JPH0489450A - Methyl-branched fatty acid ester and cosmetics containing the same ester - Google Patents

Abstract

NEW MATERIAL:Methyl-branched fatty acid esters represented by formula I (m) and (n) are integer of 0-20 and (m+n)=1-20). EXAMPLE:Pentaerythritol monoisostearate. USE:A blending material for hair and skin cosmetics capable of providing a cosmetics excellent in spreading in application, free from stickiness, having a refreshed feeling in use, excellent in moisture retention and emulsion stability. PREPARATION:A lower alkyl ester of a methyl-branched fatty acid of formula II is made to react with pentaerythritol of formula III to obtain the objective methyl-branched fatty acid ester of formula I.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a novel methyl branched fatty acid ester useful as a compounding material for hair and skin cosmetics, and a novel methyl branched fatty acid ester containing the same that spreads easily when applied, is non-sticky, and is quick to apply. The present invention relates to a cosmetic that gives a firm feeling when used, has excellent moisturizing properties, and has good emulsion stability.

[Issues that the conventional technology and invention aim to solve] Generally, various moisturizing agents are used in cosmetics, but if the amount of conventional moisturizing agents is small, sufficient moisturizing effect cannot be obtained. Moreover, if the compound is added in an amount large enough to produce an effect, there is a problem that the stability of the system is impaired.

On the other hand, emulsion type cosmetics are widely used because their composition allows them to provide appropriate amounts of oil and moisture to the skin and hair. By changing the type and amount of the oil component, various emulsions with different physical properties and texture can be obtained.

However, since emulsions are thermodynamically unstable systems, it is difficult to stabilize them, and many studies and attempts have been made to date. One of the countermeasures is the addition of an emulsifying agent. Such emulsification aids include cationic aids,
Although there are anionic auxiliaries, amphoteric auxiliaries and nonionic auxiliaries, nonionic auxiliaries are most preferred because of the wide range of oil components that can be incorporated.

As an example of adding a nonionic emulsifying agent, it is known that when higher alcohols such as cetanol and cetostearyl alcohol are added for cosmetic purposes, stability is improved because a liquid crystal structure is formed. Although this method of adding higher alcohols is effective in preventing crystallization of high melting point oils and fats, if they are added to the extent that they remain stable, the viscosity becomes extremely high, making it difficult to spread during application and creating an oily feel. It has the disadvantage of being strong and sticky. Further, with regard to liquid crystal structures of higher alcohols, there have been problems such as precipitation of crystals with pearl-like luster and reduction in viscosity due to destruction of the liquid crystal structure.

To this end, compositions have been developed in which a nonionic auxiliary agent that forms a lamellar liquid crystal structure is blended into the composition.

For example, in Japanese Patent Publication No. 3B-5050, the following general formula (
n) [wherein p represents an integer of 1 to 3] A skin and hair care agent containing a triol represented by the following is disclosed. However, since this triol becomes an inverted middle liquid crystal in an aqueous solution, it has the drawbacks of a strong oily feel and insufficient moisturizing effect. Further, JP-A-63-23737 discloses an aqueous dispersion of niosomes consisting of lipid lamellae using polyglycerol ether as a nonionic amphiphile. This improves stability by encapsulating water-soluble active substances within vesicles, which are aqueous compartments contained between lipid layers.

However, this method also requires high-temperature treatment at 80° C. or higher to form niosomes, so it has the disadvantage that it is difficult to apply it to cosmetics containing active substances that are unstable at high temperatures. Furthermore, Japanese Patent Publication No. 58-8287, Japanese Patent Publication No. 61-56016, and Japanese Unexamined Patent Publication No. 57-7
No. 7613 and JP-A-57-94326 also disclose aqueous dispersions of lipid globules using glycerol ether, but they require homogenization during production or are difficult to use in organic solvents such as chloroform-methanol. The manufacturing process is complicated, requiring the lipid to be dissolved and then the solvent to be evaporated, resulting in industrial difficulties.

As described above, conventional nonionic auxiliaries have a problem in that the liquid crystal forming temperature range is narrow and the liquid crystal forming temperature is high, making it difficult to form liquid crystals industrially.

Normally, in cosmetics, active ingredients with high melting points are uniformly emulsified.
If the particles are not dispersed but separated, sufficient effects such as moisturizing properties cannot be obtained. Furthermore, some nonionic auxiliaries have a moisturizing effect, but their effect is not satisfactory.

Therefore, it is uniformly stable without any changes such as crystal transition over a wide concentration range at the usage temperature of cosmetics, and does not have an oily feel.
The development of cosmetics that also have excellent moisturizing effects has been desired.

[Means to solve the problem]

Under such circumstances, the present inventors conducted intensive research to solve the above problems, and found that by using a methyl branched fatty acid ester with a specific structure, it is possible to obtain a cosmetic with excellent moisturizing properties, and By incorporating this into emulsion-type cosmetics, in addition to good moisturizing properties, it contributes to the stabilization of emulsions, etc., and it is possible to spread the uniform area of high melting point active ingredients, and it spreads easily and does not become sticky when applied. The present invention was completed based on the discovery that it is possible to obtain an excellent cosmetic that provides a light and refreshing feeling when used.

That is, the present invention relates to the following general formula (I) OCH,OH C)l, (CH2), -CH-(CH2)ゎ-C-0-
CH, C-CH, DHCH3C)120)1 (I
) [In the formula, m and n each represent an integer of O to 20, m
and n is 1 to 20.] The present invention provides a methyl branched fatty acid ester represented by the following formula and a cosmetic containing the same.

- In format (I), the sum of m and n is 1 to 20,
From the viewpoint of performance as a cosmetic material, preferably 10 to 1
6, particularly preferably 14. Moreover, it is particularly preferable that the branched methyl group be located near the center of the alkyl main chain.

The methyl branched fatty acid ester (I) of the present invention is produced according to the following reaction formula.

CH, (C1,)12), -CH-(CH2). -C-
ORCH, (I[) CH,OH + HOCH2-C-CH,0)1 (I[[) -
-→ (I) CH, OI ([wherein m and n have the same meanings as above, and R represents a lower alkyl group] That is, lower alkyl ester of methyl branched fatty acid (
Compound (I) of the present invention is produced by reacting pentaerythritol (III) with II).

The lower alkyl ester (n) of methyl branched fatty acid used in this reaction can be obtained by esterifying the corresponding carboxylic acid by a conventional method. Among the corresponding carboxylic acids, those obtained industrially are usually mixtures with a certain distribution of the total carbon number of the alkyl group and the position of the branched methyl group, for example, a by-product during the production of oleic acid dimer. The isostearic acid having a methyl branch obtained as , contains about 75% or more of those having a total number of carbon atoms of 18 (the sum of m and n is 14), and the remainder having a total number of carbon atoms of 14,
16 and 20, and the branched methyl group is located almost in the center of the alkyl main chain [Journal of
The American Oil Chemists Society (J.
Amer, Oil Chem, Soc,) Vol.

51, 522. (1974)).

In this reaction, the molar ratio of lower alkyl ester of methyl branched fatty acid (■) and pentaerythritol (I[I) used is (III) / (II) = 1/1.
It is preferable that it is 10/1.

The solvent used in the reaction is not particularly limited, but it is preferably one that dissolves both lower alkyl ester of methyl branched fatty acid (I[) and pentaerythritol (I[[)].
For example, dimethylformamide and the like are preferably used.

Further, as a catalyst for the reaction, an alkali catalyst is usually used, and sodium methylate or the like is preferably used. The amount of catalyst is not particularly limited, but it is preferably used in a range of 0.1 to 20 mol % based on the lower alkyl ester (n) of methyl branched fatty acid.

The reaction temperature of this reaction is selected from the range of 60 to 150°C.

The compound (I) of the present invention can be isolated from the reaction mixture by a conventional method,
For example, solvent distillation, recrystallization, chromatography, etc. can be carried out alone or in combination.

The thus obtained methyl branched fatty acid ester of the present invention (
I) has unique properties. That is, it is a lamellar liquid crystal at room temperature, exhibits excellent compatibility with most solvents, and has characteristics such as being almost uniformly dispersed when mixed with water.

When the compound (I) of the present invention is used as a compounding material in cosmetics, one or more compounds of the present invention (I) can be used in combination, and the amount of compound (I) to be incorporated into the cosmetics of the present invention is particularly limited. However, it is usually 0.01 to 80% by weight (hereinafter simply expressed as %), particularly preferably 0.1 to 50%.

Moreover, in order to further increase the effects of the present invention, a surfactant can be used in combination. Such surfactants include:
Any of nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants can be used. In particular, nonionic surfactants are used for skin cosmetics, and cationic surfactants are used for hair cosmetics. Activators are 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, fatty acid monoglyceride, glyceryl ether, etc. Typical examples of cationic surfactants include quaternary ammonium salts, and any surfactants commonly used in cosmetics can be used, but in particular those disclosed in JP-A No. 61-267505 can be used. Branched alkyl quaternary ammonium salts as described are preferred. These surfactants are blended in the total composition in an amount of 0.01 to 30%, preferably 0.1 to 10%.

Furthermore, the cosmetics of the present invention may optionally contain ingredients commonly used in cosmetics, pharmaceuticals, foods, etc., such as higher alcohols having a straight or branched alkyl group or alkenyl group; liquid paraffin. , hydrocarbons such as vaseline and solid paraffin; lanolin derivatives such as liquid lanolin and lanolin fatty acids; silicone derivatives such as dimethylpolysiloxane, polyether-modified polysiloxane, and amino-modified polysiloxane; higher alcohol higher fatty acid esters,
Oils and fats such as higher fatty acids and long-chain amidoamines having alkyl or alkenyl groups; Animal and vegetable oils and fats such as mink oil and olive oil; Medicinal agents such as anti-dandruff agents, fungicides, and vitamins; Preservatives such as parabens ; Thickeners such as water-soluble polymers; Colorants such as dyes and pigments; Ultraviolet absorbers; Astringents; Other moisturizing agents such as propylene glycol, glycerin, calpitol, 3-methyl-1,3-butanediol, sugars, etc. Agents: Water, fragrances, etc. can be added.

The cosmetics of the present invention can be produced according to a conventional method, and are used, for example, as basic cosmetics such as oil-in-water type, water-in-oil type emulsion cosmetics, and oil-based cosmetics; makeup cosmetics such as lipsticks and foundations; skin cosmetics; Cleaning agents: Can be applied as hair cosmetics such as hair rinses, treatments, and hair conditioners.

[Action and effect of invention]

The novel methyl branched fatty acid ester (I) of the present invention is excellent as a moisturizing ingredient, and since it forms a thermotropic liquid crystal at room temperature, it has a low oily feel and spreads easily. It has the effect of improving the stability of the system and making the active ingredients work effectively, and is extremely useful as a compounding material for hair and skin cosmetics.

Therefore, the cosmetic composition of the present invention spreads easily when applied, provides a light feel without stickiness, has excellent moisturizing properties, and has good emulsion stability.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these in any way.

Example 1 In 11 reaction vessels equipped with a distillation condenser equipped with a thermometer, a stirrer and a vacuum, 29. ,
9 g (f), 1 mol), 68 g (0.5 mol) of pentaerythritol, 1.9 g of 28% sodium methylate/methanol solution and 4 g of dimethylformamide
50mj! and the degree of vacuum is 100-120 at 100℃.
The reaction was carried out for 2.5 hours under mmHg conditions. During this reaction, about 100 dimethylformamide was distilled out of the reaction system.

After the reaction contents were cooled, about 400 g of water was added and the layers were separated. After adding ether to the lower layer and extracting, the ether layer is
In addition to the upper layer that was initially separated, it was washed three times with 200 ml of water each time. Purity 77 after removing ether under reduced pressure
% of crude pentaerythritol monoisostearate was obtained (70% yield). This was purified by silica gel chromatography (ethyl acetate/ethanol) until it gave a single spot on thin layer chromatography, yielding 21 g of pentaerythritol monoisostearate (yield 5
o%) was obtained (purity 94%). This was a thermotropic liquid crystal at room temperature.

IR (liquid film) cm-': (15th!J) 3450 (0-
H), 2840-2950 (C-H), 1720 (
C=O).

1640(C-)1), 1040(C-0)'H-
NMR (CDIj! a) δppm: (Figure 2) 4.
1 [(C), 2') 11, 3.6 [(b)
, 6H), 3.3CCa), 3H]
, 2.4 [(d), 2H co,
1.1-1.7 [(e), 27)1], 0
．． 9 [(f), 6H] Test Example 1 The properties at room temperature and compatibility with water of the compound of the present invention obtained in Example 1 and a conventionally known similar compound (comparative compound) were investigated. The results are shown in Table 1.

Example 2 A hair rinse agent having the composition shown in Table 2 was prepared using the compound of the present invention produced in Example 1, and its rinsing performance was investigated.

Production method: Add the ingredients shown in Table 2 that were heated and dissolved at the same temperature to water heated to 70°C, stir to mix, cool to room temperature while stirring, and prepare the hair rinse composition. I got it.

Rinse performance evaluation method: 20 g (15 cm length) of hair from a Japanese woman who has never undergone beauty treatments such as cold perm or bleach.
Then, the hair strands were washed with a commercially available shampoo containing an anionic activator as a main ingredient, and 2 g of the hair rinse agent shown in Table 2 was evenly applied, then rinsed with running water for 30 seconds, and then towel-dried. went. The softness, smoothness, and oiliness of this wet hair bundle were sensory evaluated. The evaluation criteria are: ◎ for particularly excellent results, ◯ for good results, △ for equivalent results, and × for inferior results. The results are shown in Table 2.

The hair rinse composition containing the compound of the present invention had excellent flexibility and smoothness, and had little oily feel.

Example 3 A hair rinse agent composition having the composition shown in Table 3 was prepared according to a conventional method, and its rinsing performance was examined. The results are shown in Table 3.

All of the obtained hair rinse agent compositions exhibited good rinsing performance and good stability.

Sensory evaluation was performed in the same manner as in Example 2.

[Storage stability]

100m1! The sample was placed in a transparent glass container, and after storage, the appearance was observed with the naked eye. The evaluation was based on the following criteria.

○: Uniform throughout, with no abnormalities such as dispersion or aggregation.

X: Heterogeneous, with separation and aggregation observed.

Below are the margins Example 4 Hair cream composition: (%) Hair treatment composition: (%) Dimethylpolysiloxane (500 cs) Cetosteroidal alcohol Compound of the present invention (Example 1) Liquid paraffin 1.0 3.0 3. 0 3.0 ■ Methylparaben 0.20 Fragrance 0.4 0 Purified water Balance meter
100.0 A hair treatment composition was obtained that had excellent smoothness and flexibility, had little oily feel, was light, and had a moist and good feel.

Example 5 ■ Dimethylpolysiloxane (1000cs) 0
, 5 ■ Compound of the present invention (Example 1) 1.0
■ Cetyl alcohol 5.0 ■ Dipropylene glycol 6.0 ■ Glycerin 10.0 ■ Liquid paraffin
3.0 ■Fragrance 0.4 0 Purified water Balance meter
100.0 A hair cream composition was obtained which was excellent in smoothness and flexibility, had no sticky feeling, and gave a good feel.

Example 6 Conditioning mousse IIL composition: (%)■
Methylphenylpolysiloxane 1.0 (300
cs) ■ Isotridecyl myristate 1.0 Compound of the present invention (Example 1) 2.0 ■ Glycerin ■ Liquid paraffin ■ Compound of the present invention (Example 1) ■ 95% ethyl alcohol ■ Methyl paraben ■ Fragrance ■ Propellant (LPG) ■ Purified water 2.5 2.5 0.2 5.0 0.1 0.1 10.0 Noirans scale 1: A cosmetic composition giving the same good feel as in Example 3 was obtained.

Example 7 Cream: Oil phase component: Setanol stearate trimethylol isoheptadecane 100.0 Conditioning mole (%) 2°0 3.0 3.0 Monolauryl glycerin 2.04° Water phase component Nidipropylene glycol 10. 01.3
-Butylene glycol 5.0 Ethylparaben 0.1 Methylparaben
0.2 Fragrance 0.1 Purified water Balance meter
100.0 The cream of the present invention felt good when used and exhibited excellent moisturizing effect.

[Brief explanation of drawings]

Figures 1 and 2 show IR and NMH of pentaerythritol monoisostearate obtained in Example 1, respectively.
FIG. that's all

Claims (1)

[Claims] 1. The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, m and n each represent an integer from 0 to 20, and m
and the sum of n is 1 to 20.] A methyl branched fatty acid ester represented by: 2. In general formula (I), the sum of m and n is 10 to 16
The methyl branched fatty acid ester according to claim 1. 3. The methyl branched fatty acid ester according to claim 1, wherein in the general formula (I), the sum of m and n is 14. 4. A cosmetic containing one or more of the methyl branched fatty acid esters according to claims 1 to 3.