JP2946145B2 - Cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to cosmetics, and more particularly to cosmetics, which have excellent moisturizing properties, good spreadability when applied to skin, hair, etc., excellent smoothness when dry and wet, and emulsion stability. Regarding good cosmetics.

[0002]

2. Description of the Related Art In general, various humectants are used in cosmetics. However, if the amount of the conventional humectant is too small, a sufficient moisturizing effect cannot be obtained. When blended, there are problems such as impairing the stability of the system.

[0003] Conventionally, various oils have been blended into hair cosmetics for the purpose of imparting flexibility and wettability to the hair, protecting the hair, improving the feel and giving an emollient effect. Among these oils, silicones represented by dimethylpolysiloxane are smoother and more excellent in lubricity, give a smooth feel and gloss to hair as compared with higher alcohols, glycerides, liquid paraffin, esters and the like. Is known and used in many hair cosmetics. However, silicones have a poor moisturizing effect and are smooth but lack moist feeling,
In addition, there is a drawback that the feeling of squeaking is strong when the hair is moistened due to its hydrophobicity. Silicones are also generally used in skin cosmetics for the purpose of imparting a smooth feeling without stickiness. However, silicones generally have poor compatibility with other cosmetic oils and poor emulsification and dispersibility of the system. There is also a problem that the property deteriorates and a separation phenomenon occurs with time.

[0004] On the other hand, emulsion-type cosmetics are widely used because of their composition, they can provide appropriate oil and moisture to skin and hair. 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 having a surfactant. Such emulsifying aids include cationic surfactants, anionic surfactants, amphoteric surfactants and nonionic surfactants, but the range of oil components that can be blended and the application to various cosmetics are increasing. Nonionic surfactants are most preferred from the point of view.

As nonionic emulsifying aids, higher alcohols and long-chain branched alkyltriols (JP-B-38-50)
No. 50, JP-A-63-258804), long-chain alkyl polyglycerol ether (JP-A-52-63).
Nos. 75 and 63-23737) and ethylene oxide adducts of higher alcohols (JP-A-62-965).
No. 85) and polyol ethers derived from higher fatty acids (Japanese Patent Publication No. 61-56016). However, these compounds do not form lamellar liquid crystals by themselves and have a strong oily feeling when applied to the skin or hair, and the liquid crystal formation temperature range is narrow even when other components are combined, so that cosmetics can be stably used. There were problems such as not being able to keep.

[0006]

Accordingly, an object of the present invention is to provide an excellent moisturizing property, good spreadability when applied to skin, hair, etc., excellent smoothness when dry and wet, and good stability. The purpose is to provide cosmetics.

[0007]

Under these circumstances, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a nonionic amphiphilic compound which retains a lamellar liquid crystal structure over a wide temperature range can be used. It has been found that when used in combination with silicones, a good cosmetic can be obtained at the time of application, giving a refreshing feeling without stickiness, having excellent moisture retention, and having good stability. Reached.

That is, the present invention relates to a cosmetic containing the following components (A) and (B). (A) having at least one long-chain branched alkyl or alkenyl group and at least three hydroxyl groups in one molecule;
Nonionic amphiphilic compound that maintains a lamellar liquid crystal structure at temperatures exceeding 5 ° C. and 50 ° C. (B) dimethylpolysiloxane, methylphenylpolysiloxane, amino-modified silicone, fatty acid-modified polysiloxane, alcohol-modified silicone, aliphatic One or more silicones selected from the group consisting of alcohol-modified polysiloxane, polyether-modified silicone, epoxy-modified silicone, fluorine-modified silicone, cyclic silicone and alkyl-modified silicone

The nonionic amphiphilic compound (A) used in the present invention has a lamellar liquid crystal structure at least at 25 ° C., and further has a lamellar liquid crystal structure even at a temperature exceeding 50 ° C. It is necessary. Here, the confirmation of the lamellar liquid crystal structure is performed, for example, by using The Journal of Cell Biology (The Journal).
of Cell Biology), Vol. 12, No. 2
Pages 07 to 209 and the surface, Vol. 11, No. 10, No. 57
X-ray diffraction and a differential scanning calorimeter (DSC) can be used in the method described on pages 9 to 590. Examples of the compound having such properties include the following (A-
1), (A-2) and (A-3).

(A-1) Glycerylated polyols represented by the following general formula (1). A _a (G) (1) [wherein, G represents a residue obtained by removing a hydroxyl group from a polyol selected from pentaerythritol, sorbitol, maltitol, glucose, fructose and alkyl glycoside;

[0011]

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Wherein R ¹ represents a branched alkyl group or alkenyl group having 10 to 36 carbon atoms, and a represents a number of 1 or more and does not exceed the total number of the polyol hydroxyl groups.

(A-2) A methyl-branched fatty acid ester represented by the following general formula (2).

[0014]

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Wherein b ₁ and b ₂ are each 0-20
Indicates the integer, the sum of b ₁ and b ₂ is 6-20]

(A-3) A branched fatty acid glyceroglycolipid represented by the following general formula (3)

[0017]

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The general formula (1) representing the component (A-1)
Wherein the alkyl glycoside represented by G is methyl
Glucoside, ethyl glucoside, propyl glucoside,
Octyl glucoside, methyl maltoside, ethyl malto
And the like. Also, R ¹As for carbon number 16
-36, especially 18-24 branched alkyl groups are preferred.
Such a branched alkyl group R¹The following general formula (4)
Or (5)

[0019]

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(Wherein, c _{1 to} c ₄ have the same meanings as described above). Preferred examples of these branched alkyl groups include a methylpentadecyl group, a methylhexadecyl group, a methylheptadecyl (isostearyl) group, a methyloctadecyl group, a methylbehenyl group, an ethylhexadecyl group, an ethyloctadecyl group, an ethylhenyl group, Butyl dodecyl group, butyl hexadecyl group,
Butyl octadecyl group, hexyl decyl group, peptyl undecyl group, octyl dodecyl group, decyl dodecyl group,
Decyltetradecyl group, dodecylhexadecyl group, tetradecyloctadecyl group and the like. In the general formula (1), a is particularly preferably 1 or 2.

Such glycerylated polyols (1)
Is produced, for example, according to the following formula, by reacting a polyol with a corresponding branched alkyl glycidyl ether in the presence of a basic catalyst.

[0022]

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[Wherein, R ¹ has the same meaning as described above]

The reaction molar ratio between the polyol and the branched alkyl glycidyl ether (6) in this reaction can be appropriately selected depending on the desired degree of etherification of the glycerylated polyol. For example, in order to obtain a target glycerylated polyol having a high 1-mol adduct content, the polyol is usually used in an excess of 1.2: 1.0 to 10.0: 1.0. Taking into account the amount of 1 mol adduct formed and the recovery of the polyol, 1.5:
A ratio of 1.0 to 5.0: 1.0 is preferred. In order to obtain a target glycerylated polyol having a high content of 2 mol adduct, usually 0.3: 1.0 to 1.1: 1.
An excess of the branched alkyl glycidyl ether may be used in a ratio of 0, and considering the amount of the 2-mol adduct,
A ratio of 0.4: 1.0 to 0.8: 1.0 is preferred.

The reaction is usually carried out without solvent, but it is preferable to use an organic solvent for the purpose of assisting the mixing of the polyol and the branched alkyl glycidyl ether. Examples of such an organic solvent include dimethyl sulfoxide, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and the like.
It is preferable to use 0 times the amount.

As the catalyst, an acid or basic catalyst which is generally known as a reaction catalyst for an epoxy group can be used.
It is not preferable because the decomposition reaction of the ether bond of the generated glycerylated polyols and the dehydration reaction of the hydroxyl group occur,
It is preferred to use a basic catalyst. The basic catalyst used is not particularly limited, but includes sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, sodium hydride and the like from the viewpoint of reactivity and economy. These basic catalysts are used in an amount of 0.01 to 20.0% by weight, especially 0.1 to 10.
It is preferably used in the range of 0% by weight.

The reaction is carried out at 50 to 200 ° C., preferably at 80 ° C.
Performed at ~ 150 ° C. If the reaction temperature is lower than 50 ° C., the reaction rate is low, and if it exceeds 200 ° C., the product is colored, which is not preferable.

In this reaction, if water is present in the reaction system, the epoxy group of the branched alkyl glycidyl ether reacts with water to produce glyceryl ether as a by-product.
It is preferable to dissolve or disperse the polyol in an organic solvent and heat it to blow dry nitrogen gas, or to heat and dehydrate under reduced pressure to remove water, and then react by adding a branched alkyl glycidyl ether.

After completion of the reaction, an organic acid such as acetic acid or citric acid or an inorganic acid such as sulfuric acid, hydrochloric acid or phosphoric acid is added to neutralize the catalyst, and then the organic solvent used in the reaction is removed. The organic solvent is preferably removed under reduced pressure, usually at a temperature of 120 ° C. or less, in order to avoid thermal decomposition of the reaction product.

The glycerylated polyols (1) used in the present invention are usually a 1 mol adduct obtained by adding one molecule of a branched alkyl glycidyl ether (6) to one molecule of a polyol;
In addition to the 2-mol adduct having two molecules added, three or more branched alkyl glycidyl ethers per polyol molecule (6)
Is obtained as a mixture of multimolecule adducts. Glycerylated polyols (1) thus obtained
Is usually used as a mixture of these 1-mol adducts, 2-mol adducts or multi-mol adducts. However, if there is a problem due to reasons such as performance or incorporation into products, silica gel columns or solvent extraction Purification can be performed using a known purification method. The glycerylated polyols (1) of the present invention may contain unreacted glycosides in addition to the desired 1 mol adduct, 2 mol adduct, or multimol adduct. Such an unreacted glycoside can be used as it is, provided that there is no practical problem. However, if there is a problem, for example, an organic solvent such as ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, or chloroform may be used. The layer can be removed by a method using an extraction solvent system or a known purification method such as Smith thin film distillation.

In the general formula (2) representing the above-mentioned methyl-branched fatty acid ester, the sum of b ₁ and b ₂ is from 6 to 20, preferably from 10 in view of the performance as a cosmetic material.
To 16, particularly preferably 14. Further, it is particularly preferable that the branched methyl group is located near the center of the alkyl main chain.

The methyl branched fatty acid ester (2) is produced according to the following reaction formula.

[0033]

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Wherein b ₁ and b ₂ have the same meanings as above, and R ³ represents an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. The target compound (2) is produced by reacting pentaerythritol (8) with a lower alkyl ester of a fatty acid (7).

The lower alkyl ester (7) of a methyl-branched fatty acid used in this reaction can be obtained by esterifying a corresponding carboxylic acid by a conventional method. 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 certain distribution. For example, isostearic acid having a methyl branch obtained as a by-product during the production of oleic acid dimer has a total carbon number of 18 (b ₁ And the sum of b ₂ and 14) are about 75% or more, and the remainder is a group having a total carbon number of 14, 16 or 20, and the branched methyl group is located almost at the center of the alkyl main chain. [Journal of the American Oil Chemists.
Society (J. Amer. Oil Chem. So
c. ) Vol. 51, 522, (1974)].

In this reaction, the molar ratio of the lower alkyl ester of methyl-branched fatty acid (7) and pentaerythritol (8) used is (7) / (8) = 1/1 to 1 in molar ratio.
It is preferably 0/1.

The solvent used in this reaction is not particularly limited, but may be a lower alkyl ester of a methyl-branched fatty acid (7).
It is preferable to dissolve both pentaerythritol and pentaerythritol (8). For example, dimethylformamide or the like is suitably used.

As a catalyst for the reaction, an alkali catalyst is usually used, and sodium methylate or the like is preferably used. The amount of the catalyst is not particularly limited, but is preferably used in the range of 0.1 to 20 mol% based on the lower alkyl ester (7) of the methyl-branched fatty acid. The reaction temperature of this reaction is selected from the range of 60 to 150 ° C.

The isolation of compound (2) from the reaction mixture
It can be carried out by a conventional method, for example, solvent distillation, recrystallization, chromatography, or the like, or a combination thereof.

Further, the branched fatty acid glyceroglycolipids
In general formula (3), R^TwoOf c ₁And c_TwoIs a cosmetic
From the viewpoint of performance as a material, b₁And b_TwoSame as
The sum of the socks is preferably 10 to 16, especially 14,
c_ThreeAnd c_FourFrom the same point of view, the sum is 6-14,
It is preferably 8 to 12.

The branched fatty acid glyceroglycolipid (3) is produced, for example, according to the following reaction formula.

[0042]

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Wherein X ¹ represents a halogen atom, M represents a hydrogen atom or a cation group, and R ² has the same meaning as described above.

That is, fatty acids (1) are added to compound (9).
By reacting 0), compound (3) is obtained.

The compound (9) used in this reaction can be easily produced by a known method, for example, a reaction of a monosaccharide or oligosaccharide with glycerol monohalohydrin, glycerol dihalohydrin or epihalohydrin.

The compound (10) can be produced, for example, by reacting a fatty acid with an alkali metal hydroxide such as sodium hydroxide or an amine in the presence of a suitable solvent. The cation group represented by M in the compound (10) includes, for example, an alkali metal, an ammonium group, an alkylammonium group, and a trialkanolamine.

In order to carry out the present method, for example, the compound (9) and the compound (10) may be reacted at a temperature of 30 to 150 ° C., preferably 70 to 120 ° C. The amount of the compound (10) to be used here is usually 0.3 to 3.0 times, preferably 1.0 to 1.0 times the amount of the compound (9).
It is 2.0 times mol. When M in compound (10) is a hydrogen atom, the reaction is carried out in the presence of an alkaline substance. Examples of the alkaline substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal alcoholates, and alkylamine hydroxides.

In carrying out the present reaction, a polar solvent can be used for the purpose of promoting the mixing of the compound (9) and the compound (10) and allowing the reaction to proceed smoothly. The polar solvent used here is at least one or more selected from dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, pyridine, water and the like. The amount of the polar solvent used may be appropriately selected. In carrying out the present reaction, a phase transfer catalyst can be used for the purpose of allowing the present reaction to proceed, if necessary. The amount of the phase transfer catalyst used here may be appropriately selected, but is usually 0.1 to 10 mol% based on the compound (10). Further, as the phase transfer catalyst used here, for example, tetraethylammonium bromide, tetrapropylammonium bromide,
Tetrabutylammonium bromide, tetraheptylammonium bromide, tetrahexylammonium bromide, N, N, N-trimethyl-N-octylammonium chloride, N, N, N-trimethyl-N-
Decyl ammonium chloride, N, N, N-trimethyl-N-dodecylammonium chloride, N, N, N
-Trimethyl-N-hexadecyl ammonium chloride, N, N, N-trimethyl-N-octadecyl ammonium chloride, N, N-dimethyl-N, N-dihexadecyl ammonium chloride, N, N-dimethyl-
Examples thereof include tetraalkylammonium chlorides such as N, N-dioctadecylammonium chloride.

The reaction products of the above reaction include, in addition to the desired glyceroglycolipid (3), usually an inorganic salt as a by-product, unreacted compound (9) or (10), and the like. I have. Therefore, depending on the purpose of use, it is possible to use the reaction product as it is, but if a higher purity product is required, for example, partition chromatography, adsorption chromatography, solvent fractionation, recrystallization, etc. It may be appropriately purified and used by a known method.

(A-1), (A-2) thus obtained
And (A-3) are thermotropic liquid crystals that maintain a lamellar liquid crystal structure over a wide temperature range as described above, and have good properties as a cosmetic material such as being almost uniformly dispersed as a lamellar liquid crystal when mixed with water. Having.

The component (A) can be used alone or in combination of two or more kinds.
It is preferable to add 1 to 80% by weight, particularly 0.1 to 60% by weight.

The silicones of the component (B) used in the present invention include, for example, the following (B-1) to (B-1)
(B-11). (B-1) Dimethylpolysiloxane represented by the following formula (11)

[0053]

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(Where d is a number of 3 to 20,000) (B-2) Methylphenylpolysiloxane represented by the following formula (12-1) or (12-2)

[0055]

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(Where e ₁ is a number from ₁ to 20,000, e
₂ and e ₃ represent numbers whose sum is 1 to 500. (B-3) Amino-modified silicone represented by the following formula (13-1) or (13-2)

[0057]

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Of these, particularly preferred amino-modified silicones are those represented by the following general formula.

[0059]

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(In the formula, R ⁶ , f ₁ and f ₂ have the above-mentioned meanings.) Further, typical amino-modified silicones in the present invention are represented by the following general formula, and have an average molecular weight of about 3,000 to 100,000, which is the name of Amodimethicone, CTFA Dictionary (Cosmetic Ingre, USA)
dient Dictionary), 3rd edition.

[0061]

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(In the formula, f ₁ and f ₂ have the above-mentioned meanings.) The above-mentioned amino-modified silicone is preferably used as an aqueous emulsion. The aqueous emulsion is, for example, Japanese Patent Publication No. 56-38609. In accordance with the method described in Japanese Patent Application Publication No. H10-264, a cyclic diorganopolysiloxane and an organodialkoxysilane having an aminoalkyl group and a hydroxyl group, a hydroxyalkyl group, an oxyalkylene group or a polyoxyalkylene group are converted into a quaternary ammonium salt system. It is obtained by emulsion polymerization in the presence of a surfactant and water.

When the amino-modified silicone is used as an aqueous emulsion, the amount of the amino-modified silicone contained in the aqueous emulsion is usually 20 to 60% by weight, preferably 30 to 50% by weight. .

Preferred commercially available amino-modified silicone aqueous emulsions include SM 8702C (manufactured by Toray Silicone Co., Ltd.) and DC 929 (manufactured by Dow Corning Co., Ltd.).

(B-4) Fatty acid-modified polysiloxane represented by the following formula (14)

[0066]

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Wherein g ₁ , g ₂ and g ₃ are 1 to 350
And g ₄ represents a number from 0 to 10, and R ¹² represents C _n1 H
_2n1 + ₁ indicating the (n 1 = 9~21). (B-5) Alcohol-modified silicone represented by the following formula (15-1) or (15-2)

[0068]

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Wherein h ₁ and h ₂ are each _{1 to} 500
(Preferably 1 to 200), and R ¹³ is C _n2 H
_2n2 shows the (n ₂ = 0~4). (B-6) an aliphatic alcohol-modified polysiloxane represented by the following formula (16):

[0070]

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[0071] Here, R ¹⁴ represents a methyl group or a phenyl group, i ₁ represents an integer of 1 to 3000, i ₂ and i ₃ represents an integer which is a _{i 2 + i 3 = 1~500,} R 15
Represents an alkyl group having 1 to 28 carbon atoms (preferably having 12 to 22 carbon atoms), and i ₄ represents an integer of 0 to 6. (B-7) The following formulas (17-1), (17-2), and (17)
-3) or polyether-modified silicone represented by (17-4)

[0072]

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(B-8) Epoxy-modified silicone represented by the following formula (18)

[0074]

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Wherein k ₁ is ₁ to 500 (preferably 1
The number of ~250), k ₂ is 1 to 50 (preferably 1 to 3
0) and R ¹⁷ represents an alkylene group having 1 to 3 carbon atoms. (B-9) Fluorine-modified silicone represented by the following formula (19)

[0076]

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Wherein l is 1 to 400 (preferably 1 to 400)
250). (B-10) Cyclic silicone represented by the following formula (20)

[0078]

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(Wherein m represents a number of 3 to 8, and R ¹⁸ represents an alkyl group having 1 to 3 carbon atoms.) (B-11) The following formula (21-1) or (21-2) Alkyl-modified silicone represented by

[0080]

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[Wherein o ₁ and o ₂ each represent _{1 to} 500
(Preferably 1 to 200), and R ¹⁹ has 2 carbon atoms.
To 18 alkyl groups, R ²⁰ is C _n3 H _2n3 (n ₃ = 0 to
4) and R ²¹ represents an alkyl group having 10 to 16 carbon atoms. ]

In these silicones, rinsing,
In the case of a hair cosmetic of a rinsing and rinsing type such as a conditioner, the above (B-1) [in the formula (11), d can be selected from 3 to 20,000 depending on the purpose of the finished feeling. The type is 100-100
0 is preferable], (B-3), (B-6), (B-
7) and (B-10) are preferred. In the case of hair cosmetics of the type without soot such as hair cream, styling lotion, and styling mousse, the above (B-1) [for the purpose of reducing oiliness,
In formula (11), those in which d is 2,000 to 8,000 are preferred], (B-2), (B-3), (B-7) and (B-
10) is preferred.

The total amount of the silicone (B) is 0.01 to 30% by weight, especially 0.1 to 30% by weight in the cosmetic of the present invention.
20% by weight is preferred.

In order to further increase the effect 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. Particularly, for a skin cosmetic, a nonionic surfactant is used. The agent is an anionic surfactant, a nonionic surfactant and an amphoteric surfactant for skin and hair cleansing agents, and a cationic surfactant for hair cosmetics such as hair rinses and hair styling agents. 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, sucrose fatty acid ester,
Higher fatty acid alkanolamides and the like can be mentioned, and typical examples of the cationic surfactant include a quaternary ammonium salt. The quaternary ammonium salt is preferably used as long as it is generally used in cosmetics. In particular, a branched chain represented by the following general formulas (22) and (23) described in JP-A-61-267505 is preferred. It is preferable to contain one or more quaternary ammonium salts.

[0085]

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[0086]

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Examples of the anionic surfactant include linear or branched alkylbenzene sulfonates, alkyl or alkenyl sulfates, alkyl or alkenyl ether sulfates to which ethylene oxide and / or propylene oxide are added, olefin sulfonates, Alkane sulfonate, saturated or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate to which ethylene oxide and / or propylene oxide is added, α-sulfo fatty acid salt ester, amino acid type surfactant, phosphate type surfactant , Sulfosuccinic surfactants, taurine surfactants, amide ether sulfate surfactants and the like, and the amphoteric surfactants include sulfonic acid amphoteric surfactants, betaine amphoteric surfactants and the like. . These surfactants constitute 0.01 to 30 in the total composition.
% By weight, preferably 0.1 to 10% by weight.

The cosmetic of the present invention may further comprise, if necessary, components usually used in cosmetics, pharmaceuticals, foods and the like, for example, higher alcohols having a linear or branched alkyl or alkenyl group; Hydrocarbons such as liquid paraffin, petrolatum, solid paraffin; lanolin derivatives such as liquid lanolin and lanolin fatty acids; phospholipids such as lecithin; sterols and derivatives thereof such as cholesterol; collagen-degrading peptide derivatives; perfluoropolyethers; Fats and oils such as higher fatty acid esters, higher fatty acids, and long-chain amidoamines having an alkyl or alkenyl group; animal and vegetable fats and oils such as mink oil and olive oil; pharmacologic agents such as anti-dandruff agents, bactericides, and vitamins; Preservatives such as water-soluble polymers; thickeners such as water-soluble polymers; coloring agents such as dyes and pigments; Absorbents; propylene glycol,
Humectants such as glycerin, carbitol, 3-methyl-1,3-butanediol, and sugars; astringents; fragrances;
In addition, Encyclopedia of Conditioning Rinsing Ingredients [ENCYCLOP
EDIA OF CONDITIONING RINS
E INGREDIENTS (MICELLE PRE
SS, 1987)] and Encyclopedia of Shampoo Ingredients [ENCYCLOP
EDIA OF SHAMPOO INGREDEN
TS (MICELLE PRESS, 1985)],
Components listed in the latest Cosmetic Science (Yakuji Nippo, 1988) can be appropriately blended as long as the effects of the present invention are not impaired.

The cosmetic of the present invention can be produced according to a usual method, for example, a basic cosmetic such as an oil-in-water type, a water-in-oil type emulsified cosmetic, an oil-based cosmetic, and a makeup cosmetic such as a lipstick and a foundation. Shampoo, hair rinse, hair treatment, hair cream, styling lotion, styling mousse, conditioning mousse, hair spray, hair liquid, styling gel, etc .; hair cosmetics; skin cream, skin milk, skin lotion And the like, and can be applied to bath agents and the like.

[0090]

The cosmetic composition of the present invention has an excellent moisturizing effect due to the synergistic action of the components (A) and (B), has a low oily feeling and has good spreadability, and especially when applied to hair when wet. It has the characteristic of less squeaky feeling and good smoothness,
Further, the emulsion stability is good.

[0091]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 82 g of pentaerythritol, dimethyl sulfoxide 2
In a 500 ml flask, 00 g and 1 g of sodium hydroxide were heated and melted at 105 ° C., dried nitrogen gas was blown in, and about 20 g of water and dimethyl sulfoxide were distilled off to remove water in the reaction system. To this, 39 g of isostearyl glycidyl ether was added dropwise over 1 hour.
The reaction was carried out with stirring at 05 ° C for 4 hours. After the reaction,
1.5 g of acetic acid was added to the reaction mixture to neutralize the catalyst, dimethyl sulfoxide was completely distilled off under reduced pressure at 80 ° C., and 99% ethanol was added to the residue, and unreacted pentaerythritol precipitated was filtered off. did. Ethanol was distilled off from the obtained filtrate under reduced pressure, and water was added to the residue.
The mixture was extracted with ethyl acetate, and the solvent was distilled off from the ethyl acetate-soluble fraction to obtain 63 g of a pale yellow adduct of pentaerythritol / isostearylglycidyl ether. This crude product was separated and purified using silica gel column chromatography with an elution solvent of acetone: hexane = 2: 1.
The desired 1 mol adduct of pentaerythritol / isostearyl glycidyl ether was eluted, and the eluted fractions were collected and the solvent was distilled off to obtain 16 g of the desired 1 mol adduct of pentaerythritol / isostearyl glycidyl ether ( Yield 30%). Hydroxyl value 482 (calculated value 486) NMR (CDCl ₃ ): δ (ppm) 3.95 (1H, m, —OCH ₂ —C H OH—CH ₂ O—), 3.67 (6H, s, —C (C H ₂₎ OH) ₃ ),
_{3.46 (8H, m, -OCH 2} -), 1.30~1.59 (29H, b, -CH 2 -, - CH -), 0.8
8 (6H, m, -CH ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200-3400 ν _OH (stretch) (-CH-,-CH ₂ -,-CH ₃ ) 2850,2920 ν _OH (deformation) (-CH-,-CH ₂ -,-CH ₃ ) 1375,1460 ν _CO (-CO-) 1110,1035,1010

Synthesis Example 2 91 g of sorbitol, 100 g of N-methylpyrrolidone and 1 g of sodium hydroxide were placed in a 300 ml flask, and
The mixture was dissolved by heating to 00 ° C., and dry nitrogen gas was blown thereinto to distill out about 10 g of water and N-methylpyrrolidone to remove water in the reaction system. After 33 g of isostearyl glycidyl ether was added dropwise thereto over 2 hours, the mixture was reacted at 110 ° C. with stirring for 4 hours. After the completion of the reaction, 1.5 g of acetic acid was added to the reaction mixture to neutralize the catalyst.
Methylpyrrolidone was completely distilled off at 80 ° C., 500 g of acetone was added to the residue, and unreacted sorbitol precipitated was separated by filtration. Acetone was distilled off from the obtained filtrate under reduced pressure to obtain 42 g of a crude product of an adduct of sorbitol / isostearylglycidyl ether. When this crude product is separated and purified using silica gel column chromatography with an elution solvent of chloroform: methanol = 5: 1, the desired 1 mol adduct of sorbitol / isostearylglycidyl ether is eluted. The solvent was distilled off, and the desired sorbitol / isostearyl glycidyl ether 1 mol adduct 20 g was collected.
(39% yield). Hydroxyl value 664 (calculated value 663) NMR (CDCl ₃ ): δ (ppm) 3.95 to 3.94 (15H, m, —O—CH ₂ —, O—CH—), 1.34 to 1.58 (29H, b,
-CH ₂ -,-CH-), 0.86 (6H, m, -CH ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200 ~ 3400 ν _OH (stretch) (-CH-,-CH ₂ -,-CH ₃ ) 2840,2910 ν _OH (deformation) (-CH-,-CH ₂ -,-CH ₃ ) 1370,1455 ν _CO (-CO-) 1030 ~ 1110

Synthesis Example 3 Methyl glucoside 97 g, dimethyl sulfoxide 200
g and 1 g of sodium hydroxide were placed in a 500 ml flask and dissolved by heating to 105 ° C., and water and dimethyl sulfoxide were distilled out by blowing dry nitrogen gas to remove water in the reaction system. After 33 g of isostearyl glycidyl ether was dropped into the flask over 4 hours, the mixture was reacted at 105 ° C. with stirring for 5 hours.
After completion of the reaction, 1.5 g of acetic acid was added to the reaction mixture to neutralize the catalyst, and dimethyl sulfoxide was removed at 80 ° C. under reduced pressure.
Then, 99% ethanol was added to the residue, and the unreacted methyl glucoside precipitated was filtered off.
After ethanol was distilled off from the obtained filtrate under reduced pressure, 500 ml of water and 500 ml of ethyl acetate were added to the residue, and the mixture was extracted with ethyl acetate. The solvent was distilled off from the ethyl acetate-soluble fraction to give pale yellow methyl glucoside / isopropyl. 49 g of a crude product of an adduct of stearyl glycidyl ether was obtained. When this crude product is separated and purified using silica gel column chromatography, the desired 1 mol adduct of methyl glucoside / isostearyl glycidyl ether is eluted with an elution solvent of acetone: hexane = 4: 1. The eluted fractions are collected, the solvent is distilled off, and the target methyl glucoside
1 mole adduct of isostearyl glycidyl ether 16
g was obtained. Hydroxyl value 436 (calculated value 432) NMR (CDCl ₃ ): δ (ppm) 4.75 (1H, d, —OC H —OCH ₃ ), 3.95 (1H, m, —OCH ₂ —C H OH—CH ₂ O— ),
3.77 to 3.35 (12H, m, -OC H ₂ -,-OC H- ), 3.24 (3H, s, -OCH ₃ ), 1.
30 ~ 1.59 (29H, b, -C H ₂ -,-C H- ), 0.85 (6H, m, -C H ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200 ~ 3400 ν _OH (stretch) (-CH-,-CH ₂ -,-CH ₃ ) 2840,2915 ν _OH (deformation) (-CH-,-CH ₂ -,-CH ₃ ) 1375,1460 ν _CO (-CO- ) 1110,1035,1005

Synthesis Example 4 A 300 ml flask was charged with 69 g of maltitol, 400 g of N-methylpyrrolidone and 2 g of sodium hydroxide.
The mixture was heated to 10 ° C. for dissolution, and dry nitrogen gas was blown thereinto to distill out about 10 g of water and N-methylpyrrolidone to remove water in the reaction system. After 38 g of 2-decyltetradecylglycidyl ether was added dropwise to the reaction solution over 2 hours, the mixture was reacted at 110 ° C. for 4 hours with stirring. After completion of the reaction, 5 g of phosphoric acid was added to the reaction mixture to neutralize the catalyst, and then N-methylpyrrolidone was completely distilled off at 80 ° C. under reduced pressure, and 500 g of acetone was added to the residue to precipitate. Unreacted maltitol was filtered off. From the obtained filtrate, acetone was distilled off under reduced pressure to obtain 83 g of a crude product of an adduct of maltitol-2-decyltetradecylglycidyl ether. When this crude product is separated and purified using silica gel column chromatography, the desired 1 mol adduct of maltitol 2-decyltetradecylglycidyl ether is eluted with an elution solvent of chloroform: methanol = 2: 1. The eluted fractions were collected and the solvent was distilled off to obtain 20 g of a 1 mol adduct of maltitol 2-decyltetradecylglycidyl ether. Hydroxyl value 663 (calculated value: 670) NMR (CDCl ₃ ): δ (ppm) 4.90 (1H, d, —OC H —OCH ₃ ), 3.96 (1H, m, —OCH ₂ —C H OH—CH ₂ O— ),
3.78 to 3.42 (20H, m, -OC H ₂ -,-OC H- ), 1.30 to 1.59 (41H, b, -C
H ₂ -,-C H- ), 0.81 (6H, m, -C H ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200 ~ 3400 ν _OH (stretch) (-CH-,- (CH ₂ -,-CH ₃ ) 2830,2910 ν _OH (deformation) (-CH-,-CH ₂ -,-CH ₃ ) 1370,1450 ν _CO (-CO-) 1030,1110

Synthesis Example 5 Methyl isostearate (29.9) was placed in a 1-liter reaction vessel equipped with a distillation cooling tube equipped with a thermometer, a stirrer, and a pressure reducing device.
g (0.1 mol), 68 g of pentaerythritol (0.
5 mol), 1.9 g of a 28% sodium methylate / methanol solution and 450 ml of dimethylformamide.
2.5 at 100 ° C and 100-120mmHg
A time reaction was performed. During this reaction, about 100 ml of dimethylformamide distilled out of the reaction system. After cooling the contents of the reaction, about 400 ml of water was added and the layers were separated. After ether was added to the lower layer for extraction, the ether layer was added to the upper layer separated first, and washed three times with 200 ml of water each time. After removing the ether under reduced pressure, crude pentaerythritol monoisostearate having a purity of 77% was obtained (yield 70).
%). This was purified by thin-layer chromatography using silica gel chromatography (ethyl acetate / ethanol) until a single spot was obtained, to obtain 21 g of pentaerythritol monoisostearate (yield: 50%) (purity: 94%). IR (liquid ^{film) cm -1: 3450 (OH)} , 2840~2950 (CH), 1720 (C = O), 1640 (CH), 1040 (CO) 1 H-NMR (CDCl 3) δppm:

[0097]

Embedded image

4.1 [(c), 2H], 3.6 [(b), 6H], 3.3 [(a), 3H], 2.
4 [(d), 2H], 1.1-1.7 [(e), 27H], 0.9 [(f), 6H]

Synthesis Example 6 (1) 160 g (0.88 mol) of glucose and 956 g (8.8 g) of 3-chloro-1,2-propanediol were placed in a reactor.
8 mol) and Dowex 50WX8 (H
(Mold, 50-100 mesh), and the mixture was heated to 60 ° C. with stirring and reacted for 16 hours. After the reaction,
3 unreacted under reduced pressure by filtration through a glass filter
-Chloro-1,2-propanediol was distilled off. The obtained residue was washed with 500 g of acetone three times in total, and then dried under reduced pressure to obtain 3-chloro-2-hydroxy-1-O-.
79 g of glucosylpropane was obtained (33% yield). (2) In the reactor, 83 g (0.3 mol) of 3-chloro-2-hydroxy-1-O-glucosylpropane obtained in (1).
And 47 g (0.15 mol) of sodium isostearate, 1.0 g of tetrabutylammonium bromide and 200 ml of dimethylformamide, and the mixture was heated to 100 ° C. with stirring and reacted for 8 hours. After completion of the reaction, dimethylformamide was distilled off under reduced pressure. 300 g of water and 600 g of ethyl acetate were added to the obtained residue, and the mixture was vigorously shaken and allowed to stand to collect an ethyl acetate layer. Ethyl acetate was distilled off under reduced pressure to obtain a crude product. The crude product was further purified by silica gel chromatography (chloroform / methanol = 10: 1) to give 3-O-isostearoyl-
14 g of 1-O-glucosylglycerol was obtained (isolation yield: 26%).

[0100]

Embedded image

¹ H-NMR (CDCl ₃ ) δ (ppm, based on TMS): 0.79 to 1.03 (t, 6H), 1.11 to 1.45 (broad, 25H), 1.56 (broad,
2H), 2.33 (broad, 2H), 3.23 to 4.39 (m, 11H), 4.88 (broad, 1
H) IR (liquid film) cm ^-1 : 3400, 2950-2860, 1740, 1650, 1470, 1390-950 Mass spectrometry (FAB ionization method) m / z: 521 (M + H) ⁺

Synthesis Example 7 82 g of pentaerythritol, dimethyl sulfoxide 2
In a 500 ml flask, 00 g and 1 g of sodium hydroxide were heated and melted at 105 ° C., dried nitrogen gas was blown in, and about 20 g of water and dimethyl sulfoxide were distilled off to remove water in the reaction system. To this, 39 g of isostearyl glycidyl ether was added dropwise over 1 hour.
The reaction was carried out with stirring at 05 ° C for 4 hours. After the reaction,
1.5 g of acetic acid was added to the reaction mixture to neutralize the catalyst, dimethyl sulfoxide was completely distilled off under reduced pressure at 80 ° C., and 99% ethanol was added to the residue, and unreacted pentaerythritol precipitated was filtered off. did. Ethanol was distilled off from the obtained filtrate under reduced pressure, and water was added to the residue.
The mixture was extracted with ethyl acetate by adding 500 ml of ethyl acetate, and the solvent was distilled off from the ethyl acetate-soluble fraction to obtain 63 g of a crude product of a pale yellow adduct of pentaerythritol / isostearylglycidyl ether. When gel permeation chromatography was performed on the crude product,
A monoether having 1 mol of isostearyl glycidyl ether added to pentaerythritol, a diether having 2 mol added, a triether having 3 mol added, and 4
It was confirmed that the mixture was a mixture of mole-added tetraethers, and from the peak area ratios, the composition ratios of the monoether, diether, triether and tetraether were 77%, 19% and 3%, respectively. % And 1%. Hydroxyl value 438 IR (liquid film) cm ^-1 : ν _OH (-OH) 3200-3400 ν _OH (stretch) (-CH-, -CH _2- , -CH ₃ ) 2850,2920 ν _OH (deformation) ( -CH-,-CH ₂ -,-CH ₃ ) 1375,1460 ν _CH (-CO-) 1110,1035,1010

Test Example 1 For the nonionic amphiphilic compound obtained in the synthesis example,
The properties at room temperature (25 ° C.) and 55 ° C. and the dissolved state in aqueous systems (concentration: 5% by weight) were examined. Table 1 shows the results. (Evaluation method) The properties at 25 ° C and 55 ° C were examined by a polarizing plate, a polarizing microscope, X-ray diffraction, DSC and the like. The dissolved state in the aqueous system is as follows: 1 g of a sample is collected in a 30 ml sample bottle, ion-exchanged water is added to the sample bottle so that the sample concentration becomes 5% by weight, and the mixture is repeatedly heated and stirred to obtain a uniform mixture. The dissolved state was examined by the method described above.

[0104]

[Table 1]

Example 1 A hair oil having the composition shown in Table 2 was produced, and its performance and storage stability were examined. Table 2 shows the results. (Manufacturing method) Each component is heated to 70 ° C. to dissolve and stir.
After mixing, the mixture was cooled to room temperature with stirring to obtain a hair oil. (Evaluation method) Performance evaluation Cold-permed Japanese female hair 20g
(Length 15 cm), the hair bundle was washed with a commercially available shampoo containing an anionic activator as a main component, and towel-dried. 0.02 g of the hair oil shown in Table 2 was uniformly applied, and the wet hair bundle was organoleptically evaluated for stretchability, familiarity, less moist feeling and less oiliness, and brushability in a dry state. The evaluation criteria were ◎ for particularly excellent, ○ for good, △ for ordinary, and × for poor.

Storage stability A 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, aggregation, etc. are recognized.

[0107]

[Table 2]

Example 2 Hair treatment composition:

[Table 3] (1) 2-dodecylhexadecyltrimethylammonium chloride 1.5 (% by weight) (2) Stearyltrimethylammonium chloride 1.0 (3) Dimethylpolysiloxane [where d = 1000] in the formula (11) 1 5.5 (4) Cetostearyl alcohol 3.0 (5) 1 mol adduct of pentaerythritol glyceryl / isostearyl glycidyl ether (Synthesis Example 1) 3.0 (6) Liquid paraffin 3.0 (7) Hydroxyethyl cellulose (1) % Aqueous solution viscosity 8000cp) 0.5 (8) Polyoxyethylene oleyl ether (EO = 5) 0.5 (9) Methyl paraben 0.2 (10) Fragrance 0.4 (11) Water balance

Example 3 Conditioning Mousse Composition:

TABLE 4 (1) di-2-hexadecyl dimethyl ammonium chloride 0.5 (wt%) (2) methylphenyl polysiloxane [(12-2) _{wherein, e 2 = 190, e 3} = 10 ] 1. 0 (3) isotridecyl myristate 1.0 (4) 3-methyl-1,3-butanediol 1.0 (5) liquid paraffin 2.5 (6) 1 mol adduct of methyl glucoside / isostearyl glycidyl ether ( Synthesis Example 3) 3.0 (7) 95% ethanol 5.0 (8) Methylparaben 0.1 (9) Fragrance 0.1 (10) Water balance

Example 4 Hair Cream Composition:

Table 5 (1) Di-2-hexadecyldimethylammonium chloride 2.0 (% by weight) (2) Cetyltrimethylammonium chloride 1.0 (3) Pentaerythritol monoisostearate (Synthesis example 5) 3.0 4) cetyl alcohol 5.0 (5) amino-modified silicone [(13-1) _{^{wherein, R 4 = CH 3, f}} 1 = 2, f 2 = 1, f 3 = 4, R 5 = CH 3, R ^{_{6 = - (CH 2) 3}} OCH 2 CH (OH) CH 2 N (C 2 H 5) 2, R 7 = OH ] 2.0 (6) Liquid paraffin 3.0 (7) perfume 0.4 (8 ) Water balance

Example 5 Cream composition:

Table 6 Oil phase components: (1) 1 mol adduct of maltitol 2-decyltetradecyl glycidyl ether (Synthesis Example 4) 3.0 (% by weight) (2) Polyether-modified silicone [(17-1) Wherein j ₁ = 25, j ₂ = 4, R ¹⁶ : j ₃ = 3, j ₄ = 10, j ₅ = 0, B = H] 0.5 (3) cetanol 2.0 (4) stearin Acid 3.0 (5) trimethylol isoheptadecane 3.0 (6) lipid (cholesteryl isostearate) 8.0 (7) monolauryl glycerin 2.0 (8) polyoxyethylene (20) sorbitan monolauric acid Ester 2.0 Water phase component: (9) Methyl paraben 0.2 (10) Fragrance 0.1 (11) Water balance

Example 6 Emulsion composition:

Table 7 Oil phase components: (1) 3-O-isostearoyl-1-O-glucosylglycerol (Synthesis Example 6) 3.0 (% by weight) (2) Cetanol 0.5 (3) Vaseline 1.0 (4) polyoxyethylene (10) monooleate 2.0 (5) stearic acid 2.0 (6) dimethylpolysiloxane [where d = 1000] in formula (11) 1.0 Water phase component: (7) ) Methyl paraben 0.2 (8) Fragrance 0.1 (9) Water balance

Example 7 Hair treatment composition:

[Table 8] (1) 2-dodecylhexadecyltrimethylammonium chloride 1.5 (% by weight) (2) Stearyltrimethylammonium chloride 1.0 (3) Dimethylpolysiloxane [In the formula (11), d = 1000] 1 5.5 (4) Cetostearyl alcohol 3.0 (5) Mixture of 1 mol to 4 mol adduct of pentaerythritol glyceryl / isostearyl glycidyl ether (Synthesis Example 7) 3.0 (6) Liquid paraffin 3.0 (7) ) Hydroxyethyl cellulose (1% aqueous solution viscosity 8000 cp) 0.5 (8) Polyoxyethylene oleyl ether (EO = 5) 0.5 (9) Methylparaben 0.2 (10) Fragrance 0.4 (11) Water balance

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-284608 (JP, A) JP-A-63-14705 (JP, A) JP-A-2-160709 (JP, A) JP-A-4- 9309 (JP, A) JP-B 38-5050 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB name) A61K 7/00 A61K 7/06 A61K 7/48

Claims (2)

(57) [Claims] 1. A cosmetic comprising the following components (A) and (B): (A) a nonionic compound having at least one branched alkyl or alkenyl group having 9 to 36 carbon atoms and at least three hydroxyl groups in one molecule, and having a lamellar liquid crystal structure at a temperature exceeding 25 ° C. and 50 ° C. Amphiphilic compounds (B) dimethylpolysiloxane, methylphenylpolysiloxane, amino-modified silicone, fatty acid-modified polysiloxane, alcohol-modified silicone, aliphatic alcohol-modified polysiloxane, polyether-modified silicone, epoxy-modified silicone, fluorine-modified silicone, One or more silicones selected from the group consisting of cyclic silicones and alkyl-modified silicones 2. Component (A) is present in an amount of 0.01 to 80% by weight,
2. The cosmetic according to claim 1, which contains (B) component in an amount of 0.01 to 30% by weight.