JP2961559B2 - Methyl-branched alkyl glycoside and cosmetic containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel methyl-branched alkyl glycoside useful as a compounding material for hair cosmetics, and contains a non-sticky, non-sticky and refreshing material when applied. The present invention relates to a hair cosmetic that gives a feeling of use, has excellent moisture retention, and has good emulsion stability.

[Problems to be solved by conventional technology and invention]

In general, various humectants are used in cosmetics. However, conventional humectants do not provide sufficient moisturizing effect if the amount is small, and if the amount is large enough to achieve the effect, the system becomes stable. There were problems such as impairing the performance.

On the other hand, emulsion-type cosmetics are widely used because they can provide appropriate oil and moisture to skin and hair because of their composition. By changing the type and amount of the oil component, various emulsions having different physical properties and feeling in use can be obtained.

However, since the emulsion is a thermodynamically unstable system, its stabilization is difficult, and many studies and attempts have been made so far. One of the measures is to add an emulsifying aid. Such emulsifying auxiliaries include cationic auxiliaries, anionic auxiliaries, amphoteric auxiliaries, and nonionic auxiliaries, but nonionic auxiliaries are most preferred in view of the range of oil components that can be blended.

As an example of the addition of a nonionic emulsification aid, it is known that, for example, when a higher alcohol such as cetanol or cetostearyl alcohol is added for cosmetics, a liquid crystal structure is formed, and thus the stability is improved. Although the method of adding a higher alcohol in this way is effective in preventing crystallization of high melting point fats and oils, when these are added to maintain a stable state,
There are drawbacks in that the viscosity becomes very high, the spread at the time of application is poor, the oily feeling is strong and sticky. In addition, the liquid crystal structure of higher alcohol has problems such as precipitation of pearl-like glossy crystal due to destruction of the liquid crystal structure and a decrease in viscosity.

Therefore, a composition in which a nonionic auxiliary agent that forms a lamellar liquid crystal structure is blended in the composition has been developed. For example, Japanese Patent Publication No. 38-5050 discloses the following general formula (I
I) [Wherein, p represents an integer of 1 to 3]. A skin and hair care agent containing a triol represented by the following formula is disclosed. However, this triol has a drawback that it becomes reverse middle liquid crystal in an aqueous solution and therefore has a strong oily feeling and an insufficient moisturizing effect. JP-A-63-23737 discloses an aqueous dispersion of a niosome comprising a lipid lamella using polyglycerol ether as a nonionic amphiphilic substance. This is an improvement in stability by encapsulating a water-soluble active substance in vesicles, which are aqueous compartments contained between lipid layers. However, this also requires a high-temperature treatment of 80 ° C. or more during the formation of niosomes, and thus has a drawback that it is difficult to apply it to cosmetics containing an active substance having poor stability at high temperatures. Furthermore, JP-B-58-8287, JP-B-61
JP-56016, JP-A-57-77613, JP-A-57-94
No. 326 also discloses an aqueous dispersion of lipid globules using glycerol ether.However, homogenization is required in the production, or the lipid is dissolved in an organic solvent such as chloroform-methanol, and then the solvent is evaporated. And the production process is complicated, which is disadvantageous in that it is industrially difficult.

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

Usually, in a state where active ingredients having a high melting point are separated without being emulsified and dispersed uniformly in cosmetics, effects such as moisture retention cannot be sufficiently obtained. Some of the nonionic auxiliaries have a moisturizing action, but the action was not satisfactory.

For this reason, there has been a demand for the development of a cosmetic which is uniformly stable without a change in crystal transition and the like over a wide concentration range at a use temperature of the cosmetic, has no oily feeling, and has an excellent moisturizing effect.

[Means for solving the problem]

Under such circumstances, the present inventors have conducted intensive studies to solve the above problems, and as a result, by using a methyl-branched alkyl glycoside having a specific structure, it is possible to obtain a hair cosmetic excellent in moisture retention, Furthermore, if this is blended into an emulsion hair cosmetic, in addition to good moisturizing properties, it contributes to stabilization of the emulsion and the like, and it is possible to widen the uniform region of the high-melting-point active ingredient. The present inventors have found that an excellent hair cosmetic which can give a refreshing feeling without stickiness can be obtained, and completed the present invention.

That is, the present invention provides the following general formula (I) Wherein G represents a glucosyl group, the methyl branched alkyl group is derived from isofatty acid by-produced during the production of dimer acid, the sum of m and n is 11 to 17, and the branched methyl group is Present near the center of the alkyl main chain], and one or two or more thereof.

In the general formula (I), the sum of m and n is 11 to 17,
It is preferably 15 from the viewpoint of performance as a cosmetic material.

The methyl-branched alkyl glycoside (I) of the present invention is produced, for example, according to the following reaction formula.

Wherein G, m and n have the same meaning as described above, and R represents a lower alkyl group. That is, glucose (II) and methyl branched alcohol (III) are directly reacted in the presence of an acid catalyst. Or glucose (II) in methanol, ethanol,
Lower alcohol (IV) such as propanol or butanol
To lower alkyl glycoside (V),
The compound (I) of the present invention is produced by reacting the methyl-branched alcohol (III).

The methyl branched alcohol (III) used in the above reaction is
It is obtained by converting the corresponding carboxylic acid to a methyl ester and then performing catalytic reduction with hydrogen. Of the corresponding carboxylic acids here, those obtained industrially are usually
A mixture in which the total number of carbon atoms of the alkyl group and the position of the branched methyl group have a constant distribution. For example, isostearic acid having a methyl branch obtained as a by-product in the production of oleic acid dimer has a total carbon number of 18 (m The sum of n is 14)
Containing at least about 75%, with the balance being those having a total carbon number of 15, 16, or 20, and the branched methyl group is located at approximately the center of the alkyl backbone [Journal of
The American Oil Chemistry Society (J. Am
er. Oil Chem. Soc. Vol. 51, 522, (1974)].

In the above and the above reactions, the ratio of glucose (II) or lower alkyl glycoside (V) to methyl branched alcohol (III) used is (III) / (II) or (V) = 1/1 to 10/1 in molar ratio. And particularly preferably 1/1 to 6/1. If (III) / (II) or (V) is less than 1/1, the reaction rate will decrease, and if it exceeds 10/1, no further effect will be obtained, which is not preferred.

The above reaction is preferably carried out without solvent or in an aprotic polar solvent, for example, a solvent such as dimethylsulfoxide and dimethylformamide.

The reaction rate can be controlled by the reaction temperature and the amount of catalyst.

The reaction temperature is desirably in the range of 80 to 130 ° C. When the reaction temperature is lower than 80 ° C, the reaction rate becomes extremely slow.
Above 130 ° C, oligomerization and decomposition of sugars increase.

As a catalyst, an acid catalyst is generally used, for example, sulfuric acid,
Paratoluenesulfonic acid, hydrochloric acid and the like are effective. The amount of the catalyst varies depending on the reaction conditions, but is usually selected in the range of 0.01 to 15 g per 1 mol of glucose (II) used in the reaction.

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

The thus obtained methyl-branched alkyl glycoside (I) of the present invention has unique properties. That is, it is a camera-like liquid crystal at room temperature, has excellent compatibility with most solvents, and has properties 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 a hair cosmetic, the compound (I) of the present invention can be used alone or in combination of two or more. Although not particularly limited, it is usually preferably 0.01 to 80% by weight (hereinafter simply referred to as%), particularly preferably 0.1 to 50%.

In order to further increase the effects of the present invention, a surfactant can be used in combination. As such a surfactant, any of a nonionic surfactant, a cationic surfactant, an anionic surfactant and an amphoteric surfactant can be used, and a cationic surfactant is particularly preferable. Examples of the nonionic surfactant 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, and the like. Representative examples of the cationic surfactant include a quaternary ammonium salt, and any of those generally used in cosmetics can be used. In particular, JP-A-61-267505 discloses The branched alkyl quaternary ammonium salts as described are preferred. These surfactants are incorporated in the entire composition in an amount of 0.01 to 30%, preferably 0.1 to 10%.

Further, the hair cosmetic composition of the present invention may contain, if necessary, components usually used for cosmetics, pharmaceuticals, foods, etc., for example, higher alcohols having a linear or branched alkyl or alkenyl group; liquid paraffin , Lanolin derivatives such as liquid lanolin and lanolin fatty acids; silicon derivatives such as dimethylpolysiloxane, polyether-modified polysiloxane and amino-modified polysiloxane; higher alcohol higher fatty acid esters and higher fatty acids And oils such as 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, bactericides, vitamins; preservatives such as parabens; Thickeners such as polymers; coloring agents such as dyes and pigments; ultraviolet absorbers; Call, glycerine, carbitol, 3-methyl-1,3-butanediol, other humectants such as sugars, water, can be blended perfumes.

The hair cosmetic of the present invention can be produced according to a usual method, and can be applied, for example, as a hair cosmetic such as a hair rinse, a treatment, and a hair styling agent.

[Action and effect of the invention]

Novel methyl-branched alkyl glycoside (I) of the present invention
Is excellent as a moisturizing component, has low oiliness and good spreadability because it forms a thermotropic liquid crystal at room temperature, and further incorporates a high melting point substance into the liquid crystal, thereby improving the stability of the system and effectively using the active ingredient. It has a function to work effectively and is extremely useful as a compounding material for hair cosmetics.

Therefore, the hair cosmetic composition of the present invention has good spreadability at the time of application, gives a refreshing feeling without stickiness, and has excellent moisture retention and good emulsion stability.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 In a reaction vessel equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a distillation cooling tube equipped with a decompression device, 402 g (1.5 mol) of isostearyl alcohol, 54 g (0.3 mol) of glucose, and 0.19 of paratoluenesulfonic acid were added. g (1 × 10 ⁻³ mol) was charged. While stirring, the reaction temperature was raised to 110 ° C. under a vacuum of 50 Torr while introducing nitrogen. After the temperature was raised, the mixture was reacted at 110 ° C. for 8 hours under a vacuum of 50 Torr while introducing nitrogen.
The reaction was cooled to room temperature to complete the reaction. The pH of the contents was neutralized to about 7 with 1N NaOH water. 500 ml of ethyl acetate and 500 ml of water were added to the contents, and the layers were separated. The upper layer of ethyl acetate was removed under reduced pressure, and further, using a Smith distiller, 0.02
Unreacted isostearyl alcohol was removed under the conditions of Torr and 150 ° C. 65 g of Smith distillation residue was obtained. This was purified by silica gel column chromatography (acetone / hexane) until thin spot chromatography to give a single spot, and 46 g of isostearyl glucoside was purified.
(36% yield). This was a thermotropic liquid crystal at room temperature.

IR (liquid film) cm ^-1 : (Fig. 1) 3400 (OH), 2860 to 2950 (CH), 1460 (CH), 1
380 (C—H), 1030 (C—O) ¹ H-NMR (CDCl ₃ ) δ ppm: (FIG. 2) 3.3-5.8 [proton of glucose skeleton, (11H) + water (4.2 pp)], 0.8- 1.7 [Methine, methylene, methyl protons of isostearyl chain (37H)] Test Example 1 The isostearyl glucoside (compound of the present invention) obtained in Example 1 and a conventionally known alkyl glucoside (comparative compound) at room temperature The properties and compatibility with water were investigated. The results are shown in Table 1.

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

Production method; Second water dissolved in water heated to 70 ° C at the same temperature
The components shown in the table were added, mixed with stirring, and then cooled to room temperature with stirring to obtain a hair rinse composition.

Evaluation method of rinsing performance; Bundle 20 g (15 cm length) of Japanese female hair that has never been subjected to beauty treatment such as cold perm or bleach, and use this hair bundle as a main component with an anionic activator The hair was rinsed with shampoo, 2 g of the hair rinse shown in Table 2 was applied uniformly, then rinsed with running water for 30 seconds, and then towel dried. The hair bundle in the wet state was organoleptically evaluated for flexibility, smoothness and oiliness. The evaluation criteria are indicated by 特 に when particularly excellent, ○ when good, 良好 when equivalent, and x when inferior. The results are shown in Table 2.

The hair rinse composition containing the isostearyl glucoside of the present invention was excellent in flexibility and smoothness, and less oily.

Example 3 A hair rinse 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.

Each of the obtained hair rinsing agent compositions exhibited good rinsing performance and also had good stability.

 The sensory evaluation was performed in the same manner as in Example 2.

(Storage stability)

The sample was placed in a 100 ml transparent glass container, and after storage, the appearance was visually observed. The evaluation was shown based on the following criteria.

 ：: The whole is uniform, and no abnormality such as dispersion and aggregation is observed.

 ×: Non-uniform, separation and aggregation were observed.

Example 4 Hair Treatment Composition: (%) 2-dodecylhexadecyl trime 1.5 tylammonium chloride stearyltrimethylammonium 1.0 muchloride dimethylpolysiloxane (500cs) 1.0 cetostearyl alcohol 3.0 isostearyl glucoside 3.0 (Example 1) Liquid paraffin 3.0 hydroxy Ethyl cellulose 0.5 (1% vinegar solution viscosity 8,000 cp) Polyoxyethylene oleyl ether 0.5 ter (EO = 5) Methyl paraben 0.2 Perfume 0.4 Purified water Balance meter 100.0 Excellent smoothness, flexibility, low oiliness, light weight,
A hair treatment composition moist and giving a good feel was obtained.

Example 5 Hair cream composition: (%) di-2-hexyldecyldimethyl 2.0 ammonium chloride cetyltrimethylammonium 1.0 chloride dimethylpolysiloxane (1000cs) 0.5 isostearylglucoside 1.0 (Example 1) cetyl alcohol 5.0 dipropylene glycol 6.0 glycerin 10.0 Liquid paraffin 3.0 flavor 0.4 Purified water Balance meter 100.0 A hair cream composition having excellent smoothness and flexibility, no stickiness, and imparting a good feel was obtained.

Example 6 Conditioning mousse composition: (%) dialkyldimethylammonium 0.5 muchloride ^{* 1} methylphenylpolysiloxane 1.0 (300 cs) isotridecyl myristate 1.0 3-methyl-1,3-butanedi1.0 all glycerin 2.5 liquid paraffin 2.5 isostearyl glucoside 0.2 Example 1 95% Ethyl Alcohol 5.0 Methyl Paraben 0.1 Flavor 0.1 Propellant (LPG) 10.0 Purified Water Balance Meter 100.0 * 1: Same as Example 3 A conditioning mousse composition giving good feeling was obtained.

[Brief description of the drawings]

1 and 2 show the results of IR and NMR of the isostearyl glucoside obtained in Example 1, respectively.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-57-88121 (JP, A) JP-A-60-174796 (JP, A) JP-A-60-163894 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) C07H 15/04 A61K 7/06-7/08 CA (STN)

Claims (3)

(57) [Claims] 1. The following general formula (I) Wherein G represents a glucosyl group, the methyl branched alkyl group is derived from isofatty acid by-produced during the production of dimer acid, the sum of m and n is 11 to 17, and the branched methyl group is Present near the center of the alkyl main chain]. 2. The methyl-branched alkyl glycoside according to claim 1, wherein in formula (I), the sum of m and n is 15. 3. A hair cosmetic containing one or more of the methyl-branched alkyl glycosides according to claim 1.