JP2013040162A - Hair cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair cosmetic capable of imparting high settlement feeling and smooth and soft touch having no sticky feeling to hair after being finished, even when being applied to wet hair or dry hair.SOLUTION: This hair cosmetic contains following components (A) and (B): (A) 0.1-7 mass% organopolysiloxane in which a poly(N-acylalkyleneimine) segment comprising a repeated unit represented by formula (1) [Rrepresents H, a 1-22C alkyl group or the like, and n denotes 2 or 3.] is coupled with at least one of Si atoms in an organopolysiloxane segment through an alkylene group containing a heteroatom, wherein the mass ratio between the organopolysiloxane segment and the poly(N-acylalkyleneimine) segment is 98/2-40/60, and the weight-average molecular weight is 10,000-500,000; and (B) a 0.01-1.2 mass% copolymer of an acryloyl dimethyltaurine salt with hydroxyethyl acrylate.

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 has been pointed out that bad fingering, loose hair, and loss of gloss may occur.

  Even if the hair is undamaged, it may cause the hair to become untidy or glossy due to the original hair quality (for example, hair with a lot of wrinkles and undulations) and aging changes. Generally known.

  In order to obtain a unity effect and a smooth feel to such hair, silicone oil, hydrocarbon oil, ester oil and the like are blended in the hair cosmetic. However, such hair cosmetics have a problem that there is a sticky feeling derived from oil.

  On the other hand, there are hair cosmetics such as gels containing a film-forming polymer, which can be obtained at a high level of unity effect. There was a problem that the fingering property was poor and the appearance was unnatural as if the hair was hardened.

  On the other hand, organopolysiloxane has many excellent characteristics, and therefore, various forms are frequently used as a touch improver in shampoos, hair conditioners and the like. Furthermore, hair cosmetics using an organopolysiloxane having a specific structure and a specific cationic polymer as a thickener for the purpose of imparting a smooth feel that is easy to stretch on the hair are disclosed (Patent Documents 1 and 2). . However, as described in the Examples, the hair cosmetic described in Patent Document 1 has a smoothing effect and smoothness due to excellent setting power when lightly wiped with a towel after washing and applied to naturally dried hair. However, when applied to moist hair and dried with warm air from a blow dryer, it is not satisfactory for fingering and it is difficult to prepare the hair. It was not a thing.

  In the examples described in Patent Document 2, as in Patent Document 1, evaluation is performed when applied to naturally dried hair. However, the hair cosmetic described in Patent Document 2 is applied to wet hair. The same smooth feel and non-stickiness can be obtained when finishing with drying with warm air from a blow dryer. However, when applied to severely damaged hair, performance such as feeling of unity and imparting softness was not always satisfactory.

JP 2010-138099 JP 2010-184907 A

  Therefore, it is an object of the present invention to obtain high hair coherence after finishing whether applied to wet hair or dry hair, and to give a smooth and soft feel to the hair. The object is to provide a hair cosmetic without stickiness.

  The present inventors have found that a hair treatment agent satisfying the above requirements can be obtained by using a polymer having a specific structure together with a specific organopolysiloxane.

That is, the present invention provides a hair cosmetic containing components (A) and (B).
(A): At least one of the silicon atoms of the organopolysiloxane segment, via an alkylene group containing a hetero atom, the following general formula (1);

[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 poly (N-acylalkyleneimine) segment composed of repeating units represented by the formula: wherein the mass ratio of the organopolysiloxane segment to the poly (N-acylalkyleneimine) segment is 98/2 to 40 / Organopolysiloxane having a weight average molecular weight of 10,000 to 500,000 and 0.1 to 7% by mass
(B): Copolymer of acryloyldimethyltaurine salt and hydroxyethyl acrylate 0.01 to 1.2% by mass

  The present invention also provides a hair treatment method in which the above-described hair cosmetic is applied to wet or dry hair, and then the hair cosmetic is dried by natural drying or heating and then left for at least 3 hours without being washed away. It is.

  Whether applied to wet or dry hair, the hair cosmetic composition of the present invention satisfies the cohesiveness, smooth touch, soft finish, and lack of stickiness after finishing. It is.

[(A): Organopolysiloxane]
Component (A) is represented by the following general formula (1) via an alkylene group containing a hetero atom on at least one silicon atom of the organopolysiloxane segment.

[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 poly (N-acylalkyleneimine) segment composed of repeating units represented by the formula: wherein the mass ratio of the organopolysiloxane segment to the poly (N-acylalkyleneimine) segment is 98/2 to 40 / An organopolysiloxane having a weight average molecular weight of 60 to 500,000.

  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. Examples of the alkyl group represented by R ¹ in the general formula (1) include a methyl group and an ethyl group, and examples of the cycloalkyl group represented by R ¹ 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 (A) can be produced by a known method, for example, according to the method described in JP-A-7-133352, the following general formula (2)

[Wherein R ² is the same or different and represents a saturated alkyl group having 1 to 22 carbon atoms or a phenyl group, and R ³ and R ⁴ each represent the same group as R ² , or

R ⁵ represents a group represented by the above formula, a represents an integer of 100 to 4000, and b represents an integer of 1 to 300. ]
And an organopolysiloxane represented by the following general formula (3)

Wherein, R ¹ and n are respectively R ¹ and n in the general formula (1) synonymous. ]
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 (3) can be performed 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 (3), poly (N-acylethyleneimine) (corresponding to n = 2 in the formula (1)) is obtained, and 2-substituted-dihydro- If 2-oxazine is used, poly (N-acylpropyleneimine) (corresponding to n = 3 in the formula (1)) can be obtained.

  The poly (N-acylalkyleneimine) chain and the silicone chain are linked by ester formation reaction by condensation of carboxy 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 (2), 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 general formula (3) is charged 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.

In the organopolysiloxane of component (A), the mass ratio of the organopolysiloxane segment to the poly (N-acylalkyleneimine) segment is 98/2 to 40/60, but high cohesiveness and high smooth feel are obtained. From the viewpoint, 98/2 to 46/54, 97/3 to 65/35, and 95/5 to 82/18 are preferable. This mass ratio is determined by dissolving 5% by mass of the organopolysiloxane of component (A) in deuterated chloroform, and analyzing it by nuclear magnetic resonance ( ¹ H-NMR) analysis with an alkyl group or phenyl group in the organopolysiloxane segment. The value obtained from the integral ratio of methylene groups in the poly (N-acylalkylenimine) segment.

  In addition, the weight average molecular weight (MWg) of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments of the organopolysiloxane of the component (A) is 1,000 to from the viewpoint of improvement in unity and smoothness. 40,000, further 1,300 to 35,000, more preferably 1,700 to 32,000 are preferable.

Here, the “organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments” means the bonding point of the poly (N-acylalkyleneimine) segment to the organopolysiloxane segment as shown in the following formula ( A portion surrounded by a broken line between two points from the bonding point A) to the bonding point (bonding point B) of the poly (N-acylalkylenimine) segment adjacent thereto, and one R ² SiO unit A segment composed of one A ⁴ and y + 1 R ² ₂ SiO units.

[Wherein R ² represents the same meaning as R ^{2 in the} general formula (2), R ⁶ represents an alkylene group containing a hetero atom, W represents a poly (N-acylalkylenimine) segment, and R ⁷ Represents a residue of a polymerization initiator, and y represents a positive number. ]

  MWg can be understood as the mass (g / mol) of the organopolysiloxane segment per mole of the poly (N-acylalkylenimine) segment, and the functional group of the modified organopolysiloxane as the raw material compound is poly (N- 100% substitution with acylalkylenimine) corresponds to the functional group equivalent (g / mol) of the modified organopolysiloxane.

  The MWg can be obtained by the following formula using the content (Csi) of the organopolysiloxane segment constituting the main chain and the molecular weight (MWox) of the poly (N-acylalkylenimine) segment.

  The molecular weight (MWox) of the poly (N-acylalkylenimine) segment refers to a number average molecular weight measured by a gel permeation chromatography (GPC) measurement method described later, preferably 500 to 10,000, more preferably 800 to 6000, More preferably, it is 900-4000. Thereby, the unity effect and smoothness of hair can be improved further.

  The weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain is preferably 10,000 to 200,000, but more preferably 15,000 to 160,000, and still more preferably 20,000, from the viewpoint of simultaneously satisfying a smooth feel and non-stickiness. ~ 120,000. Since MWsi has a common skeleton with the modified organopolysiloxane that is the raw material compound, MWsi is substantially the same as the weight average molecular weight of the modified organopolysiloxane that is the raw material compound. The average molecular weight of the modified organopolysiloxane that is a raw material compound is measured by GPC under the following measurement conditions and is converted to polystyrene.

Column: Super HZ4000 + Super HZ2000 (manufactured by Tosoh Corporation)
Eluent: 1 mM triethylamine / THF
Flow rate: 0.35mL / min
Column temperature: 40 ° C
Detector: UV
Sample: 50μL

  The weight average molecular weight (MWt) of the organopolysiloxane of component (A) is 10,000 to 500,000. From the viewpoint of further improving the cohesiveness, smoothness and non-stickiness, 20,000 to 400,000, and further 30,000 to 300,000, more preferably 40,000 to 200,000 are preferred. The weight average molecular weight of the organopolysiloxane of component (A) is the weight average molecular weight of the organopolysiloxane (2) as the raw material compound, the aforementioned organopolysiloxane segment and the poly (N-acylalkyleneimine) segment), and It can obtain | require from mass ratio of.

  These component (A) organopolysiloxanes can be used in combination of two or more, and the content of the component (A) ensures a high unity effect while at the same time achieving both smoothness and non-stickiness. It is contained in the hair cosmetic composition in an amount of 0.1 to 7% by mass, preferably 0.1 to 6% by mass, more preferably 0.3 to 5% by mass.

[(B): Copolymer of acryloyldimethyltaurine salt and hydroxyethyl acrylate]
Component (B) is a copolymer of acryloyldimethyltaurine salt and hydroxyethyl acrylate. Examples of the component (B) include those represented by the following general formula (4).

[Wherein, X ⁺ represents an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or an organic ammonium ion, p represents 3-90, and q represents 10-97. ]

In the general formula (4), examples of the alkali metal ion of X ⁺ include sodium ion, potassium ion and lithium ion; examples of the alkaline earth metal ion include calcium ion and magnesium ion; Examples thereof include monoethanolammonium ion, diethanolammonium ion, and triethanolammonium ion. Of these, alkali metal ions are preferable, and sodium ions are particularly preferable.

  Sepinob EMT10, Simalgel NS (above, Sepic) etc. can be used as a commercial item of a component (B).

  The content of the component (B) is within the range of 0.01 to 1.2% by mass in the hair cosmetic composition of the present invention from the viewpoints of good coatability on hair, soft finish, no stickiness, and storage stability. Preferably it is 0.04-1 mass%, More preferably, it is 0.1-0.8 mass%.

  The mass ratio (A) / (B) of the component (A) to the component (B) is preferably 0.1 to 100, more preferably 0.2 to from the viewpoints of unity effect, smoothness, soft finish, and non-stickiness. 75, more preferably 0.5-50.

[(C): Hydrophobic silicone]
The hair cosmetic composition of the present invention may further contain a hydrophobic silicone selected from silicones other than the organopolysiloxane of component (A) as component (C). Hydrophobic silicone smoothens the hair by reducing the surface frictional resistance of dry and wet hair, improving the finger passage when drying the base and the whole of the hair in the process of drying the hair by blowing air In addition, the movement of the hand can be made smooth. As a result, it is possible to create a beautiful hairstyle base that is well-organized from the root to the ends of the hair.

  Here, the hydrophobic silicone is mixed with an evaluation solution (purified water, preferably 50% by mass ethanol aqueous solution, most preferably 95% by mass ethanol aqueous solution) at a mass ratio of 1: 1 at room temperature and allowed to stand for 5 minutes. It shall mean silicone that does not become transparent after separation (separation, gelation or cloudiness). Note that, among commercially available silicones, emulsion type and those mixed with an organic solvent are hydrophobic silicones.

  Examples of the hydrophobic silicone include dimethylpolysiloxane, polyether-modified silicone (HLB less than 11), amino-modified silicone, carboxy-modified silicone, methylphenylpolysiloxane, fatty acid-modified silicone, alcohol-modified silicone, aliphatic alcohol-modified silicone, epoxy Examples include modified silicone, fluorine-modified silicone, cyclic silicone, and alkyl-modified silicone. Among these, dimethylpolysiloxane, polyether-modified silicone (HLB is less than 11, preferably less than 8, most preferably less than 5), and amino-modified silicone are preferable, and amino-modified silicone is particularly preferable.

  Examples of dimethylpolysiloxane include those represented by the general formula (c1).

[Wherein R ⁸ represents Si (CH ₃ ) ₃ or a hydrogen atom, and n ¹ represents a number of 3 to 20000. ]

  Dimethylpolysiloxane includes silicone oil (number average degree of polymerization less than 1000) and silicone gum (number average degree of polymerization of 1000 or more). Commercially available silicone oils include the SH200 series (SH200 C Fluid 1CS, 2CS, 5CS, 10CS, 20CS, 30CS, 50CS, 100CS, 200CS, 350CS, 500CS, 1,000CS, 5,000CS, SH200 Fluid 1.5CS, 3,000CS, 10,000CS, 12,500CS, 30,000CS, etc. (Toray Dow Corning), TSF-451 series (Momentive Performance Materials), KF- 96 series (Shin-Etsu Chemical Co., Ltd.). Moreover, what made these silicone oil into an emulsion can also be used.

  Commercial products of silicone gum include SH200 series (SH200 Fluid 60,000CS, 100,000CS, 1,000,000CS, etc .; Toray Dow Corning), TSF451-100MA (Momentive Performance Materials), BY11-026 (Toray・ Dow Corning: Diluted solution of highly polymerized silicone with low viscosity silicone), KF9008 (Shin-Etsu Chemical; Diluted solution of highly polymerized silicone with cyclic silicone), BY22-050A (Toray Dow Corning: Cationic emulsion of highly polymerized silicone ), BY22-060 (Toray Dow Corning; Cationic emulsion of solution obtained by diluting highly polymerized silicone with low viscosity silicone), BY22-020 (Toray Dow Corning, Inc .; cation of solution obtained by diluting highly polymerized silicone with liquid paraffin) Emulsion), KM904 (Shin-Etsu Chemical Co., Ltd.) Include the cationic emulsion), and the like.

  Polyether-modified silicone is a general term for polyoxyethylene / methylpolysiloxane copolymer, poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer, and the like, and is represented by the general formula (c2) or (c3). Things.

Wherein, R ⁹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, n ² is 1 - 2000, m ² is 1 to 1000, a ¹ is 0, b ¹ is 0 to 50, c ¹ represents 0 to 50, and b ¹ + c ¹ ≧ 1. ]

  Commercially available polyether-modified silicones with an HLB of less than 11 include SH3775M, SS-2805 (above, Toray Dow Corning), KF-6015, KF-6016, KF-6017, KF-6029 (above, Shin-Etsu Chemical) Company).

  The amino-modified silicone may have an amino group or an ammonium group, and may be either an amino-modified silicone oil in which all or part of the terminal hydroxyl groups are blocked with a methyl group or the like, or amodimethicone in which the terminals are not blocked. And those represented by the following general formula (c4) or (c5).

[Wherein, R ¹⁰ represents Si (CH ₃ ) ₃ or a hydrogen atom, R ¹¹ represents an alkylene group having 2 to 8 carbon atoms, n ³ represents a number of 1 to 20000, and m ³ represents 1 to 2000. A ² represents a number of 0 to 3. ]
The content (nitrogen content) of nitrogen atoms contained in one molecule of amino-modified silicone is preferably 0.02 to 4% by mass, particularly 0.1 to 1% by mass.

Commercially available amino-modified silicones include SF8451C (Toray Dow Corning, viscosity 600mm ² / s, nitrogen content 0.8% by mass), SF8452C (Toray Dow Corning, viscosity 700mm ² / s, nitrogen content 0.2% by mass) , SF8457C (Toray Dow Corning, viscosity 1200mm ² / s, nitrogen content 0.8% by mass), KF8003 (Shin-Etsu Chemical, viscosity 1850mm ² / s, nitrogen content 0.7% by mass), KF8005 (Shin-Etsu Chemical, viscosity 1200mm ² / s, nitrogen content 0.1% by mass), KF867 (Shin-Etsu Chemical Co., viscosity 1300mm ² / s, nitrogen content 0.8% by mass), KF8012 (Shin-Etsu Chemical Co., Ltd., viscosity 90mm ² / s, nitrogen content 0.6% by mass), etc. Modified silicone oil, SM8704C (Toray Dow Corning, nitrogen content 0.8 mass%), SM8904C (Toray Dow Corning, nitrogen content 0.3 mass%), BY22-079 (Toray Dow Corning, nitrogen content 0.6 mass%) And amodimethicone emulsion. Also, CF1046 (Toray Dow Corning, Nitrogen), which is a mixture of dimethylpolysiloxane (number average degree of polymerization 550), dimethylpolysiloxane (number average degree of polymerization 2700) and amino-modified silicone (mass ratio 10: 3.7: 2.9) A content of 0.14% by mass) can also be suitably used.

  The content of the hydrophobic silicone is preferably 0.01 to 10% by mass, more preferably 0.03 to 6% by mass, particularly 0.1 to 4% by mass in the hair cosmetic composition of the present invention, from the viewpoints of fingering and non-stickiness. % Is preferred.

[(D): Cationic surfactant]
The hair cosmetic composition of the present invention has a smoothness and high cohesiveness by imparting smoothness to the hair, facilitating the preparation of the hairstyle by smoothing the movement of the fingers and the hands when drying the hair. Therefore, a cationic surfactant can be further contained as component (D). Examples of the cationic surfactant include quaternary ammonium salts represented by the following general formula (d1).

[In the formula, R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 28 carbon atoms or a benzyl group, and simultaneously become a hydrogen atom or a benzyl group; Except when it becomes an alkyl group. An ⁻ represents an anion. ]

Here, one of R ¹² and R ¹³ 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 cationic surfactant, mono long-chain alkyl quaternary ammonium salts are preferable, and specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, and behenyltrimethylammonium chloride. Stearyl trimethyl ammonium and behenyl trimethyl ammonium chloride are preferable.

  These cationic surfactants can be used singly or in combination of two or more, and the content thereof is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass in the hair cosmetic composition of the present invention. This makes it easy to prepare the hairstyle by smoothing the movement of the fingers and hands when the hair is dried, and the smoothness and cohesion of the hair can be further improved.

  In the hair cosmetic of the present invention, as a surfactant other than the cationic surfactant of component (D), a nonionic surfactant, an amphoteric surfactant, and an anionic surfactant that are usually used in hair cosmetics are used. Either 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. Among these, betaine surfactants such as alkyldimethylaminoacetic acid betaine and fatty acid amidopropyl betaine are preferred, and fatty acid amidopropyl betaine is particularly preferred. The fatty acid amidopropyl betaine is preferably one having an acyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms, and in particular, lauric acid amidopropyl betaine, palm kernel oil fatty acid amidopropyl betaine, coconut oil fatty acid amidopropyl betaine and the like. preferable.

  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.

  Of these, nonionic surfactants are preferred from the viewpoint of feel.

(Oil agent)
The hair cosmetic composition of the present invention may contain an oil for improving the feeling of unity of the hair after drying. Moreover, it is more preferable to use solid fat and / or semi-solid fat (component (E)) as the oil agent, because it can provide unity persistence to dry hair without stickiness.

  In component (E), solid fat and semi-solid fat refer to oil agents that are solid or semi-solid at 25 ° C., respectively. Examples of the solid fat and / or semi-solid fat include hydrocarbons, aliphatic higher alcohols, higher fatty acids, esters of aliphatic alcohols and fatty acids, glycerin monoethers of aliphatic higher alcohols and higher fatty acid esters thereof, and triglycerides of higher fatty acids. These may be used alone or in combination of two or more.

  Examples of hydrocarbons include microcrystalline wax, solid paraffin, and petroleum jelly, examples of aliphatic higher alcohols include stearyl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, and behenyl alcohol. Examples of higher fatty acids include palmitic acid. Examples include acid, stearic acid, behenic acid, lauric acid, myristic acid, coconut oil fatty acid and the like. Examples of the fatty alcohol and fatty acid esters include stearyl stearate, cetyl palmitate, cetyl octanoate, isostearyl isostearate, cetyl lactate, propylene glycol monostearate, cholesteryl stearate, dipentaerythritol fatty acid ester, isostearic acid ester. Acid-hardened castor oil, tri (capryl / caprin / myristin / stearic acid) glyceryl and the like can be mentioned. Furthermore, examples of glycerin monoethers of aliphatic higher alcohols include chimyl alcohol and batyl alcohol. Examples of the higher fatty acid esters include batyl stearate. Examples of higher fatty acid triglycerides include glyceryl tris. Examples include stearate and hydrogenated beef tallow. Also, solid fats such as cholesterol, cholesteryl isostearate, sphingolipids, various animal and vegetable oils and fats, such as beef tallow, pork fat, coconut oil, palm oil, cacao butter, various waxes, whale wax, lanolin, beeswax, carnauba wax, etc. Other examples include isostearyl glyceryl ether.

  Oils other than component (E), that is, liquid oils at 25 ° C. include hydrocarbons such as squalene, squalane, liquid isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, α-olefin oligomer, liquid paraffin, cycloparaffin, and the like; Glycerides such as castor oil, mink oil, avocado oil, olive oil; higher alcohols such as oleyl alcohol, isostearyl alcohol, 2-octyldodecanol; octyldodecyl myristate, hexyl laurate, oleyl oleate, 2-ethylhexanoic acid Esters such as hexadecyl, isononyl isononanoate, tridecyl isononanoate; higher fatty acids such as capric acid, oleic acid, coconut oil fatty acid, isostearyl acid, isopalmitic acid; others, jojoba oil, polyoxypropylene butyl ether Etc., and the like. 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 as a whole including the component (E) is preferably 0.1 to 25% by mass, more preferably 0.5 to 25% by mass, particularly in the hair cosmetic, from the viewpoint of good unity and no stickiness. 1-20 mass% is preferable. In addition, the content of the component (E) is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, and particularly preferably 0.2 to 10% by mass, from the viewpoint of imparting unity persistence to dry hair without stickiness. 5 mass% is preferable.

[Medium]
In the hair cosmetic composition of the present invention, water and, if necessary, an organic solvent other than the specific organic solvent are used as a medium. Examples of such organic solvents include lower alkanols such as ethanol and 2-propanol, polyols such as propylene glycol, 1,3-butanediol, diethylene glycol, dipropylene glycol, and glycerin, ethyl cellosolve, butyl cellosolve, and benzyl cellosolve. Examples include cellosolves, carbitols such as ethyl carbitol and butyl carbitol.

[Other ingredients]
In the hair cosmetic composition of the present invention, in addition to the above-described components, various components usually used in hair cosmetic compositions can be appropriately blended according to the purpose, application, and dosage form. Examples of such components include chelating agents such as edetate, diethylenetriaminepentaacetate, gluconate, and hydroxyethane diphosphonate; preservatives such as methylparaben and butylparaben; paraaminobenzoic acid, anthranyl, UV absorbers such as salicylic acid, cinnamic acid, and benzophenone; antioxidants such as ascorbic acid, α-tocopherol, tocopherol acetate, and dibutylhydroxytoluene; colorants such as dyes and pigments; bactericides such as triclosan and trichlorocarban Anti-dandruff agents such as zinc pyrithione and octopirox; anti-inflammatory agents such as dipotassium glycyrrhizinate and tocopherol acetate; pH adjusters such as organic acids, sodium hydroxide and potassium hydroxide; vitamins, proteins, amino acids and herbal medicines , Coolness-imparting agents (menthol, etc.) Seed animal and plant extracts, vitamins, moisturizers, pearling agents, perfumes and the like.

  The hair cosmetic composition of the present invention can be prepared in various dosage forms according to a conventional method. For example, aerosol (aerosol spray, aerosol foam), pump (pump spray, pump foam), gel, wax, lotion, mist, milk , Cream and the like. Among these, pump spray, pump foam, aerosol foam, milk and cream are preferable.

  When used as an aerosol form, the hair cosmetic of the present invention may be a liquid or foam aerosol hair cosmetic containing a propellant. The propellant is not particularly limited as long as it is usually used in aerosol-type cosmetics. For example, lower saturated hydrocarbons such as propane, butane or a mixture thereof (including liquefied petroleum gas), Ethers such as dimethyl ether, nitrogen gas, carbon dioxide gas, nitrous oxide gas and the like can be used. These can be used alone or in combination of two or more. The content of the propellant is preferably 0.01 to 70% by mass, and particularly preferably 5 to 20% by mass in the hair cosmetic composition of the present invention.

  When used as a pump foam, the hair cosmetic of the present invention can be made into a non-aerosol hair cosmetic by filling a foam discharge container. The foam discharge container is not particularly limited as long as the composition is mixed with air and discharged as a foam state. For example, a squeeze foamer used by pressing the body of a soft container with fingers. Examples include a pump former and a trigger type that are used by pressing the head of a cap equipped with a pump mechanism with fingers.

  Examples of the squeeze former include those described in Japanese Utility Model Publication No. 62-042785, Japanese Utility Model Publication No. 62-042786, Japanese Utility Model Publication No. 62-042787, and those equivalent thereto. Examples described in Kaihei 7-315463, Japanese Patent Application Laid-Open No. 08-230961, and the like, and the like. These containers are often equipped with a mesh body in the discharge part for the purpose of further improving the foam quality, and among these containers, one having one or two mesh bodies of 100 to 300 mesh are preferably attached.

  The hair cosmetic composition of the present invention can be used as a hair styling agent, hair conditioning agent, hair rinse agent, hair pack agent, hair cream agent, hair lotion agent, hair treatment agent and the like. Among these, it is preferable to use it as a hair cosmetic, ie, a hair styling agent or a hair conditioning agent, that is used without being washed away after application to the hair. As one preferred form of use, the hair cosmetic composition of the present invention is applied to wet hair or dry hair, then dried by natural drying or heating, and then left to stand for at least 3 hours without washing off. Can be used. The standing time is not particularly limited but is preferably 1 day or less.

Synthesis Example 1 Organopolysiloxane A
Dissolve 0.8 g (0.005 mol) of diethyl sulfate and 12.8 g (0.14 mol) of 2-ethyl-2-oxazoline in 29 g of dehydrated ethyl acetate, and heat and reflux for 8 hours under a nitrogen atmosphere. End-reactive poly (N-propionylethylene) Imine) was synthesized. The number average molecular weight measured by GPC was 2700. 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 100000, amine equivalent 20000) was added all at once as a 33% ethyl acetate solution, and the mixture was heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubber-like 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. According to the result of neutralization titration with hydrochloric acid using methanol as a solvent, no amino group remained.

Synthesis Example 2 Organopolysiloxane B
In the same manner as in Synthesis Example 1, 19.0 g (0.12 mol) of diethyl sulfate and 81.0 g (0.82 mol) of 2-ethyl-2-oxazoline are dissolved in 203.0 g of dehydrated ethyl acetate and heated to reflux for 8 hours in a nitrogen atmosphere. Terminal reactive poly (N-propionylethyleneimine) was synthesized. The number average molecular weight measured by GPC was 1100. A 33% ethyl acetate solution of 300 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 32000, amine equivalent 2000) was added all at once and heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (390 g, yield 97%). The content of the silicone segment in the final product was 75% by mass, and the weight average molecular weight was 40000. According to the result of neutralization titration with hydrochloric acid using methanol as a solvent, about 20 mol% of amino groups remained.

Synthesis Example 3: Organopolysiloxane C
Diethyl sulfate (6.17 g, 0.04 mol) and 2-ethyl-2-oxazoline (93.8 g, 0.947 mol) were dissolved in dehydrated ethyl acetate (203 g), heated under reflux for 8 hours under a nitrogen atmosphere, and terminal-reactive poly (N-propionylethylene). Imine) was synthesized. The number average molecular weight measured by GPC was 2500. To this, 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 30000, amine equivalent 2000) was added all at once as a 33% ethyl acetate solution, and the mixture was heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow solid (190 g, yield 95%). The final product had an organopolysiloxane segment content of 50 mass% and a weight average molecular weight of 60000. According to the result of neutralization titration with hydrochloric acid using methanol as a solvent, about 20 mol% of amino groups remained.

Examples 1-8, Comparative Examples 1-7
Hair cosmetics shown in Table 1 were prepared according to a conventional method.

(Production of evaluation hair bundle)
Make a hair bundle of 20cm, 10g with Japanese hair with no chemical treatment history, and mix the first and second ingredients of Kao's “Pretia Soft Bubble Bleach Hybrid” with a bath ratio of 1: 1. Soak and leave at 40 ° C for 30 minutes, then rinse with water. Next, the hair bundle was treated with a general plain shampoo, rinsed with water, further treated with a general plain rinse and rinsed with water, and then the moisture was lightly wiped with a towel and air dried. A hair bundle to which damage was given by repeating this treatment 5 times was used as an evaluation hair bundle.

(1) “Ease of finishing”
After shampooing, 0.3 g of each hairdressing composition having the composition shown in Table 1 was uniformly applied to the evaluation hair bundle which was towel-dried, and then dried while preparing the hair bundle with a dryer (EH5311, manufactured by National). For the ease of finishing at this time (ease of spreading the agent to the evaluation hair bundle, non-stickiness, ease of hair preparation), sensory evaluation was performed in the following five stages by five specialist panelists, and the average value was shown. (Absolute evaluation).
5 points: Good 4 points: Slightly good 3 points: Not good 2 points: Not very good 1 point: Not good

(2) “Mass of hair”
After the evaluation in (1), the sense of unity of the entire hair bundle was visually evaluated in the following five stages by five expert panelists and indicated by an average value (absolute evaluation).
5 points: Good 4 points: Slightly good 3 points: Not good 2 points: Not very good 1 point: Not good

(3) “Smoothness of hair”
After the evaluation of (2), the smoothness of the hair was touched and evaluated. Sensory evaluation was carried out by five expert panelists in the following five stages, and the results were shown as average values (absolute evaluation).
5 points: Good 4 points: Slightly good 3 points: Not good 2 points: Not very good 1 point: Not good

(4) “Softness of hair”
After the evaluation in (3), the softness of the hair was touched and evaluated. Sensory evaluation was carried out by five expert panelists in the following five stages, and the results were shown as average values (absolute evaluation).
5 points: Good 4 points: Slightly good 3 points: Not good 2 points: Not very good 1 point: Not good

(5) “No stickiness when applied to dry hair”
The evaluation hair bundle was shampooed, towel-dried, and dried while preparing the hair bundle with a dryer (National: EH5311). Stretching 0.3g of each hairdressing composition having the composition shown in Table 1 into the palm and applying it to the above-mentioned hair bundle, the sensory evaluation was performed in the following five stages by five expert panelists, and the average value was obtained. Shown (absolute evaluation).
5 points: Not sticky 4 points: Slightly sticky 3 points: Neither can be said 2 points: Slightly sticky 1 point: Sticky

(6) “Sustainability of unity after applying to dry hair”
The evaluation hair bundle was shampooed, towel-dried, and dried while preparing the hair bundle with a dryer (National: EH5311). A specialized panelist about the feeling of unity of the hair bundle when 0.3g of each hairdressing composition with the composition shown in Table 1 is stretched on the palm and applied to the above-mentioned hair bundle and then left for 12 hours at 25 ° C and RH65%. Visual evaluation was carried out in the following 5 stages by 5 persons, and the average value was shown (absolute evaluation).
5 points: Good 4 points: Slightly good 3 points: Not good 2 points: Not very good 1 point: Not good

Formulation Example 1 (hair milk)
(Mass%; active amount)
Organopolysiloxane A (Synthesis Example 1) 0.6
(Hydroxyethyl acrylate / acryloyldimethyltaurine Na)
Copolymer (Simalgel NS, Sepic) 0.4
Amodimethicone (SM8904CE, Toray Dow Corning) 0.4
Stearyltrimethylammonium chloride 0.2
PEG-1540 0.5
Polyoxyethylene hydrogenated castor oil (60E.O.) 0.2
Ethanol 10.0
Fragrance 0.1
Diethylaminohydroxybenzoyl hexyl benzoate (BASF, ubinal A PLUS) 0.01
EDTA-2Na 0.2
Purified water remaining

Formulation example 2 (hair cream)
(Mass%; active amount)
Organopolysiloxane A (Synthesis Example 1) 0.6
(Hydroxyethyl acrylate / acryloyldimethyltaurine Na)
Copolymer (Simalgel NS, Sepic) 0.4
Sodium stearoxy PG hydroxyethyl cellulose sulfonate (SPS-S-SA, Kao) 0.3
Highly polymerized methylpolysiloxane (BY22-060, Toray Dow Corning) 0.6
Hydrogenated polyisobutene 10.0
Isopropyl palmitate 2.0
Neopentyl glycol dicaprate 2.0
Cetyltrimethylammonium chloride 0.2
Glycerin 1.0
Ethanol 10.0
Fragrance 0.1
Methyl paraoxybenzoate 0.2
Ethyl hexyl methoxycinnamate 0.05
EDTA-2Na 0.2
Purified water remaining

Claims (6)

A hair cosmetic containing components (A) and (B).
(A): At least one of the silicon atoms of the organopolysiloxane segment, via an alkylene group containing a hetero atom, the following general formula (1);

[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 poly (N-acylalkyleneimine) segment composed of repeating units represented by the formula: wherein the mass ratio of the organopolysiloxane segment to the poly (N-acylalkyleneimine) segment is 98/2 to 40 / Organopolysiloxane having a weight average molecular weight of 10,000 to 500,000 and 0.1 to 7% by mass
(B): Copolymer of acryloyldimethyltaurine salt and hydroxyethyl acrylate 0.01 to 1.2% by mass   The hair cosmetic according to claim 1, wherein the mass ratio (A) / (B) of component (A) to component (B) is 0.1 to 100. The hair cosmetic composition according to claim 1 or 2, further comprising a component (C).
Component (C): Hydrophobic silicone The hair cosmetic composition according to any one of claims 1 to 3, further comprising a component (D).
Ingredient (D): Cationic surfactant Furthermore, the hair cosmetics in any one of Claims 1-4 containing a component (E).
Component (E): Solid fat and / or semi-solid fat   A hair treatment method wherein the hair cosmetic according to any one of claims 1 to 5 is applied to wet hair or dry hair, and then the hair cosmetic is dried by natural drying or heating and then left for at least 3 hours without washing off. .