JPH0359735B2 - - Google Patents

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 are now 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. The present inventors have discovered that it is possible to produce emulsions with fine particle size and good stability by dissolving them in polyhydric alcohol and adding an oil component thereto, leading to the completion of the present invention. That is, the present invention provides a condensate of an amino acid alkyl ester whose alkyl group has 4 to 12 carbon atoms, excluding L-leucine, and a protein and/or a salt thereof, and a water-soluble polyester having two or more hydroxyl groups in the molecule. The present invention provides an emulsified composition containing an alcohol and an oil component, and a stable oil-in-water emulsified composition having uniform and fine emulsified particles obtained by further mixing this emulsified composition with water. be. The emulsion composition obtained according to the present invention is a transparent or translucent viscous liquid or gel, and the oil-in-water emulsion composition to which water is added is an emulsion of milky white fine particles. The cause of this fine particle formation is that the condensate of amino acid alkyl ester and protein and/or its salt is effectively oriented at the polyhydric alcohol/oil interface.
This is thought to be due to interaction. 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, glycose, maltose, maltitol, sucrose, fructose, xylitol, sorbitol, maltotriose, threitol,
These include erythritol, starch-decomposing sugar-reducing alcohol, and one or more of these are used. The blending amount is 2 to 95% by weight of the emulsion composition consisting of the condensate of amino acid alkyl ester and protein and/or its salt, polyhydric alcohol, and oil phase.
(hereinafter simply referred to as %). 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 amino group. The alkyl group is a saturated, unsaturated, linear, or branched alkyl group having 4 to 12 carbon atoms, and specifically includes butyl, heptyl, hexyl, isohexyl, hexenyl, octyl, dodecyl, isododecyl, and the like. In addition, amino acids include phenylalanine, valine, leucine, alanine, isoleucine, methionine, serine, lysine, tryptophan, glutamic acid, aspartic acid, etc., and may be in the D-form or L-form DL form, - Only leucine is excluded from the scope of the invention. Among the above amino acids except L-leucine, L
- body is preferred. The condensate of the amino acid alkyl ester having 4 to 12 carbon atoms and protein according to the present invention can be obtained, for example, as follows. First, amino acid alkyl esters include amino acid alkyl esters having 4 to 12 carbon atoms, such as butanol, heptanol, hexanol, hexenol, octanol, dodecanol, isohexanol, and isododecanol.
A saturated, unsaturated, linear, or branched alcohol and an amino acid are boiled and refluxed in an organic solvent such as carbon tetrachloride using P-toluenesulfonic acid 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, promelain, phaicin, 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, resulting in a condensation of the target amino acid alkyl ester and protein. is obtained. 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 condensate of amino acid alkyl ester and protein of the present invention is usually a protein obtained from nature, such as soybean protein, wheat protein, glutelin, whey powder, soybean casein,
Soy flour, fibroin, glucagon, collagen, gelatin, elastin, egg white lysozyme, amylase, fibrinogen, myosin, enolase, chymotrypsinogen, histones, actin, keratin, hemoglobin, avidin, pepsin, gliadin, growth hormone, albumin, glybulin, myoglobin, casein, papain,
Mention may be made of 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, arginine, histidine, lysine,
Basic amino acids such as ornithine, basic oligopeptides containing them as residues, bases such as basic amines such as monoethanolamine, diethanolamine, triethanolamine, and amino sugars, and hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, etc. Acids such as inorganic acids, organic acids such as acetic acid, citric acid, maleic acid, and fumaric acid, acidic amino acids such as glutamic acid and aspartic acid, and oligopeptides containing these 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 during the manufacturing process of the emulsion composition to form a salt. The pH of the aqueous salt solution of the condensate of L-amino acid alkyl ester and protein may be any value, but it is preferable to avoid the isoelectric point of the protein if possible. In the present invention, one or more of the above condensates of amino acid alkyl esters and proteins and salts thereof can be selected and used. The weight ratio of the condensate of amino acid alkyl ester and protein or its salt and polyhydric alcohol is in the range of 1:1 to 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 deteriorate,
When it exceeds 1000, emulsion stability deteriorates. 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, and hydrocarbons, mineral oils such as liquid paraffin and petrolatum, isopromepyl 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 the total amount of polyhydric alcohol, amino acid alkyl ester, protein, condensate and/or salt thereof is 20% of the oil content. It is desirable to adjust so that the above is achieved. 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 and the like 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 the condensation of amino acid alkyl ester and protein and/or its salt 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, in sun care jelly, beauty serum, edible jelly, medicinal jelly, pine surge jelly, lubricating oil, etc. It can be used in all fields such as cosmetics, medicine, and feed. To obtain the oil-in-water emulsion composition according to the present invention,
It can be obtained by mixing the emulsified composition described above 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 may be added to the water, such as humectants, water-soluble vitamins, water-soluble preservatives, water-soluble drugs, and water-soluble polymers. You can also do it. Regarding the quantitative relationship between the above emulsified composition and water,
Although there is a very wide range of choice, usually emulsified compositions
0.5 to 80 parts to 99.5 to 20 parts of water. 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, and shampoos even in its original form. It can be suitably used in all fields such as toiletry products such as rinses, 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-methionine 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. An emulsion composition was prepared by processing with a mixer. Furthermore, an oil-in-water emulsion composition was prepared by adding 10 times the amount of water to this emulsion composition while stirring at room temperature. 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 %.

【table】

[Table] As shown in Table 1, a composition containing no salt of the condensate of L-methionine alkyl ester and protein (Comparative Example 1), and a composition containing no polyhydric alcohol,
A stable emulsified composition could not be obtained with the composition in which water was used as an external phase (Comparative Example 2). Furthermore, a salt of a condensate of L-methionine alkyl ester and protein,
Even if polyhydric alcohol and oil were included, a stable emulsified composition could not be obtained when 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-phenylalanine dodecyl ester gelatin condensate Arginine salt 2.0 Maltitol (70% aqueous solution) 30.0 1,3-butylene glycol 10.0 Sodium chondroitin sulfate 0.5 (B) Fluidity Paraffin 30.0 Olive oil 20.8 Glyceryl tristearate 5.0 Vitamin E acetate 0.5 Vitamin A palmitate 0.5 Preservatives 0.5 Flavor 0.2 Stir the (A) phase thoroughly at 70℃, dissolve the (B) phase at 70℃, and make (A) Added to the 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 5.0 L-methionine dodecyl ester Elastin condensate 2.0 L-methionine hexenyl ester Globulin condensate 1.0 Allantoin 0.2 Sodium hydroxide 0.1 (B) Liquid paraffin 10.0 olive oil 5.0 Penta Eli Slitrito Lutetler 2 -Ethyl Hexano Eates 5.0 Vaseline 5.0 Ethinyl Estrad Earlen 0.4 Pillar 0.3 fragrance 0.3 (C) Purified Water 0.1 Kisuna Tengam 0.1 Kizuna Tengam 0.1 Kizuna extract 0.1 Sembrid extraction 0.1 Production of Example 9 According to the method, an emulsion composition was obtained from phase (A) and (B), heated to 70℃, diluted and dispersed with a thickener aqueous solution (C) phase prepared separately and kept at 70℃, and then cooled. A nutritional emulsion of oil-in-water emulsion was obtained. The viscosity of this emulsion was 4280 cp at 30°C, and the emulsion had a stable emulsion particle size of about 1 to 3 μm and a familiar texture. Example 11 Suncare cream (% by weight) (A) Digcerin 20.0 Sorbitol (70% aqueous solution) 8.0 Glucose (50% aqueous solution) 4.0 L-methionine dodecyl ester milk protein condensate hydrochloride 2.0 L-methionine dodecyl ester albumin condensate 0.5 (B) Liquid paraffin 20.0 Isopropyl myristate 10.0 Vaseline 5.0 Stearyl alcohol 5.0 PABA 2.0 Preservative 0.5 Fragrance 0.3 (C) Purified water 19.5 Hydroxyethylcellulose 0.2 (D) Mixed powder 1.0 Titanium dioxide 2.0 According to the manufacturing method of Example 10 , got the sun care cream. At this time, phase (C) was used as a diluted phase after treating (D) with a dispersion homomixer at 70°C. This sun care cream has a hardness of 17 at 25℃.
The oil-in-water emulsion composition was somewhat transparent and had a highly stable emulsion particle size of about 1 to 3 microns, making it suitable for use under sunlight.

Claims (1)

[Claims] 1 The number of carbon atoms in the alkyl group excluding L-leucine is 4
An emulsified composition comprising a condensate of ~12 amino acid alkyl esters 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. 2 The number of carbon atoms in the alkyl group excluding L-leucine is 4
An emulsified composition containing a condensate of ~12 amino acid alkyl esters and a protein and/or a salt thereof, a water-soluble polyhydric alcohol having two or more hydroxyl groups in the molecule, an oil component, and water. An oil-in-water emulsion composition characterized by: