JPH0696490B2 - External skin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a skin external preparation composition, and more particularly to a skin external preparation composition having high safety, excellent feeling in use, and excellent stability.

(Prior Art) Among the functions required for a skin external preparation composition, safety,
The three most important points are the feeling of use and the stability of the system. Conventionally, many external preparations for skin use a surfactant for the purpose of emulsification, solubilization, dispersion and the like, and the safety, stability and feel of use vary depending on the type. For example, nonionic surfactants and anionic surfactants are mainly used as emulsifiers. As the nonionic surfactant, polyoxyethylene alkyl ether, monofatty acid polyoxyethylene sorbitan, monofatty acid glycerin, monofatty acid sorbitan, monofatty acid polyoxyethylene glycerin, polyoxyethylene hydrogenated castor oil derivative, etc. are used. . These nonionic surfactants are not easily affected by pH and have an emulsifying power in a wide pH range, but the emulsifying power itself is relatively weak and requires a large amount. Therefore, there is a problem in that it causes stickiness in use and is not preferable in terms of safety.

On the other hand, as anionic surfactants, sulfuric acid ester salts such as sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium laurate, sodium stearate, sodium oleate, etc. Such fatty acid soap is typical. The sulfate ester salt has a strong emulsifying power, but is not preferable in terms of safety.
The fatty acid soap is good in safety, has a good emulsifying power in the alkaline region, and is good in feeling to use,
There is a problem that the emulsifying power is significantly reduced in the weakly acidic to neutral range. Further, there is a problem that the skin is covered with a lid in the alkaline region.

As described above, none of the conventional surfactants satisfy all the functions required for the external preparation for skin.

(Problems to be Solved by the Invention) Therefore, in the present invention, as a result of earnestly studying to obtain a skin external preparation composition excellent in safety, feeling in use, and stability, the above-mentioned general formulas (A) and (B By using one or more compounds represented by the formula (4), it is possible to obtain a skin external preparation composition having good safety, a good feeling of use without stickiness, and excellent stability over a wide pH range. The inventors have found out what can be done and have completed the present invention.

(Means for Solving Problems) That is, the present invention provides the following components (A), (B) and (A) (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms. At least one of X ₁ and X ₂ is —CH ₂ COOM, and the other may be a hydrogen atom. A hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a lower alkanolamine cation, a lower alkylamine cation, or a basic amino acid cation, and (B) a general formula (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms. At least one of X ₁ and X ₂ is —CH ₂ CH ₂ COOM, and the other may be a hydrogen atom. Is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a lower alkanolamine cation, a lower alkylamine cation, or a basic amino acid cation, and one or more kinds selected from carboxylic acids By providing a carboxylic acid, it is intended to provide a skin external preparation composition which is highly safe, has an excellent feeling in use, and has excellent stability in a wide pH range.

In the general formulas (A) and (B), the linear or branched alkyl group having 4 to 34 carbon atoms of R is a butyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, Examples thereof include docosyl group, 2-ethylhexyl group, 2-hexyldecyl group, 2-octylundecyl group, 2-decyltetradecyl group and 2-undecylhexadecyl group. Examples of the linear or branched alkenyl group having a prime number of 4 to 34 include decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group and the like. Among R, preferable is a linear alkyl group having 8 to 16 carbon atoms from the viewpoint of surface activity, and particularly preferably a decyl group or a dodecyl group. These may be a mixture of two or more.

Examples of the alkali metal represented by M in X ₁ and X _{2 of the} general formulas (A) and (B) include sodium, potassium and lithium. Examples of alkaline earth metals include calcium, magnesium and barium. Alkanolamines forming lower alkanolamine cations include mono-, di- or tri-ethanolamine, n and isopropanolamine, etc. Alkylamines forming lower alkylamine cations include monoethylamine, diethylamine, triethylamine, etc. Can be mentioned. Examples of the basic amino acid that forms the basic amino acid cation include lysine, arginine, ornithine, and histidine. Among M, alkali metal and lower alkanolamine cations are preferable, and sodium and triethanolamine cation are particularly preferable. These may be a mixed salt of two or more kinds.

By blending each of the components (A) and (B) alone or in combination of two or more, a skin external preparation composition having high safety, excellent feel in use, and excellent stability under alkaline to weak acid conditions is obtained. be able to.

In the present invention, one or more components (A) and (B) are added in a total amount of 0.001 to 50% by weight (hereinafter referred to as%), preferably 0.1 to 20%.

The external preparation for skin of the present invention may optionally contain, in addition to the above-mentioned essential components, other components usually used for external preparations for skin.

For example, liquid paraffin, squalane, petrolatum, microcrystalline wax, ozokerite, ceresin,
Cetyl alcohol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-octyldodecyl alcohol, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, 2-octyldodecyl myristate, isopropyl myristate, di-2-ethylhexanoic acid Neopentyl glycol, dicaprylate neopentyl glycol, glycerin triisooctylate, glyceryl triisostearate, olive oil, macadamian nut oil, avocado oil, sunflower oil, mink oil, lanolin, lauric acid, myristic acid, palmitic acid, stearic acid , Various kinds of hydrocarbons such as oleic acid and beeswax, higher alcohols, esters, fats and oils such as waxes, silicones, acetone, toluene, butyl acetate,
Organic solvents such as ethyl acetate, resins such as alkyd resins and urea resins, plasticizers such as camphor and acetyltributyl citrate, ultraviolet absorber surfactants, humectants, vitamins, fragrances, water, alcohols, thickeners, Inorganic powder and pigments can be used.

The external preparation for skin according to the present invention may be in the form of liquid, emulsion, cream, ointment, powder, cake, pencil, stick or the like.

The carboxylic acids which are the components (A) and (B) of the present invention are novel substances, and synthetic examples are shown below. The following may be mentioned as specific examples of the compound.

Synthetic Example 1 1,2-dodecanediol (50.0 g), dioxane (250 g) and metallic sodium (5.7 g) were added to a four-necked flask, the temperature was raised under a nitrogen stream, and the mixture was stirred at 100 ° C. for 5 hours to perform alcoholate. After cooling to 70 ° C, 28.8 g of sodium monochloroacetate was gradually added, and after the addition was completed, the reaction was continued for 3 hours.
The compound No. 10 of the present invention shown in was obtained (crude yield; 80%).
After the solvent was distilled off, column chromatography was performed to separate unreacted substances and by-products to obtain 20.5 g of a purified product of compound No10 of the present invention shown in Table-1. The analysis results are shown below.

Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 10 / 1-methanol Elemental analysis (unit:%) Analytical value Calculated value C; 59.8 59.6 H; 9.6 9.6 O; 22.5 22.7 Na: 8.1 8.2 NMR (D ₂ O) (δ) 0.86 (bt, 3H) 1.28 (bs, 18H) 3.28 to 3.61 (m, 2H) 3.70 to 4.10 (m, 3H) IR (KBr) (cm ^-1 ) 3370, 2960, 2925 , 2875 2855,1600,1465,1455 1425,1375,1325,1115 1100,720 Weak acid value (mgKOH / g) 199.5 (calculated value; 198.8) CMC (mol / l) 3.1 × 10 ^-4 Synthesis example 2 14 mouths In a flask, 1,2-tetradecanediol 50.0
g, 250 g of dioxane and 5.0 g of metallic sodium were added, and the mixture was heated under a nitrogen stream and stirred at 100 ° C. for 5 hours for alcoholation. After cooling to 70 ℃ sodium monochloroacetate 27.8
g was gradually added, and the reaction was continued for 3 hours after the addition was completed to obtain the compound No16 of the present invention shown in Table 1 (crude yield; 78
%). After the solvent was distilled off, column chromatography was carried out to separate unreacted by-products, and 19.8 g of a purified product of the compound No. 16 of the present invention shown in Table 1 was obtained. The analysis results are shown below.

Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 10 / 1-methanol Elemental analysis (unit:%) Analytical value Calculated value C; 62.2 62.0 H; 9.9 10.0 O; 20.4 20.6 Na: 7.5 7.4 NMR (D ₂ O) (δ) 0.87 (bt, 3H) 1.27 (bs, 22H) 3.25 ~ 3.60 (m, 2H) 3.70 ~ 4.08 (m, 3H) IR (KBr) (cm ^-1 ) 3350, 2960, 2925 , 2875 2855,1610,1465,1455 1425,1375,1325,1115 720 Weak acid value (mgKOH / g) 180.0 (calculated value; 180.9) Synthesis Example 3 5.0 g of sodium hydroxy ether monocarboxylate obtained in Synthesis Example 1 After dissolving in 50 g of water and acidifying with hydrochloric acid, ether extraction was carried out and hydroxy ether monocarboxylic acid
Obtained 4.5 g. The analysis results are shown below.

Elemental analysis (unit:%) Analytical value Calculated value C; 64.4 64.6 H; 10.8 10.8 O; 24.8 24.6 Acid value (mgKOH / g) 216.0 (Calculated value; 215.7) Melting point (℃) 45.3 Synthetic example 4 In a 14-neck flask 1,2-Dodecanediol (50.0 g), dioxane (250 g) and sodium metal (11.4 g) were added, the temperature was raised under a nitrogen stream, and the mixture was stirred at 100 ° C. for 5 hours for alcoholation. After cooling to 70 ° C, 57.7 g of sodium monochloroacetate was gradually added, and after the addition was completed, the mixture was reacted at the same temperature for 3 hours,
The compound No. 27 of the present invention shown in Table 1 was obtained (crude yield; 80
%). After the solvent was distilled off, column chromatography was carried out to separate unreacted substances and by-products, and 19.8 g of a purified product of the compound No. 27 of the present invention shown in Table 1 was obtained. The analysis results are shown below.

Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 10 / 1-methanol Elemental analysis (unit:%) Analytical value Calculated value C; 53.2 53.0 H; 7.5 7.7 O; 26.3 26.5 Na: 12.9 12.7 NMR (D ₂ O) (δ) 0.86 (bt, 3H) 1.28 (bs, 16H) 1.38 to 1.69 (m, 2H) 3.40 to 3.70 (m, 3H) 3.72 to 4.08 (m, 4H) IR (KBr) (cm ^-1 ) 3430,2955,2925,2850 1610,1465,1425,1320 1090,1070,720 Weak acid value (mgKOH / g) 311.0 (calculated value; 309.9) CMC (mol / l) 4.5 × 10 ^-3 Synthesis example 5 1,2-tetradecanediol 50.0 in a 14-necked flask
g, 250 g of dioxane, and 10.0 g of metallic sodium were added, the temperature was raised under a nitrogen stream, and the mixture was stirred at 100 ° C. for 5 hours for alcoholation. After cooling to 70 ℃, sodium monochloroacetate 55.6
g was gradually added, and after the addition was completed, the mixture was reacted at the same temperature for 3 hours to obtain Compound No. 30 of the present invention shown in Table-1 (crude yield; 75%). After distilling off the solvent, column chromatography was carried out to separate unreacted substances and by-products to obtain 18.2 g of the purified compound No. 30 of the present invention shown in Table 1. The analysis results are shown below.

Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 10 / 1-methanol Elemental analysis (unit:%) Analytical value Calculated value C; 55.3 55.4 H; 8.1 8.2 O; 24.7 24.6 Na: 11.9 11.8 NMR (D ₂ O) (δ) 0.87 (bt, 3H) 1.29 (bs, 20H) 1.37 to 1.64 (m, 2H) 3.42 to 3.72 (m, 3H) 3.72 to 4.08 (m, 4H) IR (KBr) (cm ^-1 ) 3450,2955,2925,2850 1610,1465,1455,1425 1375,1325,1090,1070 720 Weak acid value (mgKOH / g) 289.0 (calculated value; 287.7) Synthetic example 6 Synthetic example 4 Sodium ether carboxylate 5.
0 g was dissolved in 50 g of water, acidified with hydrochloric acid and extracted with ether to obtain 4.6 g of diethercarboxylic acid. The analysis results are shown below.

Elemental analysis (unit:%) Analytical value Calculated value C; 62.2 62.4 H; 9.8 9.8 O; 27.9 27.7 Oxidation (mgKOH / g) 324.1 (Calculated value; 324.3) Melting point (° C) 63.5 Synthesis example 7 1 in a four-necked flask 1 3,2-Octanediol (36.6 g), dioxane (250 g) and sodium metal (5.8 g) were added, and the mixture was heated under a nitrogen stream and stirred at 100 ° C. for 5 hours for alcoholation. After cooling to 70 ℃, sodium monochloroacetate 29.1g
Was gradually added, and after completion of the addition, the mixture was reacted at the same temperature for 3 hours to obtain Compound No. 3 of the present invention shown in Table-1 (crude yield;
82%). After the solvent was distilled off, column chromatography was carried out to separate unreacted by-products and 16.4 g of a purified product of Compound No. 3 of the present invention shown in Table 1 was obtained. The analysis results are shown below.

Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 10 / 1-methanol Elemental analysis (unit:%) Analytical value Calculated value C; 53.0 53.1 H; 8.5 8.5 O; 28.3 28.3 Na: 10.2 10.2 IR (KBr) (cm ^-1 ) 3370,2960,2925,2875 2855,1600,1465,1455 1425,1375,1325,1100 720 Weak acid value (mgKOH / g) 246.8 (calculated value; 247.9) Synthetic example 8 14 mouths 1,2-tetracosanediol 55.6 in a flask
g, 300 g of dioxane, and 3.4 g of sodium metal were added, and the mixture was heated under a nitrogen stream and stirred at 100 ° C. for 5 hours for alcoholation. After cooling to 70 ℃, sodium monochloroacetate 18.1
g was gradually added, and after completion of the addition, the mixture was reacted at the same temperature for 3 hours to obtain Compound No. 25 of the present invention shown in Table-1 (crude yield: 65%). After distilling off the solvent, column chromatography was carried out to separate unreacted substances and by-products to obtain 14.2 g of the purified compound No. 25 of the present invention shown in Table 1. The analysis results are shown below. Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 10/1 to methanol Elemental analysis (unit:%) Analytical value Calculated value C; 69.3 69.5 H; 11.3 11.3 O; 14.2 14.1 Na: 5.1 5.1 Weak acid Value (mgKOH / g) 123.1 (calculated value; 124.5) Synthetic Example 9 14.5 Tetracosanediol 44.5 in a four-necked flask.
g, 300 g of dioxane, and 5.5 g of sodium metal were added, the temperature was raised under a nitrogen stream, and the mixture was stirred at 100 ° C. for 5 hours for alcoholation. After cooling to 70 ℃ sodium monochloroacetate 28.3
g was gradually added, and after completion of the addition, the mixture was reacted at the same temperature for 3 hours to obtain Compound No. 35 of the present invention shown in Table-1 (crude yield; 72%). After removing the solvent by distillation, column chromatography was carried out to separate unreacted substances and by-products, and 16.5 g of a purified product of the compound No. 35 of the present invention shown in Table 1 was obtained. The analysis results are shown below.

Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 10 / 1-methanol Elemental analysis (unit:%) Analytical value Calculated value C; 63.2 63.4 H; 10.0 9.9 O; 18.2 18.1 Na: 8.6 8.7 Weak acid Value (mgKOH / g) 209.8 (calculated value; 211.4) Synthesis Example 10 1-Dodecandiol 50.0 g, dimethylformamide 100 g liquid methylate (28% methanol solution) 0.45 g were added to a four-necked flask, and under a nitrogen stream 50. Dissolved completely at ° C. Thereafter, the mixture was cooled to 20 ° C., 13.8 g of acrylonitrile was gradually added dropwise at 20 to 30 ° C., and after completion of the addition, reaction was carried out at the same temperature for 2 hours. After the reaction was completed, the catalyst was neutralized with 0.27 g of hydrochloric acid (36% aqueous solution), the solvent was distilled off under reduced pressure at 100 ° C or lower, and subsequently 62.9 g of hydrochloric acid (36% aqueous solution) was added and hydrolyzed at 85 ° C for 6 hours. , Compound No. 44 of the present invention shown in Table 1 was obtained (crude yield; 90%). The resulting hydrolyzate was thoroughly washed with water to remove excess hydrochloric acid, and column chromatography was performed to separate unreacted products and by-products, and the purified product of compound No44 of the present invention shown in Table 1 got g. The analysis results are shown below.

Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 5 / 5-chloroform / ethyl acetate = 7/3 Elemental analysis (unit;%) Analytical value Calculated value C; 65.8 65.7 H; 11.0 10.9 O; 23.2 23.4 NMR (D ₂ O) (δ) 0.87 (bt, 3H) 1.28 (bs, 18H) 2.62 (bt, 2H) 3.22 to 3.58 (ddd, 2H) 3.62 to 3.87 (m, 3H) IR (KBr) ( cm ^-1 ) 3430,2955,2925,2850 1710,1470,1440,1330 1230,1190,1130,1115 Oxidation (mgKOH / g) 203.9 (calculated value; 204.7) Melting point (℃) 55.8 Synthesis Example 11 Synthesis Example 10 Obtained hydroxy ether monocarboxylic acid
Dissolve 5.0 g in 30 g of ethanol and add an equal amount of sodium hydroxide.
After neutralization with 0.73g, deetherification was carried out, and compound No45, hydroxy ether sodium monocarboxylate, 5.4g
Got The analysis results are shown below.

Elemental analysis (unit:%) Analytical value Calculated value C; 60.7 60.8 H; 9.7 9.8 O; 21.6 21.6 Na; 8.0 7.8 Weak acid value (mgKOH / g) 188.9 (calculated value; 189.5) CMC (mol / l) 4.5 × 10 ^-4 Synthesis Example 12 50.0 g of 1,2-dodecanediol in a 500 ml four-necked flask, DMF
100 g and 0.45 g of liquid methylate (28% methanol solution) were added and completely dissolved under a nitrogen stream at 50 ° C. Then, the mixture was cooled to 20 ° C., and 27.6 g of acrylonitrile was gradually added dropwise at 20 to 30 ° C. After completion of the addition, reaction was carried out at the same temperature for 2 hours. After completion of the reaction, neutralize the catalyst with 0.27 g of hydrochloric acid (36% aqueous solution), and under reduced pressure 1
The solvent was distilled off at a temperature below 00 ° C, followed by hydrochloric acid (36% aqueous solution) 12
5.8 g was added and the mixture was hydrolyzed at 85 ° C. for 6 hours to obtain the compound No. 54 of the present invention shown in Table-1 (crude yield; 90%). The resulting hydrolyzate was thoroughly washed with water to remove excess hydrochloric acid, and column chromatography was performed to separate unreacted products and by-products, and a purified product of compound No54 of the present invention shown in Table 1-2
Obtained 0.5 g. The analysis results are shown below.

Elemental analysis (unit:%) Analytical value Calculated value C; 62.5 62.4 H; 9.7 9.8 O; 27.7 27.7 NMR (D ₂ O) (δ) 0.87 (bt, 3H) 1.24 (bs, 18H) 2.60 (bt. 4H) 3.36 to 3.55 (m, 3H) 3.60 to 3.90 (m, 4H) IR (thin film method) (cm ^-1 ) 3430,2955,2925,2850 1720,1470,1430,1350 1270,1190,1115,1070 720 Weak acid value (MgKOH / g) 324.9 (calculated value; 324.3) Synthetic Example 13 5.0 g of the diethercarboxylic acid obtained in Synthetic Example 12 was dissolved in 30 g of ethanol, neutralized with 1.2 g of an equivalent amount of sodium hydroxide, and then deethered. This was performed to obtain 5.6 g of sodium diethercarboxylate of compound No55. The analysis results are shown below.

Elemental analysis (unit:%) Analytical value Calculated value C; 55.2 55.4 H; 8.3 8.2 O; 24.7 24.6 Na; 11.9 11.8 Weak acid value (mgKOH / g) 288.0 (calculated value; 287.7) CMC (mol / l) 5.5 × 10 ^-3 Synthesis Example 14 1,2-tetradecanediol 50.0 in a 500 ml four-necked flask
g, DMF100g, liquid methylate (28% methanol solution) 0.45
g was added and completely dissolved under a nitrogen stream at 50 ° C. Then 20
After cooling to 0 ° C, 11.5 g of acrylonitrile was gradually added dropwise at 20 to 30 ° C, and after completion of the addition, reaction was carried out at the same temperature for 2 hours. After completion of the reaction, neutralize the catalyst with 0.27 g of hydrochloric acid (36% aqueous solution),
The solvent was distilled off under reduced pressure at 100 ° C. or lower, and subsequently 62.9 g of hydrochloric acid (36% aqueous solution) was added and hydrolyzed at 85 ° C. for 6 hours to obtain the compound No50 of the present invention shown in Table 1 (crude yield 88%). After thoroughly washing the obtained hydrolyzate with water, column chromatography is performed to separate unreacted products and by-products, and
18.5 g of a purified product of the compound No. 50 of the present invention shown in 1 was obtained.
The analysis results are shown below.

Elemental analysis (unit:%) Analytical value Calculated value C; 67.3 67.5 H; 11.4 11.3 O; 21.3 21.2 NMR (CDCl ₃ ) (δ) 0.87 (bt, 3H) 1.27 (bs, 22H) 2.61 (bt. 2H) 3.21 ~ 3.60 (ddd, 2H) 3.64 ~ 3.88 (m, 3H) IR (KBr) (cm ^-1 ) 3450,2955,2925,2875 2855,1710,1465,1440 1330,1230,1190,1130 1115 Acid value (mgKOH) / g) 185,0 (calculated value; 185.8) Synthesis example 15 1,2-tetradecanediol 50.0 in a 500 ml four-necked flask.
g, DMF100g, liquid methylate (28% methanol solution) 0.45
g was added and completely dissolved under a nitrogen stream at 50 ° C. Then 20
After cooling to 20 ° C., 23.0 g of acrylonitrile was gradually added dropwise at 20 to 30 ° C. After completion of the addition, reaction was carried out at the same temperature for 2 hours. After completion of the reaction, neutralize the catalyst with 0.27 g of hydrochloric acid (36% aqueous solution),
The solvent was distilled off under reduced pressure at 100 ° C. or lower, and subsequently 62.9 g of hydrochloric acid (36% aqueous solution) was added and hydrolyzed at 85 ° C. for 6 hours to obtain the compound No56 of the present invention shown in Table 1 (crude yield 90%). The obtained hydrolyzate was thoroughly washed with water to remove excess hydrochloric acid, and then unreacted products and by-products were separated using column chromatography, and the purified product of compound No56 of the present invention shown in Table 1 got g. The analysis results are shown below.

Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 5 / 5-chloroform / ethyl acetate = 7/3 Elemental analysis (unit:%) Analytical value Calculated value C; 64.1 64.2 H; 10.1 10.2 O; 25.7 25.7 NMR (CDCl ₃ ) (δ) 0.86 (bt, 3H) 1.24 (bs, 22H) 2.60 (bt. 4H) 3.35 ~ 3.56 (m, 3H) 3.60 ~ 3.90 (m, 4H) IR (thin film method) ( cm ^-1 ) 3450,2955,2925,2850 1720,1470,1430,1350 1270,1190,1115,1070 720 Acid value (mgKOH / g) 299.2 (calculated value; 300.0) (Effect of the invention) The compounds of the general formulas (A) and (B) are
It has advantages such as high safety, excellent feeling in use, and excellent stability in a wide pH range, and is useful as a raw material for external preparations for skin such as cosmetics, quasi drugs, and pharmaceuticals.

The effects of the present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.

Example 1 Emulsion 1 Compound No11 2% 2 Cetyl alcohol 0.8% 3 Squalane 10% 4 Vaseline 2% 5 Glycerin monostearate 2% 6 Lanolin 2% 7 α-tocopherol acetate 0.05% 8 Propylene glycol 5% 9 Potassium hydroxide 0.25 % 10 Carboxyvinyl polymer 0.1% 11 Perfume Suitable amount 12 Ion-exchanged water Residual Comparative Example 1 1 Stearic acid 2% 2 Cetyl alcohol 0.8% 3 Squalane 10% 4 Vaseline 2% 5 Glycerin monostearate 2% 6 Lanolin 2% 7 Acetic acid α -Tocopherol 0.05% 8 Propylene glycol 5% 9 Potassium hydroxide 0.25% 10 Carboxyvinyl polymer 0.1% 11 Perfume proper amount 12 Ion-exchanged water Residue (production method) 1-8 are heated and dissolved at 70-75 ° C. 9-11 are heated and dissolved at 70-75 ° C., and while continuing stirring, the mixture of 1-7 is gradually added to emulsify. After treatment with an emulsifier, 30 ℃
To obtain an oil-in-water emulsion.

The emulsion of Example 1 was weakly acidic and had a good feel when used on the skin. In addition, those left at 50 ° C for 1 month and 0 ° C for 1 month were stable without separation.

On the other hand, the emulsion of Comparative Example 1 had a relatively good feel to use, but had a lump when left at 0 ° C. for 1 month,
There was a problem with stability.

Example 2 Oil-in-water cream 1 Compound No11 4% 2 Cetyl alcohol 2% 3 Glycerin tristearate 2% 4 Squalane 6% 5 Hydrogenated lanolin 4% 6 Trimethylolpropane tri-2-ethylhexanoate 5% 7 Monostearic acid Propylene glycol 2% 8 Glycerin monostearate 2% 9 α-Tocopherol acetate 0.05% 10 Propylene glycol 5% 11 Polyethylene glycol 400 3% 12 L-Arginine 3% 13 Montmorillonite 0.3% 14 Perfume proper amount 15 Ion-exchanged water residual (manufacturing method) 1 to 9 are heated and dissolved at 70 to 75 ° C. 10 to 15 are heated and dissolved at 70 to 75 ° C., and the mixture of 1 to 9 is gradually added to emulsify while continuing stirring. After further processing with an emulsifying machine, it is cooled to 30 ° C. to obtain an oil-in-water cream.

The oil-in-water cream of Example 2 had a good feel when used on the skin, excellent stability, and good safety.

Example 3 Oil-in-water emulsion cleansing agent 1 Compound No16 4% 2 Compound No10 6% 3 Cetyl alcohol 0.3% 4 Liquid paraffin 1% 5 Propylene glycol monostearate 2% 6 Ion-exchanged water Residual 7 Propylene glycol 5% 8 Glycerin 7 % (Production method) 3 to 5 are heated and dissolved at 70 to 75 ° C. 1,26 ~ 8 to 70 ~ 75 ℃
The mixture is heated to dissolve in, and the above mixture of 3 to 5 is gradually added while continuing stirring to emulsify. After treatment with an emulsifier, 30 ℃
To give an oil-in-water emulsion cleansing agent.

The oil-in-water emulsion cleansing agent of Example 3 had a good feel when used on the skin, excellent stability, and good safety.

Example 4 Oil-in-water sunscreen emulsion 1 Compound No27 1.3% 2 Isostearic acid 0.7% 3 Cetostearyl alcohol 0.5% 4 Vaseline 2% 5 Isopropyl myristate 8% 6 Pentaerythritol tetra-2-ethylhexanoate 4% 7 P-dimethyl Aminobenzoic acid 2-ethylhexyl 3% 8 Acetate α-tocopherol 0.4% 9 Glycerin monostearate 2% 10 Dipropylene glycol 3% 11 Glycerin 3% 12 Montmorillonite 1.0% 13 Fine titanium oxide 2% 14 Ion-exchanged water Residual (manufacturing method) 1 to 9 are heated and dissolved at 70 to 75 ° C. 10 to 14 are heated and dissolved at 70 to 75 ° C., and the mixture of 1 to 9 is gradually added and emulsified while continuing stirring. After treatment with an emulsifier, the mixture is cooled to 30 ° C. to obtain an oil-in-water type sunscreen emulsion.

The oil-in-water type sunscreen emulsion of Example 4 had a good feel when used on the skin, excellent stability, and good safety.

Example 5 Emulsion foundation 1 1.3-Butylene glycol 5% 2 Bentonite 1% 3 Vaseline 2% 4 Liquid paraffin 10% 5 Cetanol 2% 6 Glycerin monooleate 2% 7 Isopropyl myristate 2% 8 Compound No44 2% 9 Water Potassium oxide 0.1% 10 Formulated powder * 20% 11 Preservative Suitable amount 12 Perfume Suitable amount 13 Ion-exchanged water Residual * Titanium oxide 8, Kaolin 5, Talc 6 Iron oxide 1 (Production method) 13 with 1,2,8,9 added Heat and stir to make an aqueous phase. 3,4,5,6,
7,11,12 are dissolved by heating with stirring to obtain an oil phase. After 10 is added to the aqueous phase and mixed by stirring, the oil phase is added and emulsified. This was cooled to room temperature to obtain an emulsion foundation.

When applied to the skin, this product had a good feeling in use, excellent stability, and good safety.

Example 6 Foam aerosol A Part 1 Polydimethylsiloxane 0.5% 2 Liquid paraffin 0.7% 3 Polyoxyethylene (60) hydrogenated castor oil 2% 4 Compound No10 0.5% 5 Ethanol 15% 6 Perfume proper amount 7 Dye proper amount 8 Cationized cellulose 0.2 % 9 Ion-exchanged water Residual part B Liquefied petroleum gas 4% (Production method) Prepare part A and fill it in between. Next, by focusing on the part B, a foam aerosol was obtained.

This product had an extremely smooth and fine foam quality, and when applied, it had a good feel in use, excellent stability, and good safety.

Example 7 Transparent hair styling gel 1 Liquid paraffin 1% 2 Olive oil 7% 3 Diethanolamide lauric acid 2% 4 Compound NNo16 35% 5 Preservative proper amount 6 Dye proper amount 7 Fragrance proper amount 8 Ion-exchanged water residual (manufacturing process) It is heated and stirred to dissolve, and then heat exchange cooled to obtain a transparent gel.

This product had a lustrous and moderate hair styling property, had a good feeling in use, excellent stability, and good safety.

Example 8 Hair Color First Agent 1 Compound No44 10% 2 Polyoxyethylene (2) oleyl ether 15% 3 Oleic acid 5% 4 Ethanol 5% 5 Propylene glycol 10% 6 Sodium edetate 0.5% 7 Thioglycolic acid 0.1% 8 Paraphenylenediamine 1% 9 Resorcin 0.8% 10 Metaaminophenol 0.5% 11 Perfume 0.1% 12 Ammonia water adjusted to pH 10 13 Ion-exchanged water Residual second agent 1 Hydrogen peroxide 20% 2 Phosphate buffer adjusted to pH 3 3 ion Exchanged water Residual 1st and 2nd agents are mixed in equal amounts at the time of use. This product had a good feeling in use.

Example 9 Cilia amount dye remover 1 Compound No 45 0.5% 2 Polyoxyethylene (20) oleyl ether 0.1% 3 Propylene glycol 10% 4 Glycerin 10% 5 Ethanol 20% 6 Sequestering agent 0.1% 7 Perfume 0.05% 8 Ions Exchanged water residue This product had a good feeling in use, excellent stability, and good safety.

Example 10 Eyeliner 1 Liquid paraffin 5% 2 Glycerin 5% 3 1.3-Butylene glycol 5% 4 Compound No10 2% 5 Bentonite 1% 6 Carboxymethylcellulose 1.5% 7 Sodium dehydroacetate 0.3% 8 Ion-exchanged water 61.8% 9 Black oxidation Iron 10% 10 Kaolin 10% (Production method) Add 7 to 8 and dissolve with stirring. 1-6, 9 and 10 are added to this and the mixture is uniformly emulsified with a homomixer to obtain an eyeliner.

This product had a good feel in use, excellent stability, and good safety.

Example 11 Mascara 1 Tetrastearate tetraacetic acid sucrose 15% 2 Microcrystalline wax 10% 3 Polyacrylic acid ester emulsion (50%) 20% 4 Sorbitan monostearate 1% 5 Compound No 16 1% 6 Ion-exchanged water 42.8 % 7 Black iron oxide 5% 8 Ultramarine blue 5% 9 Sodium dehydroacetate 0.2% (Manufacturing method) 1,2,4,5 are melted by heating at 80 ° C, and this is added to the dispersion of 5-9 at 80 ° C. And emulsify with a homomixer. After adding 3, the mixture was stirred and cooled to 40 ° C. to obtain a mascara.

This product had a good feel in use, excellent stability, and good safety.

As is clear from these, it was found that the use of the present invention makes it possible to obtain a skin external preparation composition which is excellent in safety, feeling in use and stability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location A61K 47/12 H 7433-4C C07C 59/125 E 8930-4H

Claims (1)

[Claims] 1. A component selected from the following components (A) and (B):
A skin external preparation composition comprising one or more kinds. (A) General formula (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms. At least one of X ₁ and X ₂ is —CH ₂ COOM, and the other may be a hydrogen atom. Carboxylic acids represented by hydrogen atom, alkali metal, alkaline earth metal, ammonium, lower alkanolamine cation, lower alkylamine cation, or basic amino acid cation. (B) General formula (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms. At least one of X ₁ and X ₂ is —CH ₂ CH ₂ COOM, and the other may be a hydrogen atom. Is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a lower alkanolamine cation, a lower alkylamine cation, or a basic amino acid cation.