JP5900326B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to a hair cosmetic composition that imparts a top rise or the like to fine hair or hair that does not age.

  One of the most problematic areas for people with thin hair or those whose hair has become thinner due to aging is the sag at the top. In order to solve this, there are technologies using polymers such as set resins and protein hydrolysates, and technologies using polyphenols, amino acids and the like. However, those using a polymer such as a set resin are insufficient in the stiffness and sustainability of the top rise. In addition, those using polyphenols, amino acids and the like require time until the effects are manifested and are not immediately effective.

  On the other hand, gloss is the best hair quality that women regardless of age. Techniques for imparting gloss to hair include oil and silicone. However, when oil, silicone, or the like is used for hair that is thin due to aging or the like, there is a problem that the top rise is impaired. From the above, there has been a demand for a hair cosmetic that gives the hair that has been thinned by aging or the like to give rise to the top and its sustainability, and is not stiff and glossy.

JP 2009-280527 A JP 2010-6749 A JP 2010-6724 A JP 2009-107959 A JP 2010-6800 A JP 2009-242256 A JP 2008-516923 A Special table 2008-520614 JP 2009-249329 A JP 2009-242257 A JP 2009-235042

  The present invention has been made in view of the above circumstances, and imparts a top rise and sustainability to hair thinned by aging and the like, and is not stiff, gives hair gloss, and has good storage stability. It aims at providing hair cosmetics.

  As a result of intensive studies to achieve the above object, the present inventor has (A) a specific acrylic acid-based polymer having acrylic acid as a structural unit, (B) a specific amino-modified silicone having an ether bond, and (C By using together ethanol and a solvent comprising a hydroxyl group-containing compound other than the components (D) and (C), the hair that has become thin due to aging, etc. is given rise to the top and its durability, and there is no wrinkle. The present inventors have found that the hair can be glossy and that the storage stability is also good, leading to the present invention.

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｒ²は水素原子又は−ＣＨ₂ＯＨ基を示し、Ａは−ＮＨ−を示す。）

（式中、Ｒ³は水素原子又はメチル基を示し、Ｍは水素原子、アルカリ金属原子、アンモニウム又はアミンを示す。）
［８］．洗い流さないタイプのトリートメントである［１］〜［７］のいずれかに記載の毛髪化粧料。
［９］．さらに、（Ｅ）カチオン界面活性剤を含有する［１］〜［８］のいずれかに記載の毛髪化粧料。
［１０］．さらに、（Ｆ）ポリオキシアルキレン化合物を含有する［１］〜［９］のいずれかに記載の毛髪化粧料。
［１１］．加齢による細い髪用である［１］〜［１０］のいずれかに記載の毛髪化粧料。 Accordingly, the present invention provides the following hair cosmetics.
[1]. Components (A) to (D) below (A) Acrylic acid / silicone copolymer, salt of (acrylates / allyl methacrylate) copolymer and 2-amino-2-methylpropanol, (vinyl pyrrolidone / acrylates / lauryl methacrylate) ) Acrylic acid polymer selected from copolymer and acrylic acid / acrylamide copolymer: 0.05 to 10% by mass
(B) At least one amino glycol-modified silicone selected from linear amino polyether-modified silicone and amino-terminated polyether-modified silicone: 0.1 to 10% by mass
(C) Hair cosmetics containing a solvent comprising a hydroxyl group-containing compound other than ethanol (D) and (C) components, and having a content mass ratio represented by (A) / (B) of 0.02 to 11.
[2]. The linear amino polyether-modified silicone of component (B) is composed of an amino-modified polysiloxane block having an amino group in the side chain and a polyoxyalkylene block, and is a block copolymer having a methyl group at the terminal, The hair cosmetic composition according to [1], wherein the polyether-modified silicone is a silicone having an amino group to which alkylene glycol is added at both ends.
[3]. (B) Hair cosmetics as described in [1] or [2] whose component is a linear amino polyether modified silicone.
[4]. (C) Hair cosmetics in any one of [1]-[3] whose content of a component is 0.3-50 mass%.
[5]. (D) The hair cosmetic according to any one of [1] to [4], wherein the component is selected from propylene glycol, dipropylene glycol, butylene glycol, glycerin, isoprene glycol, benzyl alcohol, and benzyloxyethanol.
[6]. (D) Hair cosmetics in any one of [1]-[5] whose components are propylene glycol, butylene glycol, or glycerin.
[7]. The component (A) is composed of 70 to 95 mol% of monomer units represented by the following general formula (1) and 5 to 30 mol% of monomer units represented by the following general formula (2). The hair cosmetic composition according to any one of [1] to [6], wherein the hair cosmetic composition is a copolymer.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or a —CH ₂ OH group, and A represents —NH—.)

(In the formula, R ³ represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, an alkali metal atom, ammonium or an amine.)
[8]. The hair cosmetic according to any one of [1] to [7], which is a type of treatment that does not wash away.
[9]. The hair cosmetic according to any one of [1] to [8], further comprising (E) a cationic surfactant.
[10]. Furthermore, (F) Hair cosmetics in any one of [1]-[9] containing a polyoxyalkylene compound.
[11]. The hair cosmetic according to any one of [1] to [10], which is for thin hair due to aging.

  According to the present invention, there is provided a hair cosmetic composition that imparts top rising and sustainability to hair that has become thin due to aging, etc., has no stiffness, gives gloss to the hair, and has good storage stability. can do. Furthermore, the softness of a hair tip can be provided by mix | blending a cationic surfactant. Furthermore, the spread of hair can be suppressed by blending a polyoxyalkylene compound.

Hereinafter, the present invention will be described in detail.
The hair cosmetic of the present invention is a hair cosmetic containing the following components (A) to (D).
(A) acrylic acid polymer selected from acrylic acid / silicone copolymer, acrylic acid / methacrylic acid copolymer and acrylic acid / acrylamide copolymer (B) aminoglycol modified silicone (C) ethanol (D) (C ) A solvent comprising a hydroxyl group-containing compound other than the component

(A) Acrylic acid-based polymer selected from acrylic acid / silicone copolymer, acrylic acid / methacrylic acid copolymer and acrylic acid / acrylamide copolymer By using the polymer, it is possible to give the top rise and its sustainability to hair that has become thin due to aging or the like. (A) A component can be used individually by 1 type or in combination of 2 or more types as appropriate.

(I) Acrylic acid / silicone copolymer An acrylic acid / silicone copolymer is a copolymer containing acrylic acid and siloxane as constituent units. For example, (acrylates / ethylhexyl acrylate / dimethicone methacrylate) copolymers, (acrylates / stearyl acrylate / dimethicone methacrylate) copolymers, (acrylates / tridecyl acrylate / triethoxysilylpropyl methacrylate / dimethicone methacrylate) copolymers, (acrylates) / Behenyl acrylate / dimethicone methacrylate) copolymer, (acrylates / polytrimethylsiloxy methacrylate) copolymer, and the like. These are expressed by “display names” decided in the cosmetics industry.

  (Acrylates / ethyl hexyl acrylate / dimethicone methacrylate) copolymer is a copolymer of 2-ethylhexyl acrylate, dimethic methacrylate, and one or more monomers consisting of acrylic acid, methacrylic acid or simple esters thereof. . Examples of commercially available products include graft copolymers composed of an acrylic polymer and dimethylpolysiloxane (cyclopentasiloxane dissolved product): Shin-Etsu Chemical Co., Ltd .: KP-575).

  The (acrylates / stearyl acrylate / dimethicone methacrylate) copolymer is a copolymer of stearyl acrylate, dimethicone methacrylate, and one or more monomers consisting of acrylic acid, methacrylic acid, or simple esters thereof. Examples of commercially available products include Shin-Etsu Chemical: KP-561P.

  (Acrylates / Tridecyl Acrylate / Triethoxysilylpropyl Methacrylate / Dimethicone Methacrylate) Copolymer is composed of tridecyl acrylate, triethoxysilylpropyl methacrylate, dimethicone methacrylate, acrylic acid, methacrylic acid or simple esters thereof. It is a copolymer with one or more types of monomers. Examples of commercially available products include Shin-Etsu Chemical Co., Ltd .: KP-574.

  The (acrylates / behenyl acrylate / dimethicone methacrylate) copolymer is a copolymer of at least one monomer composed of behenyl acrylate, dimethicone methacrylate and acrylic acid, methacrylic acid or simple esters thereof. Examples of commercially available products include Shin-Etsu Chemical: KP-562P.

  The (acrylates / polytrimethylsiloxy methacrylate) copolymer is a copolymer of at least one monomer comprising acrylic acid, methacrylic acid or a simple ester thereof and polytrimethylsiloxy methacrylate. Examples of commercially available products include Toray Dow Corning Corporation: FA-4001 (dissolved in a cyclic pentamer), FA-4002 (dissolved in isododecane), and the like.

(Ii) Acrylic acid / methacrylic acid copolymer An acrylic acid / methacrylic acid copolymer is a copolymer having acrylic acid and methacrylic acid as constituent units. For example, (acrylates / allyl methacrylate) copolymer AMP, (vinyl pyrrolidone / acrylates / lauryl methacrylate) copolymer and the like can be mentioned.

  (Acrylates / allyl methacrylate) copolymer AMP is a salt of acrylates / allyl methacrylate copolymer and 2-amino-2-methylpropanol (AMP). As a commercial item, Lubrizol Advanced Materials: FIXATE G-100 POLYMER (26 mass% aqueous solution) etc. are mentioned.

  The (vinyl pyrrolidone / acrylates / lauryl methacrylate) copolymer is a copolymer comprising vinyl pyrrolidone (VP), lauryl methacrylate, and one or more monomers selected from acrylic acid, methacrylic acid or esters thereof. It is. As a commercial item, IPS Japan Co., Ltd .: STYLEZE 2000 etc. are mentioned.

  The proportion of the structural units of acrylic acid in (i) acrylic acid / silicone copolymer and (ii) acrylic acid / methacrylic acid copolymer is not particularly limited, but 50 mol% or less gives rise to the top without stiffness. Excellent effect. Moreover, although a weight average molecular weight is not specifically limited, 10,000-200,000 are preferable.

(Iii) Acrylic acid / acrylamide copolymer The acrylic acid / acrylamide copolymer is represented by a monomer unit of 70 to 95 mol% represented by the following general formula (1) and the following general formula (2). An acrylic acid / acrylamide copolymer composed of a copolymer containing 5 to 30 mol% of monomer units as structural units can be used, and these can be used singly or in appropriate combination of two or more.

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｒ²は水素原子又は−ＣＨ₂ＯＨ基を示し、Ａは−ＮＨ−を示す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or a —CH ₂ OH group, and A represents —NH—.)

  Examples of the alkali metal atom include sodium atom, potassium atom, and amine include monoethanolamine, diethanolamine, triethanolamine and the like. When M is an alkali metal atom, ammonium or amine, -COOM forms a salt. To do.

As the monomer unit represented by the general formula (1), those in which R ¹ is a hydrogen atom, R ² is a hydrogen atom, and A is —NH— are preferable, and the monomer unit represented by the general formula (2) As the body unit, R ³ is preferably a hydrogen atom, and M is preferably a hydrogen atom and / or a sodium atom.

  The proportion of the monomer unit represented by the general formula (1) is preferably 70 to 95 mol% in the acrylic acid / acrylamide copolymer (in 100 mol% of all monomer units), and 75 to 90 mol%. More preferably, the proportion of the monomer unit represented by the general formula (2) is preferably 5 to 30 mol%, preferably 10 to 25 mol, of acrylic acid / acrylamide copolymer (in 100 mol% of all monomer units). % Is more preferable. If the ratio of the monomer unit represented by the general formula (1) exceeds 95 mol%, the non-stickiness may be reduced, and if it is less than 70 mol%, the top rise may be reduced.

  The acrylic acid / acrylamide copolymer may contain a monomer unit other than the monomer unit represented by the general formula (1) or (2) as long as the effects of the present invention are not impaired. Examples of other monomer units include nonionic monomers, amphoteric monomers, semipolar monomers, and cationic monomers other than the monomer units represented by the general formula (1) or (2). And monomer units corresponding to monomers and polysiloxane group-containing monomers. The proportion of monomer units other than the monomer unit represented by the general formula (1) or (2) is preferably 0 to 25 mol% in the acrylic acid / acrylamide copolymer. The acrylic acid / acrylamide copolymer of the present invention may be a random copolymer or a block copolymer, and the acrylic acid / acrylamide copolymer of the present invention is represented by the general formulas (1) and (2). An acrylic acid / acrylamide copolymer comprising a copolymer having monomer units as constituent units is preferred.

  Examples of nonionic monomers include esters of alcohols having 1 to 22 carbon atoms and (meth) acrylic acid, amides of alkylamines having 1 to 22 carbon atoms and (meth) acrylic acid, ethylene glycol, 1 , 3-propylene glycol, etc. and (meth) acrylic acid monoesters, esters in which the monoester's hydroxyl group is etherified with methanol, ethanol, etc., (meth) acryloylmorpholine, etc. Examples of the body include betaine group-containing (meth) acrylic esters, betaine group-containing (meth) acrylamides, etc., and examples of semipolar monomers include amine oxide group-containing (meth) acrylic esters and amine oxide groups (Meth) acrylamide and the like, and examples of the cationic monomer include quaternary ammonia. Um group-containing (meth) acrylic esters, quaternary ammonium group-containing (meth) acrylamide and the like.

  The polysiloxane group-containing monomer is a compound having a polysiloxane structure and a structure that can be covalently linked to an acrylic acid / acrylamide copolymer. Such structural units have a high affinity with silicone oils commonly used in cosmetic compositions, and serve to bind silicone oils to other structural units in acrylic acid / acrylamide copolymers. It is thought that it has a function of increasing the adsorption power of silicone oil to hair, particularly damaged hair.

The proportion of each monomer unit in the acrylic acid / acrylamide copolymer is the IR absorption of carbonyl group, amide bond, polysiloxane structure and various functional groups, and the methyl group or amide bond site of polydimethylsiloxane and It can be measured by ¹ H-NMR of a methyl group, methylene group or the like adjacent to them, or ¹³ C-NMR thereof.

  The weight average molecular weight of the acrylic acid / acrylamide copolymer is preferably 3,000 to 100,000. If it is less than 3,000, the effect of improving the hair feel may not be sufficiently obtained, and if it exceeds 100,000, it may feel stiff. The weight average molecular weight is more preferably 10,000 to 30,000, further preferably 10,000 to 20,000, and more preferably 12,000 to 17,000 in view of the balance between the rise of the top and the non-stickiness. Is particularly preferred.

  The weight average molecular weight can be measured by gel permeation chromatography (GPC). Specifically, apparatus: manufactured by Tosoh Corporation, SC8010, SD8022, RI8020, CO8011, PS8010, column: Wako Pure Chemical Industries, Ltd. Using Wakopak (Wakobeads G-50), developing solvent: water / methanol / acetic acid / sodium acetate = 6/4 / 0.3 / 0.41 (volume ratio)), polyethylene glycol can be obtained as a standard substance. .

  The molecular weight of the acrylic acid / acrylamide copolymer can be adjusted, for example, by controlling the degree of polymerization of the polymer. The molecular weight and viscosity can also be controlled by increasing or decreasing the addition amount of a crosslinking agent such as a polyfunctional acrylate. However, if a crosslinking agent is added as much as possible, the molecular weight and the viscosity are rapidly increased, and thus there are aspects that are difficult to control in industrial production. For this reason, it is preferable not to contain a crosslinking agent.

  The acrylic acid / acrylamide copolymer can be obtained in accordance with the methods described in JP2007-137830A and JP2007-161986A. For example, it can be obtained by mixing monomers that give respective structural units or precursors thereof and copolymerizing them by a method such as solution polymerization, suspension polymerization, emulsion polymerization or the like. In addition, the counter ion in the general formula (2) can be subjected to polymerization by substituting a part or all of it for other than hydrogen ion by a neutralization reaction before polymerization, and neutralized after polymerization or other reaction. A part or all of the reaction can be replaced with other than hydrogen ions. These can be appropriately selected depending on the ease of synthesis. The polymerization reaction is preferably carried out in a hydrophilic solvent such as ethanol, and a known polymerization initiator such as dimethyl 2,2'-azobis (2-methylpropionate) can be used as the polymerization initiator. In addition, each monomer is mix | blended so that each monomer may become specific mole with respect to the total amount (100 mol%) of all the monomers. The proportion of the structural unit composed of each monomer in the copolymer of the present invention is the same as the blending amount of each monomer at the time of copolymerization.

  The polymerization reaction is preferably performed in a hydrophilic solvent. Examples of the hydrophilic solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, alcohol solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, and sec-butanol, water, and the like. Is mentioned. These can be used individually by 1 type or in combination of 2 or more types. Among them, it is preferable to use an alcohol solvent.

  As polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethyl) Valeronitrile), dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (1-cyclohexanecarbonitrile), 2,2 ′ -Azobis (2-methyl-N- (2-hydroxyethyl) -propionamide), 2,2'-azobis (2-amidinopropane) dihydrochloride, dimethyl 2,2'-azobis (2-methylpropionate) ), Benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, etc., persulfate, or redox thereof. Scan system and the like, can be used without particular limitation. The polymerization initiator is preferably used in the range of 0.01 to 5% by mass with respect to all monomers.

  The polymerization reaction can be performed, for example, under an inert gas atmosphere such as nitrogen or argon, preferably at 30 to 120 ° C., more preferably at 40 to 100 ° C., usually for 1 to 30 hours. After completion of the polymerization, the produced copolymer may be isolated from the reaction solution by an appropriate means such as solvent distillation or addition of a poor solvent. This copolymer can be used as it is or after further purification, for example, in the production of cosmetics. Purification can be carried out by combining appropriate means such as reprecipitation, solvent washing, membrane separation and the like as necessary.

  (A) As the acrylic acid polymer, (iii) acrylic acid / acrylamide copolymer is preferable from the viewpoint of the sustainability of the rise at the top and storage stability, and among them, acrylic acid hydroxyethylacrylamide copolymer is preferable. As a commercial item, acrylic acid hydroxyethyl acrylamide (Mitsubishi Chemical Corporation: PAN105 (22.2 mass% aqueous solution)) etc. are mentioned.

  (A) As for the compounding quantity of an acrylic acid type polymer, 0.05-10 mass% is preferable in hair cosmetics. By setting it within this range, it is possible to obtain the rise of the top and its sustainability, no stiffness, and good storage stability. More preferably, it is 0.1-5 mass%, and 0.3-3 mass% is still more preferable. If the blending amount is less than 0.05% by mass, the rise of the top may be insufficient, and if it exceeds 10% by mass, the product may become stiff and the storage stability may be insufficient.

(B) Aminoglycol-modified silicone By using such a silicone having an alkoxy group in the structural unit, in a hair cosmetic containing (A), (C) and (D) components, The compatibility is improved, and the storage stability is improved. These can be used individually by 1 type or in combination of 2 or more types.

  The amino glycol-modified silicone is a silicone having an amino group to which alkylene glycol is added. This amino group may be directly bonded to Si or may have a linking group. Further, the alkylene glycol group may be arranged in the repeating unit of the polymer, or both ends of the polymer main chain may be blocked. As a specific example, a type arranged in a repeating unit of a polymer is called a linear amino polyether-modified silicone, and a type in which both ends of the polymer are blocked with an alkylene glycol group is called an amino both-end polyether-modified silicone. .

(I) Linear amino polyether-modified silicone Linear amino polyether-modified silicone refers to a silicone having a siloxane structure having an amino functional group and a polyoxyethylene group in the main chain. As the linear amino polyether-modified silicone, a silicone comprising an amino-modified polysiloxane block having an amino functional group and a polyoxyalkylene block is preferable, and in particular, an amino functional group in the side chain represented by the following general formula (3): A block copolymer consisting of an amino-modified polysiloxane block having a group and a polyoxyalkylene block and having a terminal methyl group is preferred.

（Ｒ⁴は、それぞれ独立して水素原子又は炭素数１〜６の１価の炭化水素基を示し、Ｒ⁵はＲ⁴又はＥを示し、Ｅは−Ｒ⁶−Ｚ（Ｒ⁶は直接結合手又は炭素数１〜２０の２価の炭化水素基）を示し、Ｚは１〜３級アミノ基含有基又はアンモニウム基含有基を示す。Ｘは２価の基を示し、ａは２以上の数、ｂは１以上の数、ｎは２〜１０の数、ｃは４以上の数、ｄは２以上の数を示す。）

(R ⁴ independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ⁵ represents R ⁴ or E, E represents —R ⁶ —Z (R ⁶ represents a direct bond) Z represents a primary to tertiary amino group-containing group or an ammonium group-containing group, X represents a divalent group, and a represents 2 or more. Number, b is a number of 1 or more, n is a number of 2 to 10, c is a number of 4 or more, and d is a number of 2 or more.)

The aminoglycol-modified silicone represented by the general formula (3) is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group independently of each other as R ⁴ in the general formula (3). Group and ethyl group are more preferable, and methyl group is more preferable.
Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms of R ⁶ include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a decylene group, and an octadecylene group. Methylene group, ethylene group, and propylene group are preferable.
Z is preferably an amino group-containing group or an ammonium group-containing group represented by the following general formula (4) or (5).

（式中、Ｒ⁷は

であり、Ｒ⁸は水素原子又は１価の炭化水素基を示し、それぞれのＲ⁸は同一でも異なっていてもよい。ｅ及びｆはそれぞれ０〜６の整数を示す。Ｔ^-はハロゲン化物イオン又は有機アニオンを示す。）

(Where R ⁷ is

And R ⁸ represents a hydrogen atom or a monovalent hydrocarbon group, and each R ⁸ may be the same or different. e and f each represent an integer of 0-6. T ⁻ represents a halide ion or an organic anion. )

Examples of the monovalent hydrocarbon group represented by R ⁸ in the general formulas (4) and (5) include a methyl group, an ethyl group, and a propyl group. T ^- Specific examples of the chloride ion, iodide ion, halide ions such as bromide ion, methosulfate, ethosulfate, methemoglobin phosphate, and organic anions such as ethoxy phosphate.

Preferred E groups of the general formula _{(3), - (CH 2) 3 -NH} 2, - (CH 2) 3 -N (CH 3) 2, - (CH 2) 3 -NH- (CH 2) 2 _{-NH 2, - (CH 2)} 2 -NH- (CH 2) 2 -N (CH 3) 2, - (CH 2) 3 -N + (CH 3) 3 Cl - and is, more preferably, - (CH ₂₎ a _{3 -NH- (CH 2) 2 -NH} 2.

  In the general formula (3), a preferable example of the divalent group represented by X is an alkylene group or an arylene group. Specifically, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, or an isobutylene group may be used. And a tetramethylene group and an isobutylene group are more preferable.

  In the general formula (3), a is preferably a number of 2 to 1,000, b is a number of 1 to 50, c is a number of 4 to 200, and d is a number of 2 to 100. In the block copolymer represented by the general formula (3), the ratio of the siloxane block is preferably 25 to 97% by mass, more preferably 35 to 90% by mass, and further preferably 50 to 80% by mass of the entire copolymer. Preferably, the block copolymer has a weight average molecular weight of at least 1,200. In addition, all the weight average molecular weights of (B) component are the values measured by the usual method using GPC, chloroform as an eluent, and polystyrene as a standard substance.

  Among the aminoglycol-modified silicones represented by the general formula (3), a more preferred example is an aminoglycol-modified polysiloxane / polyoxyalkylene block copolymer having a polymer unit represented by the general formula (6).

（式中、ａ、ｂ及びｄは前記と同じ意味を示し、ｉは４以上の数を示し、ｊは０〜２００の数を示す。）

(In the formula, a, b and d have the same meaning as described above, i represents a number of 4 or more, and j represents a number of 0 to 200.)

In the general formula (6), preferably, a is a number of 2 to 1,000, b is a number of 1 to 50, i is a number of 4 to 200, j is a number of 0 to 200, particularly 0 to 30, d Is preferably a number from 2 to 100. Further, the unit of —O (C ₂ H ₄ O) _i (C ₃ H ₆ O) _j — may be either block or random of polyoxyethylene and polyoxypropylene. Examples include FZ-3789, SS-3588, Toray Dow Corning, SILSTLE 104 and 201 (bisisobutyl PEG-14 / amodimethicone) copolymers, and SILSTLE 401 (bisbutyroxyamodimethicone / PEG-60) copolymers. Can be mentioned.

(Ii) Amino-terminated polyether-modified silicone Amino-terminated polyether-modified silicone is a silicone having an amino group in which alkylene glycol is added to both ends of a polymer. This amino group may be directly bonded to Si or may have a linking group. Examples of the amino-terminated polyether-modified silicone include bis (C13-15alkoxy) PG amodimethicone (indicated name), which has both ends of the polymer main chain blocked with a long-chain alkoxy group. A propylene glycol is added to the group. Commercially available products can be used as the amino-terminated polyether-modified silicone, and examples thereof include Toray Dow Corning JP8500.

  (B) The aminoglycol-modified silicone is preferably (i) a linear aminopolyether-modified silicone from the viewpoints of no stickiness, storage stability and gloss.

  (B) As for the compounding quantity of aminoglycol modified silicone, 0.1-10 mass% is preferable in hair cosmetics, 0.5-7 mass% is more preferable, 1-5 mass% is further more preferable. If the amount is less than 0.1% by mass, there is a possibility that the effect of giving gloss is not sufficient, and if the amount exceeds 10% by mass, the rise of the top, its sustainability, and storage stability may be reduced.

  The content mass ratio represented by (A) / (B) is preferably from 0.02 to 11, preferably from 0.05 to 10, from the standpoint of the rise of the top, its sustainability, and no stickiness. 3 is preferable, and 0.3 to 3 is more preferable. If the ratio is less than 0.02, the top rise and sustainability may be reduced.

(C) Ethanol When blended with ethanol, an effect can be obtained immediately after application, especially when the cosmetic is not washed away. Although this mechanism is unknown, it is expected to be expressed by quick drying by adding ethanol.

  (C) 0.3-50 mass% is preferable in hair cosmetics, and, as for the compounding quantity of ethanol, 5-30 mass% is more preferable. If the blending amount is less than 0.3% by mass, it takes time to obtain the effect, and in particular, the storage stability at a low temperature may be insufficient. If it exceeds 50% by mass, the quick drying property is too high. Since there is a possibility that the coating cannot be performed uniformly, the effect may be uneven, and the storage stability at high temperatures may be insufficient.

(D) Solvent consisting of a hydroxyl group-containing compound other than the component (C) By blending a solvent consisting of a hydroxyl group-containing compound other than ethanol, the non-stickiness can be improved. Examples of such a solvent, propylene glycol (PG), dipropylene glycol (DPG), Buchirengu recall (BG), glycerin, isoprene glycol (IG), benzyl alcohol, benzyloxy ethanol, and the like, alone Or 2 or more types can be used in appropriate combination. Among them, in terms of lack of stiffness, propylene glycol, Buchirengu recall, glycerin is preferred, propylene glycol is preferred in view of storage stability.

  The blending amount of the component (D) is preferably from 0.1 to 20% by mass in the hair cosmetic composition, and more preferably from 3 to 10% by mass from the standpoint of the rise of the top, its sustainability, and no stiffness. If the blending amount is less than 0.1% by mass, there will be no stiffness and the storage stability will be insufficient, and if it exceeds 20% by mass, the rise of the top, its sustainability and storage stability may be reduced.

(E) Cationic surfactant The hair cosmetic composition of the present invention may further contain a cationic surfactant. By blending a cationic surfactant, the softness of the hair tip can be imparted. When the top rise is improved, the softness of the hair ends is lost and the unity tends to deteriorate, but this problem can be solved by adding a cationic surfactant. Examples of the cationic surfactant include, but are not limited to, amine salts, ammonium salts, guanidine salts, benzethonium salts, pyridinium salts, pyrrolidone carboxylates, mono-N-long chain acyl basic amino acid lower alkyl ester salts, and the like. . These can be used individually by 1 type or in combination of 2 or more types.

  More specifically, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dioleyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, dimethylaminopropylamide stearate, dimethylamino laurate Propylamide, Palmitic acid dimethylaminopropylamide, Lauric acid amidobutylguanidine acetate, Myristic acid amidobutylguanidine acetate, Palmitic acid amidobutylguanidine, Distearyldimethylammonium sulfate, Stearylethyldihydroxyethylammonium ethyl sulfate, N-coconut oil fatty acid Examples include L-arginine ethyl and DL-pyrrolidone carboxylate.Of these, stearyltrimethylammonium chloride, dimethylaminopropylamide stearate, and behenyltrimethylammonium chloride are more preferable from the viewpoint of the softness of the hair tips.

  (E) 0.1-5 mass% is preferable in hair cosmetics, and, as for the compounding quantity of a cationic surfactant, 0.5-2 mass% is more preferable. If it is less than 0.1% by mass, the softness of the bristles may be insufficient, and if it exceeds 5% by mass, the non-stiffness may be reduced.

(F) Polyoxyalkylene compound The hair cosmetic composition of the present invention may further contain a polyoxyalkylene compound. By blending a polyoxyalkylene compound, the spread of hair can be suppressed. Hair damaged by color or perm causes friction inside the hair and spreads the hair, but this problem can be solved by adding a polyoxyalkylene compound. Although it does not specifically limit as a polyoxyalkylene compound, Polyethylene glycol, polypropylene glycol, polyoxyethylene (POE) polyoxypropylene (POP) glycol, polyoxyethylene (POE) polyoxypropylene (POP) cetyl ether, polyoxyethylene (POE) polyoxypropylene (POP) decyl tetradecyl ether, polyoxyethylene (POE) polyoxypropylene (POP) trimethylolpropane, polyoxyethylene (POE) polyoxypropylene (POP) butyl ether, polyoxyethylene (POE) Polyoxypropylene (POP) glyceryl ether, polyoxyethylene (POE) polyoxypropylene (POP) stearyl ether, polyoxyethylene POE) hexylene glycol ether to polyoxypropylene (POP), polyoxyethylene (POE) polyoxypropylene (POP) lauryl ether.
The number of added moles of these ethylene oxide and propylene oxide groups is not particularly limited, but specific examples include 1 to 300 moles.
Preferably, POE (36) POP (36) butyl ether and POE (24) POP (24) glyceryl ether are mentioned from the point of non-expanding of hair. The blending amount is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 7% by mass from the viewpoint of no hair spreading. If it is less than 0.1% by mass, the effect of suppressing the spread of hair may be reduced, and if it exceeds 10% by mass, the rise of the top may be reduced.

  In addition to the above-described components, the hair cosmetic of the present invention can be blended as desired with various additive components that are widely used in hair cosmetics as long as the effects of the present invention are not impaired. Examples of these components include nonionic surfactants, amphoteric surfactants, anionic surfactants, silicones other than the component (B), polymer compounds, amino acids, protein hydrolysates, and metal sequestering agents. Agents, thickeners, polyols other than the component (D), oil agents, ultraviolet absorbers, pH adjusters, antioxidants, oxidizing agents, reducing agents, alkali agents, dyes, antibacterial agents, bactericides, and propellants. Can be included.

  When a fragrance is blended in the hair cosmetic composition of the present invention, it conforms to the fragrance and fragrance composition described in JP-A No. 2003-95895. Moreover, when mix | blending a fragrance | flavor and a fragrance | flavor composition with the hair cosmetics of this invention, when it mix | blends so that a fragrance | flavor and a fragrance | flavor composition may be 0.00001-50 mass% with respect to the hair cosmetics whole quantity of this invention, it is suitable. Yes, more preferably 0.0001 to 30% by mass.

  Although pH of the hair cosmetics of this invention is not specifically limited, 3-10 are preferable and 3-7 are more preferable. In addition, a measurement measures the pH of hair cosmetics directly at normal temperature (25 degreeC).

  The hair cosmetic composition of the present invention can be prepared based on a conventional method by mixing the above-mentioned essential and optional components and water residue as necessary. Examples of the hair cosmetic composition of the present invention include shampoos, rinses, conditioners, treatments, styling agents, etc., and their dosage forms are also appropriately selected, for example, liquid, cream, mist, foam, gel, wax, etc. The There are types of rinses, conditioners, and treatments that wash away after application, and types that do not wash away. Among these, a rinse, a conditioner, and a treatment are preferable, and a treatment that does not wash away is particularly preferable. Further, since the hair cosmetic composition of the present invention is effective for fine hair such as aging, it is suitable as “a hair cosmetic composition for thin hair due to aging”.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, unless otherwise specified, “%” in the composition indicates mass%, the ratio indicates the mass ratio, and the amount of each component in the table is an amount converted into a pure component.

[Examples 1 to 53, Comparative Examples 1 to 10]
[Preparation method]
According to the composition shown in Tables 1 to 9, a type of treatment that was not washed away was prepared by a conventional method. The following evaluation was performed about the obtained treatment. The results are also shown in the table.

[Rise of the top]
To a hair bundle of 5 g and 10 cm human hair, 0.5 g of a hair cosmetic material was uniformly applied, and 25 ° C., 50% R.D. H. After drying for 1 hour, the hair bundle was fixed with a clip in a direction perpendicular to the experimental table. The angle of the hair bundle after 5 minutes was measured. A result is shown with the following evaluation criteria from an angle.
<Evaluation criteria>
A: The inclination of the hair bundle is 0 to 10 degrees. O: The inclination of the hair bundle is 11 to 30 degrees. Δ: The inclination of the hair bundle is 31 to 45 degrees. X: The inclination of the hair bundle is 46 to 90 degrees.

[Persistence of top rise]
The hair bundle evaluated for the rise of the top was 25 ° C., 50% R.D. H. After 6 hours, the hair bundle angle was measured in the same manner. A result is shown with the following evaluation criteria from an angle.
<Evaluation criteria>
A: The inclination of the hair bundle is 0 to 30 degrees O: The inclination of the hair bundle is 31 to 45 degrees Δ: The inclination of the hair bundle is 46 to 70 degrees X: The inclination of the hair bundle is 71 to 90 degrees

[No stiffness]
The roots of the hair bundles that were evaluated for the “top rise” and “continuity of the top rise” were fixed, and the panelist evaluated the tactile sensation based on the following evaluation criteria.
<Evaluation criteria>
◎: Stiffness is extremely small ○: Stiffness is small △: Stiffness ×: Stiffness is large

[Glossy hair]
The reflectance of the hair bundle evaluated for the “top rise” and “continuity of the top rise” was measured by glossiness (gloss unit) at a reflection angle of 60 ° using microgloss (manufactured by Gardner). A result is shown on the following evaluation criteria from glossiness.
<Evaluation criteria>
◎: 1.2 GU (gross unit) or more ○: 1.0 GU or more and less than 1.2 GU Δ: 0.8 GU or more and less than 1.0 GU ×: Less than 0.8 GU

[Softness of hair ends]
The roots of the hair bundles that were evaluated for the “top rise” and “continuity of the top rise” were fixed, and the panelist evaluated the tactile sensation based on the following evaluation criteria.
<Evaluation criteria>
◎: The tip is very soft ○: The tip is soft △: The tip is soft X: The tip is not soft

[No spread of hair]
A hair bundle of 30 cm and 10 g was treated once with a commercially available permanent agent and twice with a commercially available bleach agent to produce a damaged hair bundle.
With the damaged hair bundle wet with water and towel-dried, 0.7 g of the sample was uniformly applied and air-dried. Then 90% R.D. H. When the sample was allowed to stand for 1 hour at a humidity of 1, the spread of the hair bundle was evaluated in comparison with the uncoated hair bundle.
<Evaluation criteria>
(Double-circle): The spread was suppressed considerably compared with non-application | coating.
○: Slightly spread compared to uncoated.
(Triangle | delta): The same extent as uncoated.
X: Spreading compared with uncoated.

[Storage stability] <High temperature: 40 ° C>
When the sample was put in a 50 mL glass bottle and stored at 40 ° C. for 1 month, a change in appearance (coloring) was visually observed.
<Evaluation criteria>
A: There was no coloring.
○: There was a slight change in coloring.
Δ: Although there was a change in coloring, there was no problem in actual use.
X: There was a change in coloring, and there was a problem in actual use.

[Storage stability] <Low temperature: -5 ° C>
The change in appearance (precipitation / deposition) was visually observed when the sample was placed in a 50 mL glass bottle and stored at −5 ° C. for 1 month.
<Evaluation criteria>
(Double-circle): There was no precipitation and precipitation.
○: Slight precipitation / deposition occurred.
Δ: Precipitation / precipitation occurred, but redissolved at room temperature, and there was no problem in actual use.
X: There existed precipitation and precipitation, it did not redissolve at room temperature, but there was a problem in actual use.

[Test Example 1]
50 g of a non-washing type treatment of Example 1 and Comparative Example 8 is filled into a 50 mL glass bottle, the appearance after one month is observed at room temperature (15 to 30 ° C.), and stability evaluation is performed based on the following evaluation criteria. It was. Example 1 was “◎” and Comparative Example 8 was “x”.
<Evaluation criteria>
◎: Equivalent to standard product (immediately after compounding), no separation or precipitation ○: Slightly different from standard product in terms of coloring, separation and precipitation, but no problem in practical use △: Coloring, separation, There is a difference from the reference product in terms of precipitation, but there is no problem in practical use. ×: There is a clear difference from the reference product in terms of coloring, separation, and precipitation, and there is a problem in practical use.

  In addition, the preparation method of the raw material used in the table | surface, and the name of a commercial item are shown. In addition, the quantity of each component in a table | surface is the quantity converted into the pure part.

[Preparation of acrylic acid / hydroxyethylacrylamide copolymer (1)]
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 100 parts by mass of ethanol, and 88.6 parts by mass of 2-hydroxyethylacrylamide and 11.4 parts by mass of acrylic acid were added to the dropping funnel. A monomer mixed solution consisting of 80 parts by mass of ethanol and 80 parts by mass of ethanol was charged, the reactor was purged with nitrogen, and then heated to 80 ° C. Into the reactor, 1 part by mass of dimethyl 2,2′-azobis (2-methylpropionate) (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the monomer mixture was added over 2 hours. It was dripped. After the completion of dropping, the reaction was allowed to proceed for 6 hours, followed by cooling and neutralization with sodium hydroxide to obtain an acrylic acid / hydroxyethylacrylamide copolymer (1) (2-hydroxyethylacrylamide / sodium acrylate = 83 mol%). / 17 mol%).

[Preparation of acrylic acid-di-hydroxypropyl acrylamide copolymer (2)]
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirrer was charged with 100 parts by mass of ethanol, and 82.5 parts by mass of 2,3-dihydroxypropylacrylamide, and acrylic acid 17. A monomer mixture consisting of 5 parts by mass and 80 parts by mass of ethanol was charged, and the reactor was purged with nitrogen, and then heated to 80 ° C. Into the reactor, 1 part by mass of dimethyl 2,2′-azobis (2-methylpropionate) (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the monomer mixture was added over 2 hours. It was dripped. Cooled mixture was reacted after completion of the dropwise addition 6 hours to obtain neutralized by adding sodium hydroxide corresponding to half the molar ratio of acrylic acid Acrylic acid di-hydroxypropyl acrylamide copolymer (2) (2 , 3-dihydroxypropylacrylamide / acrylic acid (sodium) = 70 mol% / 30 mol%).

[Preparation of acrylic acid-di-hydroxypropyl acrylamide copolymer (3)]
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 100 parts by mass of ethanol, and 97.5 parts by mass of 2,3-dihydroxypropylacrylamide was added to the dropping funnel. A monomer mixture consisting of 5 parts by mass and 80 parts by mass of ethanol was charged, and the reactor was purged with nitrogen, and then heated to 80 ° C. Into the reactor, 1 part by mass of dimethyl 2,2′-azobis (2-methylpropionate) (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the monomer mixture was added over 2 hours. It was dripped. Cooled mixture was reacted after completion of the dropwise addition 6 hours to obtain neutralized by adding sodium hydroxide corresponding to half the molar ratio of acrylic acid Acrylic acid di-hydroxypropyl acrylamide copolymer (3) (2 , 3-dihydroxypropylacrylamide / acrylic acid (sodium) = 95 mol% / 5 mol%).

[Preparation of acrylic acid / hydroxyethylacrylamide copolymer (4)]
Except for adjusting the amount so that the following Table 1 0 building blocks, in the same manner as in Preparation Example 1, to obtain an acrylic acid-hydroxyethyl acrylamide copolymer (4).

[Preparation of acrylic acid / hydroxyethylacrylamide copolymer (5)]
Except for adjusting the amount so that the following Table 1 0 building blocks, in the same manner as in Preparation Example 1, to obtain an acrylic acid-hydroxyethyl acrylamide copolymer (5).

(Acrylates / Allyl methacrylate) Copolymer AMP: Lubrizol Advanced Materials FIXATE G-100 POLYMER 26% aqueous solution (Nikko Chemicals)
(Vinylpyrrolidone / Acrylates / Lauryl methacrylate) Copolymer: STYLEZE 2000 (Stabilise 2000) (ISP Japan)
(Acrylates / stearyl acrylate / dimethicone methacrylate) Copolymer: KP-561P (Shin-Etsu Chemical)
Carbomer: Carbopol Ultrez10
Linear amino polyether modified silicone: SILSTLE 104 (Toray Dow Corning)
Aminoglycol-modified silicone: JP8500 (Toray Dow Corning Silicone)
Amoji methicone: SM8904 (Toray Dow Corning Silicone)
POE (24) POP (24) Glyceryl ether: Carpol GH200 (ADEKA)
POE (36) POP (36) Butyl ether: Unilube 50MB-168L (NOF)

The following non-washing type treatments were prepared and evaluated in the same manner as in the above examples.
[Example 54]
[Type of treatment that does not wash away] (%)
Acrylic acid / hydroxyethylacrylamide copolymer (4) (A)
2
Linear amino polyether-modified silicone (B) 3
Dipropylene glycol (D) 3
Ethanol (C) 20
Hydroxyethyl cellulose 0.7
Stearyltrimethylammonium chloride (E) 0.5
Glycolic acid 0.1
Orange essential oil 0.2
Purified water balance
Total 100.0
(A) / (B) Mass ratio = 0.67
Top rise: ◎
Persistence of top rise: ◎
No worries: ◎
Hair gloss: ◎
Softness of hair ends: ◎
Storage stability (40 ° C): ◎
Storage stability (-5 ° C): ◎

[Example 55]
[Type of treatment that does not wash away] (%)
Acrylate Di hydroxypropyl acrylamide copolymer (3) (A)
2
Linear amino polyether-modified silicone (B) 2
Aminoglycol-modified silicone (B) 1
Benzyloxyethanol (D) 3
Ethanol (C) 20
Hydroxyethyl cellulose 0.7
Behenyltrimethylammonium chloride (E) 0.5
Ammonium glycolate 0.1
Rosemary essential oil 0.2
Purified water balance
Total 100.0
(A) / (B) Mass ratio = 0.67
Top rise: ◎
Persistence of top rise: ◎
No worries: ○
Hair gloss: ◎
Softness of hair ends: ◎
Storage stability (40 ° C): ◎
Storage stability (-5 ° C): ◎

[Example 56]
[Type of treatment that does not wash away] (%)
Alkyltrimethylammonium chloride (E) 1
Stearyl alcohol 3
Glycolic acid 0.3
Sorbitol 10
Propylene glycol (D) 5
Ethanol (C) 1
Benzyl alcohol (D) 2
Acrylic acid / hydroxyethylacrylamide copolymer (5) (A)
1
Polyethylene glycol monostearate 0.3
Hydroxyethyl cellulose 0.3
Linear amino polyether-modified silicone (B) 3
Dimethyl silicone 1
Polyoxyethylene / methylpolysiloxane copolymer 0.2
Bentonite 0.2
Hydroxypropyl methylcellulose 0.3
Sodium hydroxide proper amount perfume 0.5
Purified water balance
Total 100.0
(A) / (B) Mass ratio = 0.33
Top rise: ◎
Persistence of top rise: ◎
No worries: ◎
Hair gloss: ◎
Softness of hair ends: ◎
Storage stability (40 ° C): ◎
Storage stability (-5 ° C): ◎

[Example 57]
[Type of treatment that does not wash away] (%)
Acrylic acid / hydroxyethylacrylamide copolymer (4) (A)
2
Linear amino polyether-modified silicone (B) 3
Isoprene glycol (D) (trade name isoprene glycol, manufactured by Kuraray Co., Ltd.) 3
Ethanol (C) 20
Hydroxyethyl cellulose 0.7
Stearyltrimethylammonium chloride (E) 0.5
Glycolic acid 0.1
Orange essential oil 0.2
Purified water balance
Total 100.0
(A) / (B) Mass ratio = 0.67
Top rise: ◎
Persistence of top rise: ◎
No worries: ○
Hair gloss: ◎
Softness of hair ends: ◎
Storage stability (40 ° C): ◎
Storage stability (-5 ° C): ◎

The raw materials used are shown in the table below.

Claims (11)

Components (A) to (D) below (A) Acrylic acid / silicone copolymer, salt of (acrylates / allyl methacrylate) copolymer and 2-amino-2-methylpropanol, (vinyl pyrrolidone / acrylates / lauryl methacrylate) ) Acrylic acid polymer selected from copolymer and acrylic acid / acrylamide copolymer: 0.05 to 10% by mass
(B) At least one amino glycol-modified silicone selected from linear amino polyether-modified silicone and amino-terminated polyether-modified silicone: 0.1 to 10% by mass
(C) Hair cosmetics containing a solvent comprising a hydroxyl group-containing compound other than ethanol (D) and (C) components, and having a content mass ratio represented by (A) / (B) of 0.02 to 11.   The linear amino polyether-modified silicone of component (B) is composed of an amino-modified polysiloxane block having an amino group in the side chain and a polyoxyalkylene block, and is a block copolymer having a methyl group at the terminal, The hair cosmetic composition according to claim 1, wherein the polyether-modified silicone is a silicone having an amino group having alkylene glycol added to both ends.   The hair cosmetic composition according to claim 1 or 2, wherein the component (B) is a linear amino polyether-modified silicone.   The hair cosmetic composition according to any one of claims 1 to 3, wherein the content of the component (C) is 0.3 to 50 mass%.   The hair cosmetic composition according to any one of claims 1 to 4, wherein the component (D) is selected from propylene glycol, dipropylene glycol, butylene glycol, glycerin, isoprene glycol, benzyl alcohol, and benzyloxyethanol.   (D) A component is propylene glycol, butylene glycol, or glycerol, The hair cosmetics of any one of Claims 1-5. The component (A) is composed of 70 to 95 mol% of monomer units represented by the following general formula (1) and 5 to 30 mol% of monomer units represented by the following general formula (2). The hair cosmetic composition according to any one of claims 1 to 6, wherein the hair cosmetic composition is contained as a copolymer.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or a —CH ₂ OH group, and A represents —NH—.)

(In the formula, R ³ represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, an alkali metal atom, ammonium or an amine.)   The hair cosmetic composition according to any one of claims 1 to 7, which is a type of treatment that does not wash away.   Furthermore, the hair cosmetics of any one of Claims 1-8 containing (E) cationic surfactant.   The hair cosmetic according to any one of claims 1 to 9, further comprising (F) a polyoxyalkylene compound.   The hair cosmetic according to any one of claims 1 to 10, which is for aging thin hair.