JPS6135970B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a hair cosmetic containing an N-acyl-acidic amino acid ester as an active ingredient. For cosmetics, especially hair cosmetics, it has good affinity for hair, adds appropriate oiliness, has excellent hair styling and hair retention properties, has excellent ability to prevent dust adhesion, and is used as frame material for eyeglasses. It is required to satisfy all conditions such as being less corrosive to the celluloid used, not sticky to the hands, and less irritating and toxic. Many N-acyl-amino acid ester compounds have been proposed as skin cosmetics, hair cosmetics, or surfactant components that are less irritating and less toxic. The alcohol in the ester moiety is a polyoxyalkylene derivative, such as N-lower acyl-acidic amic acid diester (Japanese Patent Application Laid-open No. 1983-92237), which was previously researched and developed by the present inventor, and N-long chain acyl-acidic amino acid diester. Diester (Japanese Patent Publication No. 51-23395), N-long chain acyl-neutral amine acid ester (Japanese Patent Publication No. 1989-23395)
105580), etc., and in addition, N.N-di long chain acyl-basic amino acid esters (JP-A-51
-19138) are known. However, none of the above-mentioned known compounds can satisfy all the conditions that must be met as a hair cosmetic composition. We attempted to synthesize esters suitable for cosmetics from N-acyl acidic amino acids and polyhydric alcohols such as glycerin, propylene glycol, diglycerin, etc. based on the esterification method described below, but the resulting compounds were polyesters. It is an extremely sticky translucent paste that sticks to the reactor, resulting in low yield (30%).It dissolves in ethyl acetate, but does not dissolve at all in water, ethyl alcohol, or solvents such as toluene and benzene. Therefore, it did not meet the above-mentioned conditions for hair cosmetics. As a result of intensive research in order to improve the drawbacks of polyhydric alcohols and ester compounds of N-acyl acidic amino acids, the present inventors have found that polyoxyalkylene adducts thereof, particularly propylene oxide, can be used in an amount of 10 to 90 moles as a polyhydric alcohol. Addition polymerized polyhydric alcohol ether and propylene oxide
It is believed that esters of N-acyl acidic amino acids such as polyhydric alcohol ethers obtained by addition polymerization of 10 to 90 moles of ethylene oxide and 1 to 10 moles of ethylene oxide provide cosmetics that satisfy all the requirements that cosmetics should have. Heading, we arrived at the present invention. That is, the present invention uses an N-acyl-acidic amino acid ester having an acyl group having 2 to 22 carbon atoms as an active ingredient, and the ester portion thereof is derived from a polyoxyalkylene polyhydric alcohol ether. - A hair cosmetic containing one or more acidic amino acid esters. Preferred examples of the N-acyl acidic amino acid moiety of the N-acyl acidic amino acid ester which is the active ingredient of the hair cosmetic of the present invention are N-acyl-aspartic acid or N-acyl-glutamic acid, and the acyl group has 2 carbon atoms. Acyl groups derived from ~22 saturated or unsaturated fatty acids, such as acetic acid, lauric acid,
Acyl groups of single-composition fatty acids such as oleic acid and stearic acid; acyl groups of naturally-obtained mixed fatty acids such as coconut oil fatty acids, beef tallow fatty acids, and hydrogenated beef fatty acids; or synthetically obtained fatty acids (including fractional fatty acids). It is. The acidic amino acid component may be either an optically active form or a racemic form. Examples of the alcohol component forming the ester moiety of the N-acyl-acidic amino acid ester are polyoxyethylene polyhydric alcohol ether, polyoxypropylene polyhydric alcohol ether, and polyoxypropylene-polyoxyethylene mixed polyhydric alcohol ether. Examples of polyhydric alcohol components that form the polyhydric alcohol ether are propylene glycol, glycerin, diglycerin,
2-2 such as pentaerythritol, trimethylolpropane, trimethylolethane, sorbitan, mannitan, sorbitol and mannitol, etc.
Ethylene oxide or propylene oxide is added to a polyfunctional alcohol with six terminal hydroxyl groups.
The polyether compound which has been addition-polymerized with 10 to 90 moles, preferably 15 to 50 moles, has 1 to 10 moles of ethylene oxide, preferably 2 to 10 moles, to the main chain to which 10 to 90 moles of propylene oxide have been addition-polymerized.
This is a polyether compound of a block type polymer obtained by addition polymerization of 5 moles. The N-acyl-acidic amino acid ester used in the hair cosmetic of the present invention is N-acyl-acidic amino acid and polyoxypropylene (10 to 90 mol) polyhydric alcohol ether or polyoxypropylene (10 to 90 mol).
~90 mol) - polyoxyethylene (1-10 mol)
It can be synthesized by esterifying a mixed polyhydric alcohol ether using generally known esterification methods, such as heating (normal pressure or reduced pressure) dehydration condensation reaction, transesterification reaction, or azeotropic dehydration condensation reaction. In particular, azeotropic dehydration condensation reactions are suitable. For example, the following conditions are appropriate. Polyoxypropylene (10-90 mol) polyhydric alcohol ether or polyoxypropylene (10-90 mol)-polyoxyethylene (1-10 mol) mixed polyhydric alcohol per 1-2 mol of N-acyl-acidic amino acid 1.0 to 1.5 moles of ether and 10 to 50% of a nonpolar solvent such as benzene or toluene (volume % based on the charged amount of N-acyl-acidic amino acid and polyether alcohol) are charged into a reactor, thoroughly stirred and mixed, and then acidified. Add 0.01 to 1.0 mol of catalyst and heat at 70 to 200℃.
Stir under heat for ~10 hours. At this time, water produced as a by-product during the reaction is removed as much as possible to promote the reaction. N-acyl- synthesized by such a method
Acidic amino acid esters have different acyl groups, or different types of polyhydric alcohols such as polyoxyethylene polyhydric alcohol ether, polyoxypropylene polyhydric alcohol ether, or polyoxypropylene-polyoxyethylene mixed polyhydric alcohol ether, and polyhydric alcohol ether. Depending on the number of moles of oxyalkylene added, it can be varied in a wide variety of ways depending on the purpose of use, such as products with strong oiliness, products with high viscosity, and products with strong hair styling ability. What is particularly noteworthy is that when comparing, for example, an ester compound with a polyhydric alcohol ether that has been addition-polymerized with 15 moles of propylene oxide, and an ester compound that has a polyhydric alcohol ether that has been addition-polymerized with 50 moles of propylene oxide, the former is better. It has high hair styling ability, hair styling retention ability, dust adhesion prevention ability, and other properties. This is contrary to the fact that in conventional polyoxyalkylene polyhydric alcohol ethers, the viscosity generally increases and the hair styling ability improves as the addition polymerization of polyoxyalkylene increases. In addition, ester compounds with polyhydric alcohol ethers that are addition-polymerized with 10 moles or less of propylene oxide have extremely high viscosity, and although they have good hair styling and retention properties, they have the drawbacks of being sticky to the hands and strongly corrosive to celluloid. , the ester compound with polyoxypropylene-polyoxyethylene mixed polyhydric alcohol ether corrodes the celluloid when the number of moles of ethylene oxide added is 10 moles or more,
It has been found that when the amount is less than 10 moles, no corrosion occurs at all. Table 1 shows the physical properties of some representative N-acyl-acidic amino acid ester compounds of the present invention.

【table】

【table】

[Table] Differences in adsorption to hair, viscosity, hair styling ability, corrosiveness of celluloid between the ester compound of the present invention as shown in Table 1 and the above-mentioned known ester compound,
Table 2 shows a comparison of performance such as solubility and dust prevention ability.
Shown in ~7. The abbreviations 1, 2, 3, 4, 5, 6, 7 (esters of the present invention), A, B, C, and D (known esters) of the ester compounds shown in each table represent the following compounds, respectively. Abbreviation N-acyl-amino acid ester compound 1: N-2-ethylhexanoyl-glutamic acid/POP (15 mol) propylene glycol ester 2: N-2-ethylhexanoyl-glutamic acid/POP (35 mol) propylene glycol ester 3: N-2-ethylhexanoyl-glutamic acid, POP (15 mol) + POE (2 mol) propylene glycol ester 4: N-2-ethylhexanoyl-glutamic acid, POP (35 mol) + POE (5 mol) propylene glycol ester 5: N-acetyl-glutamic acid/POP (15
mole) + POE (2 mole) propylene glycol ester 6: N-lauroyl-glutamic acid/POP
(50 moles) + POE (5 moles) glycerin ester 7: N-stearoyl-glutamic acid/POP
(15 mol) + POE (2 mol) Glycerin ester A: N-2-ethylhexanoyl-N-methyl-β-alanine POP (15 mol) Propylene glycol ester B: N-N-di-2-ethylhexanoyl -Lysine POP (15 mol) Propylene glycol ester C: N-2-ethylhexanoyl-glutamic acid POP (15 mol) 2-octyldodecyl ester D: N-2-ethylhexanoyl-glutamic acid POP (15 mol) )2-octyldodecyl ester

[Table] Experimental method: Hair was immersed in an emulsion of 1.0% ester component and 1.0% emulsifier for 3 minutes, washed with water, dried, and extracted with a solvent to measure the amount of adsorption.

【table】

[Table] Experimental method: Hair bundles of a certain number and length were immersed in a solution of 20% ester component, 70% ethyl alcohol, and 10% water. After drying with a hair dryer while passing through a comb, The condition of the hair was observed with a constant rotation speed and a distance of 50 cm between the hair and the fan. ◎: State where hair is not dispersed at all 〇: State where hair is slightly dispersed △: State where more than half of the hair is dispersed ×: State where all of the hair is dispersed As is clear from Table 2, compared to known ester compounds, The ester compound of the present invention has extremely good adsorption to hair. What is particularly noteworthy is that the adsorption of a compound with a larger proportion of N-acyl-glutamic acid units constituting the ester compound increases. Furthermore, as is clear from Table 3, when the ester compounds of the present invention are compared with known ester compounds, there is a significant difference in viscosity. It is generally known that the increase in viscosity tends to increase as the degree of addition polymerization of polyoxyethylene increases; however, on the contrary, No. 1
Comparing 2, 3, and 4, the ester compound with a lower degree of polyoxyalkylene polymerization has a higher viscosity. Further, when No. 1 is compared with A and B, even though the alcohol component in the ester moiety is the same, the N-acyl acidic amino acid ester compound of the present invention has a much higher viscosity than the known ester compounds. Furthermore, as is clear from Table 4, there is a significant difference in hair styling ability between the ester compounds. That is, the ester compound of the present invention has extremely superior hair styling ability compared to known ester compounds.

[Table] Experimental method: One drop of the ester component was applied to a celluloid plate, left in a constant temperature bath at 40°C for 48 hours, and the surface condition was observed after washing. Regarding celluloid corrosion properties, as shown in Table 5, Compound D in which the polyether alcohol in the ester moiety was polyoxyethylene (15 mole addition polymer) corroded celluloid, but the polyether alcohol in the ester moiety was polyoxypropylene derivative. Or, an ester compound of a low addition product (addition polymer of 10 moles or less) of polyoxyethylene at its terminal did not corrode at all.

[Table] Next, a solubility test was carried out by adding certain amounts of the ester compound of the present invention and a known ester compound to aqueous solutions having different concentrations of ethyl alcohol. As shown in Table 6, the ester compound of the present invention dissolved transparently even in an aqueous solution with a lower ethyl alcohol concentration than the known ester compounds. As described above, the ester compound of the present invention has high hydrophilicity, and as a result, it reduces the amount of flammable ethyl alcohol required by the Hazardous Materials Law, and improves hair washability with shampoo and the like. Since it has remarkable properties such as improved washability for soiled clothing, etc., it can be applied in a multifaceted manner to a wide variety of development purposes.

【table】

[Table] Experimental method: After spraying 10ml of an ethanol solution containing 5.0% ester component evenly onto the hair and drying well, place the hair in a room at 20℃ and 65% relative humidity wearing a vinyl sandal for 20 minutes. Afterwards, comb your hair 30 times with a nylon brush. Then height 1.5
Bring the hair perpendicular to the nylon lint placed on the glass plate on the wooden stand. The distance it took for the hair to adsorb the nylon lint and the time it took for the nylon lint to fall once it had been adsorbed were measured. As is clear from Table 3, the ester compounds of the present invention have much higher viscosity than known ester compounds. Generally, it is believed that highly viscous substances tend to attract dust and the like, giving a sense of uncleanness. However, as shown in Table 7, the ester compound of the present invention has a property that is effectively excellent in preventing dust adhesion, even though it has a higher viscosity than the known ester compound. Furthermore, safety tests (animal skin irritation, ocular mucosal irritation, and human skin irritation) were conducted on the ester compound of the present invention, and it was found to have no problem with irritation and excellent stability. The ester compound of the present invention has not only the properties described above but also a wide variety of properties depending on the type of polyoxyalkylene polyhydric alcohol ether in the ester moiety. For example, ester compounds with HLB=8.0 or higher have excellent performance as emulsifiers, solubilizers, and dispersants. Also, HLB=8.0
The following ester compounds have good compatibility with oil phase raw materials such as liquid paraffin, beeswax, and higher alcohols, and have excellent affinity and safety for the skin, so they are used as the oil phase of various skin cosmetics. It can also be used as a raw material. Next, an example will be shown in which the ester compound of the present invention was blended into a hair cosmetic. Example 1 Transparent liquid hair styling agent N-2-ethylhexanoyl-glutamic acid.
POP (15 moles) + POE (2 moles) propylene glycol ester 10.0 N-2-ethylhexanoyl-glutamic acid.
POP (50 mol) Glycerin ester 5.0 Pyroglutamic acid triethanolamine salt (50
% aqueous solution) 2.0 Ethyl alcohol 40.0 Fragrance Appropriate amount Colorant 〃 Water (ion-exchanged water) 43.0 100% <Dissolution method> Add the above ingredients to ethyl alcohol one by one and stir and mix to obtain a transparent liquid hair conditioner. <Features> A hair styling agent that provides appropriate hair styling power, is non-sticky, has good hair washing properties, has low celluloid corrosion properties, and has dust adhesion prevention properties. Example 2 Transparent liquid hair styling agent N-2-ethyl-hexanoyl-glutamic acid.
POP (50 mol) + POE (5 mol) glycerin ester 4.0 N-acetyl-glutamic acid POP (50 mol)
Sorbitous ester 4.0 Akylammonium halide activator 0.1 Ethyl alcohol 70.0 L-menthol 0.3 Vitamin B6 Appropriate amount Flavor Colorant Water (ion-exchanged water) 21.6 100% <Dissolution method> Same as Example 1. <Features> A hair styling agent with a refreshing feeling and soft styling power. Since the main component compound of the hair cosmetic of the present invention is an ester compound, it can be used in combination with cationic and anionic active agents, and moreover, it has the ability to slightly solubilize perfume in an aqueous ethyl alcohol solution. Example 3 Transparent liquid hair conditioner N-lauroyl-glutamic acid POP (50 moles) + POE (5 moles) Glycerin ester 15.0 N-2-ethylhexanoyl-glutamic acid
POP (15 mol) + POE (2 mol) Propylene glycol ester 25.0 Glycerin 35.0 Fragrance Appropriate amount Colorant Water (ion-exchanged water) 25.0 100% <Dissolution method> Same as Example 1. 〈Features〉 Has strong hair setting power and is not sticky.
A hair styling agent with strong dust-prevention properties. Example 4 Hair emulsion

[Table] <Emulsification method> Heat the ingredients in and to 75℃, add the ingredients in and emulsify them while stirring, cool while stirring,
Add the ingredients at 50°C, mix well, and pour into a bottle at 40°C to obtain a hair emulsion. <Features> To obtain a non-sticky, emulsion-type hair conditioner that provides an appropriate oily feel, has excellent dust adhesion prevention properties, and is non-sticky. Example 5 Hair cream

[Table] <Emulsification method> Heat each of the ingredients in and out to 80℃, add the ingredients while stirring the ingredients, and add the ingredients while stirring thoroughly.
Add the ingredients at 50 °C while stirring and chill for 40
Pour into a bottle at ℃ to obtain hair cream. <Features> To obtain a hair cream that has excellent hair styling and hair styling ability and has a strong oily feel. Example 6 Hair treatment and rinse

[Table] 〈Emulsification method〉 Heat the ingredients in 〈Emulsification method〉 and the ingredients in 〉 respectively to 85℃, and add the ingredients in 〉while stirring the ingredients. Cool and stir mix, add the ingredients at 50°C, and pour into a container at 40°C to obtain. <Features> Used after shampooing and rinsing with water, it provides a suitable oily feel, ability to prevent dust adhesion, and provides a hair treatment or rinse agent that is non-sticky and easy to comb through. Example 7 Manual spray hair conditioner

[Table] <Emulsification method> Once the ingredients are heated to 60°C and uniformly dissolved, cooled to 37°C. Mix the ingredients at room temperature, dissolve, and then add the ingredients to this. The mixture is thoroughly mixed and emulsified, then the next ingredients are added, and the mixture is poured into a container to obtain a hair conditioner. <Characteristics> By brushing, a hair styling agent is obtained that gives the hair a moderate oiliness and soft styling properties. Example 8 Cream rinse

【table】

[Table] <Method> Heat the ingredients in and to 60℃,
Add the ingredients to this while stirring the ingredients, add the ingredients whose emulsion is at 50℃ while stirring the cooled oysters, and pour into a container at 40℃ to obtain a cream rinse. <Features> By using the ester compound of the present invention in combination with a cationic activator, the rinsing effect is increased, and after use,
To obtain a rinse agent having an appropriate oiliness and dust adhesion prevention effect. Example 9 Oil shampoo

[Table] Heat each component in <Method> to 70℃, dissolve it transparently, cool and stir while adding the ingredients at 60℃ to dissolve uniformly, pour into a container at 40℃ and make oil shampoo. get. <Features> When the ester compound of the present invention is added to detergents such as shampoo and soap, it provides the effect of superfatting agent. Example 10 Aerosol hair styling agent N-2-ethylhexanoyl-glutamic acid
POP (50 mol) + POE (5 mol) Glycerin ester 10.0 Polyoxyethylene glycerin isostearate 0.5 Propylene glycol 1.0 Ethyl alcohol 15.0 Fragrance Appropriate amount Water (ion exchange water) 15.0 Freon gas 58.5 100% <Method> Raw materials other than Freon gas An aerosol type hair styling product is obtained by uniformly mixing the mixture in an aerosol can, attaching a valve, and then sealing in Freon gas. <Features> To obtain a hair styling product that provides an appropriate amount of oil, has dust adhesion prevention properties, is non-sticky, and has good hair styling ability. Example 11 Cream

[Table] 〈Method〉 Heat the ingredients in and to 75°C, add the ingredients in to this while stirring the ingredients in, mix thoroughly, add the ingredients in, and gradually cool. Stir and pour into a container at 45℃ to obtain cream. <Features> The ester compound of the present invention used has excellent compatibility with oil phase raw materials such as liquid paraffin and beeswax,
It has excellent affinity with the skin and safety, and is also a substance with a large molecular weight, so when used as a raw material for the oil phase of emulsions with a high water content, various creams with a strong milky white and oily feel can be obtained. . Examples of manufacturing the ester compound used in the hair cosmetic of the present invention will be described below. Production example 1 N-2-ethylhexanoyl-glutamic acid.
Synthesis of polyoxypropylene (15 mol) propylene glycol ester N-2-ethylhexanoyl-glutamic acid 1
mol, polyoxypropylene (15 mol), 1.2 mol of propylene glycol ether, and 500 ml of toluene as a solvent were charged into a reactor, stirred and mixed thoroughly, and then 0.03 mol of catalyst H ₂ SO ₄ was added, and the mixture was heated between 90°C and 150°C for about 2 mols. Carry out the reaction for about an hour. At this time, water produced as a by-product during the reaction is sufficiently removed. After the reaction is complete, the catalyst
H ₂ SO ₄ was neutralized and removed, and the solvent toluene was recovered to obtain the target N-2-ethylhexanoyl-glutamic acid/polyoxypropylene (15 mol) propylene glycol ester. Yield = 98%, specific gravity D ³⁰ ₂₀ 10145, acid value = 0.3, potassium value = 81.78, PH (1.0%) = 6.27 Production example 2 N-2-ethylhexanoyl-glutamic acid.
Synthesis of polyoxypropylene (15 mol) + polyoxyethylene (2 mol) glycerin ester N-2-ethylhexanoyl-glutamic acid 1
Charge mol, polyoxypropylene (15 mol) + polyoxyethylene (2 mol), 1 mol of glycerin ether, and 300 ml of solvent benzene into a reactor.
After thorough stirring and mixing, 0.03 mol of catalyst H ₂ SO ₄ is added, and the reaction is carried out at 90°C to 150°C for about 2 hours.
At this time, water produced as a by-product during the reaction is sufficiently removed.
After the reaction, the catalyst H ₂ SO ₄ is neutralized and removed, the solvent benzene is recovered, and the target product N-2-ethylhexanoyl-gludamic acid/polyoxypropylene (15 mol) + polyoxyethylene (2 mol) glycerin An ether ester was obtained. Yield 98.5%, specific gravity D ³⁰ ₂₀ 1.0457, acid value = 0.25, saponification value 75.50, PH (1.0%) = 5.80 Production example 3 Synthesis of N-lauroyl-glutamic acid polyoxyethylene (10 mol) glycerin ether ester 1 mol of N-lauroyl-glutamic acid and 1 mol of polyoxyethylene (10 mol) glycerin ether are charged into a reactor, mixed with stirring while passing nitrogen gas, and reacted at 150°C to 190°C for about 4 hours. At this time, 2 moles of water produced as a by-product during the reaction are removed. After the reaction was completed, the mixture was decolorized using charcoal and activated clay and filtered to obtain the target product, N-lauroyl-glutamic acid/polyoxyethylene (10 mol) glycerin ether ester. Yield 98%, Specific gravity ³⁰ ₂₀ 1.1164, Acid value 0.45, Ken number =
138.20, PH6.20

Claims (1)

[Scope of Claims] 1 N-acyl acidic amino acid ester having an acyl group having 2 to 18 carbon atoms is used as an active ingredient, and the ester moiety is derived from polyoxyalkylene polyhydric alcohol ether. A hair cosmetic containing one or more acyl acidic amino acid esters. 2. Hair according to claim 1, wherein the polyoxyalkylene polyhydric alcohol ether is polyoxyethylene polyhydric alcohol ether, polyoxypropylene polyhydric alcohol ether, or polyoxypropylene-polyoxyethylene copolymerized polyhydric alcohol ether. Cosmetics. 3. Claim 1, wherein the polyoxyalkylene polyhydric alcohol ether is polyoxypropylene polyhydric alcohol ether, and the average number of added moles of oxypropylene units is 10 to 90 mol per mol of polyhydric alcohol, or Hair cosmetics according to item 2. 4. The polyoxyalkylene polyhydric alcohol ether is a polyoxyethylene-polyoxypropylene copolymer polyhydric alcohol ether, and the average number of added moles of oxyethylene units and the average number of moles of oxypropylene units are based on 1 mole of polyhydric alcohol. The hair cosmetic composition according to claim 1 or 2, wherein the amount is 1 to 10 mol and 10 to 90 mol, respectively.