JPH04173716A - Emulsified cosmetic - Google Patents

Abstract

PURPOSE:To obtain an emulsified cosmetic, containing a polyglycerol ester of a fatty acid and a diacylglycerol, excellent in skin penetration, capable of imparting moderate emphraxis and flexibility to the skin and kept in a stable emulsion state. CONSTITUTION:The objective substance is obtained by including 0.1-10wt.% polyglycerol ester of a fatty acid, 5-50wt.% diacylglycerol expressed by the formula (two of R<1>, R<2> and R<3> are 7-23C fatty acid residue and the rest is H) and further 20-90wt.% total amount of water and other water-soluble solvents (e.g. ethanol), suitably blending other normal oils, emulsifying agents, powder humectants, ultraviolet light absorbers, thickeners, preservatives, coloring matters, perfumes, etc., for cosmetics and preparing an emulsified cosmetic according to a conventional method. The aforementioned emulsified cosmetic can especially be prepared as water-in-oil type skin cosmetics, hair cosmetics, quasi-drugs, medicines for external use, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an emulsified cosmetic that has good skin permeability, provides appropriate occlusive properties and flexibility to the skin, and has a stable emulsified state.

[Prior art and problems to be solved by the invention] Emulsified cosmetics have been widely used in the past because they have excellent properties such as good adhesion to the skin due to the film formed on the skin surface and long-lasting makeup. There is.

On the other hand, since diacylglycerin has the property of imparting appropriate occlusive properties and flexibility to the skin, hair, and mucous membranes, attempts have been made to incorporate it into various cosmetics.

It is thought that if such diacylglycerin is emulsified, an excellent cosmetic material having both of the above properties can be obtained.

However, diacylglycerin has high polarity, and even when it is emulsified using a general emulsifier, the resulting emulsion system is unstable, has a poor feel on the skin, and has a poor appearance.

Therefore, a stable emulsified cosmetic containing diacylglycerin free from such drawbacks has been desired.

[Means to solve the problem]

Under these circumstances, the present inventors conducted intensive research and found that by using a polyglycerin fatty acid ester as an emulsifier, a stable emulsified cosmetic containing diacylglycerin free from the above-mentioned drawbacks could be obtained, and the present invention was completed. did.

That is, the present invention comprises the following components (A), (B) and (C) (A) polyglycerin fatty acid ester (B) the following general formula (I) CH2-0-R' CH-D -R2...( I) ■CH2-0-R3 [In the formula, two of R1, R2, and R3 represent fatty acid residues having 7 to 23 carbon atoms, which may be the same or different, and the remainder represents hydrogen. The present invention provides an emulsified cosmetic, particularly a water-in-oil (Wlo) emulsified cosmetic, which is characterized by containing diacylglycerin (C) water represented by the formula below.

The polyglycerin fatty acid ester which is the component (A) of the present invention is an emulsifier suitable for W10 emulsification, and has the following general formula (n) OR'R'O→CH2-CH-CHrO→〒R'
(II) [In the formula, R4 may be the same or different, and at least one is a fatty acid residue having 8 to 24 carbon atoms or a fused lysylyl represented by the following formula (wherein r represents a number of 3 to 6) group or the following formula (IV)H70-C)I (C)12)I OC]l (
A condensed 12-hydroxystearic acid residue represented by (TV)(CH2)5CI(3 (in the formula, the spear represents a number from 3 to 6), the remainder is a hydrogen atom, and q represents a number from 2 to 10. The following are preferred.

When R4 of these polyglycerol fatty acid esters (II) is a fatty acid residue having 8 to 24 carbon atoms, Q=
4 to 8 is preferable, and it is preferable that 20 to 90%, particularly 40 to 90% of the hydroxyl groups of the polyglycerin are esterified. Particularly preferable examples include decaglycerol decaolate, decaglycerol pentaisostearate, hexaglycerol pentaolate, and tetraglycerol pentastearate.

Polyglycerin condensed lysyl ic acid ester in which R4 is a condensed lysylyl group and polyglycerin condensed 12-hydroxystearate in which R4 is a condensed 12-hydroxystearic acid residue are those in which 20 to 70% of the hydroxyl groups of polyglycerin are esterified. It is preferable that

The polyglycerol fatty acid ester (A) may be used alone or in combination of two or more types, and is preferably blended in the emulsified cosmetic of the present invention in an amount of 0.1 to 10% by weight, particularly 0.5 to 5% by weight. .

The diacylglycerin used as the component (B) used in the present invention is represented by the above general formula (I), and is liquid and has a very good feeling when used.
Examples of the fatty acid residue having 7 to 23 carbon atoms include saturated or unsaturated straight chain fatty acid residues and branched fatty acid residues.

In particular, one of the two fatty acid residues has 11 carbon atoms.
~17 straight saturated fatty acid residues, the other one having 10 carbon atoms
Diacylglycerin, which is a branched saturated fatty acid residue of ~18, has moderate occlusive and softening effects on the skin, mucous membranes, and hair, and has good permeability to the stratum corneum, yet is non-irritating. It is particularly preferred because it has good properties and stability. Here, specific examples of straight saturated fatty acids having 11 to 17 carbon atoms include undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, and heptadecanoic acid.

Specific examples of branched saturated fatty acids having 10 to 18 carbon atoms include dimethyloctanoic acid, trimethylheptanoic acid, butylmethylhexanoic acid, ethylmethylnonanoic acid, propylmethylnonanoic acid, trimethyldecanoic acid, pentylmethyloctanoic acid, and butylmethyl Nonanoic acid, propyldodecanoic acid, pentyldecanoic acid, hexyldecanoic acid, butylpentylhebutanoic acid, hexyldodecanoic acid, pentylundecanoic acid, 7-methyl-2-(3-methylhexyl)decanoic acid, 7-methyl-2-( Examples include 3-methylbutyl)octanoic acid, 5,7.7-)limethyl-2-(1,3,3-trimethylbutyl)octanoic acid, and isodecanoic acid, isotridecanoic acid, isomyristic acid, Isopalmitic acid and isostearic acid are commercially available.

These diacylglycerols are produced by a conventional method for producing acylglycerols from fatty acids and glycerin. For example, diacylglycerin having straight fatty acid residues and branched fatty acid residues is prepared by blending the above branched saturated fatty acids, straight fatty acids, and glycerin in equimolar proportions.
These acylglycerol mixtures are formed by heating to 230° C. and removing the water formed under reduced pressure. A diacylglycerol fraction can be obtained by subjecting this product to distillation or column chromatography. However, since this diacylglycerin is a random mixture, there is diacylglycerin consisting only of branched saturated fatty acid residues, diacylglycerin consisting of branched saturated fatty acid residues and straight chain saturated fatty acid residues, and diacylglycerin consisting of straight chain saturated fatty acid residues, and straight chain saturated fatty acid residues. Since it is a mixture of diacylglycerols consisting of only diacylglycerols, the desired diacylglycerols can be obtained by recrystallization using a solvent such as hexane by utilizing the difference in their melting points.

As a more advantageous production method, either one of the fatty acids to be reacted can be converted into a more reactive derivative and then esterified. One of the highly reactive derivatives is an acid halide of a fatty acid, and in a preferred example for obtaining diacylglycerol having a straight chain fatty acid residue and a branched fatty acid residue, first, the raw material is branched and saturated. 1 to 5 moles, preferably 1 to 2 moles of a halogenating reagent such as thionyl chloride, thionyl bromide, or phosphorus trichloride are added to the fatty acid at 0 to 100°C, preferably 2 to 5 moles per mole of the branched saturated fatty acid.
The reaction is carried out at 0 to 80°C to form an acid halide. 1 mole of saturated fatty acids and 1 mole of glycerin at 200-23%
By heating to 0° C. and removing the produced water under reduced pressure, acylglycerin, a straight chain saturated fatty acid, is obtained. By carrying out molecular distillation of this product, monoacylglycerin, which is a directly decomposed saturated fatty acid, is obtained. Therefore, the above-mentioned branched saturated fatty acid halide and 0.5 to 3 mol, preferably 1 to 1.5 mol, of monoacylglycerol of straight-chain saturated fatty acid are added to the acid halide in an amount of 0.5 to 3 mol, preferably 1 to 1.5 mol, per mol of branched saturated fatty acid halide. 3 mol, preferably 1 to 1.5 mol of pyridine,
Using a dehydrohalogenating agent such as quinoline, in an appropriate inert solvent such as benzene, toluene, xylene, hexane (1 to 10 times the volume, preferably 3 to 5 times the volume of the acid halide), 100℃, preferably 60-8
The reaction is carried out at 0°C while stirring while heating. The desired diacylglycerin containing branched saturated fatty acid residues and direct saturated fatty acid residues can be obtained by subjecting the produced acylglycerin from which the hydrogen halide amine salt has been removed to molecular distillation or column chromatography.

As a more advantageous production method, it can be produced using lipase without using highly reactive derivatives. For example, first, about 1 mole of branched saturated fatty acid and about 1 mole of glycerin are heated to 200 to 230°C, and the water produced is removed under reduced pressure to obtain acylglycerin having branched saturated fatty acid residues, and the molecule Monoacylglycerin with branched saturated fatty acid residues is obtained through distillation. The desired diacylglycerol containing branched saturated fatty acid residues and straight chain saturated fatty acid residues is obtained by blending this monoacylglycerin and linear saturated fatty acid in approximately equimolar amounts and carrying out an esterification reaction using lipase as a catalyst. It will be done. Depending on the degree of esterification, molecular distillation is carried out as a post-treatment. For example, if the esterification rate of straight-chain saturated fatty acids is low, it is necessary to remove the remaining straight-chain saturated fatty acids and 1,000-noacylglycerin.

Moreover, the by-product of triazylglycerin can also be removed by molecular distillation column chromatography. When using a lipase as a catalyst, a lipase having α-position selectivity or a lipase selective for partial glycerides is most effective.

Among the above methods, the method using lipase is the most preferred in terms of economy and purity of the diacylglycerol produced.

Regardless of which method is used, the resulting oil is a mixture of monoacylglycerin, diacylglycerin, and triacylglycerin.

In order to achieve the object of the present invention, the content of diacylglycerin in this oil agent is 70% by weight or more, particularly 80% by weight or more, furthermore 90% by weight or more, and in this diacylglycerin, two 70% by weight or more, especially 80% by weight or more of the acyl groups, one of which is a straight saturated fatty acid residue having 11 to 17 carbon atoms and the other is a branched saturated fatty acid residue having 10 to 18 carbon atoms, 9 more
Preferably, the content is 0% by weight or more.

The diacylglycerin represented by formula (I) thus obtained is preferably blended in the emulsified cosmetic composition of the present invention in an amount of 5 to 50% by weight, particularly 10 to 30% by weight.

In addition, water, which is (C) ff1 minute of the present invention, can be blended in any amount, but in order to have a good feeling of use, that is, less oily or sticky feeling and good spreadability, other water-soluble It is preferable that the total amount of the organic solvent is 20 to 90% by weight, particularly 34 to 78% by weight, particularly 50% by weight or more. Here, other water-soluble solvents include ethanol,
Glycerin, sorbitol, propylene glyconobe
Refers to lower alcohols or polyols such as 1,3-butylene glycol.

In addition to the above-mentioned essential ingredients, the emulsified cosmetic composition of the present invention can also contain general cosmetic oils commonly used in cosmetic compositions. These oils are not particularly limited, but include silicone oils such as dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrodienepolysiloxane, octamethylcyclotetrasiloxane, octamethylcyclopentasiloxane, and decamethylcyclopentasiloxane. Vegetable oils such as avocado oil, camellia oil, macadamia nut oil, olive oil, jojoba oil; Fatty acids such as oleic acid and isostearic acid; Alcohols such as hexadecyl alcohol and oleyl alcohol; Cetyl 2-ethylhexanoate and valmitic acid.
2-ethylhexyl, 2-octyldodecyl myristate, neopentyl glycol di-2-ethylhexanoate, glycerol tri-2-ethylhexanoate, 2-octyldodecyl oleate, isopropyl myristate, glycerol triisostearate, tri-2- Esters such as lycerol ethylhexanoate, 2-octyldodecyl oleate, isopropyl myristate, glycerol triisostearate, diglyceride 2-ethylhexanoate, glyceryl mono-2-ethylhexanoate; liquid paraffin ,
Examples include liquid hydrocarbon oils such as squalene and squalane, and preferred examples include volatile dimethylpolysiloxane and dimethylcyclopolysiloxane, particularly when reducing oily and sticky sensations.

These common oils for cosmetics can be used alone or in combination of two or more. These oils are preferably blended in the emulsified cosmetic composition of the present invention in an amount of 10 to 60% by weight, particularly 15 to 40% by weight, in total of the amphiphilic lipids and these common oils for cosmetics.

Furthermore, in the present invention, other emulsifiers may be used as necessary within a range that does not impair the effects of the present invention. Examples of such emulsifiers include glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene hydrogenated castor oil derivative, alkyl Examples include chryceryl ether and polyoxyalkylene-modified polysiloxane. When silicone oil is used as an oil agent, it is preferable to use a polyoxyrylene-modified polysiloxane having the following general formula (V) [wherein R5 may be the same or different, and each represents a methyl group or a phenyl group. , R6 may be the same or different, and are a methyl group and a group R' (OC2H5) b (
OC2H4) -0(CH2) -(R7 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, p is a number of 1 to 5,
a and b are average values, each representing a number from 0 to 35) or a phenyl group, m and n are average values, and m is 1 to 200.
and n represents a number from 0 to 50] It is particularly preferable to use the number represented by the following. These can be used alone or in combination of two or more.

The emulsified cosmetic composition of the present invention may further contain 0 to 40% by weight of other components commonly used in cosmetic compositions, as appropriate, within a range that does not impair the effects of the present invention. Other ingredients include powder, humectants, solid fats, intercellular lipids (ceramides, etc.), ultraviolet absorbers, alcohols, chelating agents, pH
Conditioners, preservatives, thickeners, pigments, fragrances and the like can be mentioned.

By blending 10 to 40% by weight, preferably 15 to 30% by weight, of these powders in cosmetics, a liquid or cream foundation can be obtained. Examples of powders include powders commonly used in cosmetics, such as extender pigments such as talc, mica, kaolin, and sericite; inorganic pigments such as titanium oxide, zinc oxide, iron oxide, and ultramarine; titanium-mica pearl pigments; and Blue No. 404, Red No. 202
Examples include organic pigments such as No. 401 and Yellow No. 401, as well as hydrophobized products of these pigments. In the present invention,
One or more of the above powders may be arbitrarily selected and used.

Cosmetics that are the subject of the present invention are not limited to general skin cosmetics, but also include hair cosmetics, quasi-drugs, external medicines, etc., such as face care creams or emulsions, hand creams, etc. & body care cream or emulsion,
Examples include creams/emulsions such as hair milk and hair cream, liquid or cream-type foundations, and external medicines such as anti-inflammatory creams and creams for insect bites. These are prepared from the above ingredients according to conventional methods.

〔Effect of the invention〕

The emulsified cosmetic composition of the present invention is non-sticky, has a light feeling on use, has water repellency, and has excellent emulsion stability. Furthermore, since it contains diacylglycerin, it has good permeability to the stratum corneum and exhibits appropriate occlusive and softening effects on the skin, mucous membranes, and hair.

〔Example〕

EXAMPLES The present invention will be explained in more detail by showing examples below, but the present invention is not limited to these examples.

Reference example 1 Thermometer, nitrogen capillary, reflux condenser (with water separation tube)
, 7-methyl-
2-(3-methylhexyl)decanoic acid 568 g (2
,0 mol) and purified glycerin 184g (2,0 mol)
, 1.2 g of calcium hydroxide was charged, and esterification was carried out at 230 to 240° C. under nitrogen gas aeration. After about 10 hours, it was confirmed that almost no water was produced.
Switching to vacuum distillation, 210-b serine was removed. After almost no distilled glycerin was observed, the reaction mixture was distilled in a thin-film molecular distillation vessel to a temperature of 170 to 175°C, 10.03 to 0.05 mmf.
225 g of 1 g fraction was obtained. This one is 7-methyl-2
-(3-Methylhexyl)decanoic acid monoacylglycerol.

Hydroxyl value 309.0 Synthesis Example 1 In a reaction vessel with a capacity of 2β equipped with a thermometer, a reflux condenser, and a stirrer, 358 g (1 mol) of monoacylglycerin of 7-methyl-2-(3-methylhexyl)decanoic acid, Tetradecanoic acid (myristic acid) 274g (1.2 mol),
Commercially available lipase preparation Lipozyme 3A (Mucor mehi immobilized on anion exchange resin)
m1ehei) origin lipase, novoindas) IJ
-・manufactured by A-3) 80g was added. Heat to 50℃,
The esterification reaction was carried out by stirring for 5 hours under a reduced pressure of 100 to 300 mm1. After the reaction was completed, the lipase preparation was filtered, and the reactant in the filtrate was heated to 190 to 195°C, 0.03 to 0.
．． Excess myristic acid and unreacted monoacylglycerin were removed by distillation using a thin-film molecular distillation device under O 5 mmHg conditions, and the desired 7-methyl-2-(3-methylhexyl)decanoic acid and myristic acid were obtained. 548 g of diacylglycerin having the following as a residue was obtained.

Synthesis Example 2 Reaction procedure similar to Synthesis Example 1 using 302 g (1.0 mol) of 1,000-noacylglycerol of 7-methyl-2-(3-methylbutyl)octanoic acid and 274 g (1.2 mol) of myristic acid. Synthesis Example 3 Monoacylglycerin of isodecanoic acid (mixture of dimethyloctanoic acid and trimethylpebutanoic acid) 246 g
(1.0 mol) and 274 g (1.2 mol) of myristic acid, the same reaction procedure as in Synthesis Example 1 was carried out to obtain 367 g of diacylglycerol having isodecanoic acid and myristic acid as residues.

Synthesis Example 4 Capacity 2 with thermometer, reflux condenser, and stirrer! 5. Into the reaction vessel. 7. 7-drimethyl-2-(1, 3
, 356 g (1 mol) of 1,000-noacylglycerol of 3-trimethylbutyl)octanoic acid, 240 g of dodecanoic acid
(1.2 mol), commercially available lipase preparation 1ipozyme
3A (lipase of Mucor mlehei origin immobilized on anion exchange resin,
(manufactured by Novo Industries A-3) was added thereto.

The mixture was heated to 50°C and stirred for 5 hours under reduced pressure of 100 to 300 mmHg to carry out an esterification reaction. After the reaction is completed, the lipase preparation is filtered and the filtrate reactant is heated to 190-195°C.
, 0, 03-0. Excess dodecanoic acid and unreacted monoacylglycerin were removed by distillation using a thin film molecular distillation device under the condition of 05 mmHg, and the desired 5.7.7-
464 g of diacylglycerin containing octanoic acid and dodecanoic acid as residues was obtained.

Synthesis Example 5 Monoacylglycerin 356 of 5,7.7-)limethyl-2-(1,3.3-)limethylbutyl)octane r
g<1 mol) and 307 g of hexadecanoic acid (1.2
mol), the same reaction operation as in Synthesis Example 4 was carried out, and 5
.

521 g of diacylglycerin containing 7,7-drimethyl-2-(1.3.3-)limethylbutyl)octanoic acid and hexadecanoic acid as residues was obtained.

Synthesis Example 6 274 g of tetradecanoic acid was added to the hexadecanoic acid of Synthesis Example 5.
(1.2 mol), the same reaction operation as in Synthesis Example 4 was carried out, and 5.7.7-) IJ methyl-2-(
1. 3. 3-) 506g of diacylglycerin with residues of (limethylbutyl)octanoic acid and tetradecanoic acid
I got it.

Example 1 A hand cream (Wlo) having the composition shown in Table 1 was prepared, and the appearance and particle size of the aqueous phase immediately after and after 7 days were evaluated according to the subcontracted standards, and the results were shown in Table 1. .

(Evaluation criteria) Appearance 20...uniform ×・・・Separated into two layers Particle size: ○...Particle size is uniform when observed under a microscope Δ: Some coarse particles are observed by microscopic observation.

X: Particles of various sizes are observed by microscopic observation.

Margin Example 2 Moisturizing Cream (Wlo) Oil phase components; (wt%) Jojoba oil 3.0 Liquid isoparaffin 4.0 Water composition; Magnesium chloride 0.4 Glycerin 20.0 Methyl paraben
0.1 Fragrance 0.1 Purified water Balance meter
100.0 The above water composition was heated and mixed and maintained at 70°C.

The above oil phase component was similarly dissolved and dispersed by heating at 70°C.

The above water phase was added to this oil phase and emulsified using an emulsifier. The emulsion was cooled to a final temperature of 25° C. using a heat exchanger to obtain a moisturizing cream (Product 5 of the present invention).

Example 3 Suncare cream (Wlo) oil phase component;
(Weight%) Decaglycerin decaolate 2.0 Octyl methoxycinnamate 3.0 Oxybenzone
1.0 Water composition; Potassium chloride 0.7 Glycerin 2.0 1.3-Butylene glycol 2.0 Methyl paraben
0.1 Fragrance 0.1 Purified water Balance powder ingredients; Fine particle titanium oxide 3.0 total
100.0 The above aqueous phase components were heated and mixed and maintained at 70°C.

The above oil phase component was similarly heated and dissolved at 70°C, and then the powder component was added and dispersed. The above water phase was added to this oil phase/powder and emulsified using an emulsifier. The emulsion was cooled to a final temperature of 25° C. using a heat exchanger to obtain a sun care cream (Product 6 of the present invention).

Example 4 Cream foundation (Wlo) Oil phase component (wt%) Liquid paraffin 5.0 Dimethylpolysiloxane (10cs) 4.0 Methylphenylpolysiloxane 4.0 Water phase part; Magnesium sulfate 0.7 Glycerin 5. 0 methylparaben
0.1 Fragrance 0.1 Purified water Balance powder ingredients; Fine particle titanium oxide 5.0 Sericite 2.0 Talc
3.0, Aga, 0.4 Iron oxide yellow 0.7 Iron oxide black 0.1 total
100.0 book 2: PH3
-310 (manufactured by Hanhon Yakuhin Kogyo ■) Cream foundation (
Inventive product 7) was obtained.

As described above, the present invention products 5 to 7 manufactured in Examples 2 to 4 were all emulsified cosmetics with excellent stability and feel in use.

that's all Procedural amendment (voluntary) November 8, 1991

Claims (1)

[Claims] 1. The following components (A), (B) and (C) (A) Polyglycerin fatty acid ester (B) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼… (I) [In the formula, two of R^1, R^2, and R^3 represent fatty acid residues having 7 to 23 carbon atoms, which may be the same or different, and the remainder represents hydrogen. ] An emulsified cosmetic comprising diacylglycerin (C) water represented by: