JPS6097043A - Emulsified composition - Google Patents

Abstract

PURPOSE:To prepare an emulsion having fine particle size and good in stability, by dissolving a condensate of alkyl ester of amino acid and protein in polyhydric alcohol and adding an oil component to the resulting solution while further mixing water therein. CONSTITUTION:In a condensate of alkyl ester of amino acid having a 14-22C alkyl group and protein (e.g., soy protein) and/or a salt thereof, water-soluble polyhydric alcohol having two or more of hydroxyl groups in the molecule thereof (e.g., ethylene glycol) and an oil component (e.g., tallow) are contained to prepare a uniform transparent or translucent viscous solution or gel. This emulsified composition is further mixed with water to obtain a milk white stable viscous or low viscosity oil in water type emulsified composition having uniform fine particles dispersed therein. The above mentioned emulsified composition or oil in water type emulsified composition can be usefully put into practical use in cosmetics and pharmaceutical products.

Description

DETAILED DESCRIPTION OF THE INVENTION The object of the present invention is to effectively utilize a condensate of an amino acid alkyl ester and a protein or a salt thereof as an emulsifier in cosmetics, medicines, and the like.

In recent years, much research has been conducted on emulsification, a large number of emulsifiers have been developed, and emulsification technology has made remarkable progress, and extremely stable emulsions have been widely used in all industries. However, most of them use nonionic surfactants containing polyoxyethylene chains, anionic surfactants such as fatty acid soaps, cationic surfactants, and double-faced surfactants as emulsifiers, especially for general consumption. Many people have concerns about safety.

In view of these circumstances, the present inventors conducted intensive research to effectively utilize a condensate of an amino acid alkyl ester and a protein, which is considered to be highly safe for the human body, as an emulsifier. If you dissolve it in polyhydric alcohol and add oil to it,
The present inventors have discovered that it is possible to produce an emulsion with good stability and a fine particle size, and have completed the present invention.

That is, in the present invention, the alkyl group has 14 to 22 carbon atoms.
An emulsified composition comprising a condensate of an amino acid alkyl ester and a protein and/or a salt thereof, a water-soluble polyhydric alcohol having two or more hydroxyl groups in the molecule, and an oil component, and this emulsified composition The object of the present invention is to provide a stable oil-in-water emulsion composition having uniform and fine emulsion particles obtained by further mixing with water.

The emulsified composition obtained according to the present invention is a transparent or translucent viscous liquid or gel, and the oil-in-water emulsified composition obtained by adding water is an emulsion of milky white fine particles.

The reason for this fine particle formation is thought to be that the condensate of amino acid alkyl ester and protein and/or its salt are effectively oriented and interact with the polyhydric alcohol/oil interface.

Next, the configuration of the present invention will be explained in detail.

The water-soluble polyhydric alcohol used in the present invention is a water-soluble polyhydric alcohol containing two or more hydroxyl groups in the molecule, such as ethylene glycol, propylene glycol, 1.3-butylene glycol, 1.4-butylene glycol. , dipropylene glycol, glycerin, and polyglycerin such as diglycerin, triglycerin, and tetraglycerin, glucose, maltose, maltitol, sucrose, fructose, xylitol, sorbitol, maltotriose, threitol, erythritol, starch decomposition and sugar reduction Alcohol, etc., and 1 of these
A species or two or more species may be used.

The blending amount is 2 to 95% by weight (hereinafter simply referred to as %) of the emulsified composition consisting of the condensate of amino acid alkyl ester and protein and/or its salt, polyhydric alcohol, and oil phase.

The condensate of an amino acid alkyl ester and a protein used in the present invention is an amino acid in which an alkyl group is ester-bonded to a carboxyl group, and an amide bond is formed with a free carboxyl group of a protein via an amine group. The alkyl group is a saturated, unsaturated, straight chain, or branched alkyl group having 14 to 22 carbon atoms, and specifically includes myristyl, valmityl, stearyl, behenine, aracyl, instearyl, oleyl, palmitooleyl, 2-octyldodecyl group, etc. It is. In addition, the amino acids include phenylalanine, valyl, leucine, alanine, isoleucine, methionine, serine, lysine, tryptophan, glutamic acid, aspartic acid, etc., and it does not matter if D is integrated or DL is integrated, but if preferable.

The condensate of the amino acid alkyl ester having 14 to 22 carbon atoms and protein according to the present invention can be obtained, for example, as follows.

First, amino acid alkyl esters include myristyl alcohol, valmityl alcohol, stearyl alcohol,
Monovalent saturated, unsaturated, straight chain, branched alcohols with 14 to 22 carbon atoms such as behenyl alcohol, aracyl alcohol, isostearyl alcohol, oleyl alcohol, palmitooleyl alcohol, 2-octyldodecanol, etc. and "amino acids" In an organic solvent such as carbon tetrachloride, P
-) Boiling and refluxing using toluenesulfonic acid or the like as a catalyst to form an ester bond.

Next, this amino acid alkyl ester and protein are mixed in an aqueous solution system, a thiol protease such as papain, bromelain, phisin, etc. is added as a catalyst, and the mixture is allowed to react at room temperature. At this time, the protein is hydrolyzed by the enzyme, but at the same time, the amino acid alkyl ester forms an amide bond with the C-terminal carboxyl group of the hydrolyzed protein via the amino group, yielding the desired condensate of the amino acid alkyl ester and protein. It will be done. By changing the reaction time for hydrolysis and amide bonding by the protease and the type of enzyme, the molecular weight of the protein can be arbitrarily changed.

The protein constituting the amino acid alkyl ester and protein condensate of the present invention is usually a protein obtained from nature, such as soybean protein, wheat protein, glutelin, whey powder, soybean casein, soybean flour, fibroin, glucagon, Collagen, gelatin, elastin, egg white lysozyme, amylase, fibrinogen, myosin, enolase, chymotrypsinogen, histone, actin, keratin, hemoglobin, avidin, pepsin, gliadin, growth hormone, albumin, glypurin, myoglobin, casein, papain, β-galactosidase , insulin, lysozyme, and catalase.

When the condensate of the amino acid alkyl ester and protein is used as a salt, the salt-forming substances include inorganic and organic bases and basic inorganic bases including lithium ions, sodium ions, potassium ions, cesium ions, and ammonium ions. , organic salts, basic amino acids such as arginine, hisdecine, lysine, ornithine, basic oligopeptides having these as residues, basic amines such as monoethanolamine, jetanolamine, triethanolamine, amino sugars, etc. , and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, acetic acid, citric acid,
Organic acids such as maleic acid and fumaric acid, glutamic acid,
Acidic amino acids such as aspartic acid and oligopeptides containing them as residues are used. The salt may be reacted in advance to form a salt and then added, or may be added separately and reacted to form a salt during the manufacturing process of the emulsion composition. Although any number of Pl+ may be used in the aqueous salt solution of the condensate of L-amino acid alkyl ester and protein, it is preferable to avoid the isoelectric point of the protein if possible.

In the present invention, any one or two of the above condensates of amino acid alkyl esters and proteins and salts thereof may be used.
You can select and use more than one species.

The blending amount of the condensate of amino acid alkyl ester and protein or its salt and polyhydric alcohol is 1:1 to 1 by weight.
The range is 1000. If the blending amount of polyhydric alcohol is less than 1 to the condensate of amino acid alkyl ester and protein and/or its salt, the solubility of the condensate of amino acid alkyl ester and protein and/or its salt will be poor, If it exceeds , emulsion stability will deteriorate.

The oils used in the present invention include animal and vegetable oils and fats such as beef tallow, squalane, olive oil, and rice bran oil; hydrocarbons; mineral oils such as liquid paraffin and petrolatum; isopromevil myristate; and pentaerythritol-tetra-2-ethylhexanoate. , ester oils such as vitamin A palmitate and vitamin E acetate, and silicone oils such as methylphenyl silicone and dimethyl silicone, which are commonly used in the cosmetics, pharmaceutical, and food industries. In the present invention, one or more of these are selected and used, and for oil, polyhydric alcohol,
It is desirable to adjust the total amount of amino acid alkyl ester, protein, condensate and/or salt thereof to 20% or more.

In addition to the above-mentioned essential components, the emulsified composition according to the present invention may include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, drugs, ultraviolet absorbers, Preservatives, antioxidants, etc. may be mixed and added. Furthermore, alcohol, fatty acids, other water-soluble polymers, etc. may be added for the purpose of homogeneity stabilization and viscosity adjustment.

The emulsified composition of the present invention can be obtained by dissolving a condensation of an amino acid alkyl ester and a protein and/or a salt thereof in a polyhydric alcohol or an aqueous solution thereof, and adding an oil component while stirring. In this case, it is preferable to perform a homomixer treatment, but a good emulsified composition can be obtained even with a weak stirring force such as manual stirring.

The emulsified composition obtained here is a uniform, transparent or translucent gel or viscous liquid, so it can be used as it is, for example, sun care jelly, beauty serum, edible jelly, medicated jelly,
It can be used in all fields such as cosmetics such as pine surge jelly and lubricating oil, medicine, and feed.

The oil-in-water emulsion composition according to the present invention can be obtained by mixing the above-described emulsion composition and water.

In this case, it is desirable to perform homomixer treatment. The oil-in-water emulsion composition obtained here has extremely excellent stability.

Depending on the purpose, water phase components commonly used in the cosmetics, pharmaceutical, food, and other industries are added to the water, such as wetting agents, water-soluble vitamins, water-soluble preservatives, water-soluble drugs, and water-soluble polymers. You can also.

The quantitative relationship between the emulsified composition and water can be selected from a very wide range, but is usually 99.5 to 20 parts of water to 0.5 to 80 parts of the emulsified composition.

The oil-in-water emulsion composition obtained here is a milky white viscous or low viscosity liquid in which uniform fine particles are dispersed, so it can be used in cosmetics such as emulsions, creams, foundations, shampoos, etc. It can be suitably used in all fields such as toiletry products such as conditioners, pharmaceuticals such as urea cream and acne cream, and foods such as mayonnaise. Furthermore, there is no problem in adding other water-soluble polymers, drugs, surfactants, powders, etc. in order to stabilize homogeneity, adjust viscosity, or impart medicinal effects.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. The present invention is not limited thereby.

Examples 1 to 8, Comparative Examples 1 to 3 A salt of a condensate of L-leucine alkyl ester and a protein, a polyhydric alcohol, purified water, and an oil component were blended in the composition and amounts shown in Table 1, and the mixture was heated at 70°C. 1 A mixer treatment was performed to prepare an emulsified composition. Further, 10 times the amount of water was added to this emulsified composition while stirring at room temperature to prepare an oil-in-water emulsified composition. The states of the emulsified composition and oil-in-water emulsified composition were observed, and their characteristic values were measured, and the results are shown in Table 1. Note that the numbers for each component are weight %.

(The following is a margin) 2 (Note) of Table-1 The condition of the oil-in-water emulsion composition was judged based on the following criteria after being left for one day.

■ Emulsion particle diameter 1μ or less 0 1-5μ △ 5-10μ ),
and a composition that does not contain polyhydric alcohol and has water as an external phase (
In Comparative Example 2), a stable emulsified composition was not obtained.

Furthermore, even if a salt of a condensate of L-leucine alkyl ester and protein, a polyhydric alcohol, and an oil were included, a stable emulsion composition could not be obtained if the polyhydric alcohol was relatively small (Comparative Example 3). . On the other hand, in Examples 1 to 8 according to the present invention, very good transparent or translucent viscous liquids or gels were obtained at all levels, and furthermore, they were obtained by adding water. The oil-in-water emulsion composition was a stable emulsion with very fine particles dispersed therein.

Example 9 Aqueous cosmetic oil (% by weight) (A,) L-methionine stearyl ester gelatin condensate arginine salt 2.0 Maltitol (70% aqueous solution) 30.0 1.3-Butylene glycol 10.0 Sodium chondroitin sulfate 0 .511↓ (B) Liquid paraffin 30.0 Olive oil 20.8 Glyceryl tristearate 5.0 Vitamin E acetate 0.5 Vitamin A palmitate 0.5 Preservative 0.5 Fragrance 0.2 (A) phase at 70°C The mixture was thoroughly stirred, and the (B) phase dissolved at 70°C was added to the (A,) phase with stirring. This product was treated with a homomixer, stirred and cooled to obtain an aqueous cosmetic oil. This cosmetic oil is a viscous, slightly fluid, transparent gel-like emulsion that is highly safe for the skin and has excellent stability over time.When applied to the skin, it spreads very easily and in small amounts. It had a wide range of usage characteristics.

Example 10 (% by weight) (A) Pharmacopoeia glycerin 20.0 1.3-butylene glycol 5. O L-leucine behenyl ester elastin condensate 2.0 5 L-leucine oleyl ester globulin condensate 1.0 Allantoin 0.2 Sodium hydroxide 0.1 (B) Liquid paraffin 10.0 Olive oil 5.0 Pentaerythritol-tetra - 2-Ethylhexanoate 5.0 Vaseline 5.0 Ethinylestradiol 0.1 Preservative 0.4 Flavor 0.3 (C) Purified water 45.5 Sodium alginate 0.1 Xanthine gum 0.1 Kizuna extract 0 .1 Aspergillus japonica extract 0.1 According to the manufacturing method of Example 9, an emulsified composition was obtained from phase (A) and (B), and the temperature was adjusted to 70°C. The mixture was diluted and dispersed in the aqueous solution (C) phase, and then cooled to obtain a nutritional milky lotion as an oil-in-water emulsion. The viscosity of this emulsion was 4280 cp at 30°C, and the emulsion particle size was 1 to 3.
It had a stable and familiar feel on the order of μ.

Example 11 Suncare cream (wt%) (A) Diglycerin 20.0 Sorbitol (70% aqueous solution) 8.0 Glucose (50% aqueous solution) 4. O L-leucine palmitooleyl ester milk protein condensate hydrochloride 2. OL-leucine 2-octyldodecyl ester albumin m compound 0.5 (B) Liquid paraffin 20.0 Isopropyl myristate 10.0 Vaseline 5.0 Stearyl alcohol 5. O P A B A 2.0 Preservative 0.5 Fragrance 0.3 (C) Purified water 19.5 Hydroxyethyl cellulose 0.2 (D) Mixed powder 1.0 Titanium dioxide 2.0 According to the manufacturing method of Example 10 Accordingly, a sun care cream was obtained. At this time, phase (C) was used as a diluted phase after subjecting (D) to a dispersion homomixer treatment at 70°C. This sun care cream is a stable oil-in-water emulsion composition with a hardness of 7/7 at 25°C, a slightly transparent feeling, and an emulsion particle size of about 1 to 3 μm, making it suitable for use under sunlight. It was usable.

Patent applicant: Shiseido Co., Ltd. 1.8 Procedural amendment (voluntary) November 2, 1981 1, Indication of the case 1988 Patent Application No. 205528 2, Name of the invention Emulsified composition 3, Amendment 4. Detailed explanation of the invention column 9 in the specification subject to amendment Insert.

that's all

Claims (1)

[Scope of Claims] (A condensate of an amino acid alkyl ester with an 11 alkyl group having 14 to 22 carbon atoms and a protein and/or a salt thereof; and a water-soluble polyhydric alcohol having two or more hydroxyl groups in the molecule; , and an oil component. (2) A condensate of an amino acid alkyl ester whose alkyl group has 14 to 22 carbon atoms and a protein and/or a salt thereof, and two or more in the molecule. An oil-in-water emulsion composition comprising a water-soluble polyhydric alcohol having a hydroxyl group, an oil component, and water.