JP5700751B2 - Hair cosmetics - Google Patents

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.

  As hair cosmetics mainly used at present, emulsified products such as hair cream types containing wax, higher alcohols, surfactants, etc. in order to impart cohesiveness to the hair and prevent dryness, Alternatively, there is a gel containing a film-forming polymer (set polymer). However, such a hair cosmetic can attach fats and oils to the hair surface and temporarily solve problems such as poor cohesiveness and dryness, but it is essential for hair gloss and cohesiveness. It could not be improved.

  On the other hand, by essentially modifying the hair, it is possible to improve the gloss and cohesiveness of the hair, and as a hair cosmetic that is excellent in touch, a specific organic acid, an organic solvent, and a specific extract are used. Or what tried to act on the inside of hair using polypeptide is known (for example, refer patent documents 1 and 2).

  Although these hair cosmetics show an excellent hair modifying effect, the level of the modifying effect demanded by users is increasing year by year. In addition, the types of effects users are seeking are increasing. Among them, hair tip care is typical. The tip of the hair is the part where daily damage is accumulated and the damage is heavy. The hair care for such heavily damaged parts is required to have a much higher level of effect than before. For these reasons, in recent years, conventional hair cosmetics have been unable to adequately meet the user's required level.

JP 2005-206465 A JP 2005-239567 A

  Therefore, the subject of this invention is providing the hair cosmetics which have the further outstanding hair modification effect which can respond to the user's request level which is increasing year by year. Specifically, to provide a hair cosmetic that further improves the unity and feel of hair, further prevents dryness, and further satisfies the good consistency of the hair flow required by recent users. It is in.

  The present inventor has found that a hair cosmetic that satisfies the above requirements can be obtained by using a specific organic acid, a specific organic solvent, and a specific di- or tripeptide in combination.

The present invention provides hair cosmetics containing the following components (A) to (C) and having a pH of 2 to 5 at 25 ° C. when diluted 20 times by mass with water.
Ingredient (A): Malic acid or its salt 0.1-5 mass%
Component (B): benzyloxyethanol or benzyl alcohol 0.01-5% by mass
Component (C): The number of amino acid residues is 2 or 3, and the glycylglycine derivative represented by the following general formula (1) or a salt thereof: 0.01 to 5% by mass

[In the formula, X represents a C1-C4 divalent hydrocarbon group or amino acid residue which may be substituted with a hydroxyl group,
Y is an amino acid residue or the following chemical formula (2)

(In the formula,-* represents a bond bonded to an adjacent carbonyl group or oxygen atom.)
Represents a divalent group represented by
R represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group;
m and n represent 0 or 1. However, when m and n are 1 at the same time, X is not an amino acid residue. ]

  Furthermore, the present invention provides a hair treatment 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 has a higher level of unity and feel of hair than before, an effect of preventing dryness, and a good consistency of the hair flow at the ends of the hair that has been demanded by users in recent years.

[Component (A): Malic acid or salt thereof]
The content of malic acid or a salt thereof in the hair cosmetic composition of the present invention is such that when used in combination with the component (C), a hair modification effect far superior to conventional ones can be obtained, particularly the hair flow of the hair ends. From the viewpoint of achieving excellent uniformity, the free acid equivalent (as malate in the case of malate) is 0.1 to 5% by mass, preferably 0.3 to 3% by mass, more preferably 0.5 to 2% by mass. It is.

[Component (B): benzyloxyethanol or benzyl alcohol]
Either benzyloxyethanol or benzyl alcohol may be used alone, or both may be used in combination. The content of benzyloxyethanol and benzyl alcohol in the hair cosmetic composition of the present invention allows both the component (A) and the component (C) to penetrate into the hair, and a hair modification effect far superior to the conventional one is obtained. From the viewpoint of achieving excellent alignment of the hair flow, particularly at the hair ends, the total amount is 0.01 to 5% by mass, preferably 0.05 to 2% by mass, and more preferably 0.1 to 1% by mass.

[Component (C): a glycylglycine derivative represented by the general formula (1) or a salt thereof]
The component (C) is a glycylglycine derivative represented by the general formula (1) or a salt thereof, but may be in a free form or zwitterion.
Examples of salts of glycylglycine derivatives include inorganic acid salts such as hydrochlorides and sulfates; organic acid salts such as lactates; ammonium salts such as ammonium salts and alkylammonium salts; alkali metal salts such as sodium salts and the like. Can be mentioned.

  In the general formula (1), the divalent hydrocarbon group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group represented by X may be saturated or unsaturated, linear or branched. Of these, a divalent saturated hydrocarbon group or a divalent saturated hydrocarbon group substituted with a hydroxyl group is preferred.

Examples of the divalent hydrocarbon group include methylene group, ethylene group, ethylidene group, vinylene group, trimethylene group, isopropylidene group, 1-propenylene group, tetramethylene group, 2-methyltrimethylene group, 1-methyltrimethylene group. A methylene group, 1-butenylene group, etc. are mentioned.
Examples of the divalent hydrocarbon group substituted with a hydroxyl group include 1-hydroxyethylene group, 1-hydroxytrimethylene group, 1,2-dihydroxytrimethylene group, 1-hydroxytetramethylene group, 1,2-dihydroxytetramethyl group. Examples include a methylene group, 1,3-dihydroxytetramethylene group, 1,2,3-trihydroxytetramethylene group, and the like.

  In the general formula (1), the “amino acid residue” represented by X means a unit amino acid part to be formed by synthesis or derived from all amino acids present in the living body to form an oligopeptide. , D body or L body may be used.

  The amino acid residues represented by X include basic amino acid residues such as arginine residues, lysine residues and histidine residues; aliphatic amino acid residues such as alanine residues and glycine residues; phenylalanine residues and tyrosine residues Groups, aromatic amino acid residues such as tryptophan residues; acid amide amino acid residues such as glutamine residues and asparagine residues; acidic amino acid residues such as glutamic acid residues, aspartic acid residues and cysteic acid residues; serine residues And hydroxy amino acid residues such as threonine residues; cyclic amino acid residues such as proline residues, N-methylproline residues and 4-hydroxyproline residues. Of these, arginine residues, alanine residues, phenylalanine residues, glycine residues, glutamine residues, glutamic acid residues, serine residues, proline residues, N-methylproline residues, and 4-hydroxyproline residues are preferable.

  In the general formula (1), examples of the amino acid residue represented by Y are the same as those described above for X. Examples of Y include arginine residue, alanine residue, glycine residue, glutamine residue, and glutamic acid residue. A group, a serine residue, a proline residue, a 4-hydroxyproline residue, or a divalent group represented by the chemical formula (2) is preferable.

In the general formula (1), the monovalent hydrocarbon group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group represented by R may be saturated or unsaturated, linear or branched. . The monovalent hydrocarbon group is preferably an alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a s-butyl group, and a t-butyl group.
The monovalent hydrocarbon group substituted with a hydroxyl group is preferably a hydroxyalkyl group, for example, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, a 2,3-dihydroxyethyl group. 2,3,4-trihydroxybutyl group, 2,4-dihydroxybutyl group and the like.

  Examples of glycylglycine derivatives suitable in the present invention include compounds represented by any one of formulas (G1) to (G10), which are represented by any one of formulas (G3) to (G10). The compound represented by any one of formulas (G9) and (G10) (glycylglycylglycine, glycylglycine) is particularly preferable. These glycylglycine derivatives may be in a free form or zwitterion, and may form a salt. Moreover, you may use these individually or in combination of 2 or more types.

  The content of the glycylglycine derivative or a salt thereof in the hair cosmetic composition of the present invention is such that when used in combination with the component (A), a hair modifying effect far superior to the conventional one can be obtained, From the viewpoint of excellent flow uniformity, it is 0.01 to 5% by mass, preferably 0.05 to 3% by mass, and more preferably 0.1 to 1% by mass.

[Component (D): Iso fatty acid or anteiso fatty acid or salt thereof]
Component (D) used in the present invention is an iso fatty acid having 19 to 30 carbon atoms, an anteiso fatty acid having 19 to 30 carbon atoms, or a salt thereof. As these fatty acids, saturated fatty acids are preferred. Further, from the viewpoint of restoring the damage on the surface of the hair and combining the repair of the damage inside the hair by the component (A) and the component (C), a synergistic effect on the hair modification is brought out. The number of carbon atoms is preferably 19 to 24, and more preferably 19 to 22.

  Specifically, iso-fatty acids include 17-methyloctadecanoic acid, 18-methylnonadecanoic acid, 19-methylicosanoic acid, and 20-methylhenicosanoic acid. Anti-fatty acids include 16-methyloctadecanoic acid, 17-methylnonadecanoic acid, 18 -Methylicosanoic acid, 19-methylhenicosanoic acid. These salts include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, organic amines such as ammonium salt, triethanolamine salt, diethanolamine salt and monoethanolamine salt. Examples include basic amino acid salts such as salts, lysine salts, and arginine salts.

  The fatty acid of component (D) or a salt thereof can be used alone or in combination of two or more. In addition, the content of the component (D) in the hair cosmetic composition of the present invention, combined with the repair of damage inside the hair by the component (A) and the component (C), repairs damage on the surface of the hair, From the viewpoint of drawing out a synergistic effect on hair modification, 0.001 to 2% by mass is preferable, 0.005 to 1% by mass, and further 0.01 to 0.5% by mass is preferable.

[Component (E): Polysilicone-9]
The hair cosmetic composition of the present invention can further contain polysilicone-9. Polysilicone-9 is represented by the following general formula (3) via an alkylene group containing a hetero atom in 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 p 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. And an organopolysiloxane having a weight average molecular weight of 12,000 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 (3) 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.

  Polysilicone-9 can be produced by a known method, for example, according to the method described in JP-A-7-133352, the following general formula (4)

[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 the following general formula (5)

[Wherein, R ¹ and p 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 (5) 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. If, for example, 2-substituted-2-oxazoline is used as the cyclic iminoether (5), poly (N-acylethyleneimine) (corresponding to p = 2 in formula (3)) is obtained, and 2-substituted-dihydro- If 2-oxazine is used, poly (N-acylpropylenimine) (corresponding to p = 3 in formula (3)) 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 above general formula (5) 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 Polysilicone-9, the mass ratio of the organopolysiloxane segment to the poly (N-acylalkyleneimine) segment is 98/2 to 40/60. From the viewpoint of improving the unity and sustainability, 95/5 to 65/35, more preferably 93/7 to 68/32, and further preferably 90/10 to 70/30. This mass ratio was determined by dissolving 5% by mass of the organopolysiloxane of component (E) in deuterated chloroform, and analyzing the result 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 the adjacent poly (N-acylalkylenimine) segments of the polysilicone-9 is 1500 to 3500, from the viewpoint of improving the setting property and its sustainability. Is preferably 1600 to 3200, more preferably 1700 to 3000.

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 described above, R ⁶ represents an alkylene group containing a hetero atom, Z represents a poly (N-acylalkylenimine) segment, and R ⁷ represents a residue of a polymerization initiator. 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 1600, More preferably, it is 850-1500, More preferably, it is 900-1400. Thereby, a set property and its sustainability can be improved further.

  In Polysilicone-9, the weight average molecular weight of the raw material organopolysiloxane (4) is from the viewpoint of improving solubility in polar solvents such as water, ease of handling after dissolution, and setability and its sustainability. 10,000 to 100,000, more preferably 20,000 to 80,000, and even more preferably 30,000 to 60,000. The average molecular weight of the organopolysiloxane (4) as the raw material compound is a weight average molecular weight in terms of polystyrene measured by GPC under the following measurement conditions.

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

  Polysilicone-9 has a weight average molecular weight of 12,000 to 500,000, but from the viewpoint of further improving the setting property and its sustainability, 12,000 to 150,000, more preferably 24,000 to 120,000, and even more preferably 37,000 to 92,000. In addition, the weight average molecular weight of the organopolysiloxane of the component (E) is the weight average molecular weight of the organopolysiloxane (4) as the raw material compound, the aforementioned organopolysiloxane segment and the poly (N-acylalkyleneimine) segment), and It can obtain | require from mass ratio of.

  The content of polysilicone-9 in the hair cosmetic composition of the present invention has a smooth effect on the surface of the hair, combined with the repair of damage inside the hair by the component (A) and the component (C), and the effect of unity. From the viewpoint of synergistic improvement, 0.01 to 5% by mass is preferable, 0.05 to 3% by mass, and further 0.1 to 2% by mass is preferable.

  Furthermore, the hair cosmetic composition of the present invention can contain ethanol. Ethanol contributes to solubilization or stable dispersion of component (B). Furthermore, penetration of the components (A) and (C) into the hair is promoted. The content of ethanol is preferably 0.01 to 50% by mass, particularly 1 to 20% by mass in the hair cosmetic composition of the present invention. The mass ratio of ethanol and component (B) is ethanol: component (B) = 100: 1 to 2: 1, particularly 80: 1, from the viewpoint of promoting penetration of components (A) to (C) into hair. A range of ˜3: 1 is preferred.

  The hair cosmetic composition of the present invention further contains a set polymer from the viewpoint of improving hair styling, adjusting the viscosity, improving stability, improving adhesion at the time of applying the hair, improving touch, and early expression of the hair modifying effect. You may let them. Such polymers include polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, vinylpyrrolidone / vinyl acetate / vinyl propionate terpolymer, vinylpyrrolidone / alkylaminoacrylate (quaternary chloride) copolymer, vinyl Polyvinyl pyrrolidone polymer compounds such as pyrrolidone / acrylate / (meth) acrylic acid copolymer, vinyl pyrrolidone / alkylamino acrylate / vinyl caprolactam copolymer; acidic vinyl ether such as methyl vinyl ether / maleic anhydride alkyl half ester copolymer Polymer compounds; acidic polyvinyl acetate polymer compounds such as vinyl acetate / crotonic acid copolymer, vinyl acetate / crotonic acid / vinyl neodecanoate copolymer, vinyl acetate / crotonic acid / vinyl propionate copolymer; Acid acrylic polymer such as (meth) acrylic acid / (meth) acrylic acid ester copolymer, acrylic acid / acrylic acid alkyl ester / alkylacrylamide copolymer; N-methacryloylethyl-N, N-dimethylammonium α Amphoteric acrylic polymer compounds such as -N-methylcarboxybetaine / butyl methacrylate copolymer, hydroxypropyl acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymer; acrylamide / acrylic ester quaternary copolymer Examples include basic acrylic polymer compounds such as coalescence; cellulose derivatives such as cationic cellulose derivatives; chitin / chitosan derivatives such as hydroxypropyl chitosan, carboxymethyl chitin, and carboxymethyl chitosan.

  These set polymers can be used alone or in combination of two or more, and the content thereof is preferably 0.1 to 10% by mass, particularly 0.5 to 5% by mass in the hair cosmetic composition of the present invention.

In order to further improve the conditioning effect, the hair cosmetic composition of the present invention may contain a conditioning component selected from silicones and oils other than the component (E). 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 10% by mass, and particularly 0.5 to 5% by mass in the hair cosmetic composition of the present invention from the viewpoint of fingering and lack of stickiness. Is preferred

  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 and cycloparaffin; castor oil, cacao oil, mink oil, avocado oil, olive oil, etc. Glycerides; waxes such as beeswax, whale wax, lanolin, microcrystalline wax, ceresin wax, carnauba wax; higher alcohols such as cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol; myristic acid Octyldodecyl, hexyl laurate, emulsified cetyl, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, isononanoic acid Esters such as tridecyl; higher fatty acids other than component (D) such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, isostearyl acid, isopalmitic acid; 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 0.05 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 good unity and no stickiness. Is preferred.

  The hair cosmetic composition of the present invention may contain a surfactant from the viewpoints of system stability including solubilization and dispersibility of the solvent, and improvement in touch. As the surfactant, any of a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and an anionic surfactant can be used.

  Examples of the cationic surfactant include quaternary ammonium salts represented by the following general formula (6).

[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. Z ⁻ 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 Z ⁻ include halide ions such as chloride ions and bromide ions; organic anions such as ethyl sulfate ions and methyl carbonate ions, and halide ions, particularly chloride ions are preferable.

  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.

  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.

  Of these, cationic surfactants are preferred from the viewpoint of feel. 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 10% by mass, particularly 0.05 to 3% by mass is preferable.

  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 (B) and works synergistically with the component (B) to promote the improvement of the gloss and hair modifying effects. Examples of the polyhydric alcohol include ethylene glycol, glycerin, sorbitol, propylene glycol, 1,3-butylene glycol, dipropylene glycol and the like, and glycerin is 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 mass, particularly 0.5 to 5% by mass in the hair cosmetic composition of the present invention.

  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. Such components include, for example, anti-dandruff agents; vitamins; bactericides; anti-inflammatory agents, antiseptics; chelating agents; moisturizers such as sorbitol and panthenol; colorants such as dyes and pigments; hydroxyethyl cellulose, methyl cellulose, polyethylene Viscosity modifiers such as glycol and clay minerals; pH adjusters such as organic acids other than component (A), sodium hydroxide, potassium hydroxide; plant extracts; pearling agents; fragrances; dyes; Ingredients described in CYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLE PRESS) are included.

  The hair cosmetic composition of the present invention promotes the osmotic adsorption of the components (A) and (B) to the hair, and is applied to the hair from the viewpoint of imparting gloss, flexibility, cohesion and suppleness to the hair. The pH (when diluted to 20 mass times with water, 25 ° C.) is adjusted to 2 to 5, preferably pH 2.5 to 4.5, particularly preferably pH 3 to 4.5.

  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 styling agent, hair conditioning agent or the like. Examples of the dosage form include pump spray, aerosol spray, pump foam, aerosol foam, gel, lotion and the like.

  Furthermore, by applying the hair cosmetic composition of the present invention to the hair and then heating the application site, penetration of the component (A), component (B) and component (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.

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. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 100000, amine equivalent 20000) was added all at once, 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. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

Synthesis Example 2 Organopolysiloxane B
6.5 g (0.042 mol) of diethyl sulfate and 34.4 g (0.36 mol) of 2-ethyl-2-oxazoline were dissolved in 87 g of dehydrated ethyl acetate and heated under reflux for 8 hours under a nitrogen atmosphere to react with terminal reactive poly (N-propionylethylene). Imine) was synthesized. The number average molecular weight measured by GPC was 1300. A 33% ethyl acetate solution of 100 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 semi-solid (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.

Examples 1-4, Comparative Examples 1-6
Hair cosmetics having the formulations shown in Table 1 were prepared by a conventional method, and performance evaluation was performed according to the following methods and standards.

<Evaluation hair bundle>
Japanese damaged hair (30 minutes x 2 treatments with Kao Pretia Bubble Hybrid)
Torres with a mass of about 10g and a length of about 20cm

<Hair treatment method>
After washing the hair, towel dry, apply 0.4 g of hair cosmetics to the hair bundle, and dry it by hand blow while applying warm air with a dryer. At that time, sensory evaluation was performed on the following items by five specialist panelists in accordance with the following criteria (all, Comparative Example 3 was evaluated as 3). Table 1 shows the average score of evaluation points.

・ Ease of handling hair during styling:
It was evaluated whether the hair was soft during drying and whether the hair was aligned and easy to handle.
5: Easier to handle than Comparative Example 3: 4: Easier to handle than Comparative Example 3: 3: Equivalent to Comparative Example 3: 2: Slightly more difficult to handle than Comparative Example 1: 1: More difficult to handle than Comparative Example 3

・ Smoothness After drying the dryer, the smoothness of the hair when touching the entire hair bundle was evaluated.
5: Smoother than Comparative Example 3: 4: Slightly smoother than Comparative Example 3: 3: Equivalent to Comparative Example 3: 2: Not smoother than Comparative Example 3: 1: Not smoother than Comparative Example 3

・ Equipment of 2cm hair flow After drying the dryer, it was evaluated whether the hair flow of 2cm was suppressed and the hair flow was even.
5: The hair ends are aligned from Comparative Example 3. 4: The hair ends are aligned slightly from Comparative Example 3. 3: Equivalent to Comparative Example 3. 2: The hair ends are slightly aligned from Comparative Example 3. 1 : From Comparative Example 3, the hair ends are not aligned.

-Smoothness of the hair tips After drying the dryer, the smoothness of the hair tips when touching the hair tips was evaluated.
5: The tip of the hair is smoother than Comparative Example 3: 4: The tip of the hair is smoother than Comparative Example 3: 3: Equivalent to Comparative Example 3: 2: The tip of the hair is slightly smoother than Comparative Example 3: 1: From Comparative Example 3 The hair ends are not smooth

-Units The unit of the whole hair bundle after drying the dryer was evaluated.
5: Summarized from Comparative Example 3: 4: Summarized somewhat from Comparative Example 3: 3: Equivalent to Comparative Example 3: 2: Not to be settled slightly from Comparative Example 3: 1: Not to be summarized from Comparative Example 3

Formulation Example 1 Emulsion
(mass%)
Water balance Malic acid 0.6
Lactic acid 0.6
Benzyl alcohol 0.2
Glycylglycine 0.3
18-methyl Eiko San acid ^{* 2} 0.2
Organopolysiloxane A (Synthesis Example 1) 0.3
Organopolysiloxane B (Synthesis Example 2) 0.1
Behenyltrimethylammonium chloride solution (58% by mass) ^{* 3} 0.4
N, N-dimethyloctadecyloxypropylamine 0.25
Cetostearyl alcohol 2.8
Glycerin 5
Isopropyl palmitate ^{* 4} 1.3
Dimethicone ^{* 5} 0.7
Ethanol 0.7
Sodium hydroxide solution (pH adjuster) Amount adjusted to pH 3.7

* 3: Cotamine 2285E-E (Kaosha)
* 4: Exepearl IPP (Kaosha)
* 5: Average polymerization degree 2600, equivalent to 4 million mm ² / s

Formulation Example 2 Water Agent
(mass%)
Water Suitable amount Malic acid 1.4
Lactic acid 1.4
Benzyl alcohol 0.2
Glycylglycine 0.3
18-methyleicosanoic acid ^{* 2} 0.02
Organopolysiloxane A (Synthesis Example 1) 0.3
Dipropylene glycol 2.0
Cetyltrimethylammonium chloride solution (30% by mass) ^{* 6} 0.8
Ethanol 15
Polyoxyethylene (60) hydrogenated castor oil ^{* 7} 0.2
Sodium hydroxide (pH adjuster) Amount adjusted to pH 3.7

* 6: Cotamine 60W (Kaosha)
* 7: Emanon CH-60 (K) (Kaosha)

Formulation Example 3 Water preparation
(mass%)
Water Suitable amount Malic acid 1.4
Lactic acid 1.4
Benzyl alcohol 0.2
Glycylglycylglycine 0.3
18-methyleicosanoic acid ^{* 2} 0.02
Organopolysiloxane A (Synthesis Example 1) 0.3
Dipropylene glycol 2.0
Cetyltrimethylammonium chloride solution (30% by mass) ^{* 6} 0.8
Ethanol 15
Polyoxyethylene (9) tridecyl ether ^{* 8} 0.2
Sodium hydroxide (pH adjuster) Amount adjusted to pH 3.7

* 8: Softanol 90 (Nippon Shokubai Co., Ltd.)

Formulation Example 4 Two-layer water agent (upper layer is emulsified layer, lower layer is water layer)
(mass%)
Water Appropriate amount Malic acid 0.9
Lactic acid 0.9
Benzyl alcohol 0.2
Glycylglycine 0.3
18-methyleicosanoic acid ^{* 2} 0.02
Organopolysiloxane A (Synthesis Example 1) 0.3
Organopolysiloxane B (Synthesis Example 2) 0.1
Dipropylene glycol 2.0
Cetyltrimethylammonium chloride solution (30% by mass) ^{* 6} 0.8
Polyoxyethylene (9) tridecyl ether ^{* 8} 0.5
Dimethicone emulsion (X-52-2162, Shin-Etsu Chemical) 7.0
Ethanol 11.0
Polyquaternium-6 0.6
Sodium hydroxide (pH adjuster) Amount adjusted to pH 3.7

Claims (6)

A hair cosmetic comprising the following components (A) to (C) and having a pH of 2 to 5 at 25 ° C. when diluted 20 times by mass with water.
Component (A): Malic acid or a salt thereof 0.1 to 2% by mass
Component (B): benzyloxyethanol or benzyl alcohol 0.01-5% by mass
Component (C): glycylglycine 0.05-3 mass % Furthermore, the hair cosmetics of Claim 1 containing the following component (D).
Component (D): C19-19 iso fatty acid or anteiso fatty acid or salt thereof 0.01-5 mass% The hair cosmetic according to claim 1 or 2, further comprising the following component (E):
Ingredient (E): Polysilicone-9 0.1-5% by mass   The hair cosmetic according to any one of claims 1 to 3, wherein the hair cosmetic is left without being washed off after being applied to the hair.   A hair treatment method in which the hair cosmetic composition according to any one of claims 1 to 4 is applied to hair and left without being washed away.   The hair treatment method according to claim 5, wherein the application site is heated after the hair cosmetic is applied to the hair.