JP2012072090A - Two agent-mixing type hair cleanser composition - Google Patents

Abstract

Provided is a hair cleansing composition that exhibits an excellent cleaning effect and hair repairing / restoring effect on damaged hair caused by chemical treatment or the like in a one-step hair washing action.
SOLUTION: (a) a first agent containing at least 5% by mass of an anionic surfactant; (b) 0.1 to 20% by mass of a water-insoluble silicone compound; and (c) a cationic surfactant. And (d) a second agent comprising an emulsion containing a long-chain aliphatic alcohol, and the component (a) in the composition and the total amount of the components (b), (c) and (d) The ratio (a) / [(b) + (c) + (d)] is 0.5 to 20 in mass ratio, and the first agent and the second agent are mixed at the time of use. Two-component mixed hair cleanser composition.
[Selection figure] None

Description

  The present invention is a two-component mixed-type hair cleaning composition that exhibits a good cleaning effect and excellent hair damage repairing / restoring effect with a one-step hair washing action on hair damaged by chemical treatment or the like. About.

  In general, as a hair cleansing composition such as a shampoo, a composition containing an anionic surfactant and / or an amphoteric surfactant is used. However, since such a shampoo alone does not feel the hair after shampooing, a rinse or a conditioner is used to obtain a better hair feel. As described above, a two-step treatment of shampooing and rinsing and conditioner treatment is widely used for good hair feel, but on the other hand, only one step provides a cleaning effect and good hair feel. There is a demand to get. In response to such a demand, a product called a 2 in 1 (two in one) shampoo (rinse in shampoo) is commercially available.

  In recent years, hair styles that make use of coloring and perms have become popular, and hair damage caused by these chemical treatments has become serious. Specifically, the protein constituting the hair is denatured by chemical treatment, and the interaction force between the proteins is reduced. Thereby, the strength is reduced, and the cuticle is peeled off. In addition, the protein is decomposed and the protein is likely to be eluted when washing the hair.

  Furthermore, with colored hair, the fading that occurs in daily hair care behavior is also a problem. This occurs when a pigment that has penetrated into the hair by coloring or a degradation product of melanin originally possessed by the hair elutes from the hair during washing. These hair damages cause further reduction in hair strength, and serious damage such as shortening the coloring cycle. For this reason, there is a need for hair care products that have improved hair damage repair and repair functions.

  As a method for obtaining a repair / repair function, a method in which an amino acid or peptide is permeated into a cuticle layer and pressed at a high temperature (Patent Document 1: WO 2002/041857 pamphlet), a solubilized silk peptide, a water-soluble chitosan derivative and cationization A method using a protein derivative (Patent Document 2: JP 2000-191445 A), a method using a solubilized silk peptide, a sugar alcohol and a neutral amino acid (Patent Document 3: JP 2000-191446 A), a specific hydration A method using a first agent containing a degrading protein and / or a derivative thereof and a second agent containing a denaturing agent thereof (Patent Document 4: JP-A-2003-300836), a carboxyl group and a phenol group in the molecule Ingredients selected from amino acids, protein hydrolysates and keratin hydrolysates Method used (Patent Document 5: Japanese Patent Application Laid-Open No. 2004-91455), method using dibasic acid diester compound having specific structure and sericin (Patent Document 6: Japanese Patent Application Laid-Open No. 2007-15936), aqueous solution having a melting point of 40 ° C. or higher Using a functional silicone and a protein derivative (Patent Document 7: JP 2000-191447 A), a method using chitosans, sterols and oxycarboxylic acid (Patent Document 8: JP 2007-8867 A), lipophilicity A method using a cationic surfactant and a sterol (Patent Document 9: Japanese Patent Application Laid-Open No. 2003-176214), a method using a guanidino group-containing siloxane (Patent Document 10: Japanese Translation of PCT International Publication No. 2008-533218), an organic silicon having a specific structure A compound or a method of using the organosilicon compound and a polymer compound (Patent Document 11: Japanese Patent Laid-Open No. Hei 10) 158125), a method using a composition containing an amphiphilic amide lipid, a cationic surfactant, and silicones, and having a pH of 1 to 4.5 when diluted 20-fold with water (Patent Document 12: Japanese Patent Application Laid-Open No. 2004-2005). -203786) and the like have been proposed.

In recent years, it has been demanded that the hair repair / repair function can be obtained in one step simultaneously with the cleaning effect as in the case of the 2-in-1 shampoo as described above. However, in the above-described conventional method, a compound having high solubility in water such as amino acid, peptide, solubilized silk peptide, hydrolyzed protein, sericin, water-soluble silicone, oxycarboxylic acid or the like is used together with the detergent. It was easy to remove by the cleaning composition which has a cleaning effect in one step such as 2 in 1 shampoo, and a sufficient repair / restoration effect could not be obtained.
In addition, when using compounds that are difficult to dissolve in water, such as lipophilic cationic surfactants, guanidino group-containing siloxanes, organosilicon compounds, amphiphilic amide lipids, and silicones, they are stable in water using an emulsifier. Maintaining the state is required in terms of formulation and the like. However, if a stable state is maintained in water, a stable state is maintained even during water rinsing and rinsing, so many of these active ingredients are washed away during rinsing and rinsing, and sufficient effects cannot be obtained. Was the current situation.
Therefore, it has been difficult to effectively develop hair damage repair and repair effects and cleaning effects on hair damaged by chemical treatment or the like by a one-step cleaning action.

International Publication No. 2002/041857 Pamphlet JP 2000-191445 A JP 2000-191446 A Japanese Patent Laid-Open No. 2003-300836 JP 2004-91455 A JP 2007-15936 A JP 2000-191447 A JP 2007-8867 A JP 2003-176214 A Special table 2008-533218 gazette JP-A-10-158125 JP 2004-203786 A JP 59-187095 A

  The present invention has been made in view of the above circumstances, and it is intended to provide a hair cleaning composition that exhibits an excellent cleaning effect and hair repair / restoration effect on damaged hair caused by chemical treatment, etc., in a one-step hair washing action. Objective.

  As a result of intensive studies to achieve the above object, the present inventor has (a) a first agent containing at least 5% by mass of an anionic surfactant, and (b) a water-insoluble silicone compound 0.1 to 0.1%. 20% by mass and (c) a cationic surfactant and (d) a second agent consisting of an emulsion containing a long-chain aliphatic alcohol, wherein the first agent and the second agent are in use. It is mixed, and (a) / [(b) + (c) + (d)] in the mixture is in an appropriate range, so that it is excellent for damaged hair due to chemical treatment, etc. in a one-step hair washing action. It has been found that there are both a cleaning effect and a hair repair / repair effect.

  In general hair cleansing compositions such as shampoos, when an anionic surfactant and a cationic surfactant are present, a complex is formed by the ionic interaction of the two components, and the conditioning and cleaning effects as expected. It was difficult to get. Therefore, the applicant made a two-part type consisting of (A) an agent containing an anionic surfactant and (B) an agent containing a cationic substance in Patent Document 13 (Japanese Patent Laid-Open No. 59-187095), It was proposed that an anionic surfactant and a cationic surfactant are present at the time of shampooing, and that a complex of both surfactants is present at the same time so that cleaning and conditioning are effectively performed. However, it is difficult to say that this technique has a sufficient hair conditioning effect, and it has been difficult to satisfactorily obtain the effect of repairing and repairing hair damaged especially by chemical treatment.

  In contrast, in the present invention, the water-insoluble silicone compound is emulsified and dispersed in an oil-in-water emulsion containing a cationic surfactant and a long-chain aliphatic alcohol at the time of application to hair, preferably just before application. The second agent thus formulated is mixed with the first agent containing the anionic surfactant that is a cleaning component, and (a) / [(b) + (c) + (d)] in the mixture is mixed. By being in an appropriate range, an excellent hair repairing / restoring effect and cleaning effect can be obtained. According to the present invention, the presence of an anionic surfactant and a cationic surfactant at the same time can be avoided before use, and both agents are appropriately mixed at the time of use. And a part of the cationic surfactant forms a complex, and as the complex is formed, the emulsified state of the second agent collapses and becomes unstable, and a water-insoluble silicone compound having low solubility in water is obtained. It is presumed that when applied to the hair in such an unstable emulsified state, it is effectively adsorbed to the hair and has a high conditioning effect without being washed away from the hair. Furthermore, in this case, the remainder of the anionic surfactant and the cationic surfactant is present together with the above complex in the mixture without forming a complex, so that foaming is good and high detergency can be obtained. It is presumed that the presence of the anionic surfactant also increases the penetration of the silicone compound into the hair. Therefore, with a one-step cleaning action, it exhibits a sufficient foaming and good cleaning effect, is excellent in hair cuticle peeling, protein elution suppression effect, and coloring fading prevention effect, and has high hair damage repair and repair effect An unprecedented hair cleansing composition can be provided.

In the present invention, a dimethylpolysiloxane represented by the general formula (1) to be described later can be effectively blended as a water-insoluble silicone compound, and a high polymerization degree silicone compound can be stably blended to exert a high conditioning effect. it can. Further, as the anionic surfactant, one or more selected from polyoxyethylene alkyl ethers having an average addition mole number of alkyl sulfate and ethylene oxide of 1 to 3 and an alkyl group having 12 to 14 carbon atoms are preferable. It is.
Furthermore, it is more preferable that the mass ratio of component (b) / component (c) is 0.6 to 2.5 in order to obtain an excellent cleaning effect and hair repair / restoration effect.

（式中、ｎは２５〜５００の整数である。）
請求項３：
（ａ）アニオン性界面活性剤が、アルキル硫酸塩及びエチレンオキサイドの平均付加モル数が１〜３モルでアルキル基の炭素数が１２〜１４であるポリオキシエチレンアルキルエーテル硫酸塩から選ばれる１種以上の硫酸エステル型アニオン性界面活性剤である請求項１又は２記載の２剤混合型毛髪洗浄剤組成物。
請求項４：
第２剤が、（ｃ）成分を０．１〜５質量％、及び（ｄ）成分を０．２〜１０質量％含有することを特徴とする請求項１乃至３のいずれか１項記載の２剤混合型毛髪洗浄剤組成物。
請求項５：
（ｂ）成分／（ｃ）成分の質量比が０．６〜２．５であることを特徴とする請求項１乃至４のいずれか１項記載の２剤混合型毛髪洗浄剤組成物。 Accordingly, the present invention provides the following two-component mixed hair cleansing composition.
Claim 1:
(A) a first agent containing at least 5% by weight of an anionic surfactant, (b) 0.1 to 20% by weight of a water-insoluble silicone compound, and (c) a cationic surfactant and ( d) a second agent comprising an emulsion containing a long-chain aliphatic alcohol, wherein the first agent and the second agent are mixed at the time of use, and the component (a), (b), (c ) And (d) The ratio (a) / [(b) + (c) + (d)] to the total amount of the components is 0.5 to 20 in a mass ratio. Cleaning composition.
Claim 2:
The two-component mixed hair cleansing composition according to claim 1, wherein the water-insoluble silicone compound as component (b) is dimethylpolysiloxane represented by the following general formula (1).

(In the formula, n is an integer of 25 to 500.)
Claim 3:
(A) 1 type in which anionic surfactant is chosen from the polyoxyethylene alkyl ether sulfate whose average addition mole number of alkyl sulfate and ethylene oxide is 1-3 mol and whose carbon number of an alkyl group is 12-14 The two-component mixed hair cleaning composition according to claim 1 or 2, which is a sulfate ester type anionic surfactant as described above.
Claim 4:
The second agent contains 0.1 to 5% by mass of component (c) and 0.2 to 10% by mass of component (d), according to any one of claims 1 to 3. Two-component mixed hair cleanser composition.
Claim 5:
The two-component mixed hair cleansing composition according to any one of claims 1 to 4, wherein the mass ratio of component (b) / component (c) is 0.6 to 2.5.

  According to the present invention, hair that has been damaged by chemical treatment or the like is sufficiently foamed with a one-step washing action and exhibits a good cleaning effect, and has excellent cuticle peeling and protein elution suppression effects and color fading. It is possible to provide a two-component mixed hair cleaning composition that exhibits a preventive effect and is excellent in repairing and repairing hair damage.

The two chambers suitable for housing the composition of the present invention are an example of an independent tube container, [1-1] is a side view and bottom view of the discharge port, [1-2] is a front view, [1- 3] is a cross-sectional view along the aa ′ plane. It is an example of a two-chamber integrated type tube container suitable for housing the composition of the present invention, [2-1] is a side view, [2-2] is a front view and a bottom view of a discharge port, [2-3 ] Is a cross-sectional view along the bb ′ plane.

  The hair cleansing composition of the present invention comprises (a) a first agent containing an anionic surfactant, and (c) a cationic surfactant and (d) an emulsion containing a long-chain aliphatic alcohol. (B) A two-component mixed type comprising a second agent emulsified and dispersed with a water-insoluble silicone compound.

  The first agent constituting the hair cleansing composition of the present invention contains (a) an anionic surfactant as an essential component. (A) In addition to acting as a cleaning component, the anionic surfactant is also effective as a foam modifier, a solubilizer for components that are hardly soluble in water, and the like. Furthermore, in the present invention, a part of the anionic surfactant of the component (a) contained in the first agent forms a complex with the cationic surfactant when mixed with the second agent. It has the action of destabilizing the emulsified state of the emulsion of the second agent, and adsorbs the water-insoluble silicone compound, which is a conditioning component stably dispersed in the second agent, to the hair in an unstable state in water. It is presumed to make it easy. Furthermore, when mixed with the second agent, a part of the anionic surfactant is present in the mixture as it is without forming a complex, showing a cleaning effect, and the hair of the conditioning component in the second agent It is speculated that it promotes penetration into hair and contributes to the protection and repairing effect inside the hair.

Examples of the anionic surfactant include sulfuric acid ester types such as alkyl sulfates and polyoxyethylene alkyl ether sulfates, sulfonic acids such as α-olefin sulfonates, N-acyl-N-methyl taurates, and sulfosuccinic acid alkyl salts. Type, N-acyl-N-methylglycine salt, N-acyl-N-methyl-β-alanine salt, N-acylamino acid type such as N-acyl glutamate, alkyl phosphate, polyoxyethylene alkyl ether phosphate Examples thereof include phosphate ester types such as salts.
Examples of the counter ion used in these surfactant salts include alkali metal salts such as sodium salt and potassium salt, amine salts such as ammonium salt, triethanolamine salt and aminomethylpropanol salt.

  As the anionic surfactant, a sulfate ester type anionic surfactant is preferable, and an alkyl sulfate having an alkyl group with 12 to 14 carbon atoms, an average addition mole number of ethylene oxide of 1 to 3 mol and an alkyl group. Polyoxyethylene alkyl ether sulfates having 12 to 14 carbon atoms are particularly preferred.

  The amount of the anionic surfactant contained in the first agent should be at least 5% (mass%, the same applies hereinafter) in the first agent, preferably 10 to 40%, more preferably 15 to 30. %. If it is less than 5%, foaming is inferior, and hair repair / repair effects, particularly cuticle peeling and protein elution suppression effects are not satisfactorily exhibited, and the object of the present invention cannot be achieved.

  In addition to an anionic surfactant, an amphoteric surfactant can be blended in the first agent according to the present invention. Amphoteric surfactants include coconut fatty acid amide propyl betaine, lauric acid amide propyl betaine, carboxybetaine type amphoteric surfactants such as lauryldimethylaminoacetic acid betaine, sulfobetaine types such as lauryl hydroxysulfobetaine, laurylaminopropionic acid, etc. Aminocarboxylic acid type, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, imidazolinium betaine type such as N-coconut oil fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine salt, Lecithin can be used. Furthermore, in addition to the above components, the first agent is a nonionic surfactant, a polymer compound, an oil component, a pH adjuster, a dye, a fragrance, purified water, etc., as long as the effects of the present invention are not impaired. These solvents can be blended.

  Next, (b) the water-insoluble silicone compound contained in the second agent is a conditioning component. For example, methylpolysiloxane represented by the following general formula (1), dimethiconol represented by the following general formula (2), methylphenyl Examples thereof include polysiloxane, alkyl-modified silicone, amino-modified silicone, and cation-modified silicone. The water-insoluble silicone compound is a substance that does not substantially dissolve in water. Specifically, a part or all of it does not dissolve when 1 g of silicone is added to 100 g of water and stirred at 25 ° C. Indicates.

（式中、ｎは１０〜３，０００、好ましくは２５〜５００の整数である。）

(In the formula, n is an integer of 10 to 3,000, preferably 25 to 500.)

［式中、Ｒ¹は同一であっても異なっていてもよく、ヒドロキシル基又は炭素数１〜２８のアルキル基であり、Ｒ²は同一であっても異なっていてもよく、ヒドロキシル基、メチル基、又はＲ³Ｚ（Ｒ³は炭素数３〜６の２価のアルキレン基等の炭化水素基を表し、Ｚは−ＮＲ⁴（ＣＨ₂）_cＮＲ⁵ ₂及び−ＮＲ⁴（ＣＨ₂）_cＮ⁺Ｒ⁵ ₃Ａ^-から選ばれる１価の基を表す。ここで、Ｒ⁴は水素原子、又は炭素数１〜４のアルキル基、Ｒ⁵は炭素数１〜４のアルキル基等の炭化水素基を示し、Ａはハロゲン原子、又は炭素数１〜４のアルキル硫酸である。ｃは２〜６の整数を表す。）である。ｐ及びｑは平均重合度を表し、ｐは１〜２，０００の整数、ｑは１〜１，０００の整数を表す。また、Ｒ¹及びＲ²が全てメチル基である場合を除く。］

[In the formula, R ¹ may be the same or different and is a hydroxyl group or an alkyl group having 1 to 28 carbon atoms; R ² may be the same or different; Or R ³ Z (R ³ represents a hydrocarbon group such as a divalent alkylene group having 3 to 6 carbon atoms, and Z represents —NR ⁴ (CH ₂ ) _c NR ⁵ ₂ and —NR ⁴ (CH ₂ ). _{^{c N + R 5 3 a -}} . represents a monovalent group selected from wherein, R ⁴ is a hydrogen atom, or an alkyl group having 1-4 carbon atoms, R ⁵ is such as an alkyl group having 1-4 carbon atoms Represents a hydrocarbon group, A represents a halogen atom or an alkyl sulfuric acid having 1 to 4 carbon atoms, and c represents an integer of 2 to 6. p and q represent an average degree of polymerization, p represents an integer of 1 to 2,000, and q represents an integer of 1 to 1,000. Also, the case where R ¹ and R ² are all methyl groups is excluded. ]

As the water-insoluble silicone compound, those represented by the above general formula (1) are preferable, and a high polymerization degree silicone compound having a high conditioning effect can be stably blended, and the effect can be effectively exhibited. Dimethylpolysiloxane in which n in the general formula (1) is an integer of 25 to 500 can be most preferably blended from the viewpoint of repairing damaged hair. The dimethylpolysiloxane has a viscosity (measured value according to the first method of quasi-drug raw material standard 2006 general test method viscosity measurement method at 25 ° C.) of 20 to 10,000 mm ² / s.

  (B) The compounding amount of the water-insoluble silicone compound is 0.1 to 20% in the second agent, and 0.5 to 5% is preferable because it is particularly excellent in the effect of repairing hair damage and feeling of foaming. If it is less than 0.1%, a sufficient repair effect cannot be obtained, and it is inferior in hair cuticle peeling, protein elution suppression effect, and coloring fading prevention effect. If it exceeds 20%, sufficient foaming feeling cannot be obtained.

  The (c) cationic surfactant contained in the second agent is blended as an emulsifier, and is not particularly limited as long as it is used in normal hair cosmetics. For example, the following general formula (3) The quaternary ammonium salt shown etc. are mentioned.

［式中、Ｒ¹¹、Ｒ¹²、Ｒ¹³及びＲ¹⁴のうち１又は２個は、直鎖又は分岐鎖状の炭素数８〜２４のアルキル基、アルケニル基、ヒドロキシアルキル基、又はＲ¹⁵−ＣＯＮＨ−Ｒ¹⁶−（但し、式中Ｒ¹⁵は直鎖又は分岐鎖状の炭素数１１〜２５のアルキル基、アルケニル基、又はヒドロキシアルキル基を示し、Ｒ¹⁶は炭素数１〜３のアルキレン基を示す。）で、残りはベンジル基、炭素数３以下のアルキル基、又は（Ｒ¹⁷−Ｏ）_mＨ（但し、式中Ｒ¹⁷は炭素数２〜３のアルキレン基を示し、ｍは１〜１０の整数である。）である。Ｘはハロゲン原子、又は炭素数３以下のアルキル硫酸又は炭素数３以下のジアルキル硫酸を示す。］

[Wherein, one or two of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are linear or branched alkyl groups having 8 to 24 carbon atoms, alkenyl groups, hydroxyalkyl groups, or R ¹⁵ —. CONH—R ¹⁶ — (wherein R ¹⁵ represents a linear or branched alkyl group having 1 to 25 carbon atoms, an alkenyl group, or a hydroxyalkyl group, and R ¹⁶ represents an alkylene group having 1 to 3 carbon atoms. And the remainder is a benzyl group, an alkyl group having 3 or less carbon atoms, or (R ¹⁷ —O) _m H (wherein R ¹⁷ represents an alkylene group having 2 to 3 carbon atoms, and m is 1 It is an integer of -10. X represents a halogen atom, an alkyl sulfuric acid having 3 or less carbon atoms, or a dialkyl sulfuric acid having 3 or less carbon atoms. ]

  Specifically, lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, benzalkonium chloride, stearyl dimethyl benzyl ammonium chloride, dicocoyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, bromide Lauryltrimethylammonium, stearyltrimethylammonium bromide, alkyltrimethylammonium ethylsulfate, di (polyoxyethylene) oleylmethylammonium chloride, tri (polyoxyethylene) stearylammonium chloride, amidopropyl stearate trimethylammonium chloride, amidopropyl behenate chloride Trimethylammonium, ethyl lanolin sulfate fatty acid amidopropyl ester Le dimethyl ammonium and the like. In particular, stearyltrimethylammonium chloride and behenyltrimethylammonium chloride are preferred from the viewpoint of improving hair feel.

Moreover, the amine type surfactant shown by the following general formula (4) which shows cationic property in an acidic region can also be used.
^{R 21 -Y-R 22 -N (} R 23) 2 (4)
(In the formula, R ²¹ represents a linear or branched alkyl group having 11 to 25 carbon atoms, an alkenyl group or a hydroxyalkyl group, R ²² represents an alkylene group having 1 to 3 carbon atoms, and R ²³ represents 1 carbon atom. Represents an alkyl group of ˜3, Y represents an oxygen atom, or —CO—NH— or —CO—O—.

  Specifically, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, oleic acid dimethylaminopropylamide, isostearic acid dimethylaminopropylamide, coconut oil fatty acid Dimethylaminopropylamide, lauric acid diethylaminoethylamide, stearic acid diethylaminoethylamide, behenic acid diethylaminoethylamide, oleic acid diethylaminoethylamide, isostearic acid diethylaminoethylamide, coconut oil fatty acid diethylaminoethylamide, palm fatty acid diethylaminoethylamide, tallow fatty acid Diethylaminoethylamide, myristic acid diethylaminopropylamide, palmi Phosphate diethylaminopropylamide, diethylaminopropyl stearamide, behenic acid diethylaminopropyl amides, stearoxy propyl dimethylamine and the like.

［式中、Ａ¹は直鎖又は分岐鎖の炭素数８〜２４のアルキル基、アルケニル基、ヒドロキシアルキル基、Ｒ²⁴−ＣＯ−、又はＲ²⁴−Ｏ−Ｒ²⁵−（但し、Ｒ²⁴は直鎖又は分岐鎖の炭素数８〜２５のアルキル基、アルケニル基、又はヒドロキシアルキル基、Ｒ²⁵は炭素数１〜５のアルキレン基、又はヒドロキシアルキレン基である。）である。Ｂ¹は炭素数２〜５のアルキレン基、又は−ＣＨ（ＣＯＯＲ²⁶）−（ＣＨ₂）_r−（但し、Ｒ²⁶は水素原子、又は炭素数１〜３のアルキル基を示し、ｒは１〜４の整数である。）を示し、Ｘ¹はハロゲン原子又は有機アニオンを示す。］ A guanidine type surfactant represented by the following general formula (5) can also be used.

[Wherein, A ¹ represents a linear or branched alkyl group having 8 to 24 carbon atoms, an alkenyl group, a hydroxyalkyl group, R ²⁴ —CO—, or R ²⁴ —O—R ²⁵ — (where R ²⁴ represents A linear or branched alkyl group having 8 to ²⁵ carbon atoms, an alkenyl group, or a hydroxyalkyl group, and R ²⁵ is an alkylene group having 1 to 5 carbon atoms or a hydroxyalkylene group. B ¹ represents an alkylene group having 2 to 5 carbon atoms, or —CH (COOR ²⁶ ) — (CH ₂ ) _r — (wherein R ²⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; X ¹ represents a halogen atom or an organic anion. ]

  Specific examples include butyl guanidine laurate, N- [3-alkyloxy-2-hydroxypropyl] -L-arginine hydrochloride, N-coconut oil fatty acid acyl L-arginine ethyl pyrrolidone carboxylate, and the like. It is done.

  Of these, the quaternary ammonium salt represented by the general formula (3) and the amine type surfactant represented by the general formula (4) are preferable among these, and particularly the hair feel improving effect. From the above, one or more selected from stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, dimethylaminopropylamide stearate, and dimethylaminopropylamide behenate are more preferable.

  The blending amount of the cationic surfactant is not particularly limited, but is preferably 0.1 to 5% in the second agent, and more preferably 0.5 to 3% from the viewpoint of improving the hair feel. If it is less than 0.1%, an emulsion is not sufficiently obtained, and the effect of suppressing hair cuticle peeling and protein elution may not be satisfactorily exhibited. If it exceeds 5%, stickiness may be felt after washing the hair. is there.

The (d) long-chain aliphatic alcohol contained in the second agent is blended as an emulsifier, and those represented by the following general formula (6) are preferably used.
R ²⁷ —OH (6)
(In the formula, R ²⁷ is a linear or branched alkyl group or alkenyl group having 10 to 24 carbon atoms, preferably 16 to 22 carbon atoms.)

  Specifically, linear saturated alcohols such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol, branched saturated alcohols such as isostearyl alcohol and octyldodecyl alcohol, unsaturated alcohols such as oleyl alcohol, Examples of the mixture include lanolin alcohol, hydrogenated castor oil alcohol, beef tallow alcohol, and the like, and one of these can be used alone or in combination of two or more. Among these, cetyl alcohol, stearyl alcohol, and behenyl alcohol are preferable in terms of hair repair effect, and are suitable for manifesting the effects of the present invention.

  The blending amount of the long-chain aliphatic alcohol is not particularly limited, but is preferably 0.2 to 10% in the second agent, and more preferably 1 to 7% from the viewpoint of improving the hair feel. If it is less than 0.2%, a stable emulsion cannot be sufficiently obtained, and the protein elution suppression effect and the fading prevention effect may be inferior. If it exceeds 10%, stickiness may be felt after washing the hair.

  The present invention relates to an oil-in-water type in which (b) a part or all of a water-insoluble silicone compound is emulsified and dispersed in an emulsion containing (c) a cationic surfactant and (d) a long-chain aliphatic alcohol. When the second agent which is an emulsion is mixed with the first agent containing (a) an anionic surfactant, the emulsified state of the emulsion of the second agent is destabilized, thereby causing hair damage. Repair and repair effects can be obtained. In this case, the mass ratio of (b) water-insoluble silicone compound and (c) cationic surfactant to obtain a suitable emulsified state, ie, (b) / (c) is not particularly limited, but hair damage From the point of the repair and repair effect of 0.6 to 2.5, it is preferable. When the blending ratio of the components (b) and (c) is in the above range, the emulsion of the second agent is effectively destabilized when the mixture of the first agent and the second agent is applied to the hair, which is excellent. It is more preferable to obtain a hair damage repair and repair effect and a cleaning effect.

  In addition to the above components, other known components may be added to the second agent as long as the effects of the present invention are not hindered. Specifically, nonionic surfactants, glycerin, diglycerin, dipropylene glycol, propylene glycol, sorbitol and other polyhydric alcohols and sugar alcohols, polymer compounds, oils, pH adjusters, dyes, fragrances, water, etc. A solvent etc. can be mix | blended.

  The two-component mixed hair cleansing composition of the present invention is one in which the first agent and the second agent are mixed at the time of use, and (a) anionic property in the mixture, that is, the composition in which both agents are mixed. Ratio of the total mass of (b) water-insoluble silicone compound, (c) cationic surfactant, and (d) long-chain aliphatic alcohol to the mass of surfactant, ie, (a) / [(b) + (C) + (d)] is 0.5 to 20 in terms of foaming and hair repair / restoration effect, and particularly preferably 1.5 to 10. By mixing in such a ratio range, when the mixture of the first agent and the second agent is applied to the hair, the emulsion of the second agent is effectively destabilized, and excellent hair damage repairing and repairing effects And the cleaning effect can be obtained. If the ratio is less than 0.5, sufficient foaming cannot be obtained, and the effect of destabilizing the emulsion is not sufficiently exhibited, and the hair repair / restoration effect cannot be obtained satisfactorily. On the other hand, if it exceeds 20, the components (b), (c) and (d) cannot be sufficiently left on the hair, and the hair repair / restoration effect cannot be obtained satisfactorily.

  In this case, the mixing ratio of the first agent and the second agent is not particularly limited as long as the above ratio is in an appropriate range. However, the mass ratio of the first agent and the second agent is 10: 1 to 1:10. In particular, it is desirable to use a mixture of 3: 1 to 1: 3, which may be 1: 1.

The hair cleansing composition of the present invention can be prepared, for example, by the following method.
The first agent can be prepared by a method of dissolving an anionic surfactant, further an amphoteric surfactant, other compounding components and the like in a solvent such as purified water. In addition, when blending poorly water-soluble components such as oils and fragrances with the first agent, if an anionic surfactant or an amphoteric surfactant cannot be dissolved, an anionic surfactant, a nonionic surfactant, etc. Can also be blended in the form of an emulsion.

  As a method for producing the second agent, an emulsion containing a cationic surfactant and a long-chain aliphatic alcohol can be produced using a known method, and the water-insoluble silicone compound can be stably dispersed. Specifically, an oil phase containing a cationic surfactant and a long-chain aliphatic alcohol is melted by heating to 60 to 90 ° C., and then a water-insoluble silicone compound and water are added around the melting temperature, A method of mixing and cooling with stirring to obtain an emulsion can be employed. At this time, after adding about 1 to 50% of polyhydric alcohol such as glycerin, diglycerin, dipropylene glycol, propylene glycol, sorbitol or the like in the heat-melted oil phase, water-insoluble silicone compound and water In some cases, emulsification may be carried out in a highly viscous state by adding a part of the mixture and stirring. In this case, the remaining water or the like may be added after emulsification. As another preparation method, after heating an aqueous phase containing water and a water-soluble component to 50 to 90 ° C., a cationic surfactant, a long-chain aliphatic alcohol, and a water-insoluble silicone compound are added to the aqueous phase. There is a method in which an oil phase containing is added in a melted state heated to 60 to 90 ° C. and stirred to form emulsified particles and cooled to obtain an emulsion.

The two-component mixed hair cleansing composition of the present invention is not particularly limited in its dosage form and container as long as the first agent and the second agent can be mixed at the time of use, particularly immediately before application to the hair. Can use what is used for a normal hair cleaning composition.
The container form for filling the two-component mixed hair cleaning composition is not particularly limited, and squeeze containers, pump containers, tube containers, jar containers, aerosol containers, and the like can be used. The container forms of the first agent and the second agent may be the same or different. In this case, the first agent and the second agent according to the present invention may be accommodated in separate containers or in separate packages, and may be set preparations. However, a two-component mixed container such as a two-chamber type may be used. It is preferable to prepare a preparation in a form in which both preparations are mixed when discharged from the container. Appropriate amounts of the first agent and the second agent are discharged from the container, and both preparations can be mixed at an appropriate ratio, and are applied by applying to the hair immediately after mixing. Such a storage container is preferable because it is effective.

As a container form of the two-component mixed hair cleaning composition, as shown in FIGS. 1 and 2, a tube container having a preparation container divided into two chambers, JP-A-11-100082, or JP-A-2004-161292. Known containers such as aerosol containers described in the gazette and the like in which the preparation storage part is divided into two chambers are convenient because the two agents can be taken out of the container by a single discharge operation.
In this case, the cross-sectional area of the discharge port of the storage container is preferably set according to the mixing ratio of the first agent and the second agent, and the cross-sectional area ratio of the discharge port of the first agent and the second agent is 10: It is preferably set in a range of 1 to 1:10, particularly 3: 1 to 1: 3. Moreover, it is preferable that the discharge amount of one time is set according to the mixing ratio of the first agent and the second agent, and the cross-sectional area ratio of the discharge ports of the first agent and the second agent is 10: 1 to 1:10. In particular, it is preferably set in the range of 3: 1 to 1: 3, and may be 1: 1.

FIG. 1 is a tube container with two chambers, [1-1] is a side view and a bottom view of a discharge part (discharge port), [1-2] is a front view, and [1-3] is a It is sectional drawing in -a 'surface. In the tube container of FIG. 1, the tube portions 1 and 2 become two independent cylindrical tube-shaped content storage portions 3 and 4, and both upper end portions 5 of the tubes are laterally crimped and sealed. The discharge parts 7 having one content discharge port 6 are inserted into the lower end discharge parts of the content storage parts 3 and 4 so that both discharge parts are integrated. The contained contents are pushed out and simultaneously discharged from the contents discharge port 6, whereby the two agents can be taken out from the container by a single discharge operation.
FIG. 2 shows a tube container in which two chambers are integrated, [2-1] is a side view, [2-2] is a front view, and a bottom view of a discharge part (discharge port), [2-3] is It is sectional drawing in a bb 'surface. The cylindrical tube portion 11 of the tube container of FIG. 2 is formed by arranging the content accommodating portion 12 at the peripheral edge of the content accommodating portion 13 and integrating both accommodating portions, and the tube upper end portion 14 of the tube portion 11 is It is pressed and sealed in the horizontal direction. A discharge tool 16 having a content discharge port 15 is inserted into the lower end discharge portion of the tube portion 11, and the contents stored in the content storage portions 12 and 13 are pushed out from the content discharge port 15 at the same time. By discharging, two agents can be taken out from the container by a single discharge operation.

The viscosity of the first agent and the second agent is not particularly limited, but each formulation viscosity is 10 to 5 at 25 ° C. in terms of dischargeability from the container, ease of removal, and ease of mixing at the time of use. It is preferably 1,000,000 mPa · s, more preferably 100 to 500,000 mPa · s. In particular, when a two-chamber tube container as shown in FIGS. 1 and 2 is used, the viscosity of both preparations is preferably 500 to 100,000 mPa · s at 25 ° C., respectively.
Furthermore, when using a tube container divided into two chambers as shown in FIGS. 1 and 2, in order to discharge the first agent and the second agent to the end at a certain ratio, the first agent and the second agent Since the discharge amount can be adjusted by appropriately adjusting the size of each discharge port as described above, the viscosity is not particularly limited, but the ratio of the viscosity of the first agent to the second agent is preferably 1/10. -10/1. Viscosity measurement can be determined using a B-type viscometer, such as a BL-type, BM-type, or BH-type viscometer.

  EXAMPLES Hereinafter, although a preparation example, 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,% is mass% unless otherwise specified.

[Preparation Example]
Formulations (first agent and second agent) having the compositions shown in Tables 1 to 6 were prepared by the following method.
The viscosity of each preparation (measured by a rotational viscometer (B-type viscometer) at 25 ° C.) is 10 to 1,600,000 mPa · s for the first agent and 20 to 42,000 mPa · s for the second agent. Within the range of s, the viscosity ratio of both formulations was 1/800 to 200/1.

Preparation of the first agent (1-1 to 12) Add component (a), lauric acid amidopropyl betaine, polyoxyethylene lauric acid monoethanolamide (2E.O.), and citric acid to the purified water while stirring. The dissolved agent was used as the first agent.
Preparation of second agent (2-1 to 28) Component (c), component (d), and polyoxyethylene cetyl ether (20EO) were mixed and dissolved by heating at 80 ° C while stirring. To the melt maintained at 80 ° C., sorbitol heated to 80 ° C., (b) component or (b ′) component is added, purified water is gradually added and stirred, and sufficiently emulsified. It cooled to room temperature, the emulsion was obtained, glycolic acid was added, and this was made into the 2nd agent.
The preparations of Comparative Preparation Examples were prepared according to the above method.

Examples and comparative examples
The first agent and the second agent obtained in the above preparation examples are combined as shown in Tables 7 to 11, and mixed at each ratio immediately before use to prepare a hair cleansing composition (shampoo). went. The results are also shown in Tables 7-11.
In addition, although the detail of a raw material to be used is as showing in Table 12, in the silicone compound in a table | surface, n shows the value of n in following General formula (1).

Preparation of damaged hair bundles:
A commercial Asian hair bundle having a length of 30 cm and a mass of 10 g was immersed in a model bleach solution having the following composition 1 of 10 times the amount (100 mL) at room temperature for 30 minutes. Thereafter, the hair was thoroughly washed with tap water and dried to obtain damaged hair bundles.
(Composition 1) Model bleach solution Hydrogen peroxide 6%
Ammonia 3
Sodium chloride 5
Sodium hydroxide appropriate amount (adjusted to pH 10.8)
Purified water balance
Total 100%

(1) Cuticle peeling inhibitory effect 1.0 g of a mixture of hair cleansing compositions prepared by mixing each preparation was applied to the damaged hair bundle wetted with warm water at 40 ° C., and the hair was whisked using a comb. Spread to the whole bundle. This combing was performed for 2 minutes, and then rinsed in warm water (flow rate 5 L / min) at 40 ° C. for 45 seconds, and then dried. A sample hair bundle was obtained by repeating this hair washing and drying operation 10 times.
After sampling hair (length 20 mm, 50 mg) from the sample hair bundle and putting it into a 10 mL glass bottle with a screw cap, 10 mL of 10 mM sodium phosphate buffer (pH 7.0) was added thereto, and the cap was capped. Ultrasonic treatment was performed for 10 minutes with an ultrasonic cleaner (manufactured by ASONE, model: US-3). This treatment solution was transferred to a centrifuge tube with a known mass, and 5 mL of purified water was added to the remaining hair to wash it, and this washing solution was transferred to the same centrifuge tube. This washing operation was repeated three times. The combined treatment solution and washing solution were centrifuged (12,000 × g, 15 minutes), and the supernatant was discarded. About 10 mL of purified water was added to the precipitate and stirred, then centrifuged again (12,000 × g, 15 minutes), and the supernatant was discarded. After repeating this washing operation twice, the precipitate was dried together with the centrifuge tube, and finally the mass was measured. From the difference from the initial centrifuge tube mass, the peeled cuticle mass was determined.
Based on the amount of cuticle peeled (μg / mg hair), the effect of suppressing the cuticle peeling was determined according to the following three criteria.

Criteria A: Cuticle peeling amount is less than 15 μg / mg hair ○: Cuticle peeling amount is 15 μg / mg hair or more, 30 μg / mg ha
Less than ir x: Cuticle peeling amount is 30 μg / mg hair or more

(2) Protein elution inhibitory effect Hair (10 mm in length, 25 mg) is sampled from a sample hair bundle treated with a hair detergent composition to measure the cuticle peeling inhibitory effect of (1), and a test tube with a screw cap Put in. To this was added 1.0 mL of 40 mM sodium phosphate buffer (pH 7.0) so that the hair was completely immersed in the buffer, and the mixture was heated at 40 ° C. for 24 hours with the screw cap tightly plugged. This liquid was transferred to another test tube with a screw cap and dried, and then 1.0 mL of 6 mol / L hydrochloric acid was added, sealed with a screw cap, and heated at 110 ° C. for 21 hours. Using this solution, amino acids were quantified according to the method of Takada et al. (J. Oleo Sci., 52, 541-548 (2003)) to obtain the amount of protein elution.
Based on the protein elution amount (nmole / mg hair), the protein elution inhibitory effect was determined according to the following three-stage criteria.
Criteria A: Protein elution amount is less than 10 nmole / mg hair O: Protein elution amount is 10 nmole / mg hair or more, 20 nmole /
Less than mg hair x: Protein elution amount is 20 nmole / mg hair or more

(3) Discoloration inhibiting effect A black hair bundle having a length of 10 cm and a mass of 1 g was immersed in a model bleach solution having 10 times the amount of composition 1 in the same manner as the above-described damaged hair bundle preparation method at room temperature for 30 minutes. Thereafter, it was thoroughly washed with warm water and dried. Further, a commercially available hair dye (Beauty Lab Hair Color <Natural Brown>; manufactured by Hoyu Co., Ltd.) is applied in the same amount as the hair bundle mass, wrapped in a wrap and treated at room temperature for 30 minutes, and then 1/10 of the hair bundle mass. An amount of 10% POE (2) sodium lauryl ether sulfate was applied, combed for 1 minute, rinsed with warm water for 1 minute, and dried to obtain a hair bundle for fading evaluation. The color tone of the hair bundle was measured with a color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. and used as an initial value.
A hair bundle for fading evaluation was wetted with warm water at 40 ° C., and 0.1 g of a hair cleansing composition prepared by mixing immediately before use was applied to the hair bundle, and the hair bundle was combed for 1 minute to quickly adjust the whole hair bundle. Thereafter, it was rinsed with warm water for 1 minute and dried. After repeating this treatment 30 times, the color tone of the hair bundle was measured again with a color difference meter, and the color difference (ΔE *) from the initial value was determined. This value and visual impression have the following relationship.
Evaluation criteria ◎: ΔE * is 0 or more and less than 1.6 ・ ・ ・ There is almost no color change ○: ΔE * is 1.6 or more and less than 2.5 ・ ・ ・ There is a slight change in color, but at a level where there is no problem. Yes x: ΔE * is 2.5 or more ... There is a considerable color change

(4) Foaming feeling A total of 10 men and women panelists washed their hair using about 10 g of a hair cleaning composition prepared by mixing immediately before use. And "good foaming" at the time of shampooing was evaluated in the following four stages.
Score criteria 4 points: Feels very foaming 3 points: Feels foaming good 2 points: Feels foaming is not good 1 point: Not foamed Averages the evaluation results of 10 people and makes judgment based on the following criteria Went.
Evaluation criteria A: Average point is 3.5 points or more B: Average point is 2.8 points or more and less than 3.5 points A: Average point is 1.5 points or more and less than 2.8 points X: Average point is 1.5 points Less than

＊比較例１３の洗浄剤組成物は、第１剤と第２剤を十分に攪拌混合後、１日以上放置し、更に使用の直前に十分攪拌したものを試料として用いて各評価を実施した。

* The cleaning composition of Comparative Example 13 was subjected to each evaluation using a sample that had been sufficiently stirred for 1 day after the first agent and the second agent were sufficiently stirred and further stirred immediately before use. .

From the results of Tables 7 to 11, when any of the components (a) to (d) is missing (Comparative Examples 1 to 6), when the content of the component (C) is inappropriate (Comparative Examples 7 and 8), When the mass ratio of (a) / [(b) + (c) + (d)] is inappropriate (Comparative Examples 9 and 11), when it is a preparation of only one agent (Comparative Examples 10 and 12), Is inferior to any of a cuticle peeling inhibitory effect, a protein elution inhibitory effect, a fading inhibitory effect, and a foaming feeling when the first and second agents are allowed to stand for 1 day or longer after mixing (Comparative Example 13). It was confirmed that the two-component mixed hair cleansing composition (Example) has excellent hair damage repairing / restoring effects and cleaning effects.
In addition, the fading suppression effect is a measure of the degree of fading of the hair when repeatedly washed with the detergent composition. In Comparative Examples 1 and 2, and further Comparative Examples 8 to 10 described later, the feeling of foaming is low. Since there was no sufficient cleaning effect, it was difficult for the pigment in the hair to elute, so no fading occurred, and the fading suppression effect was ◎ or ○.

1, 2, 11 Tube portion 3, 4, 12, 13 Content storage portion 5, 14 Tube upper end portion 6, 15 Content discharge port 7, 16 Discharge tool

Claims (5)

  (A) a first agent containing at least 5% by weight of an anionic surfactant, (b) 0.1 to 20% by weight of a water-insoluble silicone compound, and (c) a cationic surfactant and ( d) a second agent comprising an emulsion containing a long-chain aliphatic alcohol, wherein the first agent and the second agent are mixed at the time of use, and the component (a), (b), (c ) And (d) The ratio (a) / [(b) + (c) + (d)] to the total amount of the components is 0.5 to 20 in a mass ratio. Cleaning composition. The two-component mixed hair cleansing composition according to claim 1, wherein the water-insoluble silicone compound as component (b) is dimethylpolysiloxane represented by the following general formula (1).

(In the formula, n is an integer of 25 to 500.)   (A) 1 type in which anionic surfactant is chosen from the polyoxyethylene alkyl ether sulfate whose average addition mole number of alkyl sulfate and ethylene oxide is 1-3 mol and whose carbon number of an alkyl group is 12-14 The two-component mixed hair cleaning composition according to claim 1 or 2, which is a sulfate ester type anionic surfactant as described above.   The second agent contains 0.1 to 5% by mass of component (c) and 0.2 to 10% by mass of component (d), according to any one of claims 1 to 3. Two-component mixed hair cleanser composition.   The two-component mixed hair cleansing composition according to any one of claims 1 to 4, wherein the mass ratio of component (b) / component (c) is 0.6 to 2.5.

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