JPH0753330A - Hair cosmetic - Google Patents

Abstract

PURPOSE:To provide a hair cosmetic having good slip in application, excellent moisture retention, free from greasiness, preventing tangle and twine both in wetness and dryness, providing excellent smoothness, moist feeling, dry feeling, softness and antistatic properties. CONSTITUTION:This hair cosmetic comprises (A) a cationic silicone polymer such as a compound of formula I [R<4> to R<8> are each a substitutable 1-12C hydrocarbon group, polyoxyalkylene or polysiloxane which contains end O atom replaceable with an alkyl or acyl; A is a group of formula II to formula V (R<9>, R<10>, R<12>, R<13>, R<15>, R<16>, R<18> and R<19> are each as shown by each of R<4> to R<8>; R<11>, R<14>, R<17> and R<20> are each 2-12C substitutable bifunctional hydrocarbon group; X is a halogen); B is a halogen or group of formula VI or formula VII (R<21> to R<27> are each as shown by each of R<4> to R<8>; (f) is 1-10; (g) is 0-100); (c) is 0-400; (d) is 1-10; (e) is 1-20] and (B) a nonionic amphiphatic compound which contains at least one long-chain branched alkyl group or alkenyl group in one molecule and provides a mixture with water, having liquid crystal structure at a certain temperature from 0-50 deg.C in the ratio of preferably 0.1-5wt.% of the component A and 0.1-10wt.% of the component B.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has good spreadability when applied,
Gives a refreshing feeling without stickiness, prevents entanglement when wet or dry,
Hair makeup with excellent smoothness, moisturizing, dryness, and antistatic effect, which lasts for a long time after washing hair, and also exerts these effects especially on hair damaged by a perm or dryer. Regarding fees.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Hair cosmetics in which a cationic surfactant and an oil agent such as higher alcohol, glyceride, liquid paraffin, or esters are combined are used for the purpose of imparting flexibility, smoothness, antistatic properties, etc. to hair. . However, when these oil agents are used in combination, the flexibility and smoothness are improved as compared with the case of using the cationic surfactant alone, but the residual feeling of the oil agent, that is, the greasy feeling is avoided. The drawback is that it does not.

On the other hand, silicones represented by dimethylpolysiloxane polymers are smooth and have excellent lubricity as compared with higher alcohols, glycerides, liquid paraffins, esters, etc., and give a smooth feel and gloss to hair. It is known to be used in many hair cosmetics. However, since such silicones are inferior in moisturizing effect, they lack moisturizing feeling, and the hair becomes dry and dry.
Further, there are drawbacks such that flexibility cannot be imparted.

In order to solve such drawbacks, hair cosmetics in which silicone or a derivative thereof is combined with a nonionic amphiphilic 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). Although the hair cosmetic composition has some effect on ordinary hair, it does not have sufficient sustaining effect on hair damaged by a perm or hair dye, and after 1 day of treatment, it becomes soft. It had the drawback of becoming a hair lacking in sex and moisturizing feeling.

Further, since the conventional silicone does not have an adsorbing group for hair, it must be added in a large amount to the hair cosmetic in order to ensure its effect / performance, which causes the problem of stickiness. . Furthermore, the conventional hair cosmetics have a problem that the effect does not continue due to washing the hair.

Therefore, in recent years, various hair cosmetics having improved durability have been developed by incorporating a modified silicone polymer having high adsorptivity into hair. For example, JP-A-55-6
Japanese Patent No. 6506 discloses a cosmetic containing a quaternary nitrogen-containing cation-modified silicone. The quaternary nitrogen-containing cation-modified silicone used here has excellent water solubility, is easy to mix, and has a higher adsorptivity than polyether-modified silicone and the like. However, the cosmetics containing this did not have sufficient effect in terms of slipping and cohesion on damaged hair, and also had insufficient flexibility.

Further, JP-A-60-36407 contains a water-dispersible cationic surfactant, a water-soluble quaternized cationic polymer, and a siliconized cationic polymer. Cosmetic compositions are disclosed. However, it uses a quaternized cationic polymer, although the softness and smoothness of wet and dry hair is improved by the simultaneous deposition of three components on the hair. Therefore, there are drawbacks such as a stiff feeling and weight peculiar to the polymer when dried.

Japanese Unexamined Patent Publication No. 2-111712 discloses a hair cosmetic composition containing a high molecular weight silicone and a cationized silicone polymer. However, although this hair cosmetic composition can impart set-holding power, its smoothness and flexibility when wet are not sufficient. Further, JP-A-5-117128 discloses a cosmetic composition containing a polyquaternary polysiloxane polymer. However, this cosmetic composition was also not sufficiently satisfactory in terms of moist feeling and the like.

Therefore, it is not sticky and has excellent moisture retention,
There has been a demand for a hair cosmetic composition capable of imparting a moisturizing feeling, flexibility, smoothness, and the like, and also maintaining these effects on damaged hair.

[0010]

Under the circumstances, as a result of intensive studies by the present inventors, the above problems were solved by using a combination of a cationized silicone polymer and a specific nonionic amphiphilic compound. The inventors have found that an excellent hair cosmetic composition can be obtained and completed the present invention.

That is, the present invention comprises the following components (A) and (B): (A) cationic silicone polymer (B) having at least one long-chain branched alkyl group or alkenyl group in one molecule. And a mixture with water at any temperature of 0 to 50 ° C., which contains a nonionic amphipathic compound retaining a liquid crystal structure.

The cationized silicone polymer as the component (A) used in the present invention contains a quaternary nitrogen at the terminal and / or side chain of the segment of the organopolysiloxane, and is represented by the following formula (1). It contains a group represented.

[0013]

[Chemical 4]

In the formula (1), the divalent hydrocarbon group represented by R ¹ is an alkylene group such as methylene group, ethylene group, propylene group, butylene group and --CH ₂ CH (CH ₃ ) CH _{2-. group, - (CH 2) 2 -C} 6 H 4 - is an alkylene arylene group or the like, such as an alkylene group of these, a propylene group are preferred. The monovalent hydrocarbon group represented by R ³ may be substituted with a hydroxy group, and examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, a hydroxyethyl group, a hydroxypropyl group and a phenyl group. To be The three R ³ may be the same or different. Furthermore, the preferred value of a and b is a =
1, b = 0.

Specific examples of the cationized silicone polymer as the component (A) include those represented by the following (A-1) to (A-3). (A-1) A silicone compound represented by the general formula (2).

[0016]

[Chemical 5]

[Wherein R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are}
Are hydrocarbon groups which may be the same or different and have a substituent having 1 to 12 carbon atoms, a polyoxyalkylene group or a polysiloxane group which may have an alkyl or acyl group substituted on the terminal oxygen atom, A is

[0018]

[Chemical 6]

(Wherein R ⁹ , R ¹⁰ , R ¹² , R ¹³ , R ¹⁵ ,
R ¹⁶ , R ¹⁸ and R ¹⁹ are the same or different and have 1 to 12 carbon atoms.
Shows a hydrocarbon group which may have a substituent, a polyoxyalkylene group or a polysiloxane group which may have an alkyl or acyl group substituted on a terminal oxygen atom,
R ¹¹ , R ¹⁴ , R ¹⁷ and R ²⁰ are the same or different and have 1 carbon atom.
To 12 are divalent hydrocarbon groups which may have a substituent, X'represents a halogen atom), B is a halogen atom,

[0020]

[Chemical 7]

(Here, R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ ,
R ²⁶ and R ²⁷ are the same or different and are a hydrocarbon group having 1 to 12 carbon atoms, which may have a substituent, a polyoxyalkylene group which may have an alkyl or acyl group substituted on the terminal oxygen atom, or a polyoxyalkylene group which may have a substituent. Represents a siloxane group, X'represents a halogen atom, f represents a number from 1 to 10, and g represents 0 to 4
Represents the number of 00) and c is 0 to 400.
, D is a number from 1 to 10, and e is a number from 1 to 20]

In the formula (2), R ^{4 to} R ⁸ , R ⁹ , R ¹⁰ and R
¹² , R ¹³ , R ¹⁵ , R ¹⁶ , R ¹⁸ , R ¹⁹ , and R ^{21 to} R ²⁷ are preferably hydrocarbon groups having 1 to 12 carbon atoms, and particularly preferably alkyl groups having 1 to 6 carbon atoms. Further, R ¹¹ , R ¹⁴ , R ¹⁷ and R ²⁰ are preferably an alkylene group having 1 to 12 carbon atoms. Furthermore, B is -NR
Those having a structure of ²¹ R ²² are particularly preferable.

The number average molecular weight of the silicone moiety is 300 to 300 in order to exert the original function of silicone.
It is preferably 40,000, particularly preferably 500 to 25,000.

On the other hand, the number of repeating units of the quaternary ammonio site is preferably 1 to 20 from the viewpoint of good feeling,
1-10 is more preferable.

Such silicone compound (2) is, for example, the following three kinds of monomer components (a), (b) and (c): (a) dihalide compound, (b) tertiary diamino compound, (C) One-terminal dialkylamino-modified silicone and / or one-terminal haloalkyl-modified silicone can be synthesized by reacting one or two or more selected from each group. Further, a monohalide compound or a tertiary monoamino compound can be used only when the reaction end of the polymer is blocked.

The halogen atom of the component (a) can be used regardless of the kind, and two halogen atoms may be different from each other. The two halogen atoms may have a group such as an alkyl group, an allyl group, or an aryl group, which is usually used for an organic reaction, interposed therebetween. Furthermore, the component (a) may have various other functional groups as long as it is inert to the halogen atom and the dialkylamino group.

Specific examples of the component (a) include 1,2-dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, 1,2-dichloropropane, 1,2-dibromopropane, 1,2- Diiodopropane, 1,3-dichloropropane, 1,3-dibromopropane, 1,3-
Diiodopropane, 1,3-dichlorobutane, 1,3-
Dibromobutane, 1,3-diiodobutane, 1,4-dichlorobutane, 1,4-dibromobutane, 1,4-diiodobutane, 2,3-dichlorobutane, 2,3-dibromobutane, 2,3-diiodobutane, 1 , 2-dichloro-2-methylpropane, 1,2-dibromo-2-methylpropane, 1,2-diiodo-2-methylpropane,
1,4-dichloropentane, 1,4-dibromopentane, 1,4-diiodopentane, 1,5-dichloropentane, 1,5-dibromopentane, 1,5-diiodopentane, 1,1-dichloro- 3,3-dimethylbutane,
1,2-dibromo-3,3-dimethylbutane, 1,6-
Dichlorohexane, 1,6-dibromohexane, 1,6
-Diiodohexane, 1,7-dichloroheptane, 1,
7-dibromoheptane, 1,7-diiodoheptane,
1,8-dichlorooctane, 1,8-dibromooctane, 1,8-diiodooctane, 1,4-dichloro-2
-Butene, 1,4-dibromo-2-butene, 1,4-diiodo-2-butene, α, α'-dichloro-o-xylene, α, α'-dibromo-o-xylene, α, α'- Diiodo-o-xylene, α, α'-dichloro-p-xylene, α, α'-dibromo-p-xylene, α, α'-
Diiodo-p-xylene, α, α′-dichloro-m-xylene, α, α′-dibromo-m-xylene, α, α ′
-Diiodo-m-xylene, bis (chloromethyl) dimethylsilane, 1,3-bis (chloromethyl) -1,1,
3,3-tetramethyldisiloxane, 1,3-bis (bromomethyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (iodomethyl) -1,1,3,3
-Tetramethyldisiloxane, 1,3-bis (3-chloropropyl) -1,1,3,3-tetramethyldisiloxane, α, ω-bis (chloromethyl) polydimethylsiloxane, α, ω-bis ( 3-chloropropyl) polydimethylsiloxane and the like.

Four alkyl groups each having an arbitrary chain length can be bonded to the amino group of the component (b). A group such as an alkyl group, an allyl group or an aryl group which is usually used for an organic reaction can be interposed between the respective amino groups. Further, the component (b) may have various other functional groups as long as it is inert to the halogen atom and the dialkylamino group.

Specific examples of the component (b) include N, N,
N ', N'-tetramethylethylenediamine, N, N,
N ', N'-tetramethylpropylenediamine, N,
N, N ', N'-tetramethyl-1,3-butanediamine, N, N, N', N'-tetramethyl-1,4-butanediamine, N, N, N ', N'-tetramethyl -1,
6-hexanediamine, 1,4-diazabicyclo [2,2
2,2] octane, N, N, N ′, N′-tetramethyl-2-butene-1,4-diamine, 1,4-dimethylpiperazine, 1,3-bis (3-N, N-dimethylamino Propyl) -1,1,3,3-tetramethyldisiloxane, α, ω-bis (3-N, N-dimethylaminopropyl) polydimethylsiloxane, 1,1,4,4-tetramethyl-1,4 -Bis (N, N-dimethylamino) disylethylene and the like.

The component (c) is represented by the following general formula (3) or (4)

[0031]

[Chemical 8]

(Wherein R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ ,
R ⁹ , R ¹⁰ , X, c and d have the same meanings as described above). Here, c is preferably 3 or more.
If it is less than 3, the inherent properties of the silicone compound may not be sufficiently exhibited.

Specific examples of the component (c) include the following.

[0034]

[Chemical 9]

The component (c) is, for example, after synthesizing a Si-H modified silicone having one end with hexamethylcyclotrisiloxane and alkyllithium dimethylchlorosilane, and then in the presence of a platinum acid catalyst, dimethylallylamine or allyl bromide, allyl chloride, etc. It can be easily synthesized by a hydrosilylation reaction with.

A silicone-quaternary ammonio block polymer or a silicone-quaternary ammonio-silicone block polymer is synthesized by reacting a compound selected from each of the above components (a), (b) and (c). can do.

The solvent used in the above reaction is not particularly limited. For example, when the compounds selected from the components (a), (b) and (c) have high compatibility with each other, the reaction can be performed without a solvent, but the components (a) and (b) may be further reacted. In order to further promote the quaternization reaction with), a polar solvent such as dimethylformamide (DMF), dimethylacetamide (DMA), methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether. May be added.

On the other hand, when these compounds have low compatibility and cannot be uniformly dissolved, it is preferable to add a solvent in order to ensure the compatibility. In this case, the components (a), (b)
The solvent is not particularly limited as long as it can uniformly dissolve the compounds selected from (c) and (c), but in order to further promote the quaternization reaction, dimethylformamide (D
It is preferable to use a polar solvent such as MF), dimethylacetamide (DMA), methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyleneglycone dimethyl ether, ethylene glycol diethyl ether, or ethylene glycol dibutyl ether.

The reaction temperature and reaction time of this reaction are such that the compounds selected from the components (a), (b) and (c), the solvent added to enhance the compatibility, and further the quaternization reaction. It depends on the properties and boiling point of the polar solvent added to accelerate the reaction, but preferably 40 to 160 ° C., 2 to
It is 48 hours, more preferably 60 to 120 ° C. and 4 to 24 hours.

The molecular weight of the silicone moiety or the quaternary ammonio moiety of the silicone compound (2) and the composition ratio of the silicone moiety and the quaternary ammonio moiety are the components (a),
It is possible to adjust the charge ratio, the charge method, and the charge order of the compounds selected from (b) and (c). Further, when the reactivities of the raw materials to be used are largely different, a method of adding one of the raw materials to be used in excess and successively completing the reaction and repeating purification is advantageous.

(A-2) A polyquaternary polysiloxane polymer having a repeating unit represented by the general formula (5).

[0042]

[Chemical 10]

Where Z is a divalent α, ω-bis- (alkyl) -polysiloxane group, or up to 6 consecutive carbon atoms optionally substituted by one or more hydroxyl groups and optionally It represents a saturated or unsaturated hydrocarbon chain having a linear or molecular chain having one or more chain oxygen atoms and / or aromatic rings, wherein R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are the same or different and have a carbon number. 1 to 6 represents an alkyl group or a phenyl group, R ³² represents a methyl group, an ethyl group or a hydroxyethyl group, and R ^32
33 represents an alkyl group having 1 to 18 carbon atoms, or two adjacent groups R ³³ represent a divalent piperazino together with a nitrogen atom to which these groups are bonded and a group Z therebetween. Forming a group, or two adjacent groups R ³² together with two groups R ³³ bonded to the same nitrogen atom, said nitrogen atom and the group Z between them form a triethylenediamino group. Or R ³² and R ³³ together with the nitrogen atom to which they are attached represent a heterocycle,

[0044]

[Chemical 11]

H represents an integer of 1 to 6, i is 1 to 50
These polyquaternary polysiloxane polymers can be produced, for example, according to the method described in JP-A-5-117128.

(A-3) A silicone compound represented by the general formula (6).

[0047]

[Chemical 12]

(Wherein R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ ,
R ³⁹ and R ⁴⁰ are the same or different and each represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and R ⁴¹ and R ⁴² may be substituted with a hydrogen atom or a hydroxyl group. A monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a hydroxyl group, and R ⁴³ represents a halogen atom or a hydroxyl group. 1 carbon atom which may be substituted with
10 represents a divalent hydrocarbon group, or a group in which ½ or less of carbon in the hydrocarbon group is replaced with oxygen, X ′ represents a halogen atom, and j represents a number 0 ≦ j ≦ 20. )

These silicone compounds (6) can be produced, for example, according to the method described in JP-A-2-157285.

The cationized silicone polymer as the component (A) may be used either individually or in combination of two or more, and may be used in an amount of 0.05 to 20% by weight (hereinafter simply referred to as%) in the total composition. A content of 0.1 to 5% is particularly preferable because it has an excellent effect of protecting a damaged part of hair.

The nonionic amphipathic compound of the component (B) used in the present invention has at least one long-chain branched alkyl group or alkenyl group in one molecule, and has a temperature of 0 to 50 ° C. The mixture with water at temperature forms a lamellar or inverted middle liquid crystal structure. Further, those having at least 3 hydroxyl groups in one molecule are preferable. Here, the confirmation of the liquid crystal structure can be performed, for example, by The Journal
Of Cell Biology (The Journal)
of Cell Biology), Volume 12, No. 20
Pages 7-209 and surface, Vol. 11, No. 10, 579.
~ 590 page using X-ray diffraction and differential scanning calorimeter (DSC). Examples of compounds having such properties include the following (B-1) to
(B-6) may be mentioned.

(B-1) Glycerylated polyols represented by the following general formula (7).

[0053]

[Image Omitted] D _k (G) (7)

[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 D represents

[0055]

[Chemical 14]

(Wherein E 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 the hydroxyl groups of the polyol.

In the formula (7), the alkyl glycoside represented by G includes methyl glucoside, ethyl glucoside,
Examples include propyl glucoside, octyl glucoside, methyl maltoside, ethyl maltoside and the like. Further, as B, a branched alkyl group having 16 to 36 carbon atoms, particularly 18 to 24 carbon atoms is preferable. As the branched alkyl group E,
The following general formula (8)

[0058]

[Chemical 15]

(In the formula, l and m each represent an integer of 0 to 20, and the sum of l and m is 6 to 20) or the following general formula (9).

[0060]

[Chemical 16]

A group represented by the formula (wherein n and o each represent an integer of 0 to 18 and the sum of n and o 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 the general formula (7), k is particularly preferably 1 or 2.

These glycerylated polyols (7)
Can be produced, for example, according to the method described in JP-A-5-984.

(B-2) A methyl branched fatty acid ester represented by the following general formula (10).

[0064]

[Chemical 17]

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

In the formula (10), the sum of p and q is 6 to 20, but preferably 1 from the viewpoint of performance as a cosmetic material.
It is from 0 to 16, particularly preferably 14. The branched methyl group is particularly preferably located near the center of the alkyl main chain. These methyl branched fatty acid esters (10) can be produced, for example, according to the method described in JP-A-4-89450.

(B-3) A branched fatty acid glyceroglycolipid represented by the following general formula (11).

[0068]

[Chemical 18]

In the formula (11), the sum of r and s is 10 to 16, especially 14 from the viewpoint of performance as a cosmetic material.
From the same viewpoint, the sum of t and u is preferably 6 to 14, and particularly preferably 8 to 12. These branched fatty acid glyceroglycolipids (11) can be produced, for example, according to the method described in JP-A-4-89494.

(B-4) A trimethylol derivative represented by the following general formula (12).

[0071]

[Chemical 19]

(Wherein R ⁴⁶ represents a branched alkyl or alkenyl group having 12 to 22 carbon atoms) (B-4), and the following general formula (13)

[0073]

[Chemical 20]

Trimethylol represented by the formula (wherein v and w each represent an integer of 0 to 19 and the sum of v and w is 9 to 19) is preferable. Further, the sum of v and w in the general formula (13) is preferably 11 to 15, and particularly v and w
Is preferable to be trimethylolisoheptadecane. The branched methyl group is preferably near the center of the alkyl main chain.

These trimethylol derivatives (12) can be produced according to the method described in JP-A-1-283235.

(B-5) A trimethylol derivative represented by the following general formula (14).

[0077]

[Chemical 21]

(In the formula, R ⁴⁷ represents a branched chain alkyl group or alkenyl group having 11 to 27 carbon atoms)

Among the trimethylol derivatives (14), those in which R ⁴⁷ in the formula is a group represented by the following general formula (15) or (16) are preferable.

[0080]

[Chemical formula 22]

(In the formula, x and y each represent an integer of 0 to 24, the sum of x and y is 8 to 24, and R ⁴⁸ and R ⁴⁹
Are each an alkyl group having 2 to 12 carbon atoms)

Further, particularly preferable R ⁴⁷ is a branched alkyl group having 13 to 19 carbon atoms, and further preferable R ⁴⁷ is 10 in the general formula (15) where the sum of x and y is 10.
The most preferable one is an isostearyl group in which the sum of x and y is 14.

These trimethylol derivatives (14)
Can be produced, for example, according to the method described in JP-A-4-9309.

(B-6) Terpene alcohols represented by the following general formula (17).

[0085]

[Chemical formula 23]

(In the formula, z represents a number of 1 to 3) Among these terpene alcohols, those in which z is 3 are preferable.

These terpene alcohols (17)
Are disclosed, for example, in JP-A-63-258804 and JP-B-3.
No. 8-5050.

The above (B-1) to (B-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 dispersed almost uniformly as lamellar liquid crystals. It has good properties as a material for cosmetics such as shaving. Further, (B-6) forms a reverse middle liquid crystal in an aqueous system. Of these, (B-1) to (B-5) which form lamellar liquid crystals are preferable.

The nonionic amphipathic compound as the component (B) can be used alone or in combination of two or more, and is 0.01 to 20%, particularly 0.1 to 10% in the total composition.
When blended, it is preferable because it spreads well when applied and the moist feeling is maintained.

It is preferable to add a silicone derivative other than the component (A) to the hair cosmetic composition of the present invention, because it gives a smooth and good feel to the hair. Examples of such silicone derivatives include the following (1) to (1
1) is mentioned.

(1) Dimethyl polysiloxane

[0092]

[Chemical formula 24]

[In the formula, a'represents a number of 0 to 20,000]

(2) Methylphenyl polysiloxane

[0095]

[Chemical 25]

[Wherein b ′, c ′ and d ′ are b ′ + c ′
+ D 'is a number from 1 to 5,000. However, c '= 0
, Then d ′ ≠ 0, and when d ′ = 0, c ′ ≠ 0]

(3) Amino-modified Silicone 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; vinyl group; alkenyl groups such as 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.

A typical example of such an amino-modified silicone polymer is represented by the following general formula (20) and has an average molecular weight of about 3,000 to 100,000. Amodimethicone (Amodimet
CTFA dictionary (Cosme, USA)
tic Ingredient Dictionar
y) It is described in the third edition.

[0099]

[Chemical formula 26]

[Wherein, e ′ and f ′ are molecular weights of 3,000
Indicates an integer that depends on 100,000]

(4) Fatty acid-modified silicone

[0102]

[Chemical 27]

(5) Alcohol-modified silicone

[0104]

[Chemical 28]

(6) Aliphatic alcohol-modified silicone

[Chemical 29]

(7) Polyether-modified silicone

[0107]

[Chemical 30]

[0108]

[Chemical 31]

[0109]

[Chemical 32]

[0110]

[Chemical 33]

[Wherein i ″ is 1 to 300 (preferably 1
~ 50), j "is 2 to 500 (preferably 2 to 50),
k ″ is 0 to 6 (preferably 2 to 3), l ″ is 1 to 50
(Preferably 2 to 20), m ″ represents a number of 0 to 50 (preferably 0 to 20)]

(8) Alkoxy-modified silicone

[0113]

[Chemical 34]

(In the formula, n ″ represents an integer of 1 to 100,
m represents an integer of 1 to 50, R ⁶² has 1 to 28 carbon atoms
(Preferably 12 to 22) is an alkyl group.

(9) Fluorine-modified silicone

[0116]

[Chemical 35]

[Wherein p ″ is 1 to 400 (preferably 1
~ 250)]]

(10) Cyclic silicone

[0119]

[Chemical 36]

[In the formula, q ″ represents a number of 3 to 8, and R ⁶³ and R ⁶⁴ each represent an alkyl group having 1 to 3 carbon atoms]

(11) Alkyl-modified silicone

[0122]

[Chemical 37]

[0123]

[Chemical 38]

[Wherein u ″ and v ″ are 1-1 and 1, respectively.
000 (preferably 1 to 200), and R ⁶⁷ represents an alkyl group having 10 to 22 carbon atoms]

Among these silicone derivatives, particularly high molecular weight dimethylpolysiloxane (in the formula (18), a '=
2,000-20,000) is preferable.

One or two of these silicone derivatives can be used.
It is possible to use a combination of two or more kinds, and it is preferable to add 0.1 to 20%, especially 0.5 to 10% in the total composition, because it gives a good feeling to the hair with a dry feeling.

In the hair cosmetic composition of the present invention, in addition to the above components,
Further, by adding a cationic surfactant and / or oils and fats, the effect of the present invention can be further enhanced.

Examples of such a cationic surfactant include quaternary ammonium salts represented by the following general formula (34) or (35).

[0129]

[Chemical Formula 39]

(In the formula, R⁶⁸, R⁶⁹, R⁷⁰And R⁷¹Nou
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 ⁷²And R⁷³Are alkylene groups each having 2 to 3 carbon atoms
Shows, X^-Represents a halogen ion or an organic anion,
w ″ and x ″ represent an integer of 1 to 20, and R⁷⁴And R ⁷⁵of
At least one of them 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 represents an alkyl group or a hydroxyalkyl group)
Among such cationic surfactants, the general formula (34)
The quaternary ammonium salts represented are preferred and particularly preferred
For example, the following general formulas (36) to (38)
A branched quaternary ammonium salt represented by

[0131]

[Chemical 40]

The branched quaternary ammonium salt represented by the general formula (36) is usually synthesized, for example, from 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, R ⁷⁶ and R ^{77 in the} formula (36) are used.
The branching ratio is usually 10 to 100%, and particularly preferably 10 to 50%. Moreover, although the total carbon number of R ⁷⁶ and R ⁷⁷ is 8 to 16 is used,
Those having a certain distribution are preferable, and those having the following distributions 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 (36) 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 (37) is usually a Guerbet alcohol having 8 to 28 carbon atoms.

[0134]

[Chemical 41]

(In the formula, R ⁸⁰ and R ⁸¹ are the same as those described above). 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 (38) include δ
And the sum of ε is 15.

Further, the general formulas (34), (35) and (3
Specific examples of X ⁻ which is a counter ion of the quaternary ammonium salt represented by 6), (37) and (38) include halogen ions such as chlorine, iodine and bromine; methosulfate, ethosulfate and metphosphate. , Organic anions such as etophosphate.

These mono- or di-long chain alkyl quaternary ammonium salt type cationic surfactants may be used singly or as a mixture of two or more kinds. A blending amount of 0%, particularly 0.5 to 15.0% is preferable because of excellent feel. It is not preferable because the feeling is deteriorated.

Examples of the oils and fats include higher alcohols having a linear or branched alkyl or alkenyl group; hydrocarbons such as liquid paraffin, petrolatum and solid paraffin; lanolin such as liquid lanolin and lanolin fatty acid. Derivatives; 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, esters compatible with higher alcohols having 14 to 26 carbon atoms or methyl polysiloxane are preferable. 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 the hair cosmetic composition of the present invention, if necessary, components used in ordinary cosmetics, pharmaceuticals, foods, etc., such as antidandruff agents, bactericides, vitamins and other medicinal agents; Preservatives such as parabens; perfluoropolyether,
Thickeners such as water-soluble polymers; coloring agents such as dyes and pigments;
Conditioning agents such as cationic polymers; Pearling agents such as glycol esters; Hair set polymers such as acrylic resin liquids; Various fragrances; Others, ENCYC
LOPEDIA OF CONDITIONING RI
NSE INGREDIENTS [Encyclopedia of Conditioning Rinse Ingredients (MICELLE PRESS 1987)]
The components listed in 1 above can be appropriately blended within a range that does not impair the effects of the present invention.

The hair cosmetic composition of the present invention is preferably an emulsion type hair cosmetic composition, and in this case, it can be produced by appropriately mixing water necessary for forming an emulsion, for example, a hair rinse, It can be applied as a hair conditioner, hair treatment, hair cream, styling lotion, styling mousse, conditioning mousse, hair spray and the like.

[0141]

The hair cosmetic composition of the present invention has good spreadability when applied, no stickiness, and excellent moisturizing property. It prevents tangles during moisturizing and drying, and has excellent smoothness.
A moist feeling, a dry feeling, flexibility, and an antistatic effect can be imparted, and these effects are maintained particularly on damaged hair.

[0142]

EXAMPLES Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.

Reference Example 1 (1) Production of linear silicone oligomer functionalized with Si-H group at one end: dried tetrahydrofuran 200
23.3 ml (1.6 mol / l) of n-butyllithium in ml
Hexamethylcyclotrisiloxane (commonly known as D ₃ ) (186 g) was added to the solution in which dry tetrahydrofuran (500 m) was added.
The solution dissolved in 1 was added, and the mixture was polymerized at 0 ° C. for 6 hours in a nitrogen atmosphere. Then, 8.8 g of chlorodimethylsilane was added and stirred for 1 hour to terminate the polymerization. After the formed lithium chloride precipitate was filtered off, it was washed with ion-exchanged water, methyl alcohol was added to precipitate the formed oligomer, and the product was purified by reprecipitation from a tetrahydrofuran-methyl alcohol system. A linear silicone oligomer having a -H group was obtained. The number average molecular weight of the obtained oligomer was as follows. Calculated value 507
0, GPC method (polystyrene conversion) 5500, GP
The polydispersity index Mw / Mn according to the C method was 1.20. In the IR spectrum of this compound, characteristic absorption derived from Si—H bond was observed at 2130 cm ⁻¹ .

(2) Production of a linear silicone oligomer functionalized at one end with a 3-dimethylaminopropyl group:
To 100 g of a linear silicone oligomer having one end functionalized with Si-H group synthesized in (1), 9 mg of chloroplatinic acid hexahydrate dissolved in 0.09 g of isopropyl alcohol was added, and dimethylallylamine was further added. 12.9 g was added dropwise. After the dropping is completed, the reaction temperature is set to 60 to 65 ° C,
React for about 12 hours. After the completion of the reaction, the reaction temperature was lowered to room temperature, activated carbon was added, platinum acid was adsorbed, filtered under reduced pressure, and low-boiling substances such as a solvent were distilled off under reduced pressure using an evaporator. A colorless transparent oily substance was obtained almost quantitatively. Fat and oil analysis result (KOHmg / g): Total amine value: calculated value 10.2, measured value 10.7

Reference Example 2 Reaction of 3-dimethylaminopropyl modified silicone with one terminal and 1,3-dibromopropane and N, N, N ', N'-tetramethyl-1,4-butanediamine (part-
1): 10 g of 3-dimethylaminopropyl-modified silicone having one terminal obtained in Reference Example 1 and 2 g of 1,3-dibromopropane dissolved in 4 g of xylene and 1.2 g of methyl cellosolve were reacted at a reaction temperature of 100 ° C. The reaction was allowed for 18 hours. After completion of the reaction, low boiling substances such as a solvent were distilled off under reduced pressure using an evaporator. A colorless transparent oily substance was obtained almost quantitatively. Fat and oil analysis result (KOHmg / g): Total amine value: calculated value 0.0, measured value 0.3> Residual amine value: calculated value 0.0, measured value 0.35

Next, 10 g of the compound synthesized by the above reaction and N, N, N ', N'-tetramethyl-1,4
-Butanediamine (1.44 g) to which dimethylformamide (DMF) (2.0 g) was added was used at a reaction temperature of 80 ° C.
React for about 20 hours. After completion of the reaction, hexane is about 3
0 ml was added, washed with ion-exchanged water, and dried over anhydrous sodium sulfate. When a low boiling substance such as a solvent was distilled off under reduced pressure by an evaporator, a pale yellow transparent oily substance was obtained almost quantitatively. Fat and oil analysis results (KOHmg / g): Total amine value: Calculated value 10.2, Found value 12.7 This compound is considered to be a cationized silicone polymer having the following structure.

[0147]

[Chemical 42]

Infrared absorption spectrum (cm ^-1 ): 298
0,2880,2830,2790,1478,142
0, 1265, 1100, 1030, 876, 810,
710,695,675.

[0149]

[Chemical 43]

Reference Example 3 Reaction of 3-dimethylaminopropyl modified silicone at one end with 1,3-dibromopropane and N, N, N ', N'-tetramethyl-1,4-butanediamine (part-
2): 10 g of one-terminal 3-dimethylaminopropyl-modified silicone obtained in Reference Example 1, 2 g of 1,3-dibromopropane and N, N, N ′, N′-tetramethyl-1,4-
A solution of 1.2 g of butanediamine dissolved in 4 g of xylene and 1.2 g of methyl cellosolve is reacted at a reaction temperature of 100 ° C. for about 18 hours. After completion of the reaction, low boiling substances such as a solvent were distilled off under reduced pressure using an evaporator. Next, about 30 ml of hexane was added, washed with ion-exchanged water, and dried over anhydrous sodium sulfate. When a low boiling substance such as a solvent was distilled off under reduced pressure by an evaporator, a pale yellow transparent oily substance was obtained almost quantitatively. Fat and oil analysis result (KOHmg / g): Total amine value: calculated value 10.2, measured value 12.9

Infrared absorption spectrum (cm ^-1 ): 297
0,2920,2825,2795,1450,141
8, 1263, 1095, 1030, 868, 808,
710,690.

[0152]

[Chemical 44]

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) heated to the same temperature and dissolved or dispersed was added, and the mixture was stirred to emulsify.
It cooled to room temperature and obtained the hair rinse agent.

Test method: Japanese women are thicker (about 90μ)
20 g (15 cm in length) of the 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 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.

[0157]

[Table 1]

[0158]

[Chemical formula 45]

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: To a mixture of purified water heated to 70 ° C., a preservative, and a dye, a mixture dissolved and dispersed by heating to the same temperature was added, and the mixture was stirred to emulsify. In addition, the mixture was further cooled to room temperature with stirring to obtain the desired composition.

[0161]

[Table 2]

[0162]

[Chemical formula 46]

Example 3 A hair cosmetic composition having the following composition was prepared by a conventional method.

[0164]

[Table 3] Hair rinse: (%) Dimethyl polysiloxane (Polymerization degree: 50) 1.0 One-terminal ionene-modified silicone (Reference Example 2) 1.0 Phytantriol 1.0 Propylene glycol 3.0 Stearyl trimethyl ammonium chloride 1. 0 Stearyl alcohol 3.0 Isotridosyl myristate 0.2 Methylparaben 0.1 Hydroxyethyl cellulose (1% aqueous solution viscosity 8000 cp) 0.4 Perfume 0.4 Water balance

The hair rinse of the present invention was excellent in smoothness and softness when dried, and had good dry feeling and moisturizing feeling, and also excellent sustainability of effect.

[0166]

[Table 4] Hair treatment: (%) Dimethyl polysiloxane (Polymerization degree: 3300) 1.5 Dimethyl polysiloxane (Polymerization degree: 30) 5.0 One-end ionene-modified silicone (Reference example 2) 1.5 Pentaerythritol / isostearyl 1 mol adduct of glycidyl ether 3.0 Diethylene glycol ethyl ether 5.0 Stearyl trimethyl ammonium chloride 2.0 Dialkyl dimethyl ammonium chloride ^{* 1} 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: To a 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 branch fourth With an ammonium salt,
The branching rate is 20%.

The hair treatment of the present invention has a smoothness,
It was excellent in flexibility and had a good moist feeling and dry feeling.

[0168]

Table 5 Conditioning mousse: (%) Dimethyl polysiloxane (Polymerization degree 3300) 0.5 Dimethyl polysiloxane (Polymerization degree 40) 1.5 Cationized silicone polymer (Reference example 2) 0.8 Pentaerythritol isostearyl 1 mol of adduct of glycidyl ether 1.0 glycerin 2.5 isopropyl palmitate 2.5 2-hexyldecyltrimethylammonium chloride 0.5 polyoxyethylene sorbitan monostearate 0.2 95% ethanol 5.0 methylparaben 0. 1 Perfume 0.1 LPG (4.0 kg / cm ² G, 20 ° C) 10.0 Water balance

The conditioning mousse of the present invention was excellent in smoothness, had no dryness, and had a moist and smooth feeling.

[0170]

[Table 6] Styling mousse: (%) Dimethylpolysiloxane (Polymerization degree: 3300) 0.5 Octamethylcyclotetrasiloxane 1.5 Cationized silicone polymer (Reference Example 2) 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 Pigment 0.01 Water Balance LPG (4.0 kg / cm ² G, 20 ° C) 10.0

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

Claims (4)

[Claims] 1. The following components (A) and (B): (A) Cationized silicone polymer (B) Having at least one long-chain branched alkyl group or alkenyl group in one molecule, Hair cosmetic containing a nonionic amphipathic compound whose mixture with water retains a liquid crystal structure at any temperature of ° C. 2. The hair cosmetic composition according to claim 1, wherein the nonionic amphipathic compound of the component (B) has at least 3 hydroxyl groups. 3. The (A) cationized silicone polymer is
The following general formula (2): [In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and are a hydrocarbon group which may have a substituent having 1 to 12 carbon atoms, or an alkyl or acyl group at the terminal oxygen atom. Represents an optionally substituted polyoxyalkylene group or polysiloxane group, and A is (In the formula, R ⁹ , R ¹⁰ , R ¹² , R ¹³ , R ¹⁵ , R ¹⁶ , R ¹⁸ and R ¹⁹ are the same or different and each is a hydrocarbon group which may have a substituent having 1 to 12 carbon atoms. Represents a polyoxyalkylene group or polysiloxane group in which a terminal oxygen atom may be substituted with an alkyl or acyl group, and R ¹¹ , R ¹⁴ , R ¹⁷
And R ²⁰ are the same or different and each represents a divalent hydrocarbon group which may have a substituent having 1 to 12 carbon atoms, X'represents a halogen atom), and B represents a halogen atom. Atom, (Wherein R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷
Are hydrocarbon groups which may be the same or different and have a substituent having 1 to 12 carbon atoms, a polyoxyalkylene group or a polysiloxane group which may have an alkyl or acyl group substituted on the terminal oxygen atom, X'represents a halogen atom, f represents a number of 1 to 10, g represents a number of 0 to 400), c represents a number of 0 to 400,
The hair cosmetic according to claim 1 or 2, wherein d is a number of 1 to 10 and e is a number of 1 to 20]. 4. The hair cosmetic composition according to claim 1, further comprising a silicone derivative other than the component (A).