JPH0361488B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an oil-in-water type (hereinafter referred to as O/W type) emulsion composition that has good stability over time and is used in skin cosmetics, hair cosmetics, detergents, and the like. Conventionally, ethylene oxide derivatives of castor oil (or hydrogenated castor oil) have been used as surfactants that are less irritating to the skin and have excellent emulsifying ability. However, in emulsion compositions emulsified using this surfactant, when the viscosity of the composition is 1000 centipoise or less (particularly 100 centipoise or less) or the PH is near neutral (PH 6.5 to 7.5),
If it deviates from this, the stability of the composition over time will deteriorate. The purpose of the present invention is to provide an O/O/O film with good stability over time even when the viscosity is low or the pH is outside of the neutral range.
An object of the present invention is to provide a W-type emulsion composition. That is, this invention provides (a) an oxidized castor oil ethylene adduct, a hydrogenated castor oil oxidized ethylene adduct, an esterified product of a castor oil oxidized ethylene adduct, and an esterified product of a hydrogenated castor oil oxidized ethylene adduct; Castor oil or hydrogenated castor oil derivative, (b) N-acyl acidic amino acid, alkali metal salt thereof, or organic amine salt thereof, and (c) cationic surfactant represented by the following general formula [], [] or [] An oil-in-water emulsion composition comprising an agent is provided. General formula [] (However, one of R ₁ , R ₂ , R ₃ , and R ₄ is an alkyl group having 8 to 22 carbon atoms or a hydroxyalkyl group having 8 to 22 carbon atoms, and the rest are 1 to 3 carbon atoms.)
an alkyl group, a hydroxyalkyl group having 1 to 3 carbon atoms, or a benzyl group, X ₁ is a halogen atom,
Indicates methyl sulfate group or ethyl sulfate group) General formula [] (However, two or three of R ₅ , R ₆ , and R ₇ are alkyl groups having 8 to 20 carbon atoms, and the rest are methyl groups,
Ethyl group or hydroxyethyl group, n is an integer from 3 to 10, X ₂ is a halogen atom, methyl sulfate group,
or ethyl sulfate group) General formula [] (However, R ₈ is an alkyl group having 10 to 22 carbon atoms,
R ₉ represents an alkyl group having 2 to 22 carbon atoms) The castor oil oxidized ethylene adduct and the hydrogenated castor oil oxidized ethylene adduct used in the present invention can be obtained by well-known methods (for example, industrial chemical (Refer to magazine volume 53, page 431). Castor oil oxidized ethylene adduct is 12-hydroxy-9-octadecenoic acid (ricinoleic acid) represented by the following general formula []
Mainly contains triglyceride ethylene oxide adducts. General formula [] (However, in the formula, l, m, n, x, y, and z represent integers whose sum is 5 to 500.) The hydrogenated castor oil oxidized ethylene adduct is 12-hydroxyoctadecane represented by the following general formula [] Mainly contains acid triglyceride ethylene oxide adducts. General formula [] (However, l, m, n, x, y, z have the same meaning as in the general formula []) The number of moles of ethylene oxide added is 12-hydroxy-9-octadecenoic acid triglyceride oxidation in the case of castor oil oxidized ethylene adduct. It is preferably 20 to 80 moles, calculated assuming that it consists only of an ethylene adduct, and in the case of a hydrogenated castor oil oxidized ethylene adduct, calculated that it consists only of a 12-hydroxyoctadecanoic acid triglyceride ethylene oxide adduct. The esterified product of ethylene oxide adduct of castor oil mainly includes an esterified product of 12-hydroxy-9-octadenoic acid triglyceride ethylene oxide adduct represented by the following general formula []. General formula [] (However, in the formula, R ₁₀ , R ₁₁ , and R ₁₂ are hydrogen or fatty acid residues, at least one of them is a fatty acid residue, and l, m, n, x, y, and z are the general formula [ ] The esterified products of hydrogenated castor oil ethylene oxide adducts mainly include esterified products of 12-hydroxyoctadecanoic acid triglyceride ethylene oxide adducts represented by the following general formula [ ]. General formula [] (However, in the formula, R ₁₀ , R ₁₁ , R ₁₂ , l, m, n,
x, y, z have the same meanings as in the general formula []) In the case of an esterified product of castor oil oxide ethylene adduct, the number of moles of ethylene oxide added is 12-hydroxy-9-octadecenoic acid triglyceride ethylene oxide adduct. In the case of an esterified product of hydrogenated castor oil ethylene oxide adduct, it is preferably 20 to 80 moles, calculated assuming that it consists only of an esterified product of 12-hydroxyoctadecanoic acid triglyceride ethylene oxide adduct. Furthermore, the esterified products of castor oil oxidized ethylene adducts and the esterified products of hydrogenated castor oil oxidized ethylene adducts are preferably monoesters, diesters, or triesters with fatty acids having 14 to 22 carbon atoms. The amount of the castor oil derivative or hydrogenated castor oil derivative described above is preferably 0.1 to 5% by weight, particularly preferably 0.3 to 3% by weight, based on the total amount of the composition. If it is less than 0.1% by weight, the effects of the present invention will not be fully exhibited, and if it exceeds 5% by weight, there is a risk that the composition will gel. The second essential component of this invention is an N-acyl acidic amino acid, an alkali metal salt thereof, or an organic amine salt thereof. Preferred acidic amino acids constituting the N-acyl acidic amino acids include glutamic acid and aspartic acid. Further, preferred examples of the acyl group constituting the N-acyl acidic amino acid include lauroyl group, myristoyl group, palmitoyl group, stearoyl group, and acyl group derived from coconut oil fatty acid or hydrogenated beef tallow fatty acid. Preferred salts of N-acyl acidic amino acids include monosodium salt, monolithium salt, monopotassium salt, monotriethanolamine acid, monomonoethanolamine salt, mono2-amino-2-methyl-1-propanol salt, and mono2-amino-2-methyl-1-propanol salt. -Amino-2
-Methyl-1,3-propanediol salt, mono 2
Mention may be made of -amino-2-ethyl-1,3-propanediol salts, monotris(hydroxymethyl)-aminomethane salts, monotrimethylamine salts, and similar dialkali metal salts and diorganic amine salts. In addition, when N-acyl acidic amino acids and their salts are compared, the present inventors have found that the N-acyl acidic amino acids are superior to their salts in terms of composition stability. Particularly preferred N-acyl acidic amino acids include N-cocoylglutamic acid, N-
Lauroylglutamic acid, N-palmitoylglutamic acid, N-stearoylglutamic acid, N-
Mention may be made of cocoyl aspartic acid and N-lauroyl aspartic acid. The total amount of the N-acyl acidic amino acid or its salt is preferably 0.01 to 1% by weight, particularly preferably 0.03 to 0.5% by weight, based on the total amount of the composition. If it is less than 0.01% by weight, the effect of the present invention will not be sufficiently obtained, and if it exceeds 1% by weight, there is a risk that the composition will gel. The third essential component of the compositions of this invention is a specific cationic surfactant. One of the cationic surfactants that can be used is a quaternary ammonium salt represented by the following general formula []. General formula [] In the formula, one or two of R ₁ , R ₂ , R ₃ and R ₄ are an alkyl group having 8 to 22 carbon atoms or a hydroxyalkyl group having 8 to 22 carbon atoms. If the number of these carbons is 7 or less, there is a safety problem, and 23
If it is more than that, the melting point will be high and it will be difficult to work with.
Among R ₁ , R ₂ , R ₃ , and R ₄ , those other than the above alkyl group or hydroxyalkyl group are an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a benzyl group. If the number of carbon atoms in the alkyl group or hydroxyalkyl group is 4 or more, the melting point will be high, making it difficult to dissolve in the system and causing problems in operation. X ₁ is a halogen atom,
Methyl sulfate group or ethyl sulfate group. Preferred specific examples of the cationic surfactant represented by the general formula [] include stearyltrimethylammonium chloride, eicosyltrimethylammonium chloride, cetyltrimethylammonium chloride, eicosyldimethylammonium chloride, stearylbenzyldimethylammonium chloride, and behenyldimethylbenzylammonium chloride. and behenyltrimethylammonium chloride. In addition, as the cationic surfactant which is the third essential component of the composition of this invention, the following general formula []
A quaternary ammonium salt represented by can be used. General formula [] In the formula, two or three of R ₅ , R ₆ and R ₇ are alkyl groups having 8 to 20 carbon atoms. If the number of carbon atoms is less than 7, there will be a safety problem, and if it is more than 21, the melting point will be high and will interfere with work. _R5 ,
Among R ₆ and R ₇ , those other than the above-mentioned alkyl groups are methyl groups, ethyl groups, or hydroxyethyl groups. n is an integer from 3 to 10. When n is 11 or more, hydrophilicity becomes too strong, which is not preferable. n
When is less than 2 (excluding those represented by the general formula []), on the contrary, the lipophilicity becomes too strong. X ₂ is a halogen atom, a methyl sulfate group, or an ethyl sulfate group. Preferred specific examples of the cationic surfactant represented by the general formula [] include distearyl polyethenoxymethyl ammonium halide, dipalmityl polyethenoxyethylammonium halide, dipalmityl polyethenoxyhydroxyethylammonium halide, tristearyl polyethenoxymethyl ammonium halide, and tristearyl polyethenoxymethyl ammonium halide. Mention may be made of ethenoxyammonium halide and distearylpolyethenoxyethylammonium ethyl sulfate. Furthermore, cationic surfactants that can be used as the third essential component of the compositions of this invention include:
There is a compound represented by the following general formula []. General formula [] In the formula, R ₈ is an alkyl group having 10 to 22 carbon atoms. If the number of carbon atoms is less than 9, hydrophilicity tends to be strong and performance deteriorates, which is not desirable from a safety point of view. If it is more than 23, lipophilicity increases and performance deteriorates, but the melting point is high and it is difficult to use It is not desirable because it does not melt. R ₉ is an alkyl group having 2 to 22 carbon atoms. When R ₉ is a methyl group, hydrophilicity increases,
Performance tends to deteriorate. On the other hand, if the number of carbon atoms is 23 or more, the melting point will be high and it will not dissolve in medium-sized systems, while the lipophilicity will also increase, which is unfavorable in terms of performance. General formula []
Specific examples of cationic surfactants represented by are N〓-cocoyl-L-arginine ethyl ester/DL-pyrrolidone carboxylate, N〓-cocoyl-L-arginine methyl ester/DL-pyrrolidone carboxylate, N〓 -Myristoil-L
-Arginine ethyl ester/DL-pyrrolidone carboxylate, N〓-palmitoyl-L-arginine ethyl ester/DL-pyrrolidone carboxylate and N〓-stearoyl-L-arginine ethyl ester/DL-pyrrolidone carboxylate. I can do it. The total amount of these cationic surfactants is preferably 0.01 to 3% by weight, particularly preferably 0.1 to 2% by weight, based on the total amount of the composition. If the amount of the cationic surfactant exceeds this range, the stability of the composition will deteriorate. Examples of oils in the O/W emulsion composition of the present invention include hydrocarbons such as liquid paraffin, vaseline, solid paraffin, squalane and olefin oligomer; isopropyl myristate, isopropyl palmitate, stearyl stearate, octyldodecyl myristate; , esters such as octyldodecyl oleate and 2-ethylhexanoic acid triglyceride; silicone oils such as dimethylpolysiloxane and phenylmethylpolysiloxane; higher alcohols such as cetyl alcohol, myristyl alcohol, cetostearyl alcohol, and stearyl alcohol, and batyl alcohol, etc. alcohols such as polyhydric alcohols; and animal and vegetable oils such as olive oil, avocado oil, sunflower oil and jojoba oil. These oils are usually contained in an amount of 10% by weight or less, preferably 2 to 7% by weight, based on the total amount of the composition. Other optional components can be incorporated into the composition of the present invention as long as they do not affect the effects of the present invention. Such optional components include solvents such as ethyl alcohol and isopropyl alcohol; ethylene glycol, propylene glycol,
Humectants such as 3-butylene glycol, glycerin, and sorbitol; small amounts of ingredients such as bactericides, preservatives, pigments, ultraviolet absorbers, and fragrances; and extracts of plants, etc.
Active ingredients such as vitamins can be mentioned. The composition of the present invention can be used in skin cosmetics such as skin lotions, lotions, milky lotions, hair cosmetics such as hair lotions, scalp lotions, hair conditioners, hair tonics, hair styling products, hair nourishing agents, pharmaceuticals, and glasses. It can be used as a cleaning agent, etc. The composition of this invention can also be used by being filled into a container such as a pump dispenser. Furthermore, the composition of this invention as a stock solution,
It can also be used in aerosol form using LPG, chlorofluorocarbon gas, dimethyl ether, etc. as a propellant. Next, Examples and Comparative Examples of the present invention will be shown to explain the effects of the present invention more specifically. The composition was prepared by stirring the components other than purified water at 70°C, adding purified water heated to 70°C, stirring, and cooling to room temperature. In addition, the stability of the composition was evaluated by visually determining the presence or absence of separation after storing the composition at 40° C. for 30 days according to the following criteria. ◎: No separation observed ○: Very slight separation observed, but not noticeable.
Acceptable as a commercial product ×: Separation is severe and not acceptable as a commercial product In each of the following examples, the amounts of ingredients are all expressed in weight %. Test Example 1 Eight types of O/W type emulsion compositions having the compositions shown in Table 1 were prepared and their stability was evaluated. The results are shown in the same table.

[Table] As can be seen from Table 1, O/W is stable even when only one or two components of hydrogenated castor oil ethylene oxide adduct (50 moles of ethylene oxide), N-cocoylglutamic acid, and stearyltrimethylammonium chloride are combined. A type emulsion composition cannot be obtained, and a stable O/W type emulsion can only be obtained when the three components are blended. Furthermore, N-cocoylglutamic acid has better stability than monosodium N-cocoylglutamate. Furthermore, in Comparative Examples 1, 4, and 5, the number of moles of ethylene oxide added to the hydrogenated castor oil ethylene oxide adduct was 5 to 100.
An O/W type emulsion composition was prepared in which the composition was changed from the above, but it was not as stable as the example. Examples 3 to 7 O/W type emulsion compositions having the compositions shown in Table 2 were prepared and their stability was evaluated. The results are shown in the same table.

【table】

[Table] Example 9 An O/W emulsion having the composition shown in Table 3 was prepared and its stability was evaluated. Table 3 Component content Diglycerol triisostearate 3.5 Hydrogenated castor oil oxidized ethylene adduct (ethylene oxide
50 moles) 1 N-cocoyl glutamic acid 0.1 Stearyltrimethylammonium chloride 0.2 Cetanol 1 Paraben Trace amount Trace amount of ethanol 5 Purified water Balance This O/W emulsion composition contains 5% by weight of ethanol and has a viscosity of 50 centipoise or less. It was extremely stable despite its low pH of 3. Example 10 An O/W emulsion composition having the composition shown in Table 4 was prepared and its stability was evaluated. Table 4 Ingredients Contents Liquid paraffin 5 Myristyl alcohol 1 Castor oil ethylene oxide adduct triisostearate (number of moles of ethylene oxide added) 1.5 N-palmitoylglutamic acid 0.2 Stearyltrimethylammonium chloride 0.3 Propylene glycol 0.5 Fragrance Trace amount dl-tocopherol acetate 0.1 Paraben Trace purified water Balance This O/W emulsion composition was extremely stable. Further, a composition containing 96% by weight of this composition and 4% by weight of liquefied petroleum gas can be used as an aerosol composition.

Claims (1)

[Scope of Claims] 1 (a) selected from the group consisting of castor oil oxidized ethylene adducts, hydrogenated castor oil oxidized ethylene adducts, esterified products of castor oil oxidized ethylene adducts, and esterified products of hydrogenated castor oil oxidized ethylene adducts castor oil or hydrogenated castor oil derivatives, (b) N-acyl acidic amino acids, alkali metal salts thereof, or organic amine salts thereof, and (c) cationic surfactants represented by the following general formula [], [] or [] An oil-in-water emulsion composition comprising an agent. General formula [] (However, one of R ₁ , R ₂ , R ₃ , and R ₄ is an alkyl group having 8 to 22 carbon atoms or a hydroxyalkyl group having 8 to 22 carbon atoms, and the rest are 1 to 3 carbon atoms.)
an alkyl group, a hydroxyalkyl group having 1 to 3 carbon atoms, or a benzyl group, X ₁ is a halogen atom,
Indicates methyl sulfate group or ethyl sulfate group) General formula [] (However, two or three of R ₅ , R ₆ , and R ₇ are alkyl groups having 8 to 20 carbon atoms, and the rest are methyl groups,
Ethyl group or hydroxyethyl group, n is an integer from 3 to 10, X ₂ is a halogen atom, methyl sulfate group,
or ethyl sulfate group) General formula [] (However, R ₆ is an alkyl group having 10 to 22 carbon atoms,
( _R9 represents an alkyl group having 2 to 22 carbon atoms) 2. The composition according to claim 1, wherein the component (b) is an N-acyl acidic amino acid. 3. The composition according to claim 1 or 2, wherein the number of moles of ethylene oxide added to the castor oil derivative or hydrogenated castor oil derivative is 20 to 80 moles. 4. Claim 1, wherein the esterified product of the castor oil oxidized ethylene adduct or the esterified product of the hydrogenated castor oil oxidized ethylene adduct is a monoester, diester, or triester with a fatty acid having 14 to 22 carbon atoms. The composition according to any one of items 1 to 3. 5. The ingredients in (b) above include N-cocoyl glutamic acid, N-lauroyl glutamic acid, N-myristoyl glutamic acid, N-palmitoyl glutamic acid, N-stearoyl glutamic acid, N-cocoyl aspartic acid, N-lauroyl aspartic acid, N-myristoyl asparagine. Claims 1 and 3 selected from the group consisting of acids, N-palmitoyl aspartic acid, N-stearoyl aspartic acid, and monosodium acids, monolithium salts, disodium salts, and monotriethanolamine salts thereof. , or the composition according to item 4. 6. The cationic surfactant is selected from the group consisting of stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, eicosyltrimethylammonium chloride, stearyldimethylbenzylammonium chloride, eicosyldimethylammonium chloride, behenyldimethylbenzylammonium chloride, and behenyltrimethylammonium chloride. A composition according to any one of claims 1 to 5, which is selected. 7. The cationic surfactants include distearylpolyethenoxymethylammonium halide, dipalmitylpolyethenoxyethylammonium halide, dipalmitylpolyethenoxyhydroxyethylammonium halide, tristearylpolyethenoxyammonium halide, and distearylpolyethenoxyammonium halide. The composition according to any one of claims 1 to 5, which is selected from the group consisting of xyethylammonium ethyl sulfate. 8 The cationic surfactant is N〓-cocoyl-L-arginine ethyl ester/DL-pyrrolidone carboxylate, N〓-cocoyl-L-arginine methyl ester/DL-pyrrolidone carboxylate, N〓-myristoyl-L -Arginine ethyl ester/DL-pyrrolidone carboxylate, N〓
-Palmitoyl-L-arginine ethyl ester/DL-pyrrolidone carboxylate and N-stearoyl-L-arginine ethyl ester/DL
- pyrrolidone carboxylic acid salts.