JPH0680538A - Hair cosmetic - Google Patents

Abstract

PURPOSE:To obtain a hair cosmetic providing hair with smoothness, flexibility, dry feeling and moist feeling, maintaining these effects for a long period of time after hair washing. CONSTITUTION:A hair cosmetic comprises (A) a high-molecular weight silicone of formula I (R<1> is methyl or phenyl with the proviso that a case wherein R<1> is wholly phenyl is omitted; R<2> is methyl or OH; (n) is 2,000-20,000), (B) a compound selected from B1: a low-molecular weight silicone of formula I wherein (n) is 1-500, B2: a 4-30C isoparaffinic hydrocarbon and B3: a cyclic silicone of formula II ((m) is 3-7), (C) a nitrogen atom-containing silicone compound such as amino-modified silicone compound, (D) a nonionic amphiphatic compound containing at least one long-chain branched alkyl or alkenyl group and at least three hydroxyl groups in the molecule, forming a liquid crystal structure in an aqueous system at 25 deg.C and (E) a compound of formula III [R<3> is H, alkyl or group of formula IV (R<4> is H, methyl or methoxy; R<5> is single bond or 1-3C hydrocarbon group); (p), (q) and (r) are 0-5].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent smoothness on hair,
The present invention relates to a hair cosmetic such as a hair rinse, a hair conditioner, and a hair treatment, which imparts flexibility, a dry feeling, and a moist feeling and maintains these effects for a long time after washing hair.

[0002]

2. Description of the Related Art Conventionally, hair has been given flexibility and wettability,
For the purpose of protecting the hair, improving the feel, and giving an emollient effect, various oil agents have been added to hair cosmetics. Among these oil agents, silicones typified by dimethylpolysiloxane polymers are smooth and have excellent lubricity as compared with higher alcohols, glycerides, liquid paraffins, esters, etc., and have a smooth feel and gloss on hair. It is known to give and is used in many hair cosmetics (JP-A-63-313714, JP-A-1-203314, etc.).

However, such silicones have a drawback in that they are inferior in moisturizing effect, lacking in moisturizing feeling, dryness in hair, and inability to impart flexibility.

In order to solve such drawbacks, hair cosmetics in which silicone or a derivative thereof is combined with a nonionic amphipathic compound having at least one long-chain branched alkyl or alkenyl group in one molecule as a moisturizing agent Have been developed (Japanese Patent Laid-Open No. 4-69321). The hair cosmetic composition has some effect on normal hair, but does not have sufficient sustainability for hair damaged by a perm or hair dye, and after 1 day of treatment, Flexibility,
It had the drawback that the hair would lack moisturization.

[0005] On the other hand, emulsion type cosmetics are widely used because their composition can give appropriate oil and water to the hair, and give a moist feeling to the hair. However, the conventional emulsion-type cosmetics have not been able to give a moist feeling even if a moist feeling can be imparted, and the softening effect is not sustained.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a hair cosmetic composition which imparts smoothness, softness, dryness and moisturizing feeling to the hair, and the effect of which lasts, particularly an emulsion type hair cosmetic composition. To provide.

[0007]

In view of such circumstances, the present inventors have conducted diligent research and as a result, as a result, specific high molecular weight silicone, low molecular weight oil agent, silicone compound containing nitrogen atom, nonionic amphiphilicity The present invention was completed by finding that a hair cosmetic containing a compound and alcohols is a hair cosmetic that solves the above-mentioned problems.

That is, the present invention provides the following component (A),
The present invention provides a hair cosmetic composition containing (B), (C), (D) and (E). (A) One or more high molecular weight silicones represented by the following general formula (1)

[0009]

[Chemical 4]

(In the formula, R ¹ represents a methyl group or a phenyl group, which may be the same or different, except when all of R ¹ are phenyl groups. R ² represents a methyl group or a hydroxyl group. n represents an integer of 2,000 to 20,000), (B) In the general formula (1), n is 1 to 500, a low molecular weight silicone, an isoparaffin hydrocarbon having 4 to 30 carbon atoms, and One or more selected from the cyclic silicones represented by the general formula (2)

[0011]

[Chemical 5]

(Where m is a number from 3 to 7), (C)
A silicone compound containing a nitrogen atom, (D) having at least one long-chain branched alkyl or alkenyl group in one molecule, further having at least three hydroxyl groups, and 25
Nonionic amphipathic compound that forms a liquid crystal structure in a water system at ℃, (E) Compound represented by the following general formula (3)

[0013]

[Chemical 6]

(Wherein R ⁴ represents a hydrogen atom, a methyl group or a methoxy group, and R ⁵ represents a single bond or a saturated or unsaturated divalent hydrocarbon group having 1 to 3 carbon atoms), and Y
And Z represent a hydrogen atom or a hydroxyl group, and p, q and r are 0 to
Indicates an integer of 5. However, except when p = q = r = 0 and Z = H, and when p = q = r = 0 and R ¹ = H and Z = OH].

The high molecular weight silicone of the component (A) used in the present invention is represented by the above formula (1), and n in the formula is used.
Is 2,000 to 20,000, but above all, n is 2,
Particularly preferred is 500 to 8,000 dimethylpolysiloxane.

Among the component (B), the low molecular weight silicone represented by the formula (1) has n in the formula of 1 to 500,
Preferred is dimethylpolysiloxane with n = 4 to 200.

The isoparaffin-based carbon-hydrogen having 4 to 30 carbon atoms has a boiling point of 90 to 90 at atmospheric pressure.
An example is isoparaffinic hydrocarbon in the range of 260 ° C. Specific examples of commercially available products include Nisseki Isozol 300, 400 manufactured by Nippon Petrochemical Co., Ltd., NAS-4 manufactured by NOF Corporation, Pearl Ream 4, IP Solvent 1620, 20 manufactured by Idemitsu Petrochemical Co., Ltd.
28 and the like. The isoparaffin hydrocarbons having 4 to 30 carbon atoms may be used alone or in combination of two or more.

Examples of the silicone compound containing a nitrogen atom as the component (C) include the following. (C-1) Amino-modified silicone polymer An amino-modified silicone polymer which is a polymer of an organosiloxane having at least one aminoalkyl group in one molecule. Among the organosiloxanes forming this amino-modified silicone polymer, those containing a methyl group as a functional group other than an aminoalkyl group are generally used.
In addition, alkyl groups such as ethyl group and propyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group and naphthyl group; cycloalkyl groups such as cyclohexyl group; hydroxy group, hydroxyalkyl group,
An oxyalkylene group or a polyoxyalkylene group can also be included. Typical examples of the aminoalkyl group contained in the amino-modified silicone polymer are represented by the following general formula (4)
Alternatively, it is indicated by (5).

[0019]

[Chemical 7]

Wherein R ⁸ and R ⁹ represent a hydrogen atom or a monovalent hydrocarbon group, a and b represent an integer of 0 to 6, and X
^- represents a halogen ion or an organic anion]

R⁶The divalent hydrocarbon group of
Group, ethylene group, propylene group, butylene group, -CH
₂CH (CH₃) CH₂An alkylene group such as-, (C
H₂) ₂-C₆H_FourAn alkylenearylene group, such as
Among these, alkylene groups, especially propylene,
A len group is preferred. R⁸And R⁹As a monovalent hydrocarbon group of
Are methyl, ethyl, propyl, hexyl, fluorine,
And a phenyl group. Also R⁸And R⁹Both are hydrogen sources
Child or a monovalent hydrocarbon group, R⁸But water
Elementary atom and R⁹May be a monovalent hydrocarbon group. Change
In addition, the preferred values of a and b are a = 0 and b = 1. Hi
A typical example of the droxyalkyl group is the following general formula (6).
Shown.

-R ⁶ OH (6) [wherein R ⁶ has the same meaning as described above] Representative examples of the oxyalkylene group and the polyoxyalkylene group are represented by the following general formula (7).

[0023]

[Chemical 8]

[Wherein R ⁶ has the same meaning as described above, and c
Represents 0 or 1, e represents an integer of 1 to 100, and d
Represents an integer of 1 to 5]

Among the hydroxyalkyl groups represented by the formula (7), preferred are those in which c = 1, e is an integer of 3 to 70, and d is 2 or 3. Where d is 2
Alternatively, the three may be bonded in block or random form. This also applies to other combinations of d integers. A typical amino-modified silicone polymer is represented by the following general formula (8) or (9).

[0026]

[Chemical 9]

[In the formula, R ¹⁰ represents a methyl group or a hydroxy group, and R ¹¹ represents a methyl group or a hydrogen atom. R ¹² represents the aminoalkyl group (4) or (5) described above, and R ¹³
Represents a hydroxy group, a hydroxyalkyl group, an oxyalkylene group, or a polyoxyalkylene group, and f, g,
h represents an integer depending on the molecular weight] Of these, a particularly preferable amino-modified silicone polymer is represented by the following general formula (10).

[0028]

[Chemical 10]

[In the formula, R ¹² represents the above-mentioned aminoalkyl group (4) or (5), g and h represent integers depending on the molecular weight] Further, typical examples of the amino-modified silicone polymer of the present invention The polymer represented by the following general formula (11) has an average molecular weight of a polymer of about 3,000 to 100,000, which is an amodimethicone (Amodimethei).
CTFA dictionary (Cosmeti, USA)
c Ingredient Dictionary) 3rd edition.

[0030]

[Chemical 11]

[Wherein i and j are molecular weights of 3,000 to 1]
Indicates an integer that depends on 0,000]

In the present invention, the amino-modified silicone polymer (C) is preferably used in the form of an aqueous emulsion. This aqueous emulsion is, for example, Japanese Patent Publication No. 56-38.
According to the method described in JP 609, a cyclic diorganopolysiloxane and an organodialkoxysilane having an aminoalkyl group and a hydroxy group, a hydroxyalkyl group, an oxyalkylene group or a polyoxyalkylene group are used as a quaternary ammonium salt system. It is obtained by emulsion polymerization in the presence of a surfactant and water. As a commercially available product of such an aqueous emulsion, SM8702C (Tore
Silicone Co., Ltd., DC929 (Dow Corning Co., Ltd.), etc. are mentioned.

The component (C) has an affinity for the damaged part of the hair and has a function of protecting the damaged part. When used in combination with the components (A) and (B), a uniform film is formed on the surface of the hair, so that it gives a dry feel to the surface and retains the moisture inside the hair. Furthermore, of the (C) component,
The amino-modified silicone has a high affinity not only with the components (A) and (B) but also with the components (D) and (E), and has the action of further enhancing such effects.

The amino-modified silicone compound represented by the above formulas (4) to (11) can be quaternized by a conventional method to obtain a quaternized amino-modified silicone compound.
This exhibits the same action as the above amino-modified silicone.

The nonionic amphipathic compound of the component (D) used in the present invention is an aqueous system at room temperature (25 ° C.)
It forms a lamellar or liquid crystal structure. Here, the confirmation of the liquid crystal structure can be performed by, for example, The Journal of Cell
Biology (The Journal of Cel
l Biology), Volume 12, pages 207 to 209 and surface, Volume 11, Volume 10, pages 579 to 590 using an X-ray diffraction and a differential scanning calorimeter (DSC). You can Examples of compounds having such properties include the following (D-1) to (D-6).

(D-1) Glycerylated polyols represented by the following general formula (12). A _k (G) (12) [wherein, G represents a residue obtained by removing k hydroxyl groups from a polyol selected from pentaerythritol, sorbitol, maltitol, glucose, fructose and alkyl glycosides, and A represents

[0037]

[Chemical 12]

And / or

[0039]

[Chemical 13]

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

(D-2) A methyl-branched fatty acid ester represented by the following general formula (13).

[0042]

[Chemical 14]

[In the formula, l and s each represent an integer of 0 to 20, and the sum of l and s is 6 to 20]

(D-3) Branched fatty acid glyceroglycolipid represented by the following general formula (14)

[0045]

[Chemical 15]

General formula (12) showing the component (D-1)
Examples of the alkyl glycoside represented by G include methyl glucoside, ethyl glucoside, propyl glucoside,
Examples include octyl glucoside, methyl maltoside, ethyl maltoside and the like. Further, as B, the carbon number is 16 to
36, especially 18 to 24 branched alkyl groups are preferred. As the branched alkyl group B, the following general formula (15) is used.

[0047]

[Chemical 16]

(Wherein x and y each represent an integer of 0 to 20, and the sum of x and y is 6 to 20), or the following general formula (16)

[0049]

[Chemical 17]

A group represented by the formula (wherein α and β each represent an integer of 0 to 18 and the sum of α and β is 4 to 18) is preferable. Preferred examples of these branched alkyl groups include methylpentadecyl group, methylhexadecyl group, methylheptadecyl (isostearyl) group, methyloctadecyl group, methylbehenyl group, ethylhexadecyl group, ethyloctadecyl group, ethylbehenyl group. , Butyldodecyl group, butylhexadecyl group, butyloctadecyl group, hexyldecyl group, heptylundecyl group, octyldodecyl group, decyldodecyl group, decyltetradecyl group, dodecylhexadecyl group, tetradecyloctadecyl group and the like. In general formula (12), k
Is particularly preferably 1 or 2.

Such glycerylated polyols (12)
Is produced, for example, by reacting a polyol with a corresponding branched alkyl glycidyl ether in the presence of a basic catalyst according to the following formula.

[0052]

[Chemical 18]

[In the formula, A, k, G and B have the above-mentioned meanings]

The reaction molar ratio between the polyol and the branched alkyl glycidyl ether (17) in this reaction can be appropriately selected depending on the degree of etherification of the desired glycerylated polyol. For example, in order to obtain a desired glycerylated polyol having a high content of 1 mol adduct, it is usually necessary to use the polyol in excess at a ratio of 1.2: 1.0 to 10.0: 1.0. Considering the production amount of the 1-mol adduct and the recovery of the polyol, 1.
A ratio of 5: 1.0 to 5.0: 1.0 is preferable. Also,
In order to obtain the desired product having a high content of 2 mol adduct of glycerylated polyol, it is usually 0.3: 1.0 to 1.1:
The branched alkyl glycidyl ether may be used in excess at a ratio of 1.0, and a ratio of 0.4: 1.0 to 0.8: 1.0 is preferable in consideration of the production amount of the 2 mol adduct.

The reaction is usually carried out without a 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 the organic solvent include dimethyl sulfoxide, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, etc.
It is preferable to use 0 times the amount.

As the catalyst, an acid or basic catalyst generally known as an epoxy group reaction catalyst can be used. When an acid catalyst is used, a side reaction is
It is not preferable because a decomposition reaction of the ether bond or a dehydration reaction of the hydroxyl group of the generated glycerylated polyols occurs.
It is preferable to use a basic catalyst. The basic catalyst used is not particularly limited, but sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, sodium hydride and the like can be mentioned from the viewpoint of reactivity and economy. These basic catalysts are contained in an amount of 0.01 to 20.0% by weight, particularly 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 80
It is carried out at ˜150 ° C. If the reaction temperature is less than 50 ° C, the reaction rate is slow, and if it exceeds 200 ° C, the product is colored, which is not preferable.

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

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

The glycerylated polyols (12) used in the present invention are usually polyols in addition to 1 mol adduct of 1 molecule of a polyol 1 molecule branched alkyl glycidyl ether (17) and 2 mol adduct of 2 molecules added. 1
It is obtained as a mixture of polymorphic adducts in which 3 or more molecules of branched alkyl glycidyl ether (17) are added to the molecule. The glycerylated polyols (12) thus obtained are usually those 1 mol adducts, 2 mol adducts,
Alternatively, it is used as a mixture of polymorphic adducts, but if there is a problem in terms of performance or blending with a product, it can be purified using a known purification method such as a silica gel column or solvent extraction. Glycerylated polyols (12)
May contain an unreacted glycoside in addition to the desired 1-mole adduct, 2-mole adduct, or polymole adduct. Such unreacted glycoside can be used as it is, if there is no practical problem,
If there is a problem, it can be removed by a method using a two-layer extraction solvent system using an organic solvent such as ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, chloroform, or a known purification method such as Smith thin film distillation. it can.

In the general formula (13) representing the methyl branched fatty acid ester, the sum of l and s is 6 to 20, but preferably 10 from the viewpoint of performance as a cosmetic material.
-16, particularly preferably 14. The branched methyl group is particularly preferably located near the center of the alkyl main chain.

The methyl branched fatty acid ester (13) is produced according to the following reaction formula.

[0063]

[Chemical 19]

[Wherein, l and s have the same meanings as described above and R ¹⁵ represents a lower alkyl group], that is, the lower alkyl ester (18) of a methyl branched fatty acid is reacted with pentaerythritol (19). By this, the target compound (13) is produced.

The lower alkyl ester (18) 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 a mixture having a constant distribution of the total carbon number of the alkyl group and the position of the branched methyl group, and for example, a by-product during the production of oleic acid dimer. The isostearic acid having a methyl branch obtained as above contains about 75% or more of those having a total carbon number of 18 (the sum of m and n is 14), and the balance having a total carbon number of 14, 16, 16 and 20. The branched methyl group is located approximately in the center of the alkyl backbone [J. Amer. Oil Chem. So.
c. ) Vol. 51, 522 (1974)].

In this reaction, the lower alkyl ester of methyl-branched fatty acid (18) and pentaerythritol (19) used are in a molar ratio of (18) / (19) = 1.
It is preferably / 1 to 10/1.

The solvent used in this reaction is not particularly limited, but a lower alkyl ester of methyl branched fatty acid (1
It is preferable to dissolve both 8) and pentaerythritol (19), and for example, dimethylformamide and the like are preferably used.

As the reaction catalyst, an alkali catalyst is usually used, and sodium methylate or the like is preferably used. The catalyst amount is not particularly limited, but it is preferably used in the range of 0.1 to 20 mol% with respect to the lower alkyl ester (18) of methyl branched fatty acid. The reaction temperature of this reaction is selected from the range of 60 to 150 ° C.

The compound (13) can be isolated from the reaction mixture by a conventional method, for example, solvent removal, recrystallization, chromatography and the like, alone or in combination.

Further, in the general formula (14) showing the branched fatty acid glyceroglycolipid, t and u have the same sum of 1 as 1 and s from the viewpoint of performance as a cosmetic material.
It is preferably from 0 to 16, especially from 14, and from the same viewpoint, the sum of v and w is preferably from 6 to 14, particularly from 8 to 12.

The branched fatty acid glyceroglycolipid (14) is produced, for example, according to the following reaction formula.

[0072]

[Chemical 20]

That is, the fatty acid (2
Compound (14) is obtained by reacting 1).

Compound (20) used in this method
Can be easily produced by a known method such as a reaction of a monosaccharide or oligosaccharide with glycerol monohalohydrin or glycerol dihalohydrin or epihalohydrin.

The compound (21) 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. Examples of the cation group represented by M in the compound (21) include alkali metal, ammonium group, alkylammonium group, trialkanolamine and the like.

To carry out this method, for example, the compound (20) and the compound (21) may be reacted at a temperature of 30 to 150 ° C, preferably 70 to 120 ° C. The amount of the compound (21) used here is usually the compound (20).
To 0.3 to 3.0 times mol, particularly preferably 1.
It is 0 to 2.0 times mol. When M of compound (21) 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 this reaction, a polar solvent can be used for the purpose of promoting the mixing of the compound (20) and the compound (21) and allowing the reaction to proceed smoothly. The polar solvent used here is at least one selected from dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, pyridine, water and the like. The amount of polar solvent used may be selected appropriately. Further, in carrying out this reaction, a phase transfer catalyst can be used for the purpose of promoting this reaction, if necessary. The amount of the phase transfer catalyst used here may be appropriately selected, but is usually 0.1 to 10 mol% with respect to the compound (21). Examples of the phase transfer catalyst used here include 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-dodecyl ammonium 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-
Mention may be made of tetraalkylammonium chlorides such as N, N-dioctadecyl ammonium chloride.

The reaction product of the above reaction contains the desired glyceroglycolipid (14), an inorganic salt as a by-product, an unreacted compound (20) or (21) and the like. There is. Therefore, although the reaction product can be used as it is depending on the purpose of use, when a higher purity product is required, for example, partition chromatography, adsorption chromatography, solvent fractionation method, recrystallization method, etc. It may be appropriately purified by a known method before use.

(D-4) Trimethylol derivative represented by the following general formula (22)

[0080]

[Chemical 21]

(In the formula, R ¹⁶ represents a branched chain alkyl or alkenyl group having 12 to 22 carbon atoms) (D-4), and a trimethylol derivative represented by the following general formula (23) is preferable.

[0082]

[Chemical formula 22]

Trimethylol represented by the formula (γ and δ each represent an integer of 0 to 19 and the sum of γ and δ is 9 to 19) is preferable. Further, those having a sum of γ and δ in the general formula (23) of 11 to 15 are preferable, and trimethylolisoheptadecane having a sum of γ and δ of 13 is particularly preferable. The branched methyl group is preferably near the center of the alkyl main chain.

The trimethylol derivative (22) is described in JP-A-1.
It can be produced by the method described in JP-A-283235.

(D-5) Trimethylol derivative represented by the following general formula (24)

[0086]

[Chemical formula 23]

(In the formula, R ¹⁷ represents a branched chain alkyl group or alkenyl group having 11 to 27 carbon atoms)

Among the trimethylol derivatives (24), those in which R ¹⁷ in the formula is a group represented by the following general formulas (25) and (26) are preferable.

[0089]

[Chemical formula 24]

(Wherein, ε and ζ each represent an integer of 0 to 24, the sum of ε and ζ is 8 to 24, and R ¹⁸ and R
¹⁹ each represents an alkyl group having 2 to 12 carbon atoms)

[0091] Also, particularly preferred R ^17, include alkyl groups branched 13-19 carbon atoms, the sum of the general formula (25), epsilon and ζ is the more preferred R ¹⁷ 10
The most preferable one is an isostearyl group whose sum of ε and ζ is 14.

The trimethylol derivative represented by the general formula (24) is produced, for example, according to the following reaction formula.

[0093]

[Chemical 25]

[Wherein R ¹⁷ is the same as above], that is, a branched fatty acid (27) is reacted with tris (hydroxymethyl) aminomethane (28) to form a compound (29),
A compound (24) is manufactured by hydrolyzing this.

Among the branched fatty acids (27) used in this reaction, those which are industrially obtained 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 uniform distribution. The methyl-branched isostearic acid obtained as a by-product during the production of oleic acid dimer contains about 75% or more of total carbon number 18 (the sum of ε and ζ is 14), and the balance total carbon number 14 , 16
20. The branched methyl group is located almost at the center of the alkyl main chain [J. Ame Society (J. Ame
r. Oil Chem. Soc. ) Vol. 51,52
2, (1974); ibid. 56,823A, (19
79)].

The branched fatty acid (2
7) and tris (hydroxymethyl) aminomethane (2
The reaction with 8) is an oxazolylation reaction, and it is preferable to carry out the reaction using approximately equimolar amounts. This reaction is carried out without solvent or in an inert solvent such as xylene, mesitylene, cumene, hexane and decane at 100 to 250 ° C, especially 1
It is preferable to carry out while removing water produced at a temperature of 30 to 220 ° C., further 150 to 200 ° C. When the temperature is low, the reaction does not proceed, and when it is high, the coloring is intense and side reactions occur.
Further, it may be under a nitrogen atmosphere or an air atmosphere. The reaction time may vary depending on various conditions, but is usually preferably 1 to 24 hours.

The oxazoline hydrolysis reaction in the second step is preferably carried out in a mixed solvent of a lower alcohol having 1 to 6 carbon atoms and water. A method of hydrolyzing an oxazoline having a linear alkyl group using only water as a solvent is disclosed in US Pat. No. 2,877,242. However, this method requires a large excess of water, which is about 20 times the weight of oxazoline, and there is a problem that the reaction yield is low when the amount of water is small. According to the invention,
By using the above mixed solvent, the oxazoline can be hydrolyzed in a high yield with a small amount of solvent. The volume ratio of lower alcohol to water is 1:10 to 10: 1,
In particular, 2: 5 to 5: 2, more preferably 1: 2 to 2: 1.
When it exceeds this range, the amount of water in the system decreases, and when it falls below the range, hydrolysis slows down due to inhomogeneity in the system.
The weight ratio of the mixed solvent to the compound (29) is preferably 0.1: 1 to 1: 20: 1. When it exceeds this range, the productivity is poor and unrealistic, and when it falls below this range, the hydrolysis reaction becomes slow. Examples of the lower alcohol used here include methanol, ethanol, isopropanol, propanol, butanol, isobutanol, sec-butanol, t-butanol, amyl alcohol, t-amyl alcohol, neopentyl alcohol, and hexyl alcohol.

The reaction may be carried out in a nitrogen atmosphere or an air atmosphere at 50 to 150 ° C, particularly 60 to 130 ° C, and further 70
It is preferable to carry out at a temperature of 120 ° C. If the temperature is low, the reaction does not proceed substantially, and if the temperature is high, the coloring is intense and a side reaction occurs. The reaction time varies depending on the reaction temperature etc., but is usually 1 to
30 hours is preferred. In addition, an alkaline substance or an acidic substance may coexist in this hydrolysis reaction.

The compound (24) can be isolated from the reaction mixture by a conventional method, for example, distillation of the solvent, recrystallization, chromatography and the like, alone or in combination.

(D-6) Terpene alcohols represented by the following general formula (30)

[0101]

[Chemical formula 26]

Of these, those having η of 3 are preferable.

The above (D-1) to (D-5) are thermotropic liquid crystals which retain the lamellar liquid crystal structure in a wide temperature range as described above, and when water is mixed, they are almost uniformly dispersed as lamellar liquid crystals. It has good properties as a material for cosmetics such as shaving. Further, D-6 forms an inverted middle liquid crystal in an aqueous system. Of these, (D-1) to (D-5) which form a lamellar liquid crystal are preferred.

The component (E) used in the present invention is represented by the general formula (3), and specific examples thereof include glycerin, 1,3-butylene glycol, propylene glycol, dipropylene glycol, Ethylene glycol, diethylene glycol, polyethylene glycol, isoprene glycol, sorbitol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, isopropyl alcohol, ethyl alcohol, benzyl alcohol, benzyloxyethanol and the like, among them, glycerin, propylene glycol, diethylene glycol monoethyl. Ether is particularly preferred.

By blending the component (B) with the component (A), the blending becomes easy, and the component (A) easily adheres uniformly to the hair. Therefore, it is preferable to use the component (B) in an amount of 1 to 50 times the weight of the component (A). The total amount of the components (A) and (B) is preferably 0.1 to 10% by weight in the composition of the present invention.

The component (C) may be used either individually or in combination of two or more. It is usually used in the cosmetic composition of the present invention in an amount of 0.1.
01 to 20% by weight (hereinafter referred to simply as%), especially 0.0
It is preferable to add 5 to 5%. The component D can be used alone or in combination of two or more, and it is preferably contained in the cosmetic of the present invention in an amount of usually 0.01 to 20%, particularly 0.1 to 10%. The component (E) can be used alone or in combination of two or more, and is contained in the cosmetic of the present invention in an amount of 0.1 to 90.
%, Particularly 0.5 to 50% is preferable.

In addition to the above essential components, the hair cosmetic composition of the present invention may further contain a cationic surfactant [(F) component] and / or oils and fats [(G) component] to obtain the effect of the present invention. Can be increased.

Examples of such a cationic surfactant include a quaternary ammonium salt represented by the following general formula (31) or (32).

[0109]

[Chemical 27]

(In the formula, R²⁰, R^{twenty one}, R^{twenty two}And R^{twenty three}Nou
At least one is an alkoxy having a total carbon number of 8 to 28.
Group, alkenyloxy group, alkanoylamino group or
Alkyl optionally substituted with alkenoylamino group
Group or alkenyl group, the rest is benzyl group, carbon number
1 to 5 alkyl groups or hydroxyalkyl groups are shown.
R ^{twenty four}Represents an alkylene group having 2 to 3 carbon atoms, X₂ ^-And X
₃ ^-Represents a halogen ion or an organic anion, and θ and
θ'represents an integer of 1 to 20, R^{twenty five}And R²⁶Less of
At least one is an alkoxyl group having 8 to 28 total carbon atoms,
Lucenyloxy group, alkanoylamino group or alkeno
An alkyl group optionally substituted with an ylamino group or an alkyl group
Represents a alkenyl group, the remainder is a benzyl group, having 1 to 5 carbon atoms.
An alkyl group or a hydroxyalkyl group is shown) Among such cationic surfactants, a compound represented by the general formula (31)
The quaternary ammonium salts represented are preferred and particularly preferred
For example, the following general formulas (33) to (35)
A branched quaternary ammonium salt represented by

[0111]

[Chemical 28]

The branched quaternary ammonium salt represented by the general formula (33) is usually synthesized from, for example, an oxo alcohol having 8 to 16 carbon atoms as a raw material, and examples thereof include alkyl derived from oxo alcohol. Examples thereof include a dialkyldimethylammonium salt having a group, a dialkylmethylhydroxyethylammonium salt, and a dialkylmethylbenzylammonium salt.

In the present invention, the branching ratio of R ^{27 in} the formula (33) is usually 10 to 100%, and particularly 1
It is preferably 0 to 50%. Further, those having a total carbon number of R ²⁷ of 8 to 16 are used, but those having a constant distribution are preferable, and those having the distribution shown below are particularly preferable. C ₈ ~C _11: 5% or less _{C 12: 10~35% C 13:} 15~40% C 14: 20~45% C 15: 5~30% C 16: 5% or less such branched quaternary ammonium Specific examples of the salt (33) include dialkyldimethylammonium chloride having an alkyl group having 8 to 16 carbon atoms and a branching rate of 10 to 50%. The branched quaternary ammonium salt represented by the general formula (34) is usually a Guerbet alcohol having 8 to 28 carbon atoms.

[0114]

[Chemical 29]

(Wherein R ³⁰ and R ³¹ are the same as those described above) are synthesized. Preferred examples of the branched quaternary ammonium salt include alkyltrimethylammonium salt having an alkyl group derived from Guerbet alcohol, alkyldimethylbenzylammonium salt, dialkyldimethylammonium salt, dialkylmethylhydroxyethylammonium salt, dialkylmethylbenzylammonium salt. Etc. Furthermore, among these, particularly preferable specific examples include 2-decyltetradecyltrimethylammonium chloride, 2-
Dodecyl hexadecyl trimethyl ammonium chloride, di-2-hexyl decyl dimethyl ammonium chloride, di-2-octyl dodecyl dimethyl ammonium chloride, etc. can be mentioned. Examples of the methyl-branched quaternary ammonium salt represented by the general formula (35) include λ
And the sum of μ is 15.

Further, the general formulas (31), (32) and (3
Specific examples of X ₂ ⁻ to X ₆ ⁻ which are the counterions of the quaternary ammonium salt represented by 3), 34 and 35 include halogen ions such as chlorine, iodine and bromine; methosulfate and eth Organic anions such as sulphate, metphosphate and etophosphate are mentioned.

These mono- or di-long-chain alkyl quaternary ammonium salt type cationic surfactants as the component (F) may be used alone or as a mixture of two or more kinds, and the compounding amount thereof is the composition. 0.1 to 20.0%, especially 0.5 to
15.0% is preferable. If the blending amount is less than 0.1%, there is no meaning of blending, and if the blending amount exceeds 20.0%, it is not preferable because the product becomes sticky and the touch is deteriorated.

Examples of the fats and oils as the component (G) include higher alcohols having a linear or branched alkyl group or an alkenyl group; hydrocarbons such as liquid paraffin, petrolatum and solid paraffin; liquid lanolin, Examples thereof include lanolin derivatives such as lanolin fatty acid; higher fatty acid esters, higher fatty acids, fats and oils such as long-chain amidoamine having an alkyl group or an alkenyl group; and animal and vegetable fats and oils such as mink oil and olive oil. Of these, carbon number 1
Esters compatible with 4-26 higher alcohols or methyl polysiloxanes are preferred. Specific examples of higher alcohols include cetyl alcohol, stearyl alcohol, and behenyl alcohol. Examples of the ester compatible with methylpolysiloxane include isopropyl laurate, isopropyl palmitate, isopropyl myristate, and isotridecyl myristate.

In order to further improve the feel of the hair, the hair cosmetic composition of the present invention contains, in addition to the silicone compounds (A) to (C) described above, dimethylpolysiloxane, methylphenylpolysiloxane, fatty acid-modified silicone, One or more of silicone derivatives such as alcohol-modified silicone, aliphatic alcohol-modified silicone, polyether-modified silicone, epoxy-modified silicone, fluorine-modified silicone, cyclic silicone and alkyl-modified silicone can be blended. Such silicone derivatives may be used alone or in JP-B-56-386.
It may be a latex composition emulsion-polymerized in accordance with the method described in Japanese Patent Publication No. 09-09. In the hair cosmetic composition of the present invention, if necessary, components that are usually used in cosmetics, pharmaceuticals, foods, etc., such as antidandruff agents, bactericides, vitamins and other medicinal agents; parabens and other antiseptics. Agents; thickeners such as perfluoropolyether and water-soluble polymers; coloring agents such as dyes and pigments; conditioning agents such as cationic polymers; pearling agents such as glycol esters;

Polymer for hair setting such as acrylic resin liquid; various blended fragrances; other, ENCYCLOPEDIA
OF CONDITIONING RINSE IN
GREDIENTS [Encyclopedia of Conditioning Rinse Ingredients (MI
CELLE PRESS 1987)] and the like can be appropriately blended within a range that does not impair the effects of the present invention. Since the hair cosmetic composition of the present invention relates to an emulsion type hair cosmetic composition, as is apparent from the examples, it can be produced by appropriately mixing water necessary for forming an emulsion, for example, a hair rinse, Hair conditioner, hair treatment,
It can be applied as a hair cream, a styling lotion, a styling mousse, a conditioning mousse, a hair spray and the like.

[0121]

In the hair cosmetic composition of the present invention, the contained component (E) is adsorbed to the inside of the hair, and further the component (D) is also adsorbed to the hair, whereby synergistic moisturizing and softening effects are obtained. To be enhanced. Further, since the components (A), (B) and (C) are uniformly coated on the hair surface, smoothness can be imparted. Further, the moisture inside the hair is blocked, the moisturizing effect and the softening effect are maintained, and the softening effect is excellent without using a large amount of a moisturizing agent, so that stickiness can be suppressed. Also (C)
The component enhances the affinity between the components (A) and (B) and the components (D) and (E), and can enhance the effects of these components, and further has the affinity to the damaged part of the hair. Protect. Therefore, the hair cosmetic composition of the present invention is an excellent hair cosmetic composition that imparts smoothness, softness, dryness and moisturizing feeling to the hair and that these effects last.

[0122]

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

Synthesis Example 1 Pentaerythritol 82 g, dimethyl sulfoxide 2
00 g and 1 g of sodium hydroxide were put into a 500 ml flask, heated and dissolved at 105 ° C., dry nitrogen gas was blown thereinto, and about 20 g of water and dimethyl sulfoxide were distilled out to remove water in the reaction system. After 39 g of isostearyl glycidyl ether was added dropwise to this over 1 hour, 1
The reaction was carried out at 05 ° C. for 4 hours with stirring. After the reaction,
Acetic acid (1.5 g) was added to the reaction mixture to neutralize the catalyst, dimethyl sulfoxide was completely distilled off at 80 ° C. under reduced pressure, and 99% ethanol was added to the residue to separate unreacted pentaerythritol by filtration. did. Ethanol was distilled off from the obtained filtrate under reduced pressure, and water was added to the residue 500 times.
ml and ethyl acetate (500 ml) were added and the mixture was extracted with ethyl acetate. The solvent was distilled off from the ethyl acetate-soluble fraction to obtain 63 g of a pale yellow adduct of pentaerythritol isostearyl glycidyl ether. When this crude product is separated and purified using silica gel column chromatography with an elution solvent of acetone: hexane = 2: 1,
The desired pentaerythritol-isostearyl glycidyl ether 1 mol adduct was eluted, and the elution fractions were collected and the solvent was distilled off to obtain the desired pentaerythritol isostearyl glycidyl ether 1 mol adduct 16 g ( Yield 30%) was obtained. 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 (stretching) (-CH-,-CH ₂ -,-CH ₃ ) 2850 , 2920; ν _OH (Variation) (-CH-,-CH ₂ -,-CH ₃ ) 1375,1460; ν _CO (-CO-) 1110,1035,1010

Example 1 A hair rinse composition having the composition shown in Table 1 was produced by the following preparation method and tested by the following test method. The results are shown in Table 1.

Preparation method: To purified water heated to 70 ° C., the mixture of (A) to (H), which was heated at the same temperature and dissolved or dispersed, was added, and the mixture was stirred to emulsify, then, with further stirring,
It cooled to room temperature and obtained the hair rinse agent.

Test method: Thick Japanese women (about 90μ)
20 g (15 cm in length) of the above hair bundle was wrapped in a lot and permed with a commercially available perm agent. 2 g of hair cosmetic composition was evenly applied to this hair bundle, and then rinsed with running water for 30 seconds. This was dried with a towel and then further dried with a dryer. At this point, the hair condition was evaluated. Then, the hair bundle was allowed to stand in a constant temperature room (temperature: 25 ° C., relative humidity: 50%) for 24 hours, and the hair was evaluated again.

The evaluation was based on the following criteria. A: Very good. ◯: Good. Δ: Somewhat bad. X: Bad.

[0128]

[Table 1]

Example 2 The hair rinse agent shown in Table 2 was prepared by the following preparation method,
This was evaluated in the same manner as in Example 1. The results are shown in Table 2. Preparation method: A mixture of purified water heated to 70 ° C., a preservative, and a dye, which was dissolved and dispersed by heating to the same temperature, was added and stirred to emulsify. The mixture was further cooled to room temperature with stirring to obtain the desired composition.

[0130]

[Table 2]

Example 3 A hair cosmetic composition having the following composition was prepared.

[0132]

Table 3 Hair rinse: (%) Dimethyl polysiloxane (polymerization degree 2700) 0.5 Decamethylcyclopentasiloxane 3.5 Amino-modified silicone (SM8702C) 1.0 Phytantriol 1.0 Propylene glycol 3.0 Glycerin 2 .0 Stearyl trimethyl ammonium chloride 1.0 Stearyl alcohol 3.0 Isotridosyl myristate 0.2 Methyl paraben 0.1 Hydroxyethyl cellulose (1% aqueous solution viscosity 8000 cp) 0.4 Perfume 0.4 Water balance

The product of the present invention was excellent in smoothness and flexibility during drying, had a good dry feeling and a moist feeling, and was excellent in sustainability of the effect.

[0134]

[Table 4] Hair treatment: (%) Dimethyl polysiloxane (Polymerization degree 3300) 1.5 Dimethyl polysiloxane (Polymerization degree 30) 5.0 Amino-modified silicone (SM8702C) 1.5 Pentaerythritol / isostearyl glycidyl ether 1 Molar adduct (Synthesis example 1) 3.0 Diethylene glycol ethyl ether 5.0 Stearyl trimethyl ammonium chloride 2.0 ^{* 1} Dialkyl dimethyl ammonium chloride 1.0 Cetanol 5.0 Isopropyl palmitate 1.0 Polyoxyethylene stearyl ether (S .EO) 0.5 Methylparaben 0.2 Perfume 0.5 Water balance * 1: Commercially available oxo synthetic alcohol having 12 to 15 carbon atoms (equal mixture of dovanol 23 and dovanol 45, manufactured by Mitsubishi Petrochemical Co., Ltd.) Derived from Branched quaternary ammonium salts,
The branching rate is 20%.

[0135]

[Table 5] Conditioning mousse: (%) Dimethyl polysiloxane (Polymerization degree: 3300) 0.5 Dimethyl polysiloxane (Polymerization degree: 40) 1.5 Amino-modified silicone (SM8702C) 0.8 Pentaerythritol / isostearyl glycidyl ether 1 Molar adduct (Synthesis example 1) 1.0 Glycerin 2.5 Isopropyl palmitate 2.5 2-Hexyldecyltrimethylammonium chloride 0.5 Polyoxyethylenesorbitan monostearate 0.2 95% Ethanol 5.0 Methylparaben 0 .1 Fragrance 0.1 LPG (4.0 kg / cm ² G, 20 ° C.) 10.0 Water balance

The conditioning mousse composition of the present invention was excellent in smoothness, and had a dry, smooth, and dry feel.

[0137]

Styling mousse: (%) Dimethyl polysiloxane (Polymerization degree: 3300) 0.5 Octamethylcyclotetrasiloxane 1.5 Amino-modified silicone (SM8702C) 0.5 Phytantriol 0.8 Isoprene glycol 0.5 2 -Dodecylhexadecyltrimethylammonium chloride 0.5 Isopropyl myristate 0.5 Polyoxyethylene hexadecyl ether (EO = 10) 0.5 Plastic size L53P 8.0 Ethanol 5.0 Perfume 0.2 Dyes 0. 01 Water Balance LPG (4.0kg / cm ² G, 20 ° C) 10.0

The styling mousse composition of the present invention is excellent in combability and smoothness, has no dryness, and has a moist feeling.
The feeling was also smooth.

Claims (3)

[Claims] 1. The following components (A), (B), (C),
Hair cosmetics containing (D) and (E). (A) One or more high molecular weight silicones represented by the following general formula (1): (In the formula, R ¹ represents a methyl group or a phenyl group, which may be the same or different, except when all of R ¹ are phenyl groups. R ² represents a methyl group or a hydroxyl group. N is 2 2,000 to 20,000),
(B) In the general formula (1), one selected from a low molecular weight silicone in which n is 1 to 500, an isoparaffin hydrocarbon having 4 to 30 carbon atoms, and a cyclic silicone represented by the following general formula (2). Or two or more (In the formula, m represents a number of 3 to 7), (C) a nitrogen atom-containing silicone compound, (D) at least one long-chain branched alkyl or alkenyl group in one molecule, and at least A nonionic amphipathic compound having three hydroxyl groups and forming a liquid crystal structure in an aqueous system at 25 ° C.,
(E) A compound represented by the following general formula (3): (Wherein R ⁴ represents a hydrogen atom, a methyl group or a methoxy group, R ⁵ represents a single bond or a saturated or unsaturated divalent hydrocarbon group having 1 to 3 carbon atoms), and Y and Z represent It shows a hydrogen atom or a hydroxyl group, and p, q, and r show the integer of 0-5. However, when p = q = r = 0 and Z = H, and p =
Except when q = r = 0 and R ¹ = H and Z = OH]. 2. The hair cosmetic composition according to claim 1, wherein the component (C) is an amino-modified silicone compound and / or a quaternized silicone compound. 3. The hair cosmetic composition according to claim 1, further comprising a cationic surfactant and / or oils and fats.