JP4950580B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to a non-washing-type hair cosmetic that imparts a natural unity feeling and eliminates swells.

  In recent years, due to the chemical treatment with hair color and the physical treatment with blow, etc., peeling of the cuticle on the hair surface and hollowing out of the hair due to the outflow of lipid inside the hair, etc., as a result, the hair becomes dry. It is said that bad fingering, loose hair, and loss of luster may occur.

  Currently used as a hair cosmetic that does not wash away, such as a hair cream type containing wax, higher alcohols, surfactants, etc. There are emulsified products or gels containing a film-forming polymer (set polymer). Such a hair cosmetic can attach fats and oils and polymers to the hair surface and temporarily solve problems such as poor cohesiveness and dryness, but essentially prevents hair gloss and cohesiveness. It could not be improved. In addition, the hair coloring and perms that have become popular in recent years can damage the hair and increase the friction on the hair surface, which can make the hair more likely to get entangled, resulting in poor feel during washing and combing after drying. Is known and a solution is sought. In addition, the hair tips with accumulated pain, in addition to increased friction on the surface, swells the hair different from the original shape, and the hair is oriented in a disjointed direction, for example, floating hair and splash hair There is also the problem of becoming.

  Therefore, as a technique for essentially improving the glossiness and unity and improving the touch, hair cosmetics using a specific organic acid, a specific organic solvent and an amphiphilic amide lipid (Patent Document 1), a specific A hair cosmetic (Patent Document 2) using an organic acid, a specific organic solvent, and a specific organopolysiloxane has been proposed. However, with these hair cosmetics, the fingering of the hair is insufficient and the undulation of the hair cannot be eliminated.

  On the other hand, it has been proposed to use naphthalene sulfonic acids for a hair treatment agent that is washed away for the purpose of imparting firmness and stiffness to hair (Patent Documents 3 and 4).

JP 2005-239566 JP 2006-69899 A Japanese Patent Laid-Open No. 05-229919 Japanese Patent Laid-Open No. 08-198732

  Therefore, the present invention provides a washing-type hair cosmetic that allows the hair to be smoothly applied during application, eliminates squeaks in the hair during application, eliminates swells, and can be supple and smooth. The purpose is to do.

  The present inventors have found that the above-mentioned problems can be solved by using toluenesulfonic acid or a salt thereof, an organic carboxylic acid or a salt thereof, or a specific organic solvent in a hair cosmetic that does not wash away.

That is, the present invention provides the following types of hair cosmetics containing the following components (A) to (C) and having a pH of 2 to 6 at 25 ° C. when diluted 20 times by mass with water: Is.
(A) Toluenesulfonic acid or its salt
(B) Organic carboxylic acid or salt thereof
(C) an organic solvent selected from the group consisting of aromatic alcohol, N-alkylpyrrolidone, alkylene carbonate, polypropylene glycol, lactone and cyclic ketone, wherein ClogP is −2 to 3

  Moreover, this invention provides the hair modification method which processes hair using the said hair cosmetics.

  The hair cosmetic composition of the present invention is good in fingering of the hair at the time of application, has no squeaky hair at the time of application, eliminates undulation, and can be supple and smoothly gathered naturally.

  Examples of the toluenesulfonic acid of component (A) include o-toluenesulfonic acid and p-toluenesulfonic acid, and p-toluenesulfonic acid is particularly preferable. Examples of the salts include sodium salts, potassium salts, and ammonium salts.

  A component (A) can be used individually or in combination of 2 or more types. The content of the component (A) is 0.005 to 5 mass with respect to the total amount of the hair cosmetic composition of the present invention, from the viewpoint of improving the feeling of use and restoring the bounced and wavy hair tips to their original straight state. %, Preferably 0.05 to 4.5% by mass, particularly preferably 0.5 to 4% by mass.

Examples of the organic carboxylic acid of component (B) include monocarboxylic acid, dicarboxylic acid, hydroxycarboxylic acid, polycarboxylic acid and the like, among which dicarboxylic acid and hydroxycarboxylic acid are particularly preferable.
Examples of the dicarboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, malic acid and the like, and malic acid is particularly preferable. Examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, hydroxyacrylic acid, oxybutyric acid, glyceric acid, malic acid, tartaric acid, and citric acid. Malic acid and lactic acid are particularly preferable.

  A component (B) can be used individually or in combination of 2 or more types. The content of the component (B) is 0.001 to 20% by mass with respect to the total amount of the hair cosmetic composition of the present invention, from the viewpoint of the effect of internal reforming of the hair (such as cavity repair), the effect of improving set retention, and the effect of improving the unity. Further, it is preferably 0.01 to 15% by mass, particularly preferably 0.1 to 10% by mass.

  Examples of the organic solvent of component (C) include those selected from the following (c1) to (c5).

(c1) Aromatic alcohol represented by general formula (2)

[Wherein R ² is a group R ³ —Ph—R ⁴ — (R ³ ; a hydrogen atom, a methyl group or a methoxy group, R ⁴ ; a bond or a saturated or unsaturated divalent carbon atom having 1 to 3 carbon atoms. Hydrogen group, Ph; paraphenylene group), Y and Z each represent a hydrogen atom or a hydroxyl group, and p, q, and r each represent an integer of 0 to 5. However, when p = q = 0, Z is not a hydrogen atom and R ² is not a group R ³ —Ph—. ]

(c2) N-alkylpyrrolidone having a C1-C18 alkyl group bonded to a nitrogen atom

(c3) C2-C4 alkylene carbonate

(c4) Polypropylene glycol having a number average molecular weight of 100 to 1000

(c5) Lactone or cyclic ketone represented by general formula (3), (4) or (5)

[Wherein, X represents a methylene group or an oxygen atom, R ⁵ and R ⁶ represent different substituents, and a and b represent 0 or 1. ]

Among the organic solvents that are component (C), examples of (c1) include benzyl alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, 2-benzyloxyethanol and the like. .
Examples of (c2) include N-methylpyrrolidone, N-octylpyrrolidone, N-laurylpyrrolidone and the like.
Examples of (c3) include ethylene carbonate and propylene carbonate.
As the polypropylene glycol (c4) having a number average molecular weight of 100 to 1000, those having a number average molecular weight of 100 to 500, particularly those having a polymerization degree of 2 to 5 are preferred.
In (c5), R ⁵ and R ⁶ in the general formulas (2) to (4) are linear, branched or cyclic alkyl groups, hydroxyl groups, sulfonic acid groups, phosphoric acid groups, carboxy groups, and phenyl groups. , A sulfoalkyl group, an alkyl phosphate group, a carboxyalkyl group, etc. are preferable. In particular, in the case of γ-lactone, the γ-position is substituted, and in the case of δ-lactone, the δ-position (that is, the methylene adjacent to the hetero oxygen atom) is substituted. C1-C6 linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl groups are preferred. When it is desired to increase the water solubility of the compounds (3) to (5), R ⁵ or R ⁶ has an acidic group such as a sulfonic acid group, a phosphoric acid group or a carboxy group, or an alkyl group substituted with these. Is preferred. Among (c5), examples of the lactone include γ-butyrolactone, γ-caprolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, δ-heptanolactone, and the like, from the viewpoint of lactone stability. Γ-lactone, particularly γ-butyrolactone and γ-caprolactone are preferred. Among (c5), examples of the cyclic ketone include cyclopentanone, cyclohexanone, cycloheptanone, 4-methylcycloheptanone and the like.

  Particularly preferred components (C) include benzyl alcohol, benzyloxyethanol, propylene carbonate and propylene glycol (number average molecular weight 300 to 500, particularly 400).

The component (C) used in the present invention is preferably liquid at 25 ° C. Moreover, although ClogP of a component (C) is -2-3, it is preferable that it is -1-2 from the point of penetration promotion. Here, ClogP is a calculated value of the octanol-water-partition coefficient (logP) defined by the following formula, which is a measure representing the distribution of substances between the octanol phase and the water phase. An example is described in Vol. 71, No. 6 (1971).
logP = log ([Substance] _Octanol / [Substance] _Water )
[In the formula, [Substance] _Octanol represents the molar concentration of the substance in the 1-octanol phase, and [Substance] _Water represents the molar concentration of the substance in the aqueous phase. ]

  Specifically, ClogP of the main component (C) is benzyl alcohol (1.1), 2-benzyloxyethanol (1.2), 2-phenylethanol (1.2), 1-phenoxy-2-propanol (1.1), polypropylene Glycol 400 (0.9), propylene carbonate (-0.41), and γ-butyrolactone (-0.64).

  A component (C) can be used individually or in combination of 2 or more types. The content of the component (C) is 0.001 to 20 mass with respect to the total amount of the hair cosmetic composition of the present invention from the viewpoint of feeling of use, gloss of hair and promotion of modification effect (improvement of elasticity, improvement of moisture resistance, etc.). % Is particularly preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass.

  The mass ratio of the component (B) to the component (C) is excellent in the effect of improving the elasticity and stiffness of the hair, the effect of improving set retention, and the effect of improving the mass, and (B) :( C) is 10: 1 to 1: 7, particularly in the range of 4: 1 to 1: 3.

  The hair cosmetic composition of the present invention preferably contains an amphiphilic amide lipid as the component (D) from the viewpoint of modifying the hair, improving the gloss and cohesiveness of the hair, and imparting an excellent feel. . The amphiphilic amide lipid of component (D) has 1 to 2 amide groups, and the carbon chain bonded to the carbonyl group of the amide group may be substituted with a hydroxyl group, and the main chain has an ester bond. The alkyl group or alkylene group having 5 to 60 carbon atoms which may be contained, and the compound as a whole contains 1 to 5 hydroxyl groups or alkoxy groups having 1 to 30 carbon atoms. Specific examples of the amphiphilic amide lipid include the following (d1) to (d4).

(D1) Diamide compound represented by general formula (6)

[Wherein R ⁷ represents a linear or branched hydrocarbon group having 1 to 12 carbon atoms which may be substituted by a hydroxyl group and / or an alkoxy group, and R ⁸ is a linear or branched chain having 1 to 5 carbon atoms. A branched divalent hydrocarbon group is represented, and R ⁹ represents a linear or branched divalent hydrocarbon group having 1 to 22 carbon atoms. ]

In General Formula (6), R ⁷ is a linear or branched alkyl group having 1 to 12 carbon atoms that may be substituted with 1 to 3 groups selected from a hydroxyl group and an alkoxy group having 1 to 6 carbon atoms. Is preferred. Among them, an unsubstituted alkyl group having 1 to 12 carbon atoms, or 1 to 2 hydroxyl groups, one alkoxy group having 1 to 6 carbon atoms, or one hydroxyl group and one alkoxy group having 1 to 6 carbon atoms. A substituted alkyl group having 2 to 12 carbon atoms is more preferred. Specifically, methyl group, ethyl group, propyl group, butyl group, hexyl group, dodecyl group, 2-methylpropyl group, 2-ethylhexyl group, 2-hydroxyethyl group, 9-hydroxynonyl group, 2,3- Examples include dihydroxypropyl group, 2-methoxyethyl group, 2-hydroxy-3-methoxypropyl group, 9-methoxynonyl group, among which 2-hydroxyethyl group, methyl group, dodecyl group, 2-methoxyethyl group preferable.

In the general formula (6), R ⁸ is preferably a linear or branched alkylene group having 2 to 5 carbon atoms, particularly 2 to 3 carbon atoms. Specifically, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, 1-methylethylene group, 2-methylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethyl Examples thereof include an ethylene group and a 2-ethyltrimethylene group, and among them, an ethylene group and a trimethylene group are preferable.

In the general formula (6), R ⁹ is preferably a linear or branched divalent hydrocarbon group having 2 to 22 carbon atoms, particularly a linear or branched alkylene group having 11 to 22 carbon atoms, and 1 Alkenylene groups having ˜4 double bonds are preferred. Specifically, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, heptamethylene group, octamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, hexa Decamethylene group, octadecamethylene group, 1-methylethylene group, 2-ethyltrimethylene group, 1-methylheptamethylene group, 2-methylheptamethylene group, 1-butylhexamethylene group, 2-methyl-5-ethyl Heptamethylene group, 2,3,6-trimethylheptamethylene group, 6-ethyldecamethylene group, 7-methyltetradecamethylene group, 7-ethylhexadecamethylene group, 7,12-dimethyloctadecamethylene group, 8, 11-dimethyloctadecamethylene group, 7,10-dimethyl-7-ethylhexadecamethylene group, 1-octadecylethylene group, ethenylene group, 1- Octadecenylethylene group, 7,11-octadecadienylene group, 7-ethenyl-9-hexadecamethylene group, 7,12-dimethyl-7,11-octadecadienylene group, 8,11-dimethyl- Examples include 7,11-octadecadienylene group. Among these, 7,12-dimethyloctadecamethylene group, 7,12-dimethyl-7,11-octadecadienylene group, octadecamethylene group, undecamethylene group, and tridecamethylene group are particularly preferable.

A particularly preferred diamide compound (6) is a compound in which the above-mentioned preferred groups are combined as R ⁷ , R ⁸ and R ⁹ , and specific examples thereof include the following compounds.

(D2) Ceramides represented by general formula (7)

[Wherein R ¹⁰ represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 4 to 30 carbon atoms which may be substituted by a hydroxy group, an oxo group or an amino group, and W represents a methylene group. , A methine group or an oxygen atom, a broken line indicates the presence or absence of a π bond, X ¹ represents a hydrogen atom, an acetyl group or a glyceryl group, or forms an oxo group with an adjacent oxygen atom, X ² , X ³ and X ⁴ each independently represent a hydrogen atom, a hydroxy group or an acetoxy group (provided that when W is a methine group, one of X ² and X ³ is a hydrogen atom and the other does not exist; When O-X ¹ is an oxo group, X ⁴ does not exist), R ¹¹ and R ¹² each independently represent a hydrogen atom, a hydroxy group, a hydroxymethyl group or an acetoxymethyl group, and R ¹³ represents a hydroxy group or 5 to 35 carbon atoms that the amino group may be substituted A linear, branched or cyclic saturated hydrocarbon group, or a linear, branched or cyclic saturated or unsaturated fatty acid having 8 to 22 carbon atoms, which may be substituted with a hydroxy group at the ω position of the hydrocarbon group. An ester-bonded group, R ¹⁴ represents a hydrogen atom, or may have a substituent selected from a hydroxy group, a hydroxyalkoxy group, an alkoxy group, and an acetoxy group; Indicates a saturated or unsaturated hydrocarbon group in the chain. ]

In the general formula (7), R ¹⁰ is preferably a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 7 to 22 carbon atoms which may be substituted by a hydroxy group. X ¹ is preferably a hydrogen atom or a glyceryl group. The X ^2, X ³ and X ^4, is the 0-1 is hydroxy group, preferably the remainder is a hydrogen atom. As R ¹¹ and R ¹² , one is preferably a hydrogen atom or a hydroxymethyl group, and the other is preferably a hydrogen atom. As the fatty acid that may be ester-bonded or amide-bonded to the ω position of the saturated hydrocarbon group for R ¹³ , isostearic acid, 12-hydroxystearic acid, and linoleic acid are preferable. R ¹⁴ is preferably a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms in which 1 to 3 groups selected from a hydroxy group, a hydroxyalkoxy group and an alkoxy group may be substituted.

  Preferred ceramides (7) include the following (7a) and (7b).

(7a): Natural ceramide or natural ceramide represented by the general formula (7a), and derivatives thereof (hereinafter referred to as “natural ceramides”):

[Wherein, R ^10a represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms which may be substituted by a hydroxy group, and W ¹ represents a methylene group or a methine group. , The broken line indicates the presence or absence of a π bond, X ^1a represents a hydrogen atom, or an oxo group is formed with an adjacent oxygen atom, and X ^2a , X ^3a and X ^4a are each independently a hydrogen atom, A hydroxy group or an acetoxy group (provided that when W ¹ is a methine group, one of X ^2a and X ^3a is a hydrogen atom and the other is not present, and when —O—X ^1a is an oxo group, X ^4a R ^11a represents a hydroxymethyl group or an acetoxymethyl group, and R ^13a represents a linear, branched or cyclic saturated hydrocarbon group having 5 to 30 carbon atoms which may be substituted by the hydroxy group, or The number of carbon atoms that may be substituted with a hydroxy group at the ω-terminal of the alkyl group 8 to 22 linear or branched saturated or unsaturated fatty acid is an ester-bonded group, and R ^14a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

Preferably, R ^10a is a linear alkyl group having 7 to 19 carbon atoms, more preferably 13 to 15 carbon atoms; W ¹ is a methine group and ^one of X ^2a and X ^3a is a hydrogen atom; R ^13a is 9 to 9 carbon atoms Examples thereof include compounds in which 27 hydroxy groups are linear alkyl groups that may be substituted. X ^1a is preferably a hydrogen atom or forms an oxo group together with an oxygen atom. In particular, R ^13a is preferably a tricosyl group, a 1-hydroxypentadecyl group, a 1-hydroxytricosyl group, a heptadecyl group, a 1-hydroxyundecyl group, or a nonacosyl group in which linoleic acid is ester-bonded to the ω position.

  Specific examples of natural ceramides include ceramides Type 1 to 7 in which sphingosine, dihydrosphingosine, phytosphingosine, or sphingadienin is amidated (for example, J. Lipid Res., 24: 759 (1983) and FIG. 4 of J. Lipid. Res., 35: 2069 (1994).

  Furthermore, these N-alkyl bodies (for example, N-methyl body) are also mentioned. These may be any of natural extracts and synthetic products, and commercially available products can be used.

(7b): Pseudoceramides represented by the following general formula (7b):

[Wherein, R ^10b represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms which may be substituted by a hydroxy group, and X ^1b represents a hydrogen atom, an acetyl group or glyceryl. R ^13b is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 5 to 22 carbon atoms which may be substituted by a hydroxyl group or an amino group, or the hydrocarbon group Represents a group in which a linear or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms, which may be substituted with a hydroxyl group at the ω-terminal, is ester-bonded, and R ^14b represents a hydrogen atom or a hydroxy group , A hydroxyalkoxy group, an alkoxy group or an acetoxy group, an alkyl group having 1 to 8 carbon atoms which may be substituted. ]

R ^13b is particularly a nonyl group, tridecyl group, pentadecyl group, an undecyl group in which linoleic acid is ester-bonded to the ω position, a pentadecyl group in which linoleic acid is ester-bonded to the ω position, and 12-hydroxystearic acid is an ester bond to the ω position. And an undecyl group in which methyl branched isostearic acid is amide-bonded at the ω position. The hydroxyalkoxy group or alkoxy group for R ^14b is preferably one having 1 to 8 carbon atoms.

The pseudo-ceramides (7b) are those in which R ^10b is a hexadecyl group, X ^1b is a hydrogen atom, R ^13b is a pentadecyl group, R ^14b is a hydroxyethyl group; R ^10b is a hexadecyl group, X ^1b is a hydrogen atom, R Preferably, ^13b is a nonyl group and R ^14b is a hydroxyethyl group; or R ^10b is a hexadecyl group, X ^1b is a glyceryl group, R ^13b is a tridecyl group, and R ^14b is a 3-methoxypropyl group. In which R ^9b is a hexadecyl group, X ^1b is a hydrogen atom, R ^13b is a pentadecyl group, and R ^14b is a hydroxyethyl group. Preferable specific examples include the following.

(D3) Diamide compound represented by general formula (8)

[Wherein, R ¹⁵ represents an alkyl group having 10 to 18 carbon atoms which may be substituted by a hydroxy group. ]

  Specific examples of the compound (8) include the following compounds.

(D4) Amide compound represented by general formula (9)

[Wherein R ¹⁶ represents a linear or branched, saturated or unsaturated alkyl group which may be substituted with a hydroxyl group, or a residue of 2-dodecen-1-ylsuccinic acid having 9 to 31 carbon atoms. , M represents an integer of 1 to 3, R ¹⁷ and R ¹⁸ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, and V represents a linear or branched chain having 10 to 32 carbon atoms. An alkyl group that may be substituted by a saturated or unsaturated hydroxyl group, or

(K, i and h each represents an integer of 1 to 3, j represents 0 or 1, and R ¹⁹ is substituted with a linear or branched saturated or unsaturated hydroxyl group having 9 to 31 carbon atoms. Represents a good alkyl group). ]

  Specific examples of the compound (9) include the following compounds.

  Among these amphiphilic amide lipids, those represented by the general formula (6) or (7), particularly those represented by the general formula (6) are preferable.

  The amphiphilic amide lipid of component (D) can be used alone or in combination of two or more, and the content thereof is based on the total amount of the hair cosmetic composition of the present invention from the viewpoint of the hair modifying effect. 0.001 to 20% by mass is preferable, 0.1 to 10% by mass, more preferably 0.2 to 5% by mass.

  The hair cosmetic composition of the present invention preferably contains a poly (N-acylalkylenimine) -modified silicone as component (E) from the viewpoint of modifying the hair and improving the feel of the hair after application and drying. Examples of the poly (N-acylalkylenimine) -modified silicone include the following formula (1a) in the molecule:

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, and n represents a number of 2 or 3. ]
A segment of poly (N-acylalkylenimine) consisting of a repeating unit represented by formula (1) and an organopolysiloxane segment, and a hetero atom at least one of the terminal or side chain silicon atoms of the organopolysiloxane segment It is preferable that a poly (N-acylalkylenimine) segment composed of the repeating unit represented by the general formula (1a) is bonded through an alkylene group containing The mass ratio of the poly (N-acylalkylenimine) segment to the organopolysiloxane segment is preferably 1/50 to 20/1, more preferably 1/40 to 20/1, and the molecular weight is preferably Is 500 to 500,000, more preferably 1,000 to 300,000. R is preferably a methyl group or an ethyl group.

  The alkylene group containing a hetero atom in at least one of the terminal or side chain silicon atoms of the segment of the organopolysiloxane is an alkylene group having 2 to 20 carbon atoms containing 1 to 3 nitrogen atoms, oxygen atoms or sulfur atoms. In particular, an alkylene group having 2 to 5 carbon atoms containing a nitrogen atom is preferable.

  Preferred examples of such poly (N-acylalkylenimine) -modified silicone include poly (N-formylethyleneimine) -modified silicone, poly (N-acetylethyleneimine) -modified silicone, poly (N-propionylethyleneimine) -modified silicone, etc. Is mentioned. In particular, a poly (N-propionylethyleneimine) modified silicone (INCI name: poly) having a mass average molecular weight of about 20,000 to 200,000 and a ratio of poly (N-propionylethyleneimine) segments in the molecule of about 3 to 50% by mass. Silicone-9; Elastomer OS, Kao Corporation) is preferred.

  The poly (N-acylalkylenimine) -modified silicone can be obtained by a known method, for example, a method described in JP-A-7-133352, and is synthesized, for example, by the following method. First, the segment of poly (N-acylalkyleneimine) composed of the repeating unit represented by the formula (1a) is obtained by ring-opening polymerization of the cyclic iminoether compound represented by the formula (1b).

  These cyclic imino ethers can be produced, for example, according to the method described in Liebigs Ann. Chem., P996-p1009 (1974). These compounds may be used alone as a monomer for ring-opening polymerization, or may be used in combination of two or more.

  Examples of the polymerization initiator for ring-opening polymerization of the cyclic imino ether include toluenesulfonic acid alkyl ester, sulfuric acid dialkyl ester, trifluoromethanesulfonic acid alkyl ester, and alkyl halide, but are not limited thereto. These initiators can be used alone or in a mixture.

  A molecular chain of poly (N-acylalkylenimine) can be obtained by ring-opening polymerization of the cyclic imino ether compound represented by the above formula (1b) using these initiators. It may be a polymer chain or a copolymer chain, and the copolymer chain may be a random copolymer chain or a block copolymer chain.

  The molecular weight of the molecular chain of the poly (N-acylalkylenimine) is preferably 150 to 50,000, more preferably 500 to 10,000.

  The modified silicone of component (E) reacts a polymerization active species generated by ring-opening polymerization of the cyclic imino ether compound represented by the formula (1b) and an organopolysiloxane having a functional group capable of reacting with the polymerization active species. Can be obtained.

  Examples of the functional group capable of reacting with the above-mentioned polymerization active species include primary, secondary or tertiary amino groups, mercapto groups, hydroxyl groups, carboxylate groups, etc. Among them, amino groups are preferable. The organopolysiloxane containing an amino group in the molecule preferably has a molecular weight of 300 to 400,000, more preferably 800 to 250,000.

  The reaction between the organopolysiloxane containing an amino group and the reactive terminal of poly (N-acylalkylenimine) obtained by cationic polymerization of cyclic imino ether can be carried out as follows.

  Initiator is a polar solvent, preferably acetonitrile, valeronitrile, dimethylformamide, dimethylacetamide, chloroform, methylene chloride, ethylene chloride, ethyl acetate, methyl acetate, etc., or a mixed solvent with other solvents as required And heated to 40 to 150 ° C, preferably 60 to 100 ° C. The cyclic imino ether represented by the above general formula (1b) is added all at once, or dropped when the reaction is intense, and polymerization is carried out. The progress of the polymerization can be traced by quantifying the residual amount of the cyclic imino ether as a monomer with an analytical instrument such as gas chromatography. Even when the cyclic imino ether is consumed and the polymerization is completed, the active species at the growing end maintain the reactivity. Without isolating the polymer, this polymer solution and the organopolysiloxane containing an amino group in the molecule are mixed and reacted at 5 to 100 ° C., preferably 20 to 60 ° C. The mixing ratio can be appropriately selected as desired, but it is preferable to react at a ratio of 0.1 to 1.3 molar equivalents of poly (N-acylalkylenimine) to 1 mol of amino group in the organopolysiloxane.

  By the reaction as described above, a block copolymer or graft polymer having poly (N-acylalkylenimine) segments attached to polydimethylsiloxane can be obtained.

  Component (E) can be used alone or in combination of two or more, and its content improves the touch without diminishing the hair-modifying effect of components (B) and (C). Therefore, the content is preferably 0.1 to 10% by mass, particularly 0.5 to 5% by mass, based on the total amount of the hair cosmetic composition of the present invention.

The hair cosmetic composition of the present invention may contain a conditioning component selected from silicones and oils for further improving the conditioning effect. Silicones include dimethylpolysiloxane, polyether-modified silicone, amino-modified silicone, carboxy-modified silicone, methylphenylpolysiloxane, fatty acid-modified silicone, alcohol-modified silicone, aliphatic alcohol-modified silicone, epoxy-modified silicone, fluorine-modified silicone, cyclic Examples include silicone and alkyl-modified silicone. Of these, dimethylpolysiloxane, polyether-modified silicone, and amino-modified silicone are preferable. Dimethylpolysiloxane can impart good lubricity to hair, polyether-modified silicone can impart smoothness to hair, and amino-modified silicone can impart moist feeling to hair. . In the present invention, various silicones can be used alone or in combination of two or more depending on the desired performance. Dimethylpolysiloxane can be used from a viscosity of about 5 mm ² / s depending on the desired feel to a viscosity of about 10 million mm ² / s, which is often supplied as an emulsion. It is preferably mm ² / s, particularly 50,000 to 10 million mm ² / s. Polyether-modified silicone is a general term for polyoxyethylene / methylpolysiloxane copolymer and poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer, and those having various HLBs are known, but are commercially available. Products include Silicone KF351A, KF353A, KF6008, KF6016, KF6011, and KF6012, Shin-Etsu Chemical Co., Ltd., SH3771C, 3773C, and 3775C from Toray Dow Corning Silicone. As the amino-modified silicone, amodimethicone oil or an emulsion thereof is preferable, and examples of commercially available products include Amodimethicone emulsion SM8704C manufactured by Toray Dow Corning Silicone, KT-1989, XF42-B1989 manufactured by Toshiba Silicone, and the like. It is done.

  The content of the silicone is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, and particularly preferably 0.5 to 10% by mass in the hair cosmetic composition of the present invention, from the viewpoint of fingering and lack of stickiness. Is preferred

  In addition to the above-described components, the hair cosmetic of the present invention can be appropriately mixed with components used in normal hair cosmetics depending on the purpose. Examples of such components include anti-dandruff agents; vitamin agents; bactericides; anti-inflammatory agents; antiseptics; chelating agents; moisturizers such as sorbitol and panthenol; colorants such as dyes and pigments; hydroxyethyl cellulose, methyl cellulose, Viscosity modifiers such as polyethylene glycol and clay minerals; pH modifiers such as organic acids other than component (B), sodium hydroxide, potassium hydroxide; plant extracts; pearling agents; fragrances; dyes; Inhibitors; and other components described in ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLE PRESS).

  The hair cosmetic composition of the present invention has a pH of 2 to 6 when applied to hair (25 ° C. when diluted to 20 mass times with water) from the viewpoint of imparting gloss, flexibility, cohesion and suppleness to the hair. Although adjusted, the pH is preferably 2.5 to 5, particularly preferably 3 to 4.

  The form of the hair cosmetic composition of the present invention can be appropriately selected from liquid form, gel form, paste form, cream form, wax form, etc., but a liquid form using water or a lower alcohol, particularly water, as the solvent is preferred.

  The hair cosmetic composition of the present invention is of a type that does not wash away, but is preferably used as a hair styling agent, hair conditioning agent, or the like. Examples of the dosage form include pump spray, pump mist, aerosol spray, pump foam, aerosol foam, gel, lotion and the like.

  By using the hair cosmetic composition of the present invention, it is possible to finish the hair smoothly and smooth, to eliminate waviness and to modify the hair. In particular, an excellent modification effect can be obtained when damaged hair such as chemical damage is used as the hair. By applying the hair cosmetic composition of the present invention and then heating, penetration of the components (B) and (C) into the hair can be promoted. For heating, a dryer, heater, iron or the like can be used. The temperature is preferably 60 ° C. or higher, particularly 70 ° C. or higher.

Examples 1-2 and Comparative Examples 1-5
A hair cosmetic composition having the composition shown in Table 2 was prepared and applied to the hair. “Following fingers immediately after application”, “No squeaks immediately after application”, “Resistance to undulation of hair”, “Hari Koshi's Strength, suppleness, and smoothness were evaluated. Evaluation methods and evaluation criteria are shown below.

(1) Evaluation hair bundle Japanese hair that has not undergone chemical treatment such as perm, hair color, etc., is subjected to bleach treatment (using Kao-sha, PRETIA Happy Fantasy Hybrid) 8 times, and shampooing and drying dryer 720 times And damaged hair. Using this, a hair bundle having a length of 20 cm, a width of 5.5 cm, and a weight of 10 g was prepared.

(2) Treatment of hair bundles The evaluation hair bundle was washed with a shampoo (Kao Corporation, Pure Shampoo), towel-dried, 0.5 g of the treatment agent was uniformly applied, and dried with a dryer. This operation was repeated 14 times.

(3) Evaluation Criteria Sensory evaluation was performed according to the criteria shown in Table 1 by five expert panelists, and the average score of the evaluation scores was obtained.

* 2: OS-88E-E (Kao Corporation, Polysilicone-9 (INCI name) containing 30% by mass, the same shall apply hereinafter)

  As shown in Table 2, the hair cosmetic composition of the present invention has good finger-fitting of the hair at the time of application, there is no squeak of the hair at the time of application, eliminates swell, and it is a supple, smooth, and natural collection. It was.

Example 3 (Aerosol Spray)
(mass%)
<Undiluted solution>
p-Toluenesulfonic acid 0.1
Poly (N-acylalkylenimine) modified silicone 3.0
Neopentyl glycol dicaprate 4.0
Dimethylpolysiloxane (5000mm ² / s) 5.0
Malic acid 0.1
Lactic acid 0.1
Amphiphilic amide lipid A 0.1
Dimethylpolysiloxane (50mm ² / s) 3.0
2-Benzyloxyethanol 0.1
Benzyl alcohol 0.1
Fragrance 0.1
Ethanol remaining amount <propellant>
Liquefied petroleum gas 100.0
Stock solution / propellant ratio 40/60

Example 4 (pump spray)
(mass%)
p-Toluenesulfonic acid 0.1
Poly (N-acylalkylenimine) modified silicone 1.0
Malic acid 2.0
Lactic acid 2.0
Amphiphilic amide lipid A 0.1
Stearyltrimethylammonium chloride 0.25
Glycerin 1.0
2-Benzyloxyethanol 2.0
Benzyl alcohol 0.5
Ethanol 4.5
DL-Pantenyl alcohol 1.2
Fragrance 0.1
Water remaining amount Sodium hydroxide (pH adjuster) Adjust to pH 3.7

Example 5 (pump mist)
(mass%)
p-Toluenesulfonic acid 0.1
Poly (N-acylalkylenimine) modified silicone 1.0
Malic acid 3.5
Malonic acid 1.0
Amphiphilic amide lipid A 0.1
2-Benzyloxyethanol 2.0
Benzyl alcohol 0.5
Polyvinylpyrrolidone 3.0
Ethanol 10.0
DL-pantothenyl alcohol 1.0
Pantothenyl ethyl ether 0.05
Fragrance 0.1
Water remaining amount Sodium hydroxide (pH adjuster) Adjust to pH 3.7

Example 6 (hair gel)
(mass%)
p-Toluenesulfonic acid 0.1
Poly (N-acylalkylenimine) modified silicone 1.0
Malic acid 2.5
Succinic acid 1.5
Amphiphilic amide lipid A 0.1
Glycerin 2.0
2-Benzyloxyethanol 2.0
Benzyl alcohol 0.5
Hydroxyethyl cellulose 2.0
Ethanol 10.0
Nicotinamide 0.8
Fragrance 0.05
Water remaining amount Sodium hydroxide (pH adjuster) Adjust to pH 3.7

Example 7 (hair lotion)
(mass%)
p-Toluenesulfonic acid 0.1
Poly (N-acylalkylenimine) modified silicone 1.0
Malic acid 4.0
Lactic acid 1.0
Amphiphilic amide lipid A 0.1
Glycerin 1.0
2-Benzyloxyethanol 2.5
Benzyl alcohol 0.5
Ethanol 10.0
Ascorbic acid 0.8
DL-Pantenyl alcohol 0.2
Perfume 0.02
Water remaining amount Sodium hydroxide (pH adjuster) Adjust to pH 3.7

Example 8 (hair lotion)
(mass%)
p-Toluenesulfonic acid 0.1
Poly (N-acylalkylenimine) modified silicone 1.0
Malic acid 2.5
Lactic acid 2.5
Amphiphilic amide lipid A 0.1
2-Benzyloxyethanol 2.5
Benzyl alcohol 0.5
Stearyl trimethylammonium chloride 0.1
Polyethylene glycol 400 0.45
Ethanol 4.5
DL-Pantenyl alcohol 0.8
Nicotinamide 0.2
Perfume 0.02
Water remaining amount Sodium hydroxide (pH adjuster) Adjust to pH 3.7

Example 9 (pump foam)
(mass%)
p-Toluenesulfonic acid 0.1
Poly (N-acylalkylenimine) modified silicone 1.0
Malic acid 2.5
Lactic acid 2.5
Amphiphilic amide lipid A 0.1
Polyoxyethylene lauryl ether (16E.O.) 1.0
Stearyl trimethylammonium chloride 0.1
Glycerin 1.0
2-Benzyloxyethanol 2.5
Benzyl alcohol 0.5
Ethanol 4.5
DL-Pantenyl alcohol 1.0
Perfume 0.02
Water remaining amount Sodium hydroxide (pH adjuster) Adjust to pH 3.7

Example 10 (Wax)
(mass%)
p-Toluenesulfonic acid 0.01
Poly (N-acylalkylenimine) modified silicone 1.0
Malic acid 0.1
Lactic acid 0.1
Amphiphilic amide lipid A 0.1
Cetanol 6.0
Sodium polyoxyethylene lauryl ether phosphate (4E.O.) 1.0
Polyoxyethylene sorbitan monostearate (20E.O.) 1.0
Lipophilic glyceryl monostearate 4.0
Isostearyl glyceryl ether 1.0
Polyvinylpyrrolidone 0.5
Highly polymerized polyethylene glycol 0.2
Carboxyvinyl polymer 0.1
Vaseline 1.0
Concentrated glycerin 1.0
2-Benzyloxyethanol 0.1
Benzyl alcohol 0.5
Light liquid isoparaffin 5.0
Ethanol 10.0
Methyl paraoxybenzoate 0.2
Water Remaining sodium hydroxide aqueous solution (pH adjuster) Adjusted to pH 3.7

Each of the hair cosmetics of Examples 3 to 10 has good hair fingering at the time of application, has no hair squeaks at the time of application, eliminates swells, and can be smoothly and naturally combined. It was a thing.

Claims (3)

A non-washing-out type hair cosmetic that contains the following components (A) to (D) and has a pH of 2 to 6 at 25 ° C. when diluted 20 times by mass with water.
(A) Toluenesulfonic acid or its salt
(B) an organic carboxylic acid selected from the group consisting of malic acid and lactic acid or a salt thereof
(C) an organic solvent selected from the group consisting of aromatic alcohol, N-alkylpyrrolidone, alkylene carbonate, polypropylene glycol, lactone and cyclic ketone, wherein ClogP is −2 to 3
(D) Amphiphilic amide lipid Further hair cosmetic composition according to claim 1, further comprising the following component (E).
(E) Poly (N-acylalkylenimine) modified silicone A hair modification method for treating hair using the hair cosmetic composition according to claim 1 .