JPH0763613B2 - Water-in-oil emulsion composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention provides a water-in-oil type (hereinafter referred to as "W / O type") which is suitable for cosmetics and external preparations for skin, which has low irritation and excellent moisturizing properties. (Abbreviation) emulsified composition.

[Conventional technology and its problems]

Generally, anionic surfactants and nonionic surfactants are used as emulsifiers in emulsion type compositions such as creams and emulsions. However, all of these usual surfactants have a drawback that they have some skin irritation. In addition, a W / O type emulsion cosmetic called an absorption base using petrolatum and lanolin alcohol shows a moisturizing effect based on the blockage of the skin although it is less irritating, and has a bad feeling of use, and its The moisturizing effect was also poor in sustainability.

[Means for solving problems]

Under the present circumstances, the present inventors have conducted extensive studies on the W / O type emulsion composition, and by using a novel amide derivative and cholesterol, substantially use a hydrophilic surfactant that causes irritation. The present invention has been completed by finding that a W / O type emulsion composition can be prepared without the need.

That is, the present invention provides the following four components (A) to (D) (A) an amide derivative represented by the following general formula (I):
~ 10% by weight Wherein, R ¹ represents a straight chain or a saturated or unsaturated hydrocarbon group branched, R ² is a hydrocarbon, saturated or unsaturated linear or branched 9 to 25 carbon atoms 10 to 26 carbon atoms Represents a group, X is a group CH _{2 n} , CH ₂ CH ₂ O _m CH ₂ CH ₂ —, —CH ₂ CH
A group selected from - (OH) -CH _2.

However, n and m represent numbers of 2 to 6] (B) Cholesterol 0.1 to 10% by weight (C) Oily substance 10 to 70% by weight (D) Water 10 to 88% by weight, and (A) / ( B) is 0.1 to 10 by weight,
The present invention also provides a W / O type emulsion composition which does not substantially contain a hydrophilic surfactant.

The amide derivative represented by the general formula (I), which is the component (A) used in the present invention, is a novel compound, but it is a known method [for example, Polyurethane Journal of Chemistry (Po).
. LJChem) 52, 1059 (1978); the 52, 1283 (1978); JP 54-117421, the same 54-144308 JP, can be produced according to the same 54-147937 JP]. That is, it can be produced by reacting a compound (II) obtained from glycidyl ether and ethanolamine with a fatty acid methyl ester according to the reaction formula shown below.

[In the formula, R ¹ , R ² and X are the same as above] The hydrocarbon group R ¹ of the amide derivative (I) which is the component (A) of the present invention has 10 to 26 carbon atoms, preferably 14 to 18 carbon atoms. And
The hydrocarbon group R ² has 9 to 25 carbon atoms, preferably 14 carbon atoms.
~ 18.

The content of the component (A) in the emulsion composition is the total amount of the composition.
It is 0.1 to 10% by weight (hereinafter, simply referred to as "%"). More preferably, the blending amount of 1 to 5% is a good range from the viewpoint of the moisturizing property and feel of the composition.

The cholesterol used as the component (B) in the present invention is obtained by separating the unsaponifiable matter from wool fat and extracting it with ether or the like, and typical examples of the compound are represented by the following general formula (III ).

The blending amount of the component (B) in the present invention is 0.1 to 10%, preferably 1 to 5% of the total amount of the composition of the present invention.

Most of the above-mentioned component (A) and the component (B) are solid powders at room temperature, but these are in a weight ratio (component (A) / component (B)) of 0.1 to 10, preferably, etc. Mixing in an amount gives a paste-like composition, which facilitates incorporation into cosmetics. The mixture thus obtained has a sufficient moisturizing effect when incorporated into a cosmetic composition, and also has properties as an emulsifier. Furthermore, it is characterized by low irritation and moisturizing properties that conventional emulsifiers do not have.

The oily substance which is the component (C) of the present invention is not particularly limited as long as it does not irritate the skin, and those conventionally used as a base for cosmetics, external medicines and the like should be used. You can Specific examples of the component (C) include hydrocarbons such as petrolatum, ceresin, solid paraffin, microcrystalline wax, liquid paraffin, and squalane: olive oil, jojoba oil, lanolin, castor oil, cacao butter, magadamian nuts. Natural animal and vegetable oils such as oils and mink oils: synthetic ester oils such as octyldodecyl myristate, isopropyl palmitate (IPP), and isopropyl myristate (IPM): other silicone derivatives, higher fatty acids, higher alcohols and the like.

The blending amount of the component (C) in the present invention is 10 to 70%, preferably 20 to 50% of the total amount of the composition of the present invention.

The water content of the component (D) is 10 to 10% of the total amount of the composition of the present invention.
At 88%, the balance amount is used so that the entire composition is W / O.

The W / O type emulsion composition of the present invention is prepared, for example, as follows.

First, the component (A) and the component (B) are heated and mixed at 80 to 150 ° C. Then, after the components (A) and (B) are mutually dissolved, the component (C) is added and the temperature is adjusted to 60 to 100 ° C. Further, the component (D) kept warm at 60 to 95 ° C. is added little by little while stirring the mixture. The desired W / O type emulsion composition is obtained by cooling this composition with stirring.

In the W / O type emulsion composition of the present invention, the components (A) to
In addition to the essential components of component (D), if necessary, glycerin, sorbitol, maltitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, sodium pyrrolidonecarboxylate, polyoxyethylene methyl glucoside, polyoxypropylene methyl Humidity regulators such as glucoside and glucose; amino acids such as glycine, serine, proline and hydroxyproline; anti-inflammatory agents such as glycyrrhizin, azulene and allantoin,
A germicidal preservative such as paraben, vitamins A, D, E and derivatives thereof, and other dyes, pigments, fragrances and the like can be added.

However, nonionic and anionic surfactants having an HLB (hydrophilic / lipophilic balance) of 10 or more, which are usually used in emulsion compositions, may cause irritation, and since they impair the stability of W / O emulsion compositions, Cannot be blended.

[Operation and effect of the invention]

The emulsion composition of the present invention has good moisturizing properties, low irritation and stability, and thus can be widely used as a base for skin and hair cosmetics or external medicines. Further, the details of the mechanism of action of the emulsion composition of the present invention are unknown, or it is presumed that the component (A) and the component (B) form some kind of complex to exhibit emulsion stabilization and moisturizing action.

〔Example〕

Next, the present invention will be described in more detail by way of examples and synthetic examples.

Synthesis Example 1 N- (2-hydroxy-3-hexadecyloxypropyl) -N-2-hydroxyethylhexadecanamide [in the formula (I), R ¹ = C ₁₆ H ₃₃ , R ² = C ₁₅ H ₃₁ , X = CH _2
2 )]: Ethanolamine 16 in a 54-necked flask equipped with a stirrer, a dropping funnel, a thermometer, a reflux condenser and a nitrogen inlet tube.
37g (26.8mol) and ethanol 327g (7.11mol)
And stir it under heating in a nitrogen atmosphere at 80 ° C while adding 400 g (1.34 mol) of hexadecyl glycidyl ether to this mixture.
It dripped over time. After completion of dropping, the mixture was further heated and stirred for 30 minutes under the same conditions, 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 ° C./20 Torr, 362.3 g (1.34 mol) of methyl hexadecanoate was added dropwise thereto over 3 hours. After completion of the dropping, the mixture was further heated and stirred under the same conditions for 1 hour to obtain 801 g of a pale yellow crude product. This was recrystallized once from hexane and twice from ethanol to give 649 g of the target compound as a colorless powder (yield 81
%) Was obtained.

Synthesis Example 2 N- (2-hydroxy-3-hexadecyloxypropyl) -N-6-hydroxyhexylhexadecanamide [in the formula (I), R ¹ = C ₁₆ H ₃₃ , R ² = C ₁₅ H ₃₁ , X = CH
Synthesis of _{2 6} things]: stirrer, a dropping funnel, a thermometer, a reflux condenser and N in 200ml4-necked flask provided with a _second inlet pipe 6-amino-1-hexanol 58.0 g (0.50 mol) and ethanol 150g The mixture was put in, and a solution of hexadecyl glycidyl ether (15.0 g, 0.050 mol) dissolved in ethanol (50 g) was added dropwise thereto over 1 hour while heating and stirring at 80 ° C. under N ₂ . After completion of dropping, the mixture was further heated and stirred for 30 minutes under the same conditions, then a distillation apparatus was attached, and ethanol and unreacted 6-amino-1-
Hexanol was distilled off under reduced pressure, and a pale yellow solid 15.8 g
Got Of the crude product obtained, 8.3 g (0.020 mol equivalent) was taken and dissolved in 200 ml of methylene chloride, and pyridine 4.8
Add g (0.06mol). Hexadecanoyl chloride under water cooling
16.5 g (0.06 mol) was added dropwise over about 30 minutes, and after completion of the 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 22.6 g of an amide-ester compound.

Subsequently, this was dissolved in 400 g of 95% aqueous ethanol solution, 2.24 g (0.04 mol) of potassium hydroxide was added, and the mixture was heated and stirred at 50 ° C. for 1 hour. 9.0 g of the target compound was obtained as a colorless powder by extracting the chloroform-soluble matter from the reaction product and purifying it by silica gel flash column chromatography.
(0.0138 mol) was obtained. (Total yield 52.4%).

mp 78.8-79.8 ° C IR (cm ^-1 ) 3334,2920,2854,1623,1467,1113 ¹ H-NMR 0.87 (t, 6H) 1.2-1.9 (m, 62H) 2.41 (t,
2H) 3.1 to 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%) Synthetic example 3 N- (2- hydroxy-3-hexadecene siloxy propyl) -N-2,3-dihydroxypropyl hexadecanol cyanamide _{^{[R 1 = C 16 H 33,}} R 2 = C 15 H 31, X = -CH 2 -CH (OH) - C
H ₂ - Synthesis of]: stirrer, a dropping funnel, a thermometer, a four-necked flask equipped with a reflux condenser, 3-amino - _1, 2-propanediol 48.
Add 3 g (0.50 mol) and 150 g of ethanol, and heat and stir at 80 ° C while adding hexadecyl glycidyl ether 1
1 solution of 5.0 g (0.050 mol) in 150 g of ethanol
It dripped over time. After completion of dropping, the mixture was further heated and stirred under the same conditions for 1 hour, 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 substance.

Next, dissolve this in 300 g of methylene chloride and add pyridine 1
5.8 g (0.20 mol) was added, and hexadecanoyl chloride (54.8 g, 0.20 mol) was added dropwise under water cooling over about 30 minutes. 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 64.0 g of an amide-ester. This is continuously dissolved in 500 g of 95% ethanol aqueous solution, and potassium hydroxide 8.4 g (0.15 mol)
Was added and the mixture was heated with stirring at 50 ° C. for 1 hour. The chloroform-soluble substance was extracted from the reaction product and purified by silica gel flash column chromatography to obtain 17.3 g (0.028 mol) of the target compound as colorless crystals. Yield 56% mp 81.9-83.3 ° C IR (cm ^-1 ) 3370,3292,2920,2854,1608,1470,1113 ¹ H-NMR 0.87 (t, 6H), 1.1-1.8 (m, 54H), 2.42 ( t, 2
H), 3.2 to 4.4 (m, 15H) Elemental analysis (%): measured value (theoretical value) C: 73.02 (72.67) H: 12.41 (12.36) N: 2.18 (2.23) Synthesis example 4 N- (2-hydroxy) 3-hexadecene siloxy propyl) -N-2-hydroxyethyl-ethoxyethyl hexadecanol cyanamide _{^{[R 1 = C 16 H 33,}} R 2 = C 15 H 31, X = CH 2 CH 2 OCH 2 CH 2 ]
Synthesis of 2-aminoethoxyethanol 27.4 g in a 4-necked flask equipped with a stirrer, a dropping funnel, a thermometer, and a reflux condenser.
(0.26 mol) and 100 g of ethanol were added, and hexadecyl glycidyl ether 15.0 was added thereto while heating and stirring at 80 ° C.
A solution prepared by dissolving g (0.05 mol) in 50 g of ethanol was slowly added dropwise over 2 hours. After completion of the addition, the mixture was heated and stirred for 1 hour under the same conditions, and then ethanol and unreacted 2
-Aminoethoxyethanol was distilled off under reduced pressure to obtain 17.7 g of an intermediate N- (2-hydroxy-3-hexadecyloxypropyl) -N-2-hydroxyethylamine as a pale yellow solid.

Next, dissolve this in 300 g of methylene chloride and add pyridine.
11.9 g (0.15 mol) was added, and hexadecanoyl chloride 41.1 g (0.15 mol) was added dropwise over about 30 minutes under water cooling.
After completion of dropping, 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,
53.8 g of an amide-ester compound was obtained. Continue to this, 9
Dissolved in 5% hydrous ethanol 400g, potassium hydroxide 5.6g
(0.10 mol) was added, and the mixture was heated with stirring at 40 ° C. for 30 minutes.

The chloroform-soluble portion was extracted from the reaction product and purified by silica gel flash column chromatography to obtain 17.3 g (0.027 mol) of the desired product as colorless crystals.

Total yield 54% (however, based on hexadecyl glycidyl ether) mp 68.0-69.3 ° C IR (cm ^-1 ) 3406,2920,2854,1647,1473,11193 ¹ H-NMR 0.87 (t, 6H) 1.1-1.8 ( m, 54H) 2.40 (t,
2H) 3.3 to 4.4 (m, 17H) Elemental analysis (%) C: 73.17 (72.96) H: 12.44 (12.40) N: 2.16 (2.18) Example 1 A cream having the composition shown in Table 1 below was produced and put to practical use. sex,
The heat retention effect and stability were tested. The test results are shown in Table 2.

(composition) (Production Method) The above oil phase components (1) and (2) are heated and dissolved at 120 ° C. and mixed to obtain an oil phase (I). Oil phase component (3)
(7) and the oil phase (I) are mixed, heated and melted at 90 ° C.
Keep on. On the other hand, a mixture of the above aqueous phase components (8) to (10) heated and dissolved at 80 [deg.] C. is gradually added to the oil phase and stirred while gradually cooling to 30 [deg.] C. After cooling, emulsify with an external emulsifying machine,
A cream (invention product 1) was obtained. Comparative products 1 and 2 were also prepared in the same manner.

(Test Method) (1) Practicality Test (Panel Test) The cream prepared by the above-mentioned production method was actually used by 10 expert panelists to perform practical evaluation. The evaluation items are
The four items are good finger grip, familiarity with the skin, spread, and overall evaluation. The evaluation results are shown in the following display.

◎: Eight or more out of 10 answered that they were good.

○: 6 or more out of 10 people 〃 △ 4 or more out of 10 people 〃 ×: less than 4 out of 10 people answered good.

(2) Moisturizing retention effect A fixed amount of the cream obtained by the above-mentioned production method was applied to the inner part of the forearm of the panelist, allowed to stand for 3 hours, washed with hot water, and then heated to a temperature of 20.
Enter the constant temperature and humidity chamber at ℃ and 50%, and after 30 minutes, compare the moisture content in the stratum corneum with an impedance meter (IB
The impedance of the skin was measured by S). The moisturizing effect was shown by the average value of the impedance.

(3) Stability The cream obtained by the above production method is observed with a polarizing microscope,
The crystal precipitation state was evaluated according to the following criteria.

◯: No crystal precipitation.

Δ: A slight amount of crystal precipitation is observed.

X: Crystals were precipitated and emulsion destruction occurred.

(Result) From the above results, the cosmetic of the present invention in which the ratio of amide derivative (I) and cholesterol is set to 0.1 to 2 has good stability,
It has been proved that it has both a sufficient feeling as a cream and a moisturizing lasting effect.

Example 2 The amide derivative (I) used in the present invention is a compound similar to ceramide, which is one of interkeratinocyte lipids, and cholesterol and this are used as emulsifiers. It is less irritating than an emulsifying system using an emulsifier. In order to clarify this, a cream having the composition shown in Table 3 below was prepared, and a skin irritation test was conducted to measure the irritation index. The results are shown in Table 5.

(composition) (Manufacturing Method) The manufacturing method is performed according to the method described in Example 1.

(Test Method) Each subject's upper arm was coated with each cream obtained by the above method, a closed patch test was conducted for 48 hours, and a score was obtained according to the evaluation criteria in Table 4. Then, the stimulation index was calculated from the following calculation formula.

(Result) Example 3 A cream having the composition shown in Table 6 was prepared according to the production method of Example 1.

(Composition) In the product of the present invention, sufficient W / O emulsification is possible with the amide derivative (I) and cholesterol, but naturally, other W
A / O emulsifier can be used in combination, for example, sorbitan sesquioleate, glyceryl ether, etc. with an HLB value of 10 or less
A good cream can be obtained even when the / O emulsifier is used together.

Example 4 A cream having the composition shown in Table 7 below was produced, and its moisturizing retention effect was measured. The manufacturing method and the measuring method were performed according to Example 1. The results are shown in Table 8.

(Composition) (Result) As is clear from this result, the emulsion composition of the present invention,
By blending the amide derivative and cholesterol,
It is possible to obtain sufficient moisturizing properties without adding a moisturizing agent such as glycerin.

Example 5 A W / O emulsion (cream) having a composition shown in Table 9 below and having low irritation, good moisture retention and good stability was obtained.

(Composition)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area A61K 47/16 H B01F 17/38 17/42 C07C 233/18 7106-4H 233/20 7106-4H

Claims (1)

[Claims] 1. The following four components (A) to (D) (A) An amide derivative represented by the following general formula (I): 0.1
~ 10% by weight Wherein, R ¹ represents a straight chain or a saturated or unsaturated hydrocarbon group branched, R ² is a hydrocarbon, saturated or unsaturated linear or branched 9 to 25 carbon atoms 10 to 26 carbon atoms Represents a group, X is a group CH _{2 n} , CH ₂ CH ₂ O _m CH ₂ CH ₂ — or —CH ₂
CH (OH) -CH ₂ - represents a group selected from. However, n and m represent numbers of 2 to 6] (B) Cholesterol 0.1 to 10% by weight (C) Oily substance 10 to 70% by weight (D) Water 10 to 88% by weight, and (A) / ( B) is 0.1 to 10 by weight,
A water-in-oil emulsion composition that does not substantially contain a hydrophilic surfactant.