulsion composition.
3 points: A smooth and good water-in-oil emulsion composition.
2 points: A slightly smooth water-in-oil emulsion composition.
1 point: It is a water-in-oil emulsion composition that is slightly hard and has poor elongation.
0 point: It does not have the shape of a water-in-oil emulsion composition that is very hard and has poor elongation, or a water-in-oil emulsion composition such as phase separation.

  As apparent from Tables 1 to 5, (A) N-long chain acyl neutral amino acid ester, (B) silicone oil, and (C) water-in-oil emulsification having good storage stability and feeling of use. Compositions were obtained (Examples 1-24). When N-long chain acyl acidic amino acid ester was used, no water-in-oil emulsion composition was obtained, and separation occurred immediately after preparation (Comparative Examples 1 to 6).

Examples 25-30:
The water-in-oil type emulsion composition (Examples 25-30) which consists of a mixing | blending composition of following Table 6 was prepared, and the same evaluation as Tables 1-5 was performed. In addition, decamethylcyclopentasiloxane (SH245, Toray Dow Corning Silicone Co., Ltd.) was used as (B) silicone oil.

  As is apparent from the results in Table 6, a water-in-oil emulsion composition comprising component (A) N-long chain acyl neutral amino acid ester, (B) silicone oil, and (C) water could be obtained. .

Formulation Examples 1-3
When the sunscreen formulations shown in Tables 7 to 9 below were prepared according to a conventional method, all were able to obtain good usability and storage stability.

Formulation Examples 4-31
Tables 10 to 37 disclose formulation examples.

  According to the present invention, a water-in-oil emulsified cosmetic with excellent emulsification stability and improved stickiness can be provided by blending a specific N-long chain acyl neutral amino acid ester, silicone oil, and water. It is very significant that it has become.

Claims (6)

(A) N-long-chain acyl neutral amino acid ester represented by the following general formula (I) (B) Silicone oil, (C) Water-in-oil emulsion composition characterized by containing water. (However, in the general formula (I), R ¹ represents a branched or straight chain alkyl group or alkenyl group having 5 to 21 carbon atoms, and R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ³ represents a hydrogen atom, a methyl group or an ethyl group, a branched or straight chain alkyl group having 3 to 4 carbon atoms, or a hydroxymethyl or hydroxyethyl group, and R ⁴ has 1 to 34 carbon atoms. A branched or straight chain alkyl group or alkenyl group, or an alcohol residue of sterol, and n represents an integer of 0 to 2.)

  The weight ratio of the component (A) to the component (B) is 4:96 to 90:10, and the weight of the component (C) is 0.1 to 94.6% with respect to the composition. 2. The water-in-oil emulsion composition according to 1.   The neutral amino acid of the component (A) is one or more selected from glycine, alanine, N-methyl-β-alanine, threonine, and sarcosine. The water-in-oil emulsion composition according to any one of the above.   The component (A) is one or two selected from N-myristoyl-N-methyl-β-alanine phytosteryl and N-myristoyl-N-methyl-β-alanine decyltetradecyl. A water-in-oil emulsion composition.   The water-in-oil emulsion composition according to any one of claims 1 to 4, wherein the component (B) is a cyclic silicone oil.   Cosmetics containing the water-in-oil type emulsion composition as described in any one of Claims 1-5.