JPH0565485B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to cosmetics, and more particularly to cosmetics that have a long-lasting and high moisturizing effect and are excellent in improving skin roughness. [Conventional technology and its problems] Urea has traditionally been said to increase the water retention capacity of stratum corneum, as well as have keratolytic and antibacterial effects.
It is reported to be particularly effective against keratinization abnormalities such as psoriasis and senile xeroderma, and is included in various cosmetics and medicines for the purpose of preventing rough skin and moisturizing the skin. However, conventional water-soluble moisturizers containing urea retain moisture due to their affinity for water, so their moisturizing effect is temporary, and fundamentally improves the moisture retaining ability of the stratum corneum and maintains it. It did not provide a sufficient moisturizing effect or prevent skin roughness. On the other hand, it has become increasingly clear in recent years that interkeratinocyte lipids play an important role in water retention in the stratum corneum, apart from conventional water-soluble moisturizers containing urea. It has been discovered that the amide derivative represented by the formula ') has the effect of fundamentally improving the water retention ability of the stratum corneum, and a patent application has been filed (Japanese Patent Application No. 286999/1983). (In the formula, R ¹ is a straight-chain or branched saturated or unsaturated hydrocarbon group having 10 to 26 carbon atoms, and R ² is a straight-chain or branched saturated or unsaturated hydrocarbon group having 9 to 25 carbon atoms. (indicates a group) However, simply incorporating these amide derivatives into cosmetics does not necessarily provide sufficient sustainability of the effect or the effect of improving rough skin. [Means for Solving the Problem] In view of these circumstances, the present inventors have conducted extensive research in order to obtain a cosmetic that has a long-lasting moisturizing effect, has an excellent effect on improving rough skin, and can be particularly applied to the skin. As a result, the inventors have discovered that by using the above-mentioned amide derivative and urea in combination, a long-lasting and high moisturizing effect and a sufficient effect on improving rough skin can be obtained, and the present invention has been completed. That is, the object of the present invention is to prepare the following components (A) and (B), (A) 0.5 to 15% by weight of urea, and (B) an amide derivative represented by the following general formula ().
0.01~50% by weight [In the formula, R ¹ is a straight chain or branched saturated or unsaturated hydrocarbon group having 10 to 26 carbon atoms, and R ² is a straight chain or branched saturated or unsaturated hydrocarbon group having 9 to 25 carbon atoms. group, X is a group (--CH ₂
)―― _o , (――CH ₂ CH ₂ O)―― _n CH ₂ CH ₂ - or -
Indicates a group selected from _CH2CH (OH) _-CH2- .
provided that n and m represent numbers from 2 to 6] and whose weight ratio (A)/(B) is from 0.1 to 50. In the present invention, the amount of urea used as component (A) in the cosmetic is 0.5% of the total composition of the cosmetic.
~15% by weight (hereinafter simply referred to as "%"), and a content of 1 to 10% is particularly good from the viewpoints of the moisturizing properties of the cosmetic, the effect of improving rough skin, and the feeling of irritation to the skin. Furthermore, although the amide derivative used as component (B) of the present invention is a new compound, it can be prepared using known methods [for example, Pol. J. Chem 52 , 1059 ( 1978); ,1283
(1978); JP-A No. 54-117421, JP-A No. 54-144308,
Publication No. 54-147937]. That is, according to the reaction formula shown below,
It can be produced by reacting a compound () obtained from glycidyl ether and ethanolamine with a fatty acid methyl ester. (In the formula, R ¹ , R ² and X are the same as above) The number of carbon atoms in the hydrocarbon group R ¹ of this amide derivative ( ² has 9 to 25 carbon atoms, preferably 14 to 18 carbon atoms. The amount of amide derivative () in cosmetics is as follows:
0.01 to 50% of the total composition of cosmetics, especially 0.1
~20% is good for cosmetics in terms of moisturizing properties and texture. In addition, the amide derivative (), which is component (B), is
(A) 0.02 to 10 times, preferably urea
It is preferable to mix in a range of 0.05 to 10 times. In addition to cosmetics such as creams and emulsions, the cosmetics of the present invention can also be in the form of lotions, aerosols, solids, and the like. For example, the oil used when making the cosmetic of the present invention into an emulsified cosmetic is not particularly limited as long as it is normally used in cosmetics, such as hydrocarbons, vegetable oils, animal oils, esters, synthetic oils such as silicones, etc. , higher fatty acids, higher alcohols, synthetic glycerides, etc. are used. These oils are used in a total amount of 1-60%, more preferably 2-30%. As the surfactant, any of nonionic surfactants, anionic surfactants, and amphoteric surfactants can be used, but nonionic surfactants are particularly preferred. Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester,
polyoxyethylene sorbitan fatty acid ester,
Examples include fatty acid monoglyceride and glyceryl ether. The amount of these surfactants is
It is 0.01-20%, more preferably 0.1-5%. The cosmetic composition of the present invention can be produced by blending component (A) and component (B) in a conventional manner, thereby providing an excellent moisturizing effect. In addition to the above-mentioned ingredients, the cosmetic of the present invention includes commonly used oils, humectants, ultraviolet absorbers, alcohols, chelating agents, PH adjusters, preservatives, thickeners, pigments, Any combination of fragrances and the like can be used. The thus obtained cosmetics of the present invention can also be used as make-up cosmetics; skin cleansers; hair cosmetics such as hair tonics and hair styling products. [Actions and Effects] Although it is not necessarily clear by what mechanism the excellent effects of the present invention are achieved, the urea of the component (A) is able to degrade the amide of the component (B) through its keratolytic action. Both ingredients (A) and (B), which help the derivatives penetrate into the stratum corneum, improve the moisture retention ability of the stratum corneum and show a continuous moisturizing effect, improving the effect of improving rough skin. It is estimated that excellent skin cosmetics can be obtained. [Example] Next, the present invention will be explained in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto. Synthesis Example 1 N-(2-hydroxy-3-hexadecyloxypropyl)-N-2-hydroxyethylhexadecanamide [In formula (), R ¹ =C ₁₆ H ₃₃ ,
Synthesis _of R ² = _{C 15} H ₃₁ , Add 1,637 g (26.8 mol) of amine and 327 g (7.11 mol) of ethanol, and heat to 80 ml under nitrogen atmosphere.
400 g (1.34 mol) of hexadecyl glycidyl ether was added dropwise to the mixture over 3 hours while stirring and heating the mixture to .degree. After completion of the dropwise addition, the mixture was further heated and stirred for 30 minutes under the same conditions, and then a distillation apparatus was attached, and ethanol and unreacted ethanolamine were distilled off under reduced pressure (79-81°C/20 Torr). While heating and stirring at 80℃/20Torr, add methyl hexadecanoate to this.
362.3 g (1.34 mol) was added dropwise over 3 hours.
After the addition was completed, the mixture was further heated and stirred for 1 hour under the same conditions to obtain 801 g of a pale yellow crude product. By recrystallizing this once from hexane and twice from ethanol, 649 g of the target compound was obtained as a colorless powder.
(yield 81%). Synthesis Example 2 N-(2-hydroxy-3-hexadecyloxypropyl)-N-6-hydroxyhexylhexadecanamide [In formula (), R ¹ =C ₁₆ H ₃₃ ,
_{Synthesis of} R ² = C _{15 H 31} , 6-
Add 58.0 g (0.50 mol) of amino-1-hexanol and 150 g of ethanol and heat at 80°C under _N2 atmosphere.
While heating and stirring, add 15.0 g (0.050 mol) of hexadecyl glycidyl ether and 50 g of ethanol.
A solution dissolved in water was added dropwise over 1 hour. After the addition was completed, the mixture was further heated and stirred for 30 minutes under the same conditions, and then a distillation apparatus was attached, and ethanol and unreacted 6-amino-1-hexanol were distilled off under reduced pressure to obtain 15.8 g of a pale yellow solid. . Take 8.3 g (equivalent to 0.020 mol) of the obtained crude product, dissolve it in 200 ml of methylene chloride, and add 4.8 g (0.06 mol) of pyridine. Hexadecanoyl chloride 16.5g under water cooling
(0.06 mol) was added dropwise over about 30 minutes, and after the addition was completed, the mixture was stirred at room temperature for 1 hour. By washing the reaction product with water to remove pyridine hydrochloride and distilling off the solvent,
22.6 g of amide-ester compound was obtained. Continuing, add this to 95% ethanol aqueous solution 400%
2.24 g (0.04 ml) of potassium hydroxide was added thereto, and the mixture was heated and stirred at 50° C. for 1 hour. By extracting the chloroform-soluble matter from the reaction mixture and purifying it by silica gel flash column chromatography, 9.0 g (0.0138 mol) of the target compound as a colorless powder was obtained.
(total yield 52.4%). mp 78.8～79.8℃ IR (cm ^-1 ) 3334, 2920, 2854, 1623, 1467,
1113 ¹ H-NMR0.87 (t, 6H) 1.2-1.9 (m, 62H)
2.41 (t, 2H) 3.1-4.3 (m, 13H) Elemental analysis: Actual value (theoretical value) C: 75.33% (75.28%) H: 12.83% (12.79%) N: 2.09% (2.14%) Synthesis example 3 N-(2-hydroxy-3-hexadecyloxypropyl)-N-2,3-dihydroxypropylhexadecanamide [R ¹ = C ₁₆ H ₃₃ , R ² =
_{Synthesis of} C ₁₅ H ₃₁ , 2-propanediol 48.3g (0.50mol) and ethanol
Add 150g of hexadecyl glycidyl ether and heat to 80℃ while stirring, and add 15.0g of hexadecyl glycidyl ether.
A solution of (0.050 mol) dissolved in 150 g of ethanol was added dropwise over 1 hour. After the addition was completed, the mixture was heated and stirred for 1 hour under the same conditions, and then ethanol and unreacted 3-amino-1,2-propanediol were distilled off under reduced pressure to obtain 19.8 g of a pale yellow solid. Next, dissolve this in 300g of methylene chloride,
15.8 g (0.20 mol) of pyridine was added, and 54.8 g (0.20 mol) of hexadecanoyl chloride was added dropwise over about 30 minutes while cooling with water. After the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour. The reaction product was washed with water to remove pyridine hydrochloride,
By distilling off the solvent, the amide-ester
64.0g was obtained. This was subsequently dissolved in 500 g of 95% ethanol aqueous solution, and 8.4 g of potassium hydroxide was added.
(0.15 mol) was added, and the mixture was heated and stirred at 50°C for 1 hour.
By extracting the chloroform-soluble material from the reaction product and purifying it by silica gel flash column chromatography, 17.3 g of the target compound was obtained as colorless crystals.
(0.028mol) was obtained. Yield 56% mp81.9-83.3℃ IR (cm ^-1 ) 3370, 3292, 2920, 2854, 1608,
1470, 1113 ¹ H-NMR0.87 (t, 6H), 1.1~1.8 (m, 54H),
2.42 (t, 2H), 3.2-4.4 (m, 15H) Elemental analysis (%): Actual value (theoretical value) C: 73.02 (72.67) H: 12.41 (12.36) N: 2.18 (2.23) Synthesis example 4 N- Synthesis of (2-hydroxy-3-hexadecyloxypropyl)-N-2-hydroxyethoxyethylhexadecanamide: In a four-necked flask equipped with a stirrer, dropping funnel, thermometer, and reflux condenser, 2- Aminoethoxyethanol 27.4g (0.26mol) and ethanol 100g
was added, and while heating and stirring at 80°C, a solution of 15.0 g (0.05 mol) of hexadecyl glycidyl ether dissolved in 50 g of ethanol was added over 2 hours.
It dripped slowly. After the completion of dropping, further under the same conditions 1
After heating and stirring for an hour, ethanol and unreacted 2-aminoethoxyethanol were distilled off under reduced pressure, and 17.7 g of intermediate N-(2-hydroxy-3-hexadecyloxypropyl)-N-2-hydroxyethylamine was obtained as a pale yellow solid. Next, dissolve this in 300g of methylene chloride,
11.9 g (0.15 mol) of pyridine was added, and 41.1 g (0.15 mol) of hexadecanoyl chloride was added dropwise over about 30 minutes under water cooling. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour. The reaction product was washed with water to remove pyridine hydrochloride, and the solvent was distilled off to obtain 53.8 g of an amide ester. Subsequently, this was dissolved in 400 g of 95% aqueous ethanol, and 5.6 g of potassium hydroxide was added.
g (0.10 mol) was added thereto, and the mixture was heated and stirred at 40°C for 30 minutes. By extracting the chloroform-soluble part from the reaction product and purifying it by silica gel flash column chromatography, 17.3 g of the target product was obtained as colorless crystals.
(0.027 mol) was obtained. Overall yield 54% (based on hexadecyl glycidyl ether) mp 68.0-69.3℃ IR (cm ^-1 ) 3406, 2920, 2854, 1647, 1473,
1119 ¹ H-NMR0.87 (t, 6H) 1.1~1.8 (m, 54H)
2.40 (t, 2H) 3.3-4.4 (m, 17H) Elemental analysis (%) C: 73.17 (72.96) H: 12.44 (12.40) N: 2.16 (21.8) Example 1 Cream with the composition shown in Table 1 below The product was manufactured, and its practical test and moisturizing effect and moisturizing sustaining effect were measured by the methods described below. Table 2 shows the results.
Shown below. (composition)

[Table] * Monofatty acid glycerin: Monolaurylglycerin (manufacturing method) Mix the above oil phases (1) to (6), heat and dissolve, and maintain at 70°C. Meanwhile, gradually add the above aqueous phase parts (7) to (12),
Emulsify using an emulsifying machine. The emulsion is brought to a final temperature using a heat exchanger.
Creams (products of the present invention 1 and 2) were prepared by cooling to 30°C and then filling. Comparison product 1~
4 was produced in the same manner. (Test method) (1) Practical test (panel test) Ten expert panelists actually used the samples prepared above for practical evaluation. The evaluation was based on the following criteria for five items: familiarity with the skin, moisturizing feeling, less stickiness, smoothness of the skin 4 hours after application, and overall evaluation. ◎: More than 8 out of 10 people answered that it was good. ○: More than 6 out of 10 people answered that it was good. △: 4 or more people out of 10 answered that it was good. ×: Less than 4 out of 10 people answered that it was good. (2) Moisturizing effect, lasting moisturizing effect Apply a certain amount of the above sample to the inside of the forearm, leave it for 4 hours, wash with hot water, enter a constant temperature and humidity room at 20℃ and 50% humidity, and wait 30 minutes. The water content in the stratum corneum is measured using an impedance meter (manufactured by IBS).
The value was taken as the moisturizing effect. Furthermore, the same sample was applied again, and after 24 hours, it was washed again with hot water and placed in a constant temperature and humidity room at a temperature of 20℃ and humidity of 40%. After 30 minutes, the water content in the stratum corneum was measured using a skin conductance meter (manufactured by IBS). It was measured as the value of the lasting moisturizing effect. The average value (N=7) is shown in the table. (result)

[Table] * Unit is μ
As is clear from Table 2, the cosmetics of the present invention have superior moisturizing effects and long-lasting moisturizing effects compared to cosmetics containing urea or amide derivatives alone, and these ingredients act synergistically. It has been proven that. Example 2 A cream having the composition shown in Table 3 below was manufactured,
Skin conductance and skin roughness improvement effects were evaluated by the methods described below. The results are shown in Table 4. (composition)

【table】

[Table] (Test method) 30- to 30-year-olds who have mild skin roughness on their cheeks during winter
Ten 60-year-old women were tested and had different skin cosmetics applied to their left and right cheeks for two weeks. The next day after the two-week application was completed, the following tests were conducted. (1) Skin conductance After washing the face with warm water at 37℃ and resting for 20 minutes in a room with a temperature of 20℃ and humidity of 40%, the moisture content of the stratum corneum was measured using a skin conductance meter (manufactured by IBS). . (2) Skin roughness score Skin roughness was observed with the naked eye and judged according to the following criteria. Scores are shown as average values.

【table】

[Table] Example 3 Emulsion: Oil phase component (1) Setanol 0.5 (%) (2) Vaseline 1.5 (3) Olive oil 5.0 (4) Amide derivative (Synthesis Example 3) 1.0 (5) POE (10) Monooleic acid ester
2.5 (6) Stearic acid 1.6 (7) Fragrance 0.1 Aqueous phase components (8) Urea 1.0 (9) Propylene glycol 3.0 (10) Triethanolamine 0.8 (11) Methylparaben 0.2 (12) Ethanol 3.0 (13) Purified water Total Amount to make 100 Mix the oil phase components (1) to (7) in the above formulation, heat and dissolve and keep at 70°C. Similarly, the above aqueous phase components (8) to (13)
The mixture is heated and mixed at 70°C, and the above-mentioned oil phase is added to this water phase and emulsified using an emulsifier. An emulsion was prepared by cooling the emulsion to a final temperature of 30°C using a heat exchanger and then filling the mixture. Example 4 Lotion: (1) POE (40) Hydrogenated castor oil 2.0 (%) (2) Ethanol 6.0 (3) POE (10) Methyl glucoside 3.0 (4) Amide derivative (Synthesis Example 4) 0.2 (5) Urea 3.0 (6) β-alanine 2.0 (7) Citric acid 0.1 (8) Sodium citrate 0.4 (9) Fragrance 0.1 (10) Blue-No. 1 0.0001 (11) Purified water Amount to make the total 100 In the above formulation (1 ) to (4) and (9) mixed and dissolved,
Add a mixed solution of (5) to (8), (10), and (11),
A lotion was prepared. Example 5 Emulsified foundation: Oil phase component (1) Cetostearyl alcohol 1.0 (%) (2) Stearic acid 5.0 (3) Sorbitan monostearate 1.5 (4) Cholesteryl isostearate 2.0 (5) Amide derivative (Synthesis example 1) 7.0 (6) Propylene glycol monolaurate 2.0 Water phase components (7) Glycerin 5.0 (8) Urea 2.0 (9) Triethanolamine 1.5 (10) Methylparaben 0.1 (11) Ethylparaben 0.1 (12) Fragrance 0.1 (13) Purified water Powder components (14) Titanium oxide 9.0 (%) (15) Talc 5.0 (16) Iron oxide 0.5 Mix the oil phase components in the above formulation and heat and dissolve.
Keep at 70℃. The powder component is added to the above aqueous phase component, dispersed, and then heated to 70°C. The aforementioned oil phase is added to this water phase and emulsified and dispersed using an emulsifier. This emulsion was cooled to a final temperature of 30° C. using a heat exchanger and then filled to prepare an emulsified foundation. The skin cosmetics of the present invention obtained in Examples 3 to 5 above all exhibited excellent long-lasting moisturizing effects and rough skin improvement effects.

Claims (1)

[Claims] 1. The following two components (A) Urea 0.5 to 15% by weight (B) An amide derivative represented by the following general formula ()
0.01~50% by weight [In the formula, R ¹ is a straight chain or branched saturated or unsaturated hydrocarbon group having 10 to 26 carbon atoms, and R ² is a straight chain or branched saturated or unsaturated hydrocarbon group having 9 to 25 carbon atoms. group, X is a group (--CH ₂
)―― _o , (――CH ₂ CH ₂ O)―― _n CH ₂ CH ₂ - or -
Indicates a group selected from _CH2CH (OH) _-CH2- .
provided that n and m represent numbers from 2 to 6] A cosmetic whose weight ratio (A)/(B) is from 0.1 to 50.