JP2009149597A - Hair cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair cosmetic which excels in an effect of imparting smoothness to the hair and its durability, is free of stickiness on application, and furthermore excels in storage stability as well. <P>SOLUTION: The hair cosmetic includes component (A) of a branched fatty acid represented by formula (1) or its salt and component (B) of an organopolysiloxane in which a poly(N-acylalkyleneimine) composed of a repeating unit represented by formula (2) is bonded to at least one silicon atom of an organopolysiloxane segment through an alkylene group having a heteroatom, the organopolysiloxane having a mass ratio of the organopolysiloxane segment to the poly(N-acylalkyleneimine) segment of 98/2 to 40/60 and a mass-average molecular weight of 50,000-500,000. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hair cosmetic.

  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 only attaches fats and oils and polymers to the hair surface, and only temporarily solves problems such as poor cohesiveness and dryness.

  On the other hand, a technology that uses a specific organic acid and organic solvent to modify (increase glossiness and improve cohesion) from the inside of the hair is known. It had problems of stickiness and heavy feel of the hair after drying.

  In order to deal with this problem, by using organic dicarboxylic acid, specific organic solvent and specific organopolysiloxane in combination, the hair modification effect (gloss, unity) and touch improvement effect (smoothness etc.) by organic acid and organic solvent ), And a type of hair cosmetic that does not wash away has been proposed (Patent Document 1). However, although this hair cosmetic is excellent in the effect of imparting smoothness, its durability has not been fully satisfactory.

  In addition, an aqueous hair cosmetic containing an ether amine compound, an aromatic alcohol, and a specific branched fatty acid, which has an effect of preventing hair damage and imparting a good feel (flexibility, smoothness, etc.) has been proposed (patent) Reference 2). However, this hair cosmetic is non-sticky and excellent in the effect of imparting smoothness, but is limited to an aqueous solution system and has low solubility of the components and easily precipitates, so it is separated in a transparent and low viscosity system. There was a problem that was conspicuous.

JP 2006-69899 A JP 2007-176923 A

  Accordingly, an object of the present invention is to provide a hair cosmetic that is excellent in the effect of imparting smoothness to hair and its durability, does not become sticky at the time of application, and also has excellent storage stability.

  The present inventors have found that a hair cosmetic satisfying the above requirements can be obtained by using a specific branched fatty acid and a specific organopolysiloxane in combination.

The present invention provides a hair cosmetic containing the following components (A) and (B).
(A) Branched fatty acid represented by the general formula (1) or a salt thereof

[Wherein, R ¹ represents a methyl group or an ethyl group, and n represents an integer of 3 to 36. ]
(B) At least one silicon atom of the organopolysiloxane segment is bonded to the following general formula (2) via an alkylene group containing a hetero atom.

[Wherein R ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, and m represents a number of 2 or 3. ]
A poly (N-acylalkyleneimine) comprising repeating units represented by the formula is bonded, and the mass ratio of the organopolysiloxane segment to the poly (N-acylalkyleneimine) segment is 98/2 to 40/60. An organopolysiloxane having a weight average molecular weight of 50,000 to 500,000

  Furthermore, the present invention provides a hair modification method in which the above-described hair cosmetic is applied to hair and left without being washed away.

  The hair cosmetic composition of the present invention is excellent in the effect of imparting smoothness to the hair and its durability, is not sticky at the time of application, and is excellent in storage stability.

[(A): Branched fatty acid (1)]
The hair cosmetic used in the present invention contains a branched fatty acid represented by the general formula (1) (hereinafter referred to as branched fatty acid (1)) or a salt thereof.

  The branched fatty acid (1) can be separated and extracted from hair or the like according to the description of LIPIDS, vol.23, No.9, 878-881 (1988), for example, JP-A-4-137719, WO98 It can also be synthesized according to / 30532. The branched fatty acid (1) preferably has a total carbon number of 7 to 40, more preferably 8 to 30, particularly 10 to 22, and specifically, 18-methyleicosanoic acid, 14-methylpentadecanoic acid, 14 -Methylhexadecanoic acid, 15-methylhexadecanoic acid, 15-methylheptadecanoic acid, 16-methylheptadecanoic acid, 16-methyloctadecanoic acid, 17-methyloctadecanoic acid, 17-methylnonadecanoic acid. The branched fatty acid salts include alkali metal salts such as sodium salt, lithium salt and potassium salt; alkaline earth metal salts such as calcium salt and magnesium salt; ammonium salt; triethanolamine salt, diethanolamine salt and monoethanol. Organic amine salts such as amine salts; basic amino acid salts such as lysine salts and arginine salts.

  Examples of the extract include an extract from lanolin, that is, a lanolin fatty acid and a salt thereof. Lanolin fatty acid contains about 50% by mass of methyl branched long chain fatty acid called iso fatty acid or anteiso fatty acid. Specific examples include Crodacid 18-MEA [Crowda Japan Co., Ltd.], Scrairo [Crowda Japan Co., Ltd.], and FA-NH [Nippon Seika Co., Ltd.].

  Two or more kinds of the branched fatty acid (1) or a salt thereof may be used in combination. Moreover, you may mix and use a synthetic product and an extract. The content thereof is preferably 0.001 to 1% by mass, more preferably 0.002 to 0.5% by mass, and particularly preferably 0.005 to 0.3% by mass in the hair cosmetic used in the present invention, from the viewpoint of the effect of recovering or suppressing hair damage. preferable.

[(B): Organopolysiloxane]
In the organopolysiloxane of component (B), the mass ratio of the organopolysiloxane segment to the poly (N-acylalkyleneimine) segment is 98/2 to 40/60, but is 94/6 to 60/40. The mass average molecular weight is preferably 50,000 to 500,000, but preferably 100,000 to 300,000.

  The alkylene group containing a hetero atom intervening in the bond between an organopolysiloxane segment and poly (N-acylalkyleneimine) has 2 to 20 carbon atoms containing 1 to 3 nitrogen atoms, oxygen atoms and / or sulfur atoms. An alkylene group is mentioned. As a specific example,

Etc. In particular, a C2-C5 alkylene group containing a nitrogen atom is preferable. In addition, examples of the alkyl group represented by R ² in the general formula (2) include a methyl group and an ethyl group, and examples of the cycloalkyl group represented by R ² include those having 3 to 6 carbon atoms. Examples of the aralkyl group include phenylalkyl and naphthylalkyl, and examples of the aryl group include phenyl, naphthyl, and alkyl-substituted phenyl.

  The organopolysiloxane of component (B) can be produced by a known method, for example, according to the method described in JP-A-7-133352, the following general formula (3)

[Wherein, R ⁴ is the same or different and represents a saturated alkyl group having 1 to 22 carbon atoms or a phenyl group, and R ⁵ and R ⁶ each represents the same group as R ⁴ , or

R ⁷ represents a group represented by the above formula, p represents an integer of 100 to 4000, and q represents an integer of 1 to 300. ]
And an organopolysiloxane represented by the following general formula (4)

[Wherein, R ² and m are as defined above. ]
It is produced by reacting a terminal reactive poly (N-acylalkyleneimine) obtained by ring-opening polymerization of a cyclic imino ether represented by the formula:

  Here, the ring-opening polymerization of the cyclic iminoether (4) can be carried out according to the method described in, for example, Liebigs Ann. Chem., P996-p1009 (1974). The polymerization initiator is a compound having strong electrophilic reactivity, such as methyl, ethyl, 3-propenyl, benzyl ester, etc. of strong acid such as benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, sulfuric acid and the like. Can be used. In particular, toluenesulfonic acid alkyl ester, sulfuric acid dialkyl ester, trifluoromethanesulfonic acid alkyl ester, and the like can be preferably used. When, for example, 2-substituted-2-oxazoline is used as the cyclic imino ether (4), poly (N-acylethyleneimine) (corresponding to m = 2 in formula (2)) is obtained, and 2-substituted-dihydro- If 2-oxazine is used, poly (N-acylpropyleneimine) (corresponding to m = 3 in the formula (2)) can be obtained. 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 poly (N-acylalkyleneimine) chain and the silicone chain are linked by ester formation reaction by condensation of carboxyl group and hydroxyl group; amide formation reaction by condensation of carboxyl group and amino group; alkyl halide Reaction of primary, secondary or tertiary amino group with secondary, tertiary or quaternary ammonium; addition reaction of Si-H group to vinyl group; β-hydroxyamine with epoxy group and amino group Many techniques such as formation reactions can be used. Of these, as disclosed in JP-A-2-276824, JP-A-4-85334, JP-A-4-85335, JP-A-4-96933, etc. The method of reacting the end-reactive poly (N-acylalkylenimine) obtained by polymerization with the organopolysiloxane represented by the formula (3), that is, the modified organopolysiloxane having the above substituent in the side chain, is simple and effective. It is.

  The reaction between the organopolysiloxane containing an amino group and the reactive terminal of poly (N-acylalkylenimine) obtained by cationic polymerization of a cyclic imino ether can be performed, for example, 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 (4) 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 cyclic iminoether 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) with respect to 1 mol of amino group in the organopolysiloxane. A block copolymer or graft polymer having a poly (N-acylalkylenimine) segment on polydimethylsiloxane can be obtained.

  Examples of the component (B) organopolysiloxane include poly (N-formylethyleneimine) organosiloxane, poly (N-acetylethyleneimine) organosiloxane, and poly (N-propionylethyleneimine) organosiloxane. The INCI name includes Polysilicone-9.

  Component (B) may be used in combination of two or more, and the content thereof is 0.01 to 5% by mass in the hair cosmetic composition of the present invention from the viewpoint of imparting good flexibility and slipperiness during use. Further, 0.05 to 4% by mass, particularly 0.1 to 3% by mass is preferable.

  Also, from the viewpoint of imparting smoothness and achieving both product appearance stability, the mass ratio (B) / (A) of the component (B) to the component (A) is 0.5 to 60, more preferably 1 to 60, It is preferable that it is 4-50, especially 8-40.

[(C): quaternary ammonium salt]
The hair cosmetic composition of the present invention can further contain a quaternary ammonium salt as component (C). Examples of the quaternary ammonium salt include those represented by the following general formula (5).

[In the formula, R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 28 carbon atoms or a benzyl group, and simultaneously a hydrogen atom or a benzyl group; Except when it becomes an alkyl group. An ⁻ represents an anion. ]

Here, one of R ⁸ and R ⁹ is preferably an alkyl group having 16 to 24 carbon atoms, more preferably 22 alkyl groups, particularly a linear alkyl group, and the other is a lower alkyl group having 1 to 3 carbon atoms, particularly A methyl group is preferred. Examples of the anion An ^- include halide ions such as chloride ions and bromide ions; organic anions such as ethyl sulfate ions and methyl carbonate ions. Halide ions, particularly chloride ions are preferred.

  As the quaternary ammonium salt, a mono long chain alkyl quaternary ammonium salt is preferable, and specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, and behenyltrimethylammonium chloride. Cetyltrimethylammonium chloride and stearyltrimethylammonium chloride are preferred.

  The quaternary ammonium salt of component (C) may be used in combination of two or more thereof, and the content thereof is 0.01 to 1% by mass from the viewpoint of elongation and softness when applied to the hair, 0.03 to 0.5 mass%, particularly 0.05 to 0.25 mass% is preferable.

  In addition, from the viewpoint of imparting the non-stickiness and smoothness of the hair when applied to the hair, the mass ratio (C) / (A) of the component (C) to the component (A) is 1 to 50, more preferably 3 to 45, Particularly preferred is 5-40.

[(D): Organic carboxylic acid]
The hair cosmetic composition of the present invention preferably further contains (D) an organic carboxylic acid from the viewpoints of internal modification of hair, improvement of unity, and provision of set-holding properties. As the organic carboxylic acid of component (D), hydroxycarboxylic acid, dicarboxylic acid, tricarboxylic acid, and acidic amino acid are preferable. Specifically, glycolic acid, lactic acid, malic acid, tartaric acid, citric acid and the like as hydroxycarboxylic acid, and malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, as dicarboxylic acid, Oxalic acid, malic acid, tartaric acid, etc., tricarboxylic acid includes citric acid, and acidic amino acids include glutamic acid and aspartic acid. Of these, malic acid, tartaric acid, malonic acid, succinic acid, maleic acid, and lactic acid are preferable. In particular, malic acid and lactic acid are preferable. In addition, examples of salts of these organic carboxylic acids include salts with alkali metals, alkaline earth metals, ammonia, and organic amine compounds.

  Two or more kinds of these components (D) may be used in combination, and the content thereof is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, particularly 0.5 to 10% by mass of the hair cosmetic composition of the present invention. % Is preferred.

[(E): Organic solvent]
The hair cosmetic composition of the present invention preferably contains an organic solvent selected from the following (e1) to (e5) as the component (E) from the viewpoint of promoting the feeling of use and improving the gloss of the hair.

(E1) Aromatic alcohol represented by general formula (e1)

[Wherein R ¹⁰ represents a hydrogen atom, a methyl group or a methoxy group, R ¹¹ represents a 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 is shown, s, t, and u show the integer of 0-5. However, when s = t = 0, Z is a hydroxyl group, and R ¹¹ is a saturated or unsaturated divalent hydrocarbon group having 1 to 3 carbon atoms. ]

(E2) N-alkylpyrrolidone or N-alkylpyrrolidone in which a C1-C18 alkyl group or alkenyl group is bonded to a nitrogen atom

(E3) C3-C4 alkylene carbonate

(E4) Polypropylene glycol having a number average molecular weight of 100 to 1000

(E5) Lactone or cyclic ketone represented by general formula (e5-a), (e5-b) or (e5-c)

[Wherein, X represents a methylene group or an oxygen atom, R ¹² and R ¹³ represent different substituents, and v and w represent 0 or 1. ]

Among the organic solvents as component (E), examples of (e1) include benzyl alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, 2-benzyloxyethanol and the like. . Examples of (e2) include N-methylpyrrolidone, N-octylpyrrolidone, N-laurylpyrrolidone and the like. Examples of (e3) include ethylene carbonate and propylene carbonate. As the polypropylene glycol having a number average molecular weight of 100 to 1000 of (e4), those having a number average molecular weight of 100 to 500, particularly those having a polymerization degree of 2 (ie dipropylene glycol) to 5 are preferred. In (e5), R ¹² and R ¹³ in the general formulas (e5-a) to (e5-c) are linear, branched or cyclic alkyl groups, hydroxyl groups, sulfonic acid groups, phosphoric acid groups, carboxy groups Group, phenyl group, sulfoalkyl group, phosphoric acid alkyl group, carboxyalkyl group, etc. are preferable, and in the case of γ-lactone, γ-position, and in the case of δ-lactone, δ-position (that is, adjacent methylene group of heterooxygen atom) And a linear or branched alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. In addition, when it is desired to increase the water solubility of the compounds (e5-a) to (e5-c), acidic groups such as sulfonic acid groups, phosphoric acid groups, carboxy groups or the like are substituted as R ¹² or R ¹³ . It preferably has an alkyl group. Among (e5), lactones 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 (e5), examples of the cyclic ketone include cyclopentanone, cyclohexanone, cycloheptanone, 4-methylcycloheptanone and the like.

  Particularly preferred components (E) include benzyl alcohol, benzyloxyethanol, propylene carbonate and polypropylene glycol (number average molecular weight 100 to 500).

  In addition, the component (E) is preferably liquid at 25 ° C., and ClogP is required to be −2 to 3, and is preferably −1 to 2 from the viewpoint of promoting penetration. Here, ClogP is a calculated value of the octanol-water-partition coefficient (logP) defined by the following formula, which is a scale 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 (E) 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).

  Component (E) may be used in combination of two or more, and the content thereof is preferably 0.01 to 10% by mass, more preferably 0.05 to 7% by mass, particularly 0.1 to 5% by mass of the hair cosmetic composition of the present invention. % Is preferred.

  Furthermore, the hair cosmetic composition of the present invention can contain a polyhydric alcohol. The polyhydric alcohol contributes to the solubilization and stable dispersion of the component (E), and works synergistically with the component (E) to promote the improvement effect of gloss and hair. Examples of the polyhydric alcohol include ethylene glycol, glycerin, sorbitol, propylene glycol, 1,3-butylene glycol, and glycerin and 1,3-butylene glycol are particularly preferable. The polyhydric alcohol can be used alone or in combination of two or more, and the content thereof is preferably 0.1 to 10% by weight, particularly preferably 0.5 to 5% by weight in the hair cosmetic composition of the present invention.

[Surfactant]
The hair cosmetic composition of the present invention may further contain a surfactant other than the component (C) from the viewpoint of system stability including solubilization and dispersibility of the solvent, and improvement in feel. As the surfactant, any of a nonionic surfactant, an amphoteric surfactant, and an anionic surfactant can be used.

  Nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, higher fatty acid sucrose ester, polyglycerin fatty acid ester, higher fatty acid mono- or diethanolamide, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid Examples thereof include esters, polyoxyethylene sorbite fatty acid esters, alkyl saccharide surfactants, alkyl amine oxides, and alkyl amido amine oxides. Of these, polyoxyalkylene alkyl ether and polyoxyethylene hydrogenated castor oil are preferable, and polyoxyethylene alkyl ether is particularly preferable.

  Examples of amphoteric surfactants include imidazoline series, carbobetaine series, amide betaine series, sulfobetaine series, hydroxysulfobetaine series, and amide sulfobetaine series.

  Anionic surfactants include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, Examples include α-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphate mono- or diester type surfactants, and sulfosuccinate esters. Counter ions of the anionic residue of the surfactant include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; alkanol group having 2 or 3 carbon atoms Alkanolamine having 1 to 3 (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.). Examples of the counter ion of the cationic residue include halide ions such as chloride ion, bromide ion and iodide ion, methosulphate ion and saccharinate ion.

  The surfactant can be used alone or in combination of two or more, and from the viewpoint of the stability of the system including solubilization of the solvent and emulsification of the oil agent, the content thereof is in the hair cosmetic composition of the present invention. 0.01 to 5% by mass, particularly 0.05 to 3% by mass is preferable.

[Conditioning ingredients]
In order to further improve the conditioning effect, the hair cosmetic composition of the present invention may contain a conditioning component selected from a cationic polymer, silicones other than component (B), and oils other than component (A). .

  Examples of cationic polymers include cationized cellulose, cationic starch, cationized guar gum, cationized fenucreak gum, cationized tara gum, cationized roast bin gum, homopolymer of diallyl quaternary ammonium salt, diallyl quaternary ammonium salt / Acrylamide copolymer, quaternized polyvinyl pyrrolidone, polyglycol polyamine condensate, vinyl imidazolium trichloride / vinyl pyrrolidone copolymer, hydroxyethyl cellulose / dimethyldiallylammonium chloride copolymer, vinyl pyrrolidone / quaternized dimethylaminoethyl methacrylate Copolymer, polyvinylpyrrolidone / alkylaminoacrylate copolymer, polyvinylpyrrolidone / alkylaminoacrylate / vinylcaprolactam copolymer , Vinylpyrrolidone / methacrylamidopropyl trimethylammonium chloride copolymer, alkylacrylamide / acrylate / alkylaminoalkylacrylamide / polyethylene glycol methacrylate copolymer, adipic acid / dimethylaminohydroxypropylethylenetriamine copolymer (US Sandos, Cartaletin) And cationic polymers described in JP-A-53-139734 and JP-A-60-36407, particularly diallyl quaternary ammonium salts / acrylamide copolymers, vinylpyrrolidone / quaternized dimethyl. Aminoethyl methacrylate copolymer is preferred.

  Two or more of these cationic polymers may be used in combination, and the content thereof is preferably 0.01 to 5% by mass, particularly preferably 0.1 to 3% by mass in the hair cosmetic composition of the present invention.

As silicones, 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 give good lubricity to hair, polyether-modified silicone can give smoothness to hair, and amino-modified silicone can give 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. Examples of the products include Silicone KF351A, KF353A, KF6008, KF6016, KF6011, and KF6012, Shin-Etsu Chemical Co., Ltd., SH3771C, 3773C, and 3775C from Toray Dow Corning. As the amino-modified silicone, amodimethicone oil or an emulsion thereof is preferable, and commercially available products include amojimethicone emulsion SM8704C manufactured by Toray Dow Corning Co., Ltd., KT-1989, XF42- manufactured by Momentive Performance Materials Shapan Co., Ltd. B1989 etc. are mentioned.

  The content of silicones is preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass in the hair cosmetic composition of the present invention, from the viewpoint of easy fingering and no stickiness.

  Oils are used to improve the feeling of hair unity after drying. Oils include hydrocarbons such as squalene, squalane, liquid isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, α-olefin oligomer, liquid paraffin, cycloparaffin; castor oil, cacao oil, mink oil, avocado oil, olive oil, etc. Glycerides; waxes such as whale wax, lanolin, beeswax, microcrystalline wax, ceresin wax, carnauba wax; octyldodecyl myristate, isopropyl myristate, isopropyl palmitate, hexyl laurate, cetyl lactate, propylene glycol monostearate, Esters such as oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, tridecyl isononanoate; capric acid, lauric acid, myristic acid, palmitic acid Higher fatty acids such as stearic acid, behenic acid, oleic acid, coconut oil fatty acid, isostearic acid, isopalmitic acid; myristyl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, 2-octyldodecanol, seto Higher alcohols such as stearyl alcohol; other examples include isostearyl glyceryl ether and polyoxypropylene butyl ether. Among these, branched hydrocarbons such as squalene, squalane, liquid isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, and α-olefin oligomer are particularly preferable.

  The content of the oil agent is preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass in the hair cosmetic composition of the present invention, from the viewpoint of good unity and no stickiness.

[Other optional ingredients]
The hair cosmetic of the present invention may further contain other components generally used in hair cosmetics depending on the purpose. For example, polymer compounds such as hydroxylated cellulose and highly polymerized polyethylene oxide; anti-dandruff agents such as zinc pyrithione and benzalkonium chloride; vitamins; bactericides; anti-inflammatory agents; antiseptics; chelating agents; trimethylglycine, panthenol, etc. Moisturizing agents; coloring agents such as dyes and pigments; polar solvent extracts of eucalyptus, shells or nacres with nacre, or proteins obtained from silk, proteins obtained from silk or hydrolysates thereof, legumes Protein extract, ginseng extract, rice germ extract, hibamata extract, camellia extract, aloe extract, moon peach leaf extract, chlorella extract, rose water (rose flower distilled from rice seeds) Water containing aromatic components obtained), canina rose fruit extract, pomegranate fruit extract, whey, honey, royal jelly, loya Naturally derived components such as jelly extract; Pearl powder such as titanium oxide; Fragrance; Dye; Ultraviolet absorber; Antioxidant; Other ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLE PRESS )]) And the like

[PH]
The hair cosmetic composition of the present invention preferably has a pH (25 ° C.) of 3.0 to 5.0 when diluted 20 times by mass with water. Within this range, it has a function of recovering damage such as hair color, and is excellent in a function capable of imparting good flexibility and a supple feel from wet to dry. The pH value is particularly preferably adjusted to 3.2 to 4.7, more preferably 3.4 to 4.4 from the viewpoint of the effect of recovering damaged hair. For adjusting the pH, acidic substances such as inorganic acids and organic acids, and sodium hydroxide as a basic substance can be used in combination. Organic acids include those listed as component (D).

(Drug type)
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 preferably used as a hair conditioning agent, hair styling agent or the like. Examples of the dosage form include pump spray, aerosol spray, pump foam, aerosol foam, gel, lotion and the like.

[Hair modification method]
The hair cosmetic composition of the present invention can obtain a hair-modifying effect by being applied to the hair and then left without being washed away. Here, “leaving without washing” means that the time from application to hair until the next washing is at least 3 hours, preferably 6 hours or more.

  Furthermore, the effect of this invention can be heightened more by heating hair cosmetics after apply | coating to hair. For heating, a dryer, a heater, a trowel, an iron, or the like can be used. When using a drier, a heater, etc., as temperature, 60 to 150 degreeC, especially 70 to 120 degreeC is preferable. The heating time is preferably 10 seconds to 30 minutes, more preferably 20 seconds to 20 minutes, and particularly preferably 30 seconds to 10 minutes. When using a trowel, iron or the like, the temperature is preferably 80 ° C to 250 ° C, particularly 100 ° C to 200 ° C. The heating time is preferably 0.5 seconds to 3 minutes, more preferably 1 second to 2 minutes, and particularly preferably 2 seconds to 30 seconds. Also, the time from applying the hair cosmetic to heating and heating is preferably within 1 hour, more preferably within 45 minutes, and particularly preferably within 30 minutes.

  Moreover, in daily life, by repeating the treatment with the hair cosmetic composition of the present invention every day, it is possible to further improve the cohesiveness and fingering property of the hair itself.

Synthesis example 1
Synthesis of Organopolysiloxane A 6.5 g (0.042 mol) of diethyl sulfate and 34.4 g (0.36 mol) of 2-ethyl-2-oxazoline are dissolved in 87 g of dehydrated ethyl acetate and heated under reflux for 8 hours under a nitrogen atmosphere to obtain a number average molecular weight. 1300 poly (N-propionylethyleneimine) was synthesized. Here, 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 32000, amine equivalent 2000) was used, and N-propionylethyleneimine-dimethylsiloxane copolymer was converted into a pale yellow rubber-like semisolid (138 g, yield). 98%). The final product had an organopolysiloxane segment content of 71 mass% and a weight average molecular weight of 46000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that about 22 mol% of amino groups remained.

Synthesis example 2
Synthesis of organopolysiloxane B In the same manner as in Synthesis Example 1, 0.8 g (0.005 mol) of diethyl sulfate, 12.8 g (0.14 mol) of 2-ethyl-2-oxazoline, and 29 g of dehydrated ethyl acetate were used. Poly (N-propionylethyleneimine) was obtained. Further, using 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 100000, amine equivalent 20000), N-propionylethyleneimine-dimethylsiloxane copolymer was converted into a pale yellow rubbery solid (111 g, yield 98%). ). The content of the organopolysiloxane segment in the final product was 88% by mass, and the weight average molecular weight was 114,000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

  Hair cosmetics (mist) shown in Table 1 were prepared according to a conventional method and evaluated according to the following method.

Evaluation methods for “no stickiness at the time of application”, “smoothness of hair after finishing”, “continuation of smoothness of hair” 1) Evaluation hair bundle (common to each evaluation)
Using hair of a Japanese woman who has not undergone chemical treatment such as perm, hair color, etc., make a hair bundle of 15cm in length, 3cm in width, and 3g in weight, and then bleaching treatment (Kao Co., Ltd., PRETIA Soft Bubble Bleach Hybrid) ) Twice to obtain an evaluation hair bundle.

2) Treatment of hair bundles “No stickiness during application”
After shampooing the evaluation hair bundle (Curel shampoo, manufactured by Kao Corporation) and towel drying, 0.3 g of mist shown in Table 1 was uniformly applied, and ring comb (manufactured by Delrin, New Delrin Metalling Comb No. 1; The same applies below).
"The smoothness of the hair after finishing"
Shampoo the evaluation hair bundle (Curel shampoo manufactured by Kao Corporation), towel dry, apply uniformly 0.3g of the mist listed in Table 1, and then comb for 5 minutes using a ring comb with hot air at 70 ° C. Dried.
"Continuation of smooth hair"
Shampoo the evaluation hair bundle (Curel shampoo manufactured by Kao Corporation), towel dry, apply uniformly 0.3g of the mist listed in Table 1, and then comb for 5 minutes using a ring comb with hot air at 70 ° C. Dried and left at room temperature for 6 hours.

3) Evaluation Criteria Evaluation was conducted by 5 expert panelists, each with 1 to 5 points, and sensory evaluation was performed according to the evaluation criteria table shown in Table 1. The total score of 5 people was 20 to 25 points: ◎, 15 to 19 points: ◯, 10-14 points: Δ, 5-9 points: x.

Evaluation method of “storage stability (−5 ° C., 1 month)” After the preparation of the hair cosmetic, it was stored at −5 ° C. for 1 month, and then the appearance was observed, ◎: separated (precipitated) No, Δ: Slightly separated (precipitated), x: Separated.

Example 11 Hair foam (pH 3.7)
(mass%)
Soft lanolin fatty acid 0.05
Organopolysiloxane B 1
Organopolysiloxane A 1
Cetyltrimethylammonium chloride 0.45
Malic acid 0.2
Lactic acid 2
Benzyl alcohol 0.2
Dipropylene glycol 1
1,3-butylene glycol 1
Polyoxyethylene tridecyl ether 0.5
Polyoxyethylene cetyl ether 0.5
Polyoxyethylene hydrogenated castor oil 0.2
Vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate copolymer 0.5
Hydrolyzed silk solution (Ichimaru Falcos, Silken G Solvel-3) 0.01
Fragrance 0.1
95 degree synthetic alcohol 10
pH adjuster (sodium hydroxide, lactic acid)
LPG (0.38MPa) 7
(B) / (A) = 40
(C) / (A) = 9

  When the hair foam was evaluated in the same manner as described above, all items were “◎”.

Example 12 Hair Cream (pH 3.7)
(mass%)
Soft lanolin fatty acid 0.2
Organopolysiloxane B 0.3
Behenyltrimethylammonium chloride 0.24
Malic acid 0.5
Benzyl alcohol 0.2
Dipropylene glycol 2
N, N-dimethyloctadecyloxypropylamine 0.2
Cetanol 1.6
Isopropyl palmitate 0.5
Dimethicone (Toray Dow Corning, BY22-060) 2
Hydrolyzed silk solution (Ichimaru Falcos, Silken G Solvel-3) 0.01
Fragrance 0.1
pH adjuster (sodium hydroxide, lactic acid)
(B) / (A) = 1.5
(C) / (A) = 1.2

  When the hair cream was evaluated in the same manner as described above, all items were “◎”.

Example 13 Hair Cream (pH 3.7)
(mass%)
Soft lanolin fatty acid 0.2
Organopolysiloxane A 0.6
Organopolysiloxane B 0.1
Behenyltrimethylammonium chloride 0.21
Malic acid 1
Benzyl alcohol 0.2
Dipropylene glycol 2
N, N-dimethyloctadecyloxypropylamine 0.24
Polyoxyethylene hydrogenated castor oil 0.24
Cetanol 2
Amino-modified silicone 0.2
Vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate copolymer 0.5
Highly polymerized polyethylene oxide 1
Fragrance 0.1
pH adjuster (sodium hydroxide, lactic acid)
(B) / (A) = 3.5
(C) / (A) = 1.1

When the hair cream was evaluated in the same manner as described above, all items were “◎”.

Example 14 Hair Cream (pH 3.7)
(mass%)
Soft lanolin fatty acid 0.2
Organopolysiloxane A 0.04
Organopolysiloxane B 0.16
Behenyltrimethylammonium chloride 0.21
Malic acid 0.01
Benzyl alcohol 0.2
Dipropylene glycol 2
N, N-dimethyloctadecyloxypropylamine 0.24
Polyoxyethylene hydrogenated castor oil 0.24
Cetanol 2
Dimethicone 0.6
Amino-modified silicone 0.2
Isopropyl palmitate 0.5
Fragrance 0.1
pH adjuster (sodium hydroxide, lactic acid)
(B) / (A) = 1.0
(C) / (A) = 1.1

When the hair cream was evaluated in the same manner as described above, all items were “◎”.

Example 15 Hair lotion (pH 3.7)
(mass%)
Soft lanolin fatty acid 0.01
Organopolysiloxane B 0.3
Cetyltrimethylammonium chloride 0.24
Malic acid 1.25
Benzyl alcohol 1.25
Dipropylene glycol 2
Polyoxyethylene hydrogenated castor oil 0.2
Polyoxyethylene tridecyl ether 0.5
Polyoxyethylene / methylpolysiloxane copolymer (Shin-Etsu Chemical Co., KF-6029) 2
Trimethylglycine (Asahi Kasei Chemical Co., Amino Coat) 0.01
Eucalyptus extract (Maruzen Pharmaceutical Co., Ltd., Eucalyptus extract BG-KA) 0.01
Camellia oil (Yokoseki Yushi Kogyo Co., Ltd., refined cocoon oil) 0.01
Fragrance 0.1
pH adjuster (sodium hydroxide, lactic acid)
(B) / (A) = 30
(C) / (A) = 24

  When the hair lotion was evaluated in the same manner as described above, all items were “◎”.

Claims (7)

A hair cosmetic comprising the following components (A) and (B):
(A) Branched fatty acid represented by the general formula (1) or a salt thereof

[Wherein, R ¹ represents a methyl group or an ethyl group, and n represents an integer of 3 to 36. ]
(B) At least one silicon atom of the organopolysiloxane segment is bonded to the following general formula (2) via an alkylene group containing a hetero atom.

[Wherein R ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, and m represents a number of 2 or 3. ]
A poly (N-acylalkyleneimine) comprising repeating units represented by the formula is bonded, and the mass ratio of the organopolysiloxane segment to the poly (N-acylalkyleneimine) segment is 98/2 to 40/60. An organopolysiloxane having a weight average molecular weight of 50,000 to 500,000   The hair cosmetic composition according to claim 1, wherein the mass ratio (B) / (A) of the component (B) to the component (A) is 0.5-60.   The hair cosmetic composition according to claim 1 or 2, further comprising a component (C) a quaternary ammonium salt.   The hair cosmetic composition according to claim 3, wherein the mass ratio (C) / (A) of the component (C) to the component (A) is 1 to 50.   The hair cosmetic composition according to any one of claims 1 to 4, further comprising a component (D) an organic carboxylic acid or a salt thereof, and having a pH of 3.0 to 5.0 at 25 ° C when diluted 20 times by mass with water. . Furthermore, the hair cosmetics in any one of Claims 1-5 containing the organic solvent chosen from (e1)-(e5) below component (E).
(e1) Aromatic alcohol represented by general formula (e1)

[Wherein R ¹⁰ represents a hydrogen atom, a methyl group or a methoxy group, R ¹¹ represents a 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 is shown, s, t, and u show the integer of 0-5. However, when s = t = 0, Z is a hydroxyl group, and R ¹¹ is a saturated or unsaturated divalent hydrocarbon group having 1 to 3 carbon atoms. ]
(e2) N-alkylpyrrolidone or N-alkylpyrrolidone having a C1-C18 alkyl group or alkenyl group bonded to a nitrogen atom
(e3) C3-C4 alkylene carbonate
(e4) Polypropylene glycol having a number average molecular weight of 100 to 1000
(e5) Lactone or cyclic ketone represented by general formula (e5-a), (e5-b) or (e5-c)

[Wherein, X represents a methylene group or an oxygen atom, R ¹² and R ¹³ represent different substituents, and v and w represent 0 or 1. ]   A hair modification method in which the hair cosmetic composition according to any one of claims 1 to 6 is applied to hair and left unwashed.