JPS595106A - Water-in-oil type cosmetic - Google Patents

Abstract

PURPOSE:A water-in-oil type cosmetic, prepared by using an emulsifying agent consisting of a 2-hydroxy-3-alkoxypropylglyceryl ether, etc., a multivalent metallic salt of a fatty acid and a specific inorganic salt in a specific proportion, containing a large amount of water stably, and having a low viscosity. CONSTITUTION:A water-in-oil type cosmetic containing an oil base for the cosmetic, an emulsifying agent and water. 2-Hydroxy-3-alkoxypropyl glyceryl ether or 2,3-dialkoxypropyl glyceryl ether of the formula (R is 10-20C saturated or unsaturated straight chain hydrocarbon group; R' is H or alkyl), a multivalent metallic salt of a 10-22C saturated or unsaturated fatty acid, e.g. aluminum monostearate, and an inorganic salt, e.g. potassium sulfate, having >=0.2g/100g water solubility in water at 20 deg.C are used as the emulsifying agent at (90.9-54)/ (0.1-20)/(9-45) ratio. Preferably, the resultant emulsifying agent is contained in an amount of 0.5-10wt% in the cosmetic.

Description

[Detailed description of the invention] The present invention relates to water-in-oil cosmetics, and more particularly, to water-in-oil cosmetics.

The present invention relates to a water-in-oil cosmetic that can stably contain a large amount of water.

Water-in-oil type cosmetics (hereinafter referred to as "W10 type cosmetics") have higher microbial resistance than oil-in-water type cosmetics (hereinafter referred to as RO/W type cosmetics), and when used, they do not cause damage to the skin surface. It leaves an oil film with low moisture permeability on the skin and protects the skin from drying out over a long period of time, which is beneficial for the skin.

This oil film has excellent properties such as less re-emulsification when it comes into contact with water during water bathing or water work.

However, W/Q type cosmetics, which have superior performance compared to O/W type cosmetics, also have the following characteristics: ■Since the continuous phase in the cosmetic is an oil phase, the water stably contained therein is The amount is limited; ■As a result, when actually used, it leaves an oily feeling and has a strong sticky feeling; ■To eliminate these disadvantages,
If the water content in cosmetics is increased, the stability of the emulsion in the cosmetics will decrease, and eventually the stability of the W/O type cosmetics themselves will also decrease, so they are not widely used as cosmetics. This was the current situation.

Therefore, it has been desired to develop a VO-type feedstock that can contain a large amount of water and is stable for a long period of time.

Recently, W/Q type cosmetics using α-mono(methyl-branched alkyl)glyceryl ether as an emulsifier have been developed, and it has been found that the cosmetics obtained thereby can achieve the above-mentioned objectives (Japanese Patent Application Laid-Open No. 1983-1979-1). No. 39005). However, the cosmetics obtained by this method are all creamy W10 type cosmetics with high viscosity, and no milky W/Q type cosmetics with low viscosity have been obtained.

Therefore, the present inventor has developed an excellent W/Q type cosmetic, in particular,
If the emulsion-like W10 type cosmetic has the advantage of being easier to spread and apply to the skin than cream-type cosmetics, a W/Q type cosmetic that stably contains a large amount of water in the system can be obtained. The present invention was completed based on the discovery that the thus obtained W10 type cosmetic has a low viscosity and excellent skin feel, and is suitable as a milky lotion cosmetic.

That is, Honbatsu-cho proposes a W/Q type cosmetic containing a cosmetic oil base, an emulsifier, and water, in which the emulsifier is the following three components: (1) The following general formula (I).

(In the formula, R represents a saturated or unsaturated straight chain hydrocarbon group having 10 to 20 carbon atoms, and R' represents a hydrogen atom or a lower alkyl group) Glyceryl ether or 2,3-dialkokidib apyglyceryl ether, ■ Polyvalent metal salt of saturated or unsaturated fatty acid having 10 to 22 carbon atoms, ■ Inorganic salt with solubility in water of 0.2 F/1001 water or higher at 20°C. Contains, and the relative ratio (weight ratio) of these components is the component
Ingredient ■ / Ingredient ■ = 90.9 ~ 5410.1 ~ 20/9 ~
The present invention provides a W/O type cosmetic characterized by the fact that:

In the formula (11) of component (1), a saturated or unsaturated straight-chain hydrocarbon group having 12 to 18 carbon atoms is preferable.

Among nf, lower alkyl groups having 1 to 5 carbon atoms are preferred, particularly methyl and ethyl groups. The compound of formula (1) is, for example, glycerin prepared by protecting an alkyl glycidyl ether that can be easily produced from alcohol with an appropriate protecting group at the 2- and 3-positions in the presence of a monobasic or acidic catalyst, that is, an acetal or ket of glycerin. After reacting to form a 1,3-dioquinrane compound, Km is easily produced by hydrolyzing this.

In particular, the polyvalent metal salt of the fatty acid of component (1) has 12 carbon atoms.
-18 are preferred. In addition, these salts are
Examples include calcium, magnesilano, zinc, and aluminum salts, among which aluminum salts are particularly preferred. The polyvalent metal salt can be used in the mono-, di- or tri-isomer form, but may also be produced by a substitution reaction with a water-soluble polyvalent metal salt, such as a -valent group, in the compounding system. .

Among the fatty acid polyvalent metal salts, preferred are aluminum monostearate, aluminum distearate, calcium monostearate, aluminum monooleate, aluminum monopalmitate, aluminum monolaurate, and the like.

Examples of the inorganic salt of component (2) include alkali metal salts, alkaline earth metal salts, and aluminum salts of inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and enzymatic acid.

These inorganic salts may be incorporated into cosmetic compositions in the form of salts, but when manufacturing cosmetics, the corresponding acids and bases are added in stoichiometric amounts necessary to form the salts. May be manufactured.

Preferred inorganic salts include potassium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, potassium nitrate, sodium nitrate, magnesium nitrate, calcium nitrate, aluminum nitrate, potassium chloride, sodium chloride, magnesium chloride, calcium chloride, aluminum chloride, potassium carbonate, Examples include sodium carbonate, aluminum carbonate, etc., and potassium sulfate, magnesium sulfate, potassium chloride, magnesium chloride, and aluminum chloride are particularly preferred.

The W/O type sugar syrup of the present invention is prepared by preparing an emulsifier by pre-mixing the above-mentioned components (1) to (2) within the above-mentioned relative ratios, and using this to emulsify an oil base for cosmetics, water, etc. Alternatively, it can be produced by mixing ingredients 0) to 1), a cosmetic oil base, water, etc. in an arbitrary order in an amount such that the above-mentioned relative ratios are achieved.

Cosmetic oil bases used in the W/Q type cosmetic of the present invention include hydrocarbons such as squalane, paraffin oil, and ceresin oil; waxes such as beeswax, spermaceti, and carnauba wax; olive oil, camellia oil, and lanolin. natural animal and vegetable oils and fats such as; fatty acids having 10 to 20 carbon atoms, higher alcohols having 10 to 20 carbon atoms, esters thereof, silicone oils, and the like.

In addition to the above-mentioned essential components, the W/O type sugar syrup of the present invention may contain known cosmetic components depending on the purpose, such as surfactants as auxiliary emulsifiers, viscosity modifiers, medicinal agents, wetting agents, and preservatives. etc. can be blended.

Among these ingredients, surfactants include polyoxyethylene alkyl ether, holoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene hydrogenated castor oil, sucrose ester, and trutan fatty acid. Ester, glycerin fatty acid ester, fatty acid alkali metal salt, alkyl sulfate ester, alkyl phosphate ester, polyoxyethylene alkyl sulfate ester, polyoxychetylene alkyl phosphate ester, etc., and as a viscosity modifier, polyvinyl alcohol, carboxyvinyl polymer, Synthetic polymer compounds such as carboxymethylcellulose, polyvinylpyrrolidone, hydroxyethylcellulose, and methylcellulose; natural gums such as gelatin and gum tragacanth; and alcohols such as ethanol and isonorobyl alcohol are medicinal agents.

Bactericidal agents, anti-inflammatory agents, vitamin preparations, etc. are used as humectants, such as chloride glycol, glycerin, 1,3-butylene glycol, sodium pyrrolidone carboxylate, and sorbitol, and as preservatives, ethyl paraoxybenzoate and paraoxygen Examples thereof include ethyl benzoate, noropyru paraoxybenzoate, butyl paraoxybenzoate, benzoic acid, sodium benzoate, sorbic acid, vine, potassium birate, and phenoxyethanol.

A preferred composition of the W/0 type cosmetic of the present invention is as follows.

Amount (%) Water 60-98
80-95 viscosity modifier 0-io
6-2 Surfactant 0-10
0-5 medicinal agent 0-1゜wetting agent 0-30 2-1゜preservative 0-1 0;02-0.5 stabilizer
0~io o~1° In the above composition, component ■
If the amount of the emulsifier consisting of ~■ is less than 0.5% in the composition, it is difficult to completely emulsify the emulsifier of %"l/'0 type, and if more than 10% is mixed, However, the effect cannot be expected to increase and it is uneconomical.

Furthermore, although any amount of water can be blended, it is preferable to blend 60 or more water in order to have a good feeling of use, that is, to reduce the oily feeling or stickiness on the skin.

The W10 type cosmetic of the present invention is available in various forms, such as body lotion, cleansing milk, and milky lotion.

Liquid cosmetics such as hair lotions and liquid foundations and cream cosmetics can be used.

The thus obtained W/Q type sweetened sugar of the present invention is W
/ It has the inherent advantages of type O cosmetics, and contains a large amount of water, so it has less oily and sticky feeling.
In addition, it is an extremely excellent cosmetic that is stable even when the viscosity is low even though it is Wlo.

Next, reference examples for producing 2-hydroxy-6-alkoxypropylglyceryl ether (or 2,6-dialkoxypropylglyceryl ether) and examples of the present invention will be described.

Reference Example 1 (1) II equipped with a reflux condenser, thermometer, dropping funnel and stirrer! 298 g (2.25 moles) of acetone glycerin ketal and 12.99 g (0,075 moles) of tetramethyldiaminohexane were placed in a reaction vessel and stirred. The reaction mixture was heated to i o o 'c and dodecyl glycisol ether 1 B 2
y (0-75 mol) is added dropwise little by little.

During the addition of glycisol ether, the temperature of the reaction mixture was kept at 1
Maintain at 00-110'C. The dropwise addition of glycidyl ether was completed in about 30 minutes, and the reaction mixture was further heated to 100-110%
Heat at °C for 6 hours. After cooling, excess acetone glycerin ketal etc. are distilled off from the reaction product under reduced pressure, and the remainder is subjected to vacuum distillation to obtain 230p of colorless and transparent liquid (
A yield of 82%) was obtained. This product was confirmed to have a single component from its gas chromatograph, and was found to be 2,2-dimethyl-4-(2'-hydroxy-6'-dobusyloxy).
It was confirmed to be propoxymethyl-1,3-dioxolane.

Boiling point: 196-200℃ (o, 5ttty Hg)
Elemental analysis value (calculated value); 021H4205:C:
67. Oq6 (67, 34 section), H: 11.4% (1
1,30%), O: Section 21.1 (Section 21, 36) IR (
Liquid film, cN-”): 3470, 1380°1370.
1255.1213.1140°1080.1050.
845 NMR (Co/4 solvent, δ) 23.2-4.2 (multiplet, 12H1 2,8 (-multiplet, jH, O,, H230H2QC!H2
0H-OH20-)QH.

1.20 (-double line, 2 Q H, 0H3(CH2),
. an2o-)0.87 (triple line* 3 H* CH
3(CH2)10CH20-) Acid value: 0.0. Saponification value: 0.05. Hydroxyl value: 155 (calculated value 150), iodine value: 0.6, oxirane oxygen: 0, molecular weight (VPO method 7aHt43): 376 (calculated value 675) (11) Equipped with a reflux condenser, thermometer and stirrer. Into 11 reaction vessels, add 200 tttl of water and 10 tttl of 97% concentrated sulfuric acid.
．． Take 1 cup and stir vigorously to make a 1N sulfuric acid aqueous solution. Next, 76.49 (0.2 mol) of the 1,3-dioxolane compound obtained in the above (1), 150 mol of ethanol
ml in this order and heat. Initially, the reaction mixture resembles a milky white emulsion, but as soon as reflux begins, it becomes a clear homogeneous solution. After heating to reflux for about 4 hours, the reaction mixture was cooled.

This was neutralized by adding 8.6 g of 97% sodium hydroxide. After neutralization, ether (300 ttrl) was added for extraction, the ether layer was collected by liquid separation, and after drying with Glauber's salt,
The ether is distilled off under reduced pressure. After distilling off the ether, it was further dried under reduced pressure at about 100°C for about 6 hours at Q, 1WffHg.

A colorless and transparent viscous liquid 66f (yield 98.7%) was obtained. This product becomes a white solid when left to cool.

The above substance was confirmed to be a single component by gas chromatography, and was 2-hydroxy-6-dobusyloxyprobyl glyceryl ether.

Melting point: 42-446C Elemental analysis value (calculated value): 018H380!5:C
: 64.3 q6 (64,63%), 11:11.2
% < 11.4 schi), O: 23.5 schi (23,92
h) IR (liquid film, CM-1): 3380, 11
70-1000.880° NMR (00Z, solvent, δ): 4.5 (broad-heavy line, 3H.

6.2~4.0 (multiplet, 10H2 OM QHQH 1,6(-multiplet, 20 H, CH3(CH2)10CH
20) 0.9(triple line s 5 ” + 0H3((3f
(2),. 0)(20-) Acid value: 0.03. Saponification value:
o, i, hydroxyl value: 495 (calculated value 502), iodine value: 0.1 molecular weight (VPO method 7cHat, ri: 334
(Calculated value: 365) Example 1 Emulsion stabilization effect: The emulsion stability and viscosity of cosmetics prepared from the following emulsion composition containing the compound of the present invention or a known emulsifier (comparative product) were investigated. The results are shown in Table 1.

(Composition) Liquid paraffin 5 (parts by weight) Water
96 aluminum monostearate 0.02 magnesium sulfate
0.4 Test compound 1.
58 (Preparation of cosmetic base) Aluminum monostearate, madanesium sulfate, and a total of 2 parts by weight of the test compound were added to 5 parts by weight of liquid paraffin, mixed, and heated to 70°C. To this mixture, 96 parts by weight of water heated to 70° C. was gradually added while stirring to emulsify. After emulsification, the mixture was cooled in a room temperature room while stirring to obtain a cosmetic.

W lower margin As is clear from the above results, a water-in-oil cosmetic containing a large amount of water can be easily obtained from a composition containing component (1) of the present invention, and has a low viscosity and good emulsion stability. Met. On the other hand, when conventionally known emulsifiers are used, it is difficult to obtain stable water-in-oil cosmetics, and even when stable water-in-oil cosmetics are obtained, the viscosity of the emulsion is high. However, it was not possible to obtain a water-in-oil cosmetic with low viscosity.

That is, it is clear that, although it has been impossible to obtain stable water-in-oil cosmetics with low viscosity using the prior art, this can be easily achieved using the compound of the present invention.

Example 2 An emulsifier having the composition shown in Table 2 was produced, and 1 part by weight of this emulsifier was added to 5 parts by weight of liquid paraffin and 94 parts by weight of water, and a cosmetic was prepared in the same manner as in Example 1.

The stability of this cosmetic was investigated and the results are shown in line 9 of Table 6.

As is clear from the results shown in Table 2, Table 3, and the following margins, in order to obtain a stable W10 emulsion, it is necessary to mix the three components ■■ and ■ with the emulsifier; Even when the emulsion is blended, if the blending ratio is out of a certain range, the emulsified state will be good immediately after production, but will become unstable over time.

Example 3 Regarding the water-in-oil cosmetic of the present invention and comparative products.

A sensory test was conducted by 10 expert panelists to examine the feeling of use. Additionally, the emulsion stability after one month was also examined.

The criteria for determining the feeling in use and emulsion stability were as shown below, and the results are shown in Table 4.

(Usability evaluation criteria) Very +2 Some +1 Fair 0 None -1 Not at all -2 (Emulsion stability criteria) ○: No separation or creaming occurred even after being left at room temperature for one month.

△: Slight creaming and mingling occurred after being left at room temperature for one month.

×: Separation is observed after being left at room temperature for one month.

As is clear from the results shown in the margins below, the W10 type cosmetic of the present invention contains a large amount of water, so it does not suffer from the stickiness and oiliness, which were the drawbacks of conventional W/Q type cosmetics. It is clear that there is a decrease in

Example 4 Emulsion (W2O type): (Composition) (0 diglycerin monooleyl ether 2.0%
■Aluminum monosteer array) 0.04
■ Potassium sulfate 0.5 ■ Isopropyl myristate 2.0 ■ Liquid paraffin 4.0 ■ Hexadecyl-2-ethylhexanoate 2.0 ■ Sodium benzoate 0.66) Glycerin
2.0 ■ az-α-tocopherol acetate 0.10 or fragrance
0.1 (-wa purified water
Remaining amount (manufacturing method) ① to ② were mixed and heated to 1.75°C. ■■0 was mixed into this mixture, and the mixture heated to 70°C was added under stirring to emulsify. After emulsification, cool to 50℃ and add ■[
phase] was added and further cooled to room temperature to obtain a product.

The emulsion obtained as described above had good emulsion stability, and sensory evaluation showed that it was less sticky and oily, and had an excellent feeling of use.

Example 5 Cleansing milk (W2O type): (composition) ■2-Methoxy3-dodecyloxyzolopylglyceryl ether 2.0%■
Aluminum monopalmitate 0.1 ■ Potassium chloride 0.7 ■ Glycerol monooleate) 2.5 ■ Liquid paraffin 12.0 ■ Bleached beeswax 1.0 ■ Vaseline
1. O ■ Kudi-ethylhexyl adipate 17.0 ■ Zotyl paraoxybenzoate
0.2 [Phase] Dibutylhydroxytoluene o, oi ('ii
) Glycerin 2.002) Fragrance 0o10 purified water
Remaining amount (manufacturing method) 0) to (Φ) were mixed and heated to 75°C.
The mixture of 0 and 00 heated to C was emulsified under stirring.

After emulsification, the mixture was cooled to 50°C, 0 was added thereto, and the mixture was further cooled to room temperature to obtain a product.

The cleansing milk obtained as described above had good emulsion stability and also had an excellent feeling of use.

Example 6 Moisture cream (W2O type): (composition) ■Diglycerin monooleyl ether 2.5%■Aluminum monostearate 0.05■Magnesium sulfate 0.3■Octyldodecyl myristate 5.0■Squalane
3.5 ■ Cetyl alcohol
1.0 ■ Stearyl glyceryl ether 1
．． 0 ■ Sodium benzoate 0.3 ■
1.3-Butylene glycol 6.0 [Phase] Fragrance 0.080 Purified water Remaining amount (manufacturing method) ① to ② were heated to 7θ°C. A mixture of the other components except for the [phase] heated to 70° C. was gradually added to this mixture while stirring, and emulsified. After emulsification, cool to 50°C, and the K [phase]
was added and further cooled to room temperature to prepare a product.

The moisture cream obtained as described above had good emulsion stability, spreadability, and an excellent feeling of use.

that's all

Claims (1)

[Scope of Claims] 1. A water-in-oil cosmetic containing an oil base for cosmetics, an emulsifier, and water, in which the emulsifier comprises the following three components, ■ the following general formula (1), (wherein R represents a saturated or unsaturated linear hydrocarbon group having 10 to 20 carbon atoms, and R' represents a hydrogen atom or a lower alkyl group) or 2.3-dialkoxypropylglyceryl ether; ■ A polyvalent metal salt of a saturated or unsaturated fatty acid having 10 to 22 carbon atoms; ■ An inorganic salt with a solubility in water of 0.2 S'/100 or more at 20°C. The relative ratio (weight ratio) of these components is the component σ)
/ component ■ / component ■ = 90.9 ~ 54 / 0.1 ~ 2
A water-in-water type cosmetic characterized by having a weight ratio of 0/9 to 45. 2. The water-in-oil cosmetic according to claim 1, wherein the content of the emulsifier is 0.5 to 10% by weight in the water-in-oil cosmetic.