JP4446176B2 - Shampoo composition - Google Patents

Description

  The present invention relates to a shampoo composition that improves the squeaky feeling of hair that is generated when shampooing is performed, and more particularly to a shampoo composition that improves the squeaky feeling of hair that is susceptible to squeaky and a method for producing the same.

  In recent years, an increasing number of consumers are coloring their hair in order to make their appearance brighter or to give a light hair impression. Coloring is usually chemically treated with alkali, hydrogen peroxide, or the like, so that the hair is damaged. This damage undesirably causes the squeaky feeling when the shampoo is rinsed by exposing the hydrophilic portion on the hair surface, which is not preferable for the user.

  In order to improve the squeak sensation, conventionally, a method of combining an amide carboxylic acid type surfactant and / or a dicarboxylic imide type surfactant with another surfactant (Japanese Patent Laid-Open No. 10-121090), cation A method of blending a functional polymer compound in a shampoo (Japanese Patent Laid-Open No. 11-236320), a method using an amino acid compound (Japanese Patent Laid-Open No. 7-310100), a method using a plant extract (Japanese Patent Laid-Open No. 2001-207191) However, the effect was not sufficient for colored hair.

  In addition, the liquid crystal forming composition includes a liquid crystal dispersion cleaning composition comprising a cationic surfactant, a higher alcohol and a polyglycerol fatty acid ester (Japanese Patent Laid-Open No. 2001-311099), and a vesicle comprising a cationic surfactant. Although there are hair cosmetics (Japanese Patent Laid-Open No. 9-87147) containing an ultraviolet absorber and a water-soluble substance, the effect is not sufficient for improving squeak.

JP-A-10-121090 JP-A-11-236320 JP-A-7-310100 JP 2001-207191 A JP 2001-311099 A JP-A-9-87147

  The present invention improves the squeaky feeling of the hair that occurs when shampooing is rinsed, especially for colored hair that is prone to squeaky feeling, improves the squeaky feeling, has excellent foaming, and improves dispersion stability over time. An object is to provide an excellent shampoo composition.

  The present inventor is a liquid crystal alone with a component (A) selected from a specific (A) cationic surfactant, (B ′) a linear alcohol having 16 to 22 carbon atoms and a linear fatty acid having 16 to 22 carbon atoms. An oil component that forms a structure, (B ″) an oil component selected from a condensate of an alcohol having 8 to 22 carbon atoms and a polyhydric alcohol and a condensate of a fatty acid having 8 to 24 carbon atoms and a polyhydric alcohol (however, (Excluding those less than HLB4), and (C) an amphoteric surfactant, (A) component, (B ′) component and (C) component in specific amounts, and (A) component, Component (B ′) has a specific mass ratio and a shampoo composition in which the liquid crystal structure is dispersed to improve shampoo squeak, especially squeaky squeaky coloured hair, and foaming Excellent dispersion stability over time It is obtained the excellent shampoo composition.

（式中、Ｒ¹、Ｒ²、Ｒ³、及びＲ⁴は、それぞれアルキル基、ヒドロキシアルキル基、アルケニル基、ポリアルキレンオキシド基又はベンジル基を示し、Ｒ¹、Ｒ²、Ｒ³、及びＲ⁴のうち１つ又は２つは炭素数１０〜２４のアルキル基、ヒドロキシアルキル基又はアルケニル基であり、残りはメチル基、エチル基、ベンジル基、又は−（Ｃ₂Ｈ₄Ｏ）_q−Ｈもしくは−（Ｃ₃Ｈ₆Ｏ）_r−Ｈ（但し、ｑ及びｒはそれぞれ１〜５の整数）で表されるポリアルキレンオキサイド基であり、これらは互いに同一であっても異なっていてもよい。また、Ｚ^-は陰イオンを示す。）

（式中、Ｒ⁵は炭素数１〜２１の直鎖もしくは分岐鎖のアルキル基又はアルケニル基、Ａは炭素数１〜１０の直鎖もしくは分岐鎖のアルキレン基又はアルケニレン基であり、ｔは１〜５の整数であって、ｔが２以上の場合、各ブロック中のＡは互いに異なってもよい。）
（Ｂ’）炭素数１６〜２２の直鎖アルコール及び炭素数１６〜２２の脂肪酸から選ばれる（Ａ）成分と単独で液晶構造体を形成する油分１．２〜７．５質量％と、
（Ｂ’’）炭素数８〜２２のアルコールと多価アルコールとの縮合物及び炭素数８〜２４の脂肪酸と多価アルコールとの縮合物から選ばれる油分（ただし、ＨＬＢ４未満のものを除く）と、
（Ｃ）両性界面活性剤、又は必要に応じてアニオン性界面活性剤と
を含有し、（Ｂ’）／［（Ａ）＋（Ｂ’）］（質量比）が、０．３５〜０．９０であり、両性界面活性剤及びアニオン性界面活性剤の配合量が２質量％を超え、但し、アニオン性界面活性剤が５質量％未満であり、（Ａ）成分と（Ｂ’）成分とから形成された液晶構造体が組成物中に分散してなることを特徴とするシャンプー組成物。
［２］．液晶構造体の平均粒径が２０μｍ未満であることを特徴とする［１］記載のシャンプー組成物。
［３］．さらに、（Ｄ）水膨潤性の粘土鉱物を０．０１質量％以上含有することを特徴する［１］又は［２］記載のシャンプー組成物。
［４］．さらに、（Ｅ）アミンオキシドを含有することを特徴する［１］〜［３］のいずれかに記載のシャンプー組成物。
［５］．さらに、（Ｆ）屈折率１．４６未満のシリコーン誘導体を含有することを特徴とする［１］〜［４］のいずれかに記載のシャンプー組成物。
［６］．さらに、（Ｇ）粘性付与剤として、下記式

（式中、分子末端及びＲは水素原子、メチル基又はヒドロキシプロピル基を示す。）
で表される構造単位を有し、メトキシ基２５〜３５質量％、ヒドロキシプロポキシ基５〜１５質量％（ただし、水酸基、メトキシ基及びヒドロキシプロポキシ基の合計を１００質量％とする。）であって、２質量％水溶液の２０℃での粘度が２１００〜３５０００ｍＰａ・ｓであるヒドロキシプロピルメチルセルロースを含有することを特徴とする［１］〜［５］のいずれかに記載のシャンプー組成物。
［７］．カラーリングした髪用であることを特徴とする［１］〜［６］のいずれかに記載のシャンプー組成物。
［８］．上記（Ｃ）成分を含有する水相に、上記（Ａ）成分と（Ｂ’）成分を構成成分として形成された液晶構造体が分散してなるシャンプー組成物の製造方法であって、液晶構造体の構成成分の結晶化温度以上で、（Ｃ）成分を含有する水相に、（Ａ）、（Ｂ’）及び上記（Ｂ’’）成分を混合し、得られた混合物を結晶化温度以上の温度から冷却することを特徴とする［１］記載のシャンプー組成物の製造方法。
［９］．上記混合物の一部を連続的に抜き出し、これを急冷すると共に、この急冷したものを混合物に戻すことを繰り返すことにより、混合物を結晶化温度以上の温度から冷却することを特徴とする［８］記載の製造方法。
［１０］．さらに、水に分散又は膨潤させた（Ｄ）粘土鉱物を、（Ｃ）成分を含有する水相と混合する工程を含むことを特徴とする［８］又は［９］記載の製造方法。 Accordingly, the present invention provides the following shampoo composition.
[1]. (A) 0.5 to 6% by mass of a cationic surfactant selected from alkyl quaternary ammonium salts represented by the following general formula (1) and guanidine derivatives represented by the following general formula (2) or salts thereof When,

(Wherein R ¹ , R ² , R ³ , and R ⁴ each represents an alkyl group, a hydroxyalkyl group, an alkenyl group, a polyalkylene oxide group, or a benzyl group, and R ¹ , R ² , R ³ , and R one or two alkyl groups of 10 to 24 carbon atoms of ^4, a hydroxyalkyl group or an alkenyl group and the remainder is a methyl group, an ethyl group, a benzyl group, or _{- (C 2 H 4 O)} q -H Or a polyalkylene oxide group represented by — (C ₃ H ₆ O) _r —H (where q and r are each an integer of 1 to 5), and these may be the same or different from each other. Z ^- represents an anion.)

(Wherein R ⁵ is a linear or branched alkyl group or alkenyl group having 1 to 21 carbon atoms, A is a linear or branched alkylene group or alkenylene group having 1 to 10 carbon atoms, and t is 1 And when t is 2 or more, A in each block may be different from each other.
(B ′) an oil content of 1.2 to 7.5% by mass that forms a liquid crystal structure alone with the component (A) selected from a linear alcohol having 16 to 22 carbon atoms and a fatty acid having 16 to 22 carbon atoms;
(B ″) an oil component selected from a condensate of an alcohol having 8 to 22 carbon atoms and a polyhydric alcohol and a condensate of a fatty acid having 8 to 24 carbon atoms and a polyhydric alcohol (except for those less than HLB4) When,
(C) An amphoteric surfactant or, if necessary, an anionic surfactant is contained, and (B ′) / [(A) + (B ′)] (mass ratio) is 0.35 to 0. 90, the compounding amount of the amphoteric surfactant and the anionic surfactant exceeds 2% by mass, provided that the anionic surfactant is less than 5% by mass, and the components (A) and (B ′) A shampoo composition characterized in that a liquid crystal structure formed from is dispersed in the composition.
[2]. The shampoo composition according to [1], wherein the liquid crystal structure has an average particle size of less than 20 μm.
[3]. The shampoo composition according to [1] or [2], further comprising (D) 0.01% by mass or more of a water-swellable clay mineral.
[4]. Furthermore, (E) amine oxide is contained, The shampoo composition in any one of [1]-[3] characterized by the above-mentioned.
[5]. The shampoo composition according to any one of [1] to [4], further comprising (F) a silicone derivative having a refractive index of less than 1.46.
[6]. Furthermore, as the (G) viscosity imparting agent, the following formula

(In the formula, the molecular terminal and R represent a hydrogen atom, a methyl group or a hydroxypropyl group.)
A methoxy group of 25 to 35% by mass and a hydroxypropoxy group of 5 to 15% by mass (provided that the total of the hydroxyl group, methoxy group and hydroxypropoxy group is 100% by mass). The shampoo composition according to any one of [1] to [5], comprising hydroxypropylmethylcellulose having a viscosity of 2 mass% aqueous solution at 20 ° C of 2100 to 35000 mPa · s.
[7]. The shampoo composition according to any one of [1] to [6], wherein the shampoo composition is for colored hair.
[8]. A method for producing a shampoo composition, in which a liquid crystal structure formed with the components (A) and (B ′) as constituents is dispersed in an aqueous phase containing the component (C). (A), (B ′) and the above component (B ″) are mixed with the aqueous phase containing the component (C) at a temperature equal to or higher than the crystallization temperature of the body component, and the resulting mixture is crystallized at the crystallization temperature. Cooling from the above temperature, The manufacturing method of the shampoo composition as described in [1].
[9]. A part of the mixture is continuously drawn out, rapidly cooled, and returned to the mixture by repeatedly cooling the mixture from a temperature equal to or higher than the crystallization temperature [8] The manufacturing method as described.
[10]. The method according to [8] or [9], further comprising a step of mixing (D) the clay mineral dispersed or swollen in water with an aqueous phase containing the component (C).

  The component (A) is a cationic surfactant and is not particularly limited as long as it can be blended into a shampoo composition. For example, the alkyl quaternary ammonium represented by the following general formula (1) A salt or the like is preferably used.

［式中、Ｒ¹、Ｒ²、Ｒ³、及びＲ⁴は、それぞれアルキル基、ヒドロキシアルキル基、アルケニル基、ポリアルキレンオキシド基又はベンジル基を示し、Ｒ¹、Ｒ²、Ｒ³、及びＲ⁴のうち１つ又は２つは炭素数１０〜２４、好ましくは１６〜２２の直鎖アルキル基、ヒドロキシアルキル基又はアルケニル基であり、残りはメチル基、エチル基、ベンジル基、又は−（Ｃ₂Ｈ₄Ｏ）_q−Ｈもしくは−（Ｃ₃Ｈ₆Ｏ）_r−Ｈ（但し、ｑ及びｒはそれぞれ１〜５の整数）で表されるポリアルキレンオキサイド基であり、これらは互いに同一であっても異なっていてもよい。また、Ｚ^-は陰イオンを示す。］

[Wherein, R ¹ , R ² , R ³ , and R ⁴ each represents an alkyl group, a hydroxyalkyl group, an alkenyl group, a polyalkylene oxide group, or a benzyl group, and R ¹ , R ² , R ³ , and R 1 or 2 of ⁴ is a linear alkyl group, hydroxyalkyl group or alkenyl group having 10 to 24 carbon atoms, preferably 16 to 22 carbon atoms, and the rest are methyl group, ethyl group, benzyl group, or-(C ₂ H ₄ O) _q- H or — (C ₃ H ₆ O) _r —H (where q and r are each an integer of 1 to 5), which are the same as each other. It may or may not be. Z ⁻ represents an anion. ]

  Cationic surfactants are usually formulated in the form of salts, specifically inorganic salts such as hydrochlorides, bromates, sulfates, phosphates, glycolates, acetates, lactates, succinic acids. It can be used as an organic acid salt such as a salt, a tartrate salt, a citrate salt, an acidic amino acid salt, a higher fatty acid salt, a pyroglutamate salt and a p-toluenesulfonate salt.

  Specific examples of the component (A) represented by the general formula (1) include, for example, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, cetostearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, diester Examples include behenyldimethylammonium chloride.

  Among them, those having a linear alkyl group of 16 to 22 are preferable, and specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, and distearyldimethylammonium chloride. Of these, the hydrochloride and bromate forms are preferred.

（式中、Ｒ⁵は炭素数１〜２１の直鎖もしくは分岐鎖のアルキル基又はアルケニル基、Ａは炭素数１〜１０の直鎖もしくは分岐鎖のアルキレン基又はアルケニレン基であり、ｔは１〜５の整数であって、ｔが２以上の場合、各ブロック中のＡは互いに異なってもよい。） Moreover, the guanidine derivative represented by following General formula (2) or its salt can also be used suitably as a cationic surfactant.

(Wherein R ⁵ is a linear or branched alkyl group or alkenyl group having 1 to 21 carbon atoms, A is a linear or branched alkylene group or alkenylene group having 1 to 10 carbon atoms, and t is 1 And when t is 2 or more, A in each block may be different from each other.

R ⁵ in the general formula (2) is a linear or branched alkyl or alkenyl group having 1 to 21 carbon atoms, preferably 11 to 19 carbon atoms, and examples thereof include C ₁₁ H ₂₃ — and C ₁₂ H _{25. -, C 13 H 27 -,} C 14 H 29 -, C 15 H 31 -, C 16 H 33 -, C 17 H 35 -, (C 8 H 17) 2 CH-, 4-C 2 H 5 C 15 H ₃₀ - group and the like.

  The substituent A is a linear or branched alkylene group or alkenylene group having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, An isopropylene group, 2-pentenyl group, 2-ethylbutylene group, etc. are mentioned.

  The guanidine derivative represented by the general formula (2) is usually blended in the form of a salt, specifically, inorganic salts such as hydrochloride, bromate, sulfate, phosphate, glycolate, acetate , Lactate, succinate, tartrate, citrate, acidic amino acid salt, higher fatty acid salt, pyroglutamate, p-toluenesulfonate, and other organic acid salts. Of these, the hydrochloride, bromate, acetate, glycolate, citric acid and acidic amino acid salt forms are preferred.

  Furthermore, amino acid-based cationic surfactants can also be suitably used as the cationic surfactant. Examples of amino acid-based cationic surfactants include mono-N-long chain acyl basic amino acid lower alkyl ester salts. Examples of basic amino acids constituting this compound include natural amino acids such as ornithine, lysine and arginine. It is also possible to use synthetic amino acids such as α, γ-diaminobutyric acid. These may be optically active or racemic.

  The acyl group is a saturated or unsaturated higher fatty acid residue having 8 to 22 carbon atoms. These may be natural or synthesized. For example, single higher fatty acid residues such as lauroyl group, myristoyl group, palmitoyl group and stearoyl group, and natural mixed higher fatty acid residues such as coconut oil fatty acid residue and beef tallow higher fatty acid residue can be employed.

  As the lower alkyl ester component, methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester and octyl ester are suitable. The lower alkyl ester component is usually blended in the form of a salt, specifically, inorganic salts such as hydrochloride, bromate, sulfate, phosphate, glycolate, acetate, lactate, succinate , Tartrate, citrate, acidic amino acid salt, higher fatty acid salt, L- or DL-pyrrolidone carboxylate, pyroglutamate, p-toluenesulfonate, and other organic acid salts. Of these, the hydrochloride, L- or DL-pyrrolidone carboxylate and acidic amino acid salt forms are preferred.

  Furthermore, an amidoamine type surfactant can also be suitably used as a cationic surfactant. As the amidoamine type surfactant, a compound represented by the following general formula (3) can be used.

（式中、Ｒ⁶は炭素数７〜２３、好ましくは９〜２２の脂肪酸残基、さらに好ましくは１３〜２２であり、Ｒ⁷は炭素数１〜４のアルキル基、好ましくはメチル基又はエチル基、ｍは２〜４の整数を示す。）

Wherein R ⁶ is a fatty acid residue having 7 to 23 carbon atoms, preferably 9 to 22 carbon atoms, more preferably 13 to 22 carbon atoms, and R ⁷ is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or ethyl. Group m represents an integer of 2-4.

  Examples of the amidoamine type surfactant represented by the general formula (3) include stearic acid diethylaminoethylamide, stearic acid dimethylaminoethylamide, palmitic acid diethylaminoethylamide, coconut oil fatty acid diethylaminopropylamide, palmitic acid dimethylaminoethylamide. , Myristic acid diethylaminoethylamide, myristic acid dimethylaminoethylamide, behenic acid diethylaminoethylamide, behenic acid dimethylaminoethylamide, stearic acid diethylaminopropylamide, stearic acid dimethylaminopropylamide, palmitic acid diethylaminopropylamide, palmitic acid dimethylamino Propylamide, myristic acid diethylaminopropylamide, myristic acid dimethylaminopropylamide De, behenic acid diethylaminopropyl amide, behenic acid dimethylaminopropylamide. These are usually formulated in the form of salts, specifically, inorganic salts such as hydrochloride, bromate, sulfate, phosphate, glycolate, acetate, lactate, succinate, tartrate Citrate, acidic amino acid salt, higher fatty acid salt, pyroglutamate, p-toluenesulfonate, and other organic acid salts. Of these, acidic amino acid salts, citrates and hydrochlorides are preferred. In addition, the salt used for neutralization may use together 1 type, or 2 or more types. Among these, stearic acid dimethylaminopropylamide, stearic acid diethylaminoethylamide, and coconut oil fatty acid diethylaminopropylamide are preferably used. In the present invention, one or more of these amidoamine surfactants can be used.

  In particular, as the cationic surfactant of the present invention (A), the number of carbon atoms in the carbon number (chain length) distribution of the aliphatic hydrocarbon group of the cationic surfactant is considered from the viewpoint of the temporal stability of the liquid crystal structure. It is preferable that 22 contains 50% or more, preferably 80% or more.

  The blending amount of the cationic surfactant as the component (A) of the present invention is not particularly limited, but the lower limit in the shampoo composition of the present invention is preferably 0.05% by mass or more, more preferably 0.5% by mass. As described above, the content is particularly preferably 1% by mass or more, and the upper limit is preferably 7% by mass or less, more preferably 5% by mass or less, and particularly preferably 4% by mass or less. If the blending amount is too small, sufficient smoothness and flexibility cannot be imparted to the hair at the time of rinsing, while if too large, the hair may become sticky. As the component (A), one type may be used alone, or two or more types may be used in combination.

  In particular, when the alkyl quaternary ammonium salt represented by the general formula (1) and the guanidine derivative represented by the general formula (2) or a salt thereof are blended, the blending amount is the lower limit in the shampoo composition. Is preferably 0.05% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and the upper limit is preferably 6% by mass or less, more preferably 4% by mass or less, particularly preferably. 3% by mass or less.

  When an amino acid-based cationic surfactant such as a mono-N-long chain acyl basic amino acid lower alkyl ester salt is blended, the blending amount is preferably 0.1% by mass or more at the lower limit in the shampoo composition. The upper limit is preferably 5% by mass or less, and more preferably 3% by mass or less.

  When the amidoamine type surfactant is blended, the blending amount thereof is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and the upper limit is 7% by mass or less, in the shampoo composition. Is more preferable, and more preferably 5% by mass or less.

(B) A component is an oil component which does not contain a silicon atom. Here, in the composition with the component (A) in the component (B), the oil component (B ′) capable of forming a liquid crystal structure alone has the effect of dramatically improving the squeeze during shampooing. Yes, it is essential in this shampoo composition. (B) As a component, the following (1)-(5) simple substance or condensate is mentioned. As the component (B) of the present invention, these may be used alone or in appropriate combination of two or more.
(1) Alcohol I represented by the general formula R ¹² —OH
(2) Fatty acid II represented by the general formula R ¹³ —COOH
(3) Condensate IV of I and polyhydric alcohol III
(4) Condensate V of II and III
(5) Condensate of I or IV with II, V or polybasic acid VI

The alcohol I represented by the general formula R ¹² —OH is R ¹² = saturated, unsaturated or branched alcohol or hydroxy alcohol having 1 to 40 carbon atoms, specifically, methyl alcohol, isopropyl alcohol, n-butyl. Alcohol, isobutyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, isononyl alcohol, n-decyl alcohol, isodecyl alcohol, undecyl alcohol, dodecyl alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, 2 -Hexyldecyl alcohol, cetostearyl alcohol, stearyl alcohol, isostearyl alcohol, octyldodecyl alcohol, aralkyl alcohol, behenyl alcohol, oleyl alcohol Lumpur, elaidyl alcohol, linoleyl Al Nord, Carna over buildings alcohol, ceryl alcohol, cholesterol, phytosterol and the like. Of these, from the viewpoint of stability over time, straight chain (cetyl alcohol, stearyl alcohol, behenyl alcohol, etc.) and branched chain (2-hexyldecyl alcohol, 2-ethylhexyl alcohol, isostearyl alcohol, etc.) are preferable, and in particular, linear Those are preferred. In the case of a branched chain, the closer the branch is to the tip, the better. In terms of chain length, alcohols having 8 to 22 carbon atoms are preferable. Above all, linear alcohols having 16 to 22 carbon atoms (cetyl alcohol, stearyl alcohol, behenyl alcohol, etc.) are more preferable from the viewpoint of stability over time. Most preferred is behenyl alcohol. These alcohols may be used alone or in combination of two or more, but from the viewpoint of stability over time, those having 22 carbon atoms are preferably contained in an amount of 40% or more, preferably 70% or more.

Fatty acid II represented by the general formula R ¹³ —COOH is R ¹³ = saturated, unsaturated or branched fatty acid or hydroxy fatty acid having 4 to 40 carbon atoms, specifically, butyric acid, caprylic acid, isononanoic acid, tetra Methyl nonanoic acid, capric acid, lauric acid, myristic acid, 2-hexyldecanoic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, 2-heptylundecanoic acid, lignoceric acid, cellosic acid, montanic acid, melicic acid , Lauroleic acid, oleic acid, elaidic acid, erucic acid, eicosenoic acid, 3,5,5-trimethylhexanoic acid, linoleic acid, eleostearic acid, linolenic acid, ricinoleic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, Castor hardened fatty acid, coconut oil fatty acid, lanolin fatty acid Methacrylic acid, octylic acid (2-ethylhexanoic acid), neodecanoic acid (2,2-dimethyloctanoic acid), citronellic acid, abietic acid, dehydroabietic acid, neoabietic acid, parastolic acid, pimaric acid, isopimaric acid, lactic acid, 12 -Hydroxy stearic acid etc. are mentioned. When used alone as an oil component, fatty acids having 8 to 24 carbon atoms are desirable, and among these, fatty acids having 16 to 22 carbon atoms (palmitic acid, stearic acid, behenic acid, etc.) are more preferable from the viewpoint of stability over time.

Examples of the polyhydric alcohol III include polyhydric alcohols represented by the following general formula (4).
HO ((C _a H _2a ) O) _b ((C _c H _2c ) O) _d H (4)
(In the formula, a, b, c and d are not particularly limited and may be a = c. Preferably, a and c are integers of 2 to 10, b and d = 1 to 150.)

  Examples of the polyhydric alcohol represented by the general formula (4) include ethylene glycol, diethylene glycol, hexylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, isoprene glycol, glycerin, diglycerin, triglycerin, tetra Glycerin, hexaglycerin, decaglycerin, 1,3-butylene glycol, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, glucose, mannose, galactose, sucrose, fructose, maltose, maltitol, xylitol, inositol, sorbitan, Examples include sorbitol and EO adducts of these polyhydric alcohols.

  Examples of the polybasic acid VI include carboxylic acids such as succinic acid, glutaric acid, adipic acid, maleic acid, tartaric acid, malic acid, citric acid, phthalic acid, trimellitic acid, and sebacic acid, and inorganic acids such as phosphoric acid and sulfuric acid. It is done.

  (3) Condensate IV of I and polyhydric alcohol III, (4) Condensate V of II and III, (5) Condensate of I or IV with II, V or polybasic acid VI includes higher alcohols EO, PO adduct, fatty acid EO, PO adduct, glyceryl monostearate, diglyceryl monostearate, hexaglyceryl monostearate, decaglyceryl monostearate, diglyceryl distearate, hexaglyceryl distearate , Destearate decaglycerin, tristearate pentaglycerin, tristearate hexaglycerin, tristearate decaglycerin, tetrastearate hexaglycerin, tetrastearate decaglycerin, pentastearate tetraglycerin, pentastearate hexaglycerin, pe Decaglycerol tastearate, pentaglycerol hexastearate, hexaglycerol hexastearate, hexaglycerol octastearate, decaglycerol decastearate, glycerol monoisostearate, diglycerol monoisostearate, hexaglycerol monoisostearate, monoisostearic acid Decaglycerin, diglycerin diisostearate, hexaglycerin diisostearate, decaglycerin diisostearate, pentaglycerin triisostearate, hexaglycerin triisostearate, decaglycerin triisostearate, hexaglycerin tetraisostearate, decaglycerin tetraisostearate, pentaisostearate Acid tetraglycerin, pentaisostearic acid Xaglycerin, pentaisostearic acid decaglycerin, hexaisostearic acid pentaglycerin, hexaisostearic acid hexaglycerin, octaisostearic acid hexaglycerin, decaisostearic acid decaglycerin, monooleate diglyceryl, diglyceryl dioleate, glyceryl oxystearate, monomyristine Acid glycerin heptabehenate decaglycerol, trioleic acid pentaglycerin, tribehenic acid pentaglycerin, tetrabehenic acid pentaglycerin, pentabehenic acid pentaglycerin, dibehenic acid triglycerin, tribehenic acid triglycerin, tetrabehenic acid triglycerin, tri-2 -Polyglycerin fats such as glyceryl ethylhexanoate and tri (capryl, capric acid) glycerin Fatty acid esters, trimethylolpropane trioctanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane tristearate, trimethylolpropane triisostearate, pentaerythrityl tetraoctanoate, pentaerythritol tetra-2-ethylhexanoate Lithyl, dipentaerythryl hexaoxystearate, dipentaerythritol fatty acid ester, propylene glycol dicaprate, propylene glycol monocaprylate, propylene glycol dicaprylate, sorbitan sesquioleate, octyldodecyl lactate, hexyl laurate, myristyl octanoate , Palmityl octanoate, stearyl octanoate, cetyl isooctanoate, isononyl isononanoate, tridecyl isononanoate, myristic Isopropyl, butyl myristate, myristyl myristate, 2-octyldodecyl myristate, 2-hexyldecyl myristate, 2-hexyldecyl stearate, isopropyl palmitate, isostearyl palmitate, octyl palmitate, 2-hexyl palmitate Decyl, cetyl palmitate, methyl stearate, butyl stearate, hexyl stearate, octyl stearate, stearyl stearate, 2-hexyldecyl isostearate, isopropyl isostearate, octyl hydroxystearate, ethyl oleate, oleyl oleate, Octyldodecyl oleate, octyl eicosenoate, lanolin fatty acid isopropyl, lanolin fatty acid octyldodecyl, ethyl linoleate, linole Isopropyl acid, dioctyl succinate, diethoxyethyl succinate, diisopropyl adipate, diisopropyl dimer, diethyl sebacate, diisopropyl sebacate, diisostearyl malate, tri-2-ethylhexyl citrate, 2-heptylundecyl adipate, Diethoxyethyl succinate, glyceryl fatty acid ester adipic acid condensate, diglyceryl isopalmitic acid ester sebacic acid condensate, cholesteryl stearate, cholesteryl isostearate, cholesteryl hydroxystearate, phytosteryl stearate, phytosteryl hydroxystearate, phytosteryl isostearate And the like.

  As other oils, alkyl ether phosphoric acid or its salt and alkyl ether phosphoric acid POE (polyoxyethylene) derivative, alkylamine and its POE derivative, fatty acid amide and its POE derivative, castor oil or hydrogenated castor oil, and its POE derivative , Plant waxes such as carnauba wax, candelilla wax, tree wax, animal waxes such as beeswax, whale wax, wool wax, petroleum waxes such as paraffin wax and microcrystalline wax, mineral waxes such as montan wax, ceresin and ozokerite Is mentioned. Among the components (B), higher (16 to 22 carbon atoms) higher melting point alcohol (cetostearyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, etc.) having a melting point of 45 ° C. or higher is preferable from the viewpoint of storage stability over time. .

  In the present invention, an oil component that forms a liquid crystal structure alone with the component (A) as (B ′) (the above (1) and (2), and (3) and (4)) because it easily forms a liquid crystal. It is necessary to mix | blend the thing of less than HLB4) in a composition in the ratio with the (A) component mentioned later. In addition, (B ') component may be used individually by 1 type, and may be used in combination of 2 or more type. As the component (B), an oil component that does not form a liquid crystal alone with the component (A) and does not contain a silicon atom (for example, a pearl imparting agent such as ethylene glycol difatty acid ester, glycol distearate, POE hydrogenated castor oil, POE dioleic acid methylglycoside, alkyl fatty acid amide, etc. may be blended with a thickening, thickening and stabilizing agent. The mass ratio of (A) and (B ′) in the shampoo composition is such that (B ′) / [(A) + (B ′)] is 0.35 to 0.90, and the lower limit is 0.50. The upper limit is preferably 0.80. If the mass ratio is less than 0.35 or exceeds 0.90, the squeeze improvement at the time of rinsing becomes weak.

The most preferable combinations of the components (A) and (B) include the following.
(B) / [(A) + (B ′)] = (A) a combination of (A) a monoalkyl cationic surfactant having 16 to 22 carbon atoms and (B) an alcohol having 16 to 22 carbon atoms. 0.6-0.8
(Ii) (A) a dialkyl cationic surfactant having 16 to 22 carbon atoms, (B) an alcohol combination having 16 to 22 carbon atoms, and (B ′) / [(A) + (B ′)] = 0. 5-0.7

  The blending amount of the whole oil component not containing silicon atoms other than the component (B ′) and the component (B ′) is not particularly limited, but usually the lower limit in the shampoo composition is preferably 0.5% by mass or more, more preferably 2 The upper limit is preferably 10% by mass or less, and more preferably 8% by mass or less. When the blending amount is less than 0.5% by mass, the feeling of use may be insufficient. On the other hand, when it exceeds 10% by mass, the temporal stability may be deteriorated.

  Component (C) is one or more amphoteric surfactants. The shampoo composition of the present invention may contain an anionic surfactant and a nonionic surfactant other than (B ″) as a detersive surfactant.

  Amphoteric surfactants include alkylbetaine activators, amide betaine activators, sulfobetaine activators, hydroxysulfobetaine activators, amide sulfobetaine activators, phosphobetaine activators, imidazolinium betaine activators. Examples include activators, aminopropionic acid activators, amino acid activators, and the like.

  Among them, lauric acid amidopropyl betaine, lauryldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyl betaine, coconut oil fatty acid dimethylaminoacetic acid betaine, lauryl hydroxysulfobetaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium Betaine, lauryliminodipropionic acid, and N- [3-alkyl (12,14) oxy-2-hydroxypropyl] -L-arginine hydrochloride are preferred.

  Examples of the anionic surfactant include alkyl sulfonate, alkyl sulfate, acylated amino acid salt, polyoxyethylene alkyl ether sulfate, alkyl benzene sulfonate, N-acyl-N-methyl taurate, α-olefin. Sulfonate, higher fatty acid ester sulfonate, alkyl ether acetate, polyoxyethylene alkyl ether acetate, fatty acid soap, alkyl phosphate ester salt, N-lauroyl glutamate, N-palmitoyl glutamate, N-lauroyl- N-ethylglycine salt, N-lauroyl sarcosine salt, N-myristoyl-β-alanine salt and the like can be mentioned.

  Nonionic surfactants include polyoxyethylene fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene glycol, coconut oil fatty acid Examples include alkanolamides, sucrose fatty acid esters, alkyl glycosides, alkyl glyceryl glycosides, methyl glucoside fatty acid esters, and the like. Among them, polyethylene glycol monostearate, decaglyceryl monolaurate, monoglyceryl behenate, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene behenyl ether, polyoxyethylene (160) polyoxypropylene (30) glycol, alkyl Glucosides and the like are preferable.

  The lower limit of the amount of component (C) is preferably 2% by mass or more in the shampoo composition, more preferably 10% by mass or more, and the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less. . In the present invention, the blending amount of the ionic active agent (amphoteric surfactant, anionic surfactant) in terms of foaming needs to exceed 2% by mass with respect to the entire composition, and 5% by mass. The above is preferable, and 10% by mass or more is particularly preferable. Although the upper limit of the compounding quantity of the active agent which shows ionicity is not specifically limited, Usually, it is 30 mass%. Further, from the viewpoint of dispersion stability, the blending amount of the anionic active agent (anionic surfactant) is less than 5% by mass with respect to the whole composition, preferably 2% by mass or less, particularly 1% by mass. The following is preferred. Although the minimum of the compounding quantity of the activator which shows anionic property is not specifically limited, Usually, it is 0.1 mass%. In addition, it is preferable to use an amphoteric surfactant alone from the viewpoint of sustaining prevention of squeaking during rinsing.

  The shampoo composition of the present invention preferably contains (D) a water-swellable clay mineral. By adding (D) a water-swellable clay mineral to the shampoo composition of the present invention, the dispersion stability is remarkably improved. Examples of water-swellable clay minerals include natural or synthetic smectite clays, and organic modified clays obtained by treating clay minerals with quaternary ammonium salt type cationic surfactants and / or nonionic surfactants. Among them, clay minerals with good dispersibility in the presence of an activator are preferable. Examples thereof include bentonite, montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite, etc., and swellable mica is also used. it can. Among these, bentonite, montmorillonite, and saponite are particularly preferable. As the component (D), these can be used alone or in combination of two or more.

  Water-swellable clay minerals, especially those collected from nature, exhibit the effects of clay minerals sufficiently when they contain a large amount of non-swellable impurities such as calcite, tridymite, cristobalite, quartz, and various inorganic substances. In some cases, the purity of the clay mineral is preferably 90% by mass or more, and particularly preferably 95% by mass or more.

  The blending amount of the component (D) is preferably 0.01% by mass or more in the shampoo composition from the viewpoint of dispersion stability, and the lower limit is preferably 0.05% by mass or more. The upper limit of the amount is preferably 5% by mass or less, more preferably 2% by mass or less.

  The shampoo composition of the present invention preferably contains (E) an amine oxide component. (E) By adding an amine oxide component, foaming becomes creamy. (E) As an amine oxide of a component, the amine oxide represented by following General formula (5) is mentioned.

（式中、Ｒ⁸は炭素数８〜２４、好ましくは８〜１８の１価炭化水素基であり、特に炭素数８〜１８の直鎖アルキル基であることが好ましい。Ｒ⁹、Ｒ¹⁰はそれぞれ炭素数１〜３のアルキル基もしくはヒドロキシアルキル基、又は下記一般式（６）で表される一価の置換基であり、メチル基、ヒドロキシエチル基が好ましい。ｎは０又は１〜５の整数であり、ｎは０が好ましい。）

（式中、Ｒ¹¹は、水素原子又はメチル基、ｐは１〜５である。）

(In the formula, R ⁸ is a monovalent hydrocarbon group having 8 to 24 carbon atoms, preferably 8 to 18 carbon atoms, and particularly preferably a linear alkyl group having 8 to 18 carbon atoms. R ⁹ and R ¹⁰ are Each of them is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or a monovalent substituent represented by the following general formula (6), preferably a methyl group or a hydroxyethyl group, where n is 0 or 1 to 5. It is an integer, and n is preferably 0.)

(In the formula, R ¹¹ is a hydrogen atom or a methyl group, and p is 1 to 5.)

  As the amine oxide used in the present invention, lauryl dimethylamine oxide, stearyl dimethylamine oxide, lauryl dihydroxyethylamine oxide, polyoxyethylene lauryl dimethylamine oxide (average addition number of ethylene oxide: 3 mol) and the like are suitable.

  The shampoo composition of the present invention preferably contains one or more amine oxides represented by the above structural formula. When these amine oxides are indicated by trade names, Softamin L manufactured by Toho Chemical Industry Co., Ltd., Oxamine-ALS manufactured by Kyoei Chemical Industry Co., Ltd., Aromox C / 12 manufactured by Lion Akzo Co., Ltd., Aromox C / 12W , Aromox DMC-W, Aromox CM12D-W (C) and the like.

  (E) From the point which expresses creamy foaming, the minimum of the compounding quantity of the amine oxide of (E) component is 0.1 mass% or more in a shampoo composition, More preferably, it is 0.3 mass% or more, and an upper limit is 5 mass% or less is preferable, More preferably, it is 2 mass% or less.

  In the shampoo composition of the present invention, in addition to the above essential components, optional components and water such as purified water, various kinds of shampoo compositions generally used as necessary are provided as long as the object of the present invention is not impaired. An additive component can be blended. These can be used alone or in combination of two or more.

  Various additives include, for example, silicone derivatives, anionic polymers, cationic polymers, nonionic polymers, polyols, inorganic salts such as salt and sodium sulfate, organic salts, humectants such as propylene glycol, tonic agents, solubilizers, etc. , Antioxidants such as BHT and α-tocopherol, bactericides such as triclosan and trichlorocarban, polymer compounds, viscosity modifiers such as fatty acid monoethanolamide, fatty acid diethanolamide, ultraviolet absorbers, antioxidants, protein derivatives, Animal and plant extracts, anti-dandruff agents such as piroctone olamine and zinc pyrithione, anti-inflammatory agents such as dipotassium glycyrrhizinate, benzoic acid and salts thereof, parabens, preservatives such as caisson CG, pH such as citric acid and triethanolamine Regulators, ethylene glycol difatty acid esters, etc. Lumpur agents, opacifiers, hydrotropes, lower alcohols, vitamins, volatile oil, hydrophobic solvents, dilution solvents, pigments, perfumes and the like. These additive components may be used alone or in admixture of two or more, but can be added within a range not impairing the effect of the shampoo composition of the present invention.

  The type of the silicone derivative is not particularly limited, and those usually used in shampoo compositions can be used. For example, dimethylpolysiloxane (including highly polymerized dimethylpolysiloxane and silicone rubber), methylphenylpolysiloxane, polyether modified silicone, polyamino modified silicone, betaine modified silicone, alcohol modified silicone, fluorine modified silicone, epoxy modified silicone, mercapto Modified silicone, carboxy-modified silicone, fatty acid-modified silicone, silicone graft polymer, cyclic silicone, alkyl-modified silicone, trimethylsilyl group-terminated dimethylpolysiloxane, silanol group-terminated dimethylpolysiloxane, and the like can be mentioned. Two or more species can be used in appropriate combination. Among these, dimethylpolysiloxane, polyether-modified silicone, and polyamino-modified silicone are particularly preferably used.

  Among these silicone derivatives, those having a refractive index of less than 1.46 are preferable, and those having a refractive index of less than 1.42 are more preferable in terms of improving the smoothness of the finish. The lower limit of the refractive index is not particularly limited, but is preferably 1.39 or more.

  (F) Specific examples of silicone derivatives having a refractive index of less than 1.46 include Rheoflow DMS-55 (manufactured by Lion Corporation), SM8704C (manufactured by Toray Dow Corning Corporation), and SH3775M (Toray Dow). Corning Co., Ltd.). In the present invention, the refractive index is obtained by measuring at 25 ° C. by the General Test Method for Aboriginal Base (Abbe refractometer).

The viscosity of these silicone derivatives is not particularly limited, but the viscosity at a temperature of 25 ° C. is usually 1 to 20000000 cSt (centistokes, 10 ⁻⁶ m ² / s,), preferably 30 to One having 1000000 cSt is preferably used.
In addition, as the silicone derivative, an emulsion obtained by emulsifying the silicone derivative with a surfactant can also be used. In addition, what was emulsified like this does not have a restriction | limiting in particular in an emulsifier and the emulsification method, and can use variously. When blending these silicone derivatives, from the viewpoint of dispersion stability, the product viscosity of the shampoo composition of the present invention is preferably 500 to 15000 mPa · s, particularly preferably 1000 to 10,000 mPa · s. If it is less than 500 mPa · s, the dispersion stability of the silicone may be deteriorated. If it exceeds 15000 mPa · s, the dischargeability from the container may be poor and the usability may be inferior.

  Specific examples of anionic polymers and nonionic polymers include pectin, carrageenan, guar gum, locust bean gum, gelatin, xanthan gum, carboxyvinyl polymer, carboxymethylhydroxyethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, alginate, starch, polyvinyl alcohol , Polyacrylate, polymethacrylate, polymethylacrylate, polyethylene glycol, polyethylene oxide, tragarant rubber and the like.

  In the present invention, (G) the structural unit represented by the following formula is used as the viscosity-imparting agent, and the methoxy group is 25 to 35% by mass and the hydroxypropoxy group is 5 to 15% by mass (however, a hydroxyl group, a methoxy group and a hydroxy group) The total of the propoxy groups is 100% by mass), and it is preferable to blend hydroxypropylmethylcellulose having a 2% by mass aqueous solution having a viscosity of 2100 to 35000 mPa · s at 20 ° C. Thereby, especially the solubility of a shampoo composition is favorable, there is no squeak feeling at the time of a rinse, and a fine foam quality can be obtained at the time of foaming.

（式中、分子末端及びＲは水素原子、メチル基又はヒドロキシプロピル基を示す。）

(In the formula, the molecular terminal and R represent a hydrogen atom, a methyl group or a hydroxypropyl group.)

  In this hydroxypropylmethylcellulose, one part of the hydroxyl group of cellulose is substituted with a methoxy group or a hydroxypropoxy group. When the total of the hydroxyl group, methoxy group and hydroxypropoxy group is 100% by mass, the content of methoxy group is 25 to 35% by mass, preferably 28 to 30% by mass, and the content of hydroxypropoxy group is 5 to 15% by mass. , Preferably it is 7-12 mass%. If each content rate is not within the above range, it may be difficult to exert the effect of improving foam creaminess.

  Viscosity is measured at 20 ° C. and 30 revolutions / minute using a BM viscometer with a 2% by weight aqueous solution of hydroxypropylmethylcellulose. If the viscosity is less than 2100 mPa · s, the sufficient foam modifying effect may be insufficient, and if it exceeds 35000 mPa · s, the solubility may be poor. This hydroxypropyl methylcellulose can be synthesized by a known method or can be obtained as a commercial product.

  When blending this hydroxypropyl methylcellulose, from the viewpoint of good foam quality, the lower limit of the blending amount in the shampoo composition of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, Particularly preferably, it is 0.2% by mass or more, and the upper limit is preferably 2% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

  Cationic polymers include dimethyldiallylammonium chloride homopolymer, dimethyldiallylammonium chloride-acrylamide copolymer, dimethyldiallylammonium chloride functional group, cationized cellulose, cationized guar gum, cationized dextran, cationized pullulan, quaternary Vinylpyrrolidone-aminoethyl methacrylate copolymer, polyethyleneimine, dipropylenetriamine condensate, dimethyl-aminohydroxypropyldiethyltriamine copolymer adipate, quaternary nitrogen-containing starch, etc., hydrolyzed keratin, hydrolyzed silk , Hydrolyzed collagen, hydrolyzed wheat, cationized hydrolyzed keratin, cationized hydrolyzed silk, cationized hydrolyzed collagen, cationized hydrolyzed wheat, silico Of hydrolyzed collagen, such as those obtained by introducing a cationic group into the protein hydrolysis siliconized hydrolyzed silk and the like. In addition, the said polymer may be used individually by 1 type, and may use 2 or more types together.

  Specific examples of the fragrances include hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons and aromatic hydrocarbons, alcohols such as aliphatic alcohols, terpene alcohols and aromatic alcohols, aliphatic ethers and aromatic ethers. Oxides such as ethers, aliphatic oxides, terpene oxides, aliphatic aldehydes, terpene aldehydes, aliphatic cyclic aldehydes, aldehydes such as thioaldehydes, aromatic aldehydes, aliphatic ketones, terpene ketones, aliphatic cyclics Ketones, non-benzene aromatic ketones, ketones such as aromatic ketones, acids such as acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, aliphatic cyclic carboxylic acids, aromatic carboxylic acids , Acid amides, aliphatic lactones, macrocyclic lactones, terpenes Lactones such as lactones, aliphatic cyclic lactones, aromatic lactones, aliphatic esters, furan carboxylic acid esters, aliphatic cyclic carboxylic acid esters, cyclohexyl carboxylic acid esters, terpene carboxylic acid esters, aromatic carboxylic acid esters Synthetic fragrances such as nitrogen-containing compounds such as esters, nitromusks, nitriles, amines, pyridines, quinolines, pyrrole, indole, etc., and formulations containing natural fragrances, natural fragrances and / or synthetic fragrances from animals and plants A fragrance | flavor is mentioned, These 1 type can be used individually or in mixture of 2 or more types.

  For example, as a synthetic fragrance, Motoichi Into published by Chemical Industry Daily, “Synthetic fragrance chemistry and product knowledge”, 1969 MONCLAIR, N. J. et al. The fragrances described in the publication “STEFEN Arctander” “Perfume and Flavor Chemicals” can be used. As natural fragrances, the fragrances described in “Scent Encyclopedia” (edited by the Japanese Fragrance Association) can be used.

Specific examples of the main perfume names include aldehydes C _{6 to} C ₁₂ , anisaldehyde, acetal R, acetophenone, acetyl cedrene, adxal, allyl amyl glycolate, allyl cyclohexane propionate, α-damascon, β-damascon , Δ-damascone, ambroxan, amylcinnamic aldehyde, amylcinnamic aldehyde dimethyl acetal, amyl valericate, amyl salicylate, isoamyl acetate, isoamyl salicylate, uranium thiol, acetyl eugenol, bacdanol, benzyl acetate, benzyl alcohol, benzyl salicylate, Bergamyl acetate, bornyl acetate, butyl butyrate, pt-butylcyclohexanol, pt-butylcyclohexyl acetate Tate, ot-butylcyclohexanol, ot-butylcyclohexyl acetate, benzaldehyde, benzyl formate, cariophylene, cashomeran, carvone, cedro umber, cedryl acetate, cedrol, celestolide, cinnamic alcohol, cinnamic aldehyde , Cisjasmon, citral, citral dimethyl acetal, citrusal, citronellal, citronellol, citronellyl acetate, citronellyl formate, citronellonitrile, cyclaset, cyclamenaldehyde, cyclaprop, caron, coumarin, cinnamyl acetate, δ-C ₆ -C ₁₃ lactone, dimethyl benzyl carbinol, dihydrojasmonate, dihydro linalool, dihydromyrcenol, dimethoxyethane Le, Jimirusetoru, diphenyl oxide, Echiruwanirin, eugenol, Furuiteto, Fen chill alcohol, phenylethyl phenylacetate, Garakusorido, γ-C ₆ ~C ₁₃ lactone, alpha-pinene, beta-pinene, limonene, myrcene, beta-Kariofuiren, geraniol Geranyl acetate, geranyl formate, granilnitrile, hedion, helional, heliotropin, cis-3-hexenol, cis-3-hexenyl acetate, cis-3-hexenyl salicylate, hexylcinnamic aldehyde, Hexyl salicylate, hyacinth dimethyl acetal, hydrotropic alcohol, hydroxycitronellal, indole, ionone, isobornyl acetate, isocyclocitral, SoE Super, Isoeugenol, Isononyl Acetate, Isobutyl Quinoline, Jasmar, Jasmolactone, Jasmofilan, Coabon, Ligstral, Lilyal, Lime Oxide, Linalol, Linalol Oxide, Linalyl Acetate, Lyral, Manzanate, Mayol, Mensanil Acetate , Mentonate, methylanthranilate, methyleugenol, menthol, α-methylionone, β-methylionone, γ-methylionone, methylisoeugenol, methyl lavender ketone, methyl salicylate, mugealdehyde, mugol, musk TM-II, musk 781, musk C _14, muscone, civetone, cyclopentadecanone, cyclohexadecen cyclohexenone, cyclopentadecanolide, Ann Bled , Cyclohexadecanolide, 10-oxahexadecanolide, 11-oxahexadecanolide, 12-oxahexadecanolide, ethylene brushate, ethylenedodecandioate, oxahexadecen-2-one, 14- Methyl-hexadecenolide, 14-methyl-hexadecanolide, musk ketone, musk tipetine, nopyrualcohol, nopylacetate, neryl acetate, nerol, methylphenylacetate, milacaldehyde, neobergameto, oak moss no. 1, Oligorib, oxyphenylone, p-cresol methyl ether, pentalid, phenylethyl alcohol, phenylethyl acetate, rubafuran, damasenone, raspberry ketone, dimethylbenzyl carvinyl acetate, jasmacyclene, methyl naphthyl ketone, rose phenone, rose oxide, sandaroa , Sandera, Santa Rex, Styral Acetate, Styral Reel Propionate, Terpineol, Tervinyl Acetate, Tetrahydrolinalol, Tetrahydrolinalyl Acetate, Tetrahydrogeraniol, Tetrahydrogeranyl Acetate, Tonalid, Traceolide, Tripral, Thymol, Vanillin, Beldox, Yarayara, Anise oil, Bay oil, Boadrose oil, Cananga oil, Cardamo Oil, Cassia oil, Cedarwood oil, Orange oil, Mandarin oil, Tangerine oil, Basil oil, Nutmeg oil, Citronella oil, Clove oil, Coriander oil, Elemi oil, Eucalyptus oil, Fennel oil, Galvanum oil, Geranium oil, Hiba oil, Persimmon oil, jasmine oil, lavandi oil, lavender oil, lemon oil, lemongrass oil, lime oil, neroli oil, oak moss oil, okotia oil, pastry oil, peppermint oil, perilla oil, petitgren oil, pine oil, rose oil, rose Marie oil, camphor oil, melamine oil, clary sage oil, sandalwood oil, spearmint oil, spike lavender oil, star anise oil, thyme oil, tonka bean tincture, turpentine oil, vanilla bean tincture, vetiver oil, ylang ylang oil, grapefruit oil , Yuzu oil, benzoin, peruvian balsam, true Rusamu, tuberose oil, absolute oak moss, fur balsam, Musukutenki, dregs thorium tincture, civet tincture, is an amber grease numeric keypad and the like.

  Further, diethyl phthalate, dipropylene glycol, benzyl benzoate, isopropyl myristate, hercoline, isopentane, orange terpene, etc. can be used as a solvent or a retaining agent for the fragrance.

  The shampoo composition of the present invention is a composition in which a liquid crystal structure formed of (A) a cationic surfactant and a specific (B ′) oil not containing a silicon atom is dispersed in the composition. Dispersing the liquid crystal structure in the composition improves the shampoo squeak, especially the intense squeaky feeling of colored hair, has excellent foaming, and has excellent dispersion stability over time. It is done. The liquid crystal structure is formed from the component (A) and the component (B ′), but in addition to the two components, a small amount of other components may be contained. The liquid crystal structure can be confirmed by X-ray diffraction, an optical microscope, an electron microscope, or the like. The dispersed state indicates that the liquid crystal structure is dispersed without being solubilized.

  Further, the upper limit of the average particle size of the liquid crystal structure dispersed in the shampoo composition is preferably less than 20 μm, more preferably 10 μm or less, particularly preferably 5 μm or less, and the lower limit is preferably 0.05 μm or more. Preferably it is 0.1 micrometer or more. When the average particle size of the liquid crystal structure is 20 μm or more, the effect of preventing squeezing at the time of rinsing and the smoothness of the finish are lowered, stickiness may occur, and dispersion stability may deteriorate. Moreover, if it is less than 0.05 micrometer, foaming may fall, and also stickiness may arise by the influence of an emulsifier, and it may become disadvantageous also in cost. In this case, the average particle size of the liquid crystal structure is obtained by arbitrarily capturing images of particles captured by an optical microscope into 100 computers and setting the same magnification, and then performing image processing (for example, computer software winROOF). Can do.

  The shampoo composition of the present invention can be prepared according to a conventional method or a method described in JP-A No. 2001-311099. As a production method, (C) an aqueous phase containing a detersive surfactant, (A) a cationic surfactant and (B) an oil component not containing a silicon atom, the above components (A) and (B) A method of mixing at a temperature equal to or higher than the crystallization temperature and cooling the resulting mixture from a temperature equal to or higher than the crystallization temperature is preferred. Furthermore, (C) an aqueous phase containing a detersive surfactant, (A) a cationic surfactant, and (B) an oil component not containing silicon atoms are mixed, and a part of the resulting mixture is continuously added. A method of cooling the mixture from a temperature equal to or higher than the crystallization temperature by repeating extraction of the sample into a mixture, quenching the mixture, and returning the quenched product to the mixture is preferable. According to this method, the cooling time can be shortened. Moreover, when mix | blending (D) water-swellable clay mineral, it is preferable to mix the water-swellable clay mineral disperse | distributed or swollen in water with the water phase containing detersive surfactant. By this method, when a plurality of production batches are continuously produced, tank cleaning between batches is not necessary, and production efficiency can be dramatically increased.

  The order in particular at the time of mixing is not restrict | limited, The structural component of a liquid crystal structure may be added to the water phase containing detersive surfactant, and vice versa. Since the liquid crystal structure is easily solidified at a low temperature, it is preferable that the liquid crystal structure is heated and dissolved while adding the detersive surfactant while warming and stirring.

  The mixing temperature is equal to or higher than the crystallization temperature of the constituent components of the liquid crystal structure. By mixing at such a temperature, the liquid crystal structure can be uniformly mixed and dispersed in the detersive surfactant.

  The crystallization temperature (abbreviated as T ° C.) of the component of the liquid crystal structure of the present invention does not indicate the crystallization temperature of the component obtained by simply mixing and heating and dissolving the component of the liquid crystal structure. It is the temperature at which crystallization occurs in an aqueous phase containing a surfactant. T ° C. can be easily measured using a shampoo composition as a sample and using a differential scanning calorimeter (DSC). As measurement conditions, the sample temperature is 5 to 50 mg and the temperature increase rate is 0.5 to 2.0 ° C./min.

  A chart obtained by DSC measurement of a typical shampoo composition having the following composition is shown in FIG. 33 mg of the shampoo composition was measured at a heating rate of 1 ° C./min. The leftmost large endothermic peak in FIG. 2 is a transition peak of the liquid crystal structure, but a small endothermic peak is seen on the higher temperature side. The temperature at which the endotherm of the endothermic peak ends is T ° C., and in the case of this sample is 73 ° C.

Composition Mass%
Detergent surfactant Palm oil fatty acid amidopropyl betaine 14.0
Liquid crystal structure behenyltrimethylammonium chloride 2.0
Behenyl alcohol 4.8
Other ingredients 7.0
Water balance
Total 100.0

  In the shampoo composition for measuring T ° C., first, a mixture of components of the liquid crystal structure in the composition is prepared and heated to examine the dissolution temperature. Next, after thoroughly mixing the detersive surfactant component and the liquid crystal structure at a temperature that is 10 ° C. or more higher than the melting temperature, the mixture is cooled to 30 ° C. or less (the cooling method is to use a general jacket cooling method). The cooling rate is 0.5 to 2.0 ° C./min). After preparation, T ° C. is measured by DSC using a sample left for 3 days or more as a sample.

  In the production method of the present invention, the obtained mixture is then cooled from a temperature higher than the crystallization temperature. Although the cooling method is not particularly limited, it may be a cooling method in which cooling water is passed through the jacket outside the mixing tank, or a part of the mixture is continuously extracted and rapidly cooled, and this rapidly cooled mixture is mixed. It may be a method of repeating the process (hereinafter, abbreviated as a continuous partial quenching method). In particular, the continuous partial quenching method is preferable from the viewpoint of shortening the cooling time. In this case, rapid cooling means that the mixture in a heated state is instantaneously cooled to 10 to 35 ° C.

The continuous partial quenching method will be described.
In the production process of the shampoo composition of the present invention, the state immediately before starting cooling is a mixture of a detersive surfactant having a temperature of T ° C. or higher and a liquid crystal structure. The continuous partial quenching method is a cooling method in which a part of the mixture is continuously extracted, rapidly cooled, and repeatedly returned to the mixture to lower the temperature of the entire mixture. FIG. 1 is a block diagram showing a preferred embodiment of an apparatus used for the continuous partial quenching method.

  The shampoo composition having a temperature of T ° C. or higher produced in the blending tank 1 is circulated in the circulation line 2. A heat exchanger 4 is provided in the middle of the circulation line 2, and cold water is sent to the heat exchanger 4 from the cold water producing machine 5 through the cooling water line 3 and discharged. The shampoo composition circulated in the circulation line 2 is continuously cooled by the heat exchanger 4 and returned to the blending tank 1 again.

  According to this method, it is possible to shorten the cooling time to 1/2 to 1/5 as compared with a general method in which cooling is gradually performed by passing cooling water through a jacket outside the tank. The temperature of the cooling water in this case is 1 to 25 ° C, preferably 1 to 15 ° C. If it is lower than 1 ° C, the cooling water freezes and it becomes difficult to cool, and if it is higher than 25 ° C, the cooling efficiency is low. Moreover, if the processing capacity of the heat exchanger 4 is high, the cooling efficiency can be further increased by increasing the circulation capacity per fixed time of the shampoo composition. Further, from the viewpoint of ease of management of the cooling end temperature, the temperature of the shampoo composition and the cooling water after the partial cooling coming out of the heat exchanger 4 is −5 to −20 from the planned cooling end temperature of the entire composition. ° C is preferred.

  In order to carry out this continuous partial quenching method, it is necessary that the viscosity of the shampoo composition in the vicinity of the temperature of the cooling water to be used does not increase significantly. When the viscosity becomes high, the shampoo composition is solidified in the cooling part in the heat exchanger, and thus cooling is impossible. In order to avoid this, the temperature of the cooling water may be set higher. However, the cooling rate of the shampoo composition may be reduced and the economic merit may be reduced. For example, if the viscosity of the shampoo composition at 5 ° C. is 2.0 Pa · s or less, high cooling efficiency can be obtained. In addition, this viscosity has shown the composition viscosity at the time of manufacture, and after cooling is finished and it finished as a final composition, it differs greatly from the viscosity when it is cooled at 5 degreeC. The reason is that after finishing as a composition, the system becomes structured with time and the viscosity increases.

  Furthermore, the method for producing a shampoo composition of the present invention preferably includes a step of mixing (D) a clay mineral dispersed or swollen in water with an aqueous phase containing a detersive surfactant. As a result, the crystal precipitation of the constituent components of the liquid crystal structure can be significantly suppressed, so that the liquid crystal structure can be stably dispersed even in the continuous partial quenching method in which crystal precipitation is likely to occur. Further, in the method of directly adding water-swellable clay mineral, when it is necessary to continuously produce a plurality of batches in the same blending tank, the shampoo composition remaining on the wall surface in the tank in the production of the batch However, there is a problem that it interferes with the crystal precipitation suppression effect of the water-swellable clay mineral. In this case, it is necessary to prepare the next batch after washing the inside of the tank, but the water-swellable clay mineral is mixed with an aqueous phase containing a detersive surfactant dispersed or swollen in water. This eliminates the need for in-bath cleaning between batches, greatly improving production efficiency. In addition, the water dispersion or swelling liquid of 1 to 5% by mass of water-swellable clay mineral is heated to 50 to 80 ° C. as necessary, so that the water is highly stable and easy to transport with low viscosity. A dispersion swelling liquid can be obtained.

  In the shampoo composition of the present invention, a normal dose of shampoo can be used according to a conventional method. The shampoo composition of the present invention has the effect of improving the squeakiness of hair, being excellent in foaming, and being excellent in dispersion stability over time. Therefore, it is preferable to use it for colored hair that is particularly severely damaged.

  Examples of the container of the shampoo composition of the present invention include aluminum laminated tubes, EVAL tubes, aluminum tubes, glass-deposited plastic tubes and the like, as well as dispenser containers and squeeze containers by mechanical or differential pressure, laminated film containers, dropper containers, It can be filled into stick containers, bottle containers and the like. Laminate film usually has two or more layers, and the material is polyethylene, polyethylene terephthalate, polyester, biaxially stretched polypropylene, unstretched polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, etc., paper, aluminum Consists of vapor-deposited plastic. In consideration of strength, flexibility, weather resistance and the like, generally 2 to 5 layers are used. As the material of the bottle, polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyvinyl chloride, ethylene-vinyl alcohol resin, acrylonitrile / styrene resin, ABS resin, polyamide, etc., and a single layer or a combination of two or more layers may be used. it can.

  According to the present invention, the squeezed feeling of hair that occurs when shampooing is rinsed is improved, especially in colored hair that is prone to squeaky, and it has excellent foaming and dispersion stability over time. A shampoo composition excellent in the above can be obtained.

  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,% of composition indicates mass%.

[Examples 1-12, Comparative Examples 1-8]
According to the compositions described in Tables 1 and 2, shampoo compositions were prepared by the following production methods and evaluated for good foaming, no squeak during rinsing and dispersion stability. The results are shown in Tables 1 and 2. In addition, (B ') in a table | surface shows the oil component which forms a liquid crystal structure independently with (A) component in (B) component.
[Production method]
i. The oil phase was prepared by heating and dissolving the component (A), the oil-soluble component of the component (B) and other oil-soluble components at 45 to 80 ° C.
ii. A surfactant and other water-soluble components were dissolved in purified water at room temperature to 80 ° C. to prepare an aqueous phase.
iii. The oil phase obtained in i was added to the water phase obtained in ii, and the mixture was stirred with an azimuth mixer to form an O / W emulsion.
iv. While stirring with a paddle mixer, the mixture was gradually cooled to room temperature, and the pH was adjusted as necessary to obtain a shampoo composition.

Evaluation of shampoo foaming <Method>
Ten female panelists with short to semi-long hair dyed brownish were evaluated for shampoo foaming when the shampoo composition was used for 10 days based on the following ratings. In the table, the total score of 10 people is represented by the following criteria.
In-bath products such as rinse conditioners used after shampooing and out-bath products such as styling agents and hair care agents were used as they were used daily.
<Score>
+2 points: Very good +1 point: Slightly good -1 point: Slightly bad -2 points: Very bad <Standard>
◎: Total score of 15 or more ◎ ~ ○: 14-10 points ○: Total score of 9-5 points △: Total score of 4-0 points △ -X: Total score of -1 to -4 points x: Total Points are -5 points or less

Evaluation of squeakiness when shampooing is rinsed <Method>
Ten female panelists with short to semi-long hair dyed brownish were evaluated for the squeaky sensation at the time of rinsing when the shampoo composition was used for 10 days based on the following score. In the table, the total score of 10 people is represented by the following criteria.
In-bath products such as rinse conditioners used after shampooing and out-bath products such as styling agents and hair care agents were used as they were used daily.
<Score>
+2 points: Very good +1 point: Slightly good -1 point: Slightly bad -2 points: Very bad <Standard>
◎: Total score of 15 or more ◎ ~ ○: 14-10 points ○: Total score of 9-5 points △: Total score of 4-0 points △ -X: Total score of -1 to -4 points x: Total Points are -5 points or less

Evaluation of dispersion stability over time <Method>
The prepared shampoo composition was stored at 50 ° C. for 1 month, and its uniform dispersibility was evaluated based on the appearance and observation with a polarizing microscope based on the following criteria.
<Standard>
◎: Very good ○: Good △: Normal ×: Bad

The storage over time was performed by filling all of the following containers (1) to (9) with a shampoo composition. In the following, PE is polyethylene, PP is polypropylene, PET is polyethylene terephthalate, PA is polyamide, and HDPE is high-density polyethylene.
<Bottle container>
(1) Bottle part: Material PP Cap: Material PP
(2) Bottle: Material HDPE Cap: Material PP
(3) Bottle part: Material PET Cap: Material PP
(4) Bottle part: Material PP / HDPE Cap: Material PP
<Pump container>
(5) Bottle part: Material PP Dispenser part: Used material PP, PE and SUS304
(6) Bottle part: HDPE Dispenser part: Materials PP, PE and SUS304 used
(7) Bottle part: PET Dispenser part: Materials PP, PE and SUS304 used
(8) Bottle part: PP / HDPE Dispenser part: Materials PP, PE and SUS304 used
<Pouch container>
(9) Material Aluminum vapor deposition polyethylene pouch

[Examples 13 to 22, Comparative Examples 9 to 14]
According to the composition described in Tables 3 and 4, a shampoo composition was prepared by the following production method. Based on the following evaluation method, good foaming, no squeak during rinsing, smooth finish, no sticky finish The dispersion stability was evaluated. The results are also shown in Tables 3 and 4.
[Production method]
i. The oil-soluble component (A), the oil-soluble component (B), and other oil-soluble components were heated and dissolved at 60 to 80 ° C. to prepare an oil phase.
ii. A surfactant and other water-soluble components were added to purified water and dissolved at 60 to 80 ° C. to prepare an aqueous phase.
iii. The oil phase obtained in i was added to the water phase obtained in ii, and the mixture was stirred with an azimuth homomixer to form an O / W emulsion.
iv. While stirring with a paddle mixer, the mixture was gradually cooled to room temperature, and the pH was adjusted as necessary to obtain a shampoo composition.
The component (F) was mixed with i or ii or mixed with iv at room temperature depending on the type.

  The average particle diameter of the liquid crystal structure was obtained by arbitrarily capturing 100 images of particles captured with an optical microscope into a computer, setting the same magnification, and performing image processing (for example, computer software winROOF).

Evaluation of shampoo foaming and evaluation of squeakiness when shampooing was performed Evaluation was performed in the same manner as in Example 1.
Evaluation method and standard of smoothness and non-stickiness of finished hair <Method>
The hair of 10 female panelists performing hair coloring is divided into left and right halves, and the shampoo composition shown in the examples or comparative examples is applied to one side and the control shampoo having the following composition is applied to the other side by 3.0 mL each. Shampooing was performed, and the smoothness and non-stickiness of the finished hair were evaluated based on the following scores. In the table, the total score of 10 people was expressed by the following criteria.
Control shampoo <br/> Composition%
Sodium polyoxyethylene alkyl ether sulfate 10%
(Average number of EO addition moles: 3)
Coconut oil fatty acid amidopropyl betaine 5%
Sodium chloride 2%
Dimethyl silicone (100,000 cSt) 1%
Cationized cellulose 0.3%
Trimethylglycine 0.2%
Citric acid 0.2%
Palm oil fatty acid monoethanolamide 0.8%
1% ethylene glycol distearate
Sodium benzoate 0.4%
Fragrance 0.5%
Purified water balance
Total 100%
<Score>
+2 points: good compared to the control shampoo +1 point: slightly better than the control shampoo 0 points: equivalent to the control shampoo -1 point: slightly bad compared to the control shampoo -2 points: bad compared to the control shampoo <Criteria>
◎: Total score is 10 or more ○: Total score is 9-5 points △: Total score is 4-4 points x: Total score is -5 points or less In addition, in-bath products such as rinse conditioners used after shampooing Out bath products such as styling agents and hair care agents were used as they are everyday.
Evaluation of dispersion stability over time Evaluation was made in the same manner as in Example 1.

[Examples 23 to 26]
According to the composition described in Table 5, a shampoo composition was prepared by the following production method, and the dispersion stability of the liquid crystal structure, foaming and squeaky feeling during rinsing were evaluated based on the following evaluation method. The results are also shown in Table 5.
[Production method]
i. The oil-soluble component (A), the oil-soluble component (B) and other oil components were heated and dissolved at 45 to 80 ° C. to prepare an oil phase.
ii. The component (D), component (G) (added to the oil phase depending on the type), surfactant and other aqueous components were stirred and dissolved in purified water at room temperature to 80 ° C. to prepare an aqueous phase.
iii. The oil phase obtained in i was added to the water phase obtained in ii, gradually cooled to room temperature while stirring with a paddle mixer, and the pH was adjusted as necessary to obtain a shampoo composition.

[Examples 27 to 37]
Based on the following composition, a shampoo composition was prepared in the same manner as in Example 23, and Examples 27-30 were evaluated for solubility, Examples 31-37 were evaluated for solubility and foam creaminess. Tables 6 and 7 show the mass% of methoxy group and hydroxypropoxy group of hydroxypropylmethylcellulose used in each example, the viscosity of a 2% aqueous solution, and the evaluation results.

Shampoo composition composition% by mass
Behenyltrimethylammonium chloride 2.0
Behenyl alcohol 5.0
Bentonite 0.5
Hydroxypropyl methylcellulose 0.2
Amidopropyl betaine laurate 13.0
Lauryldimethylamine oxide 1.0
Palm oil fatty acid diethanolamide 3.0
Purified water balance
Total 100.0

[Examples 38 to 44]
According to the composition described in Table 8, a shampoo composition was prepared by the production method of Example 23 described above. Based on the following evaluation methods, good foaming, foam slip, foam creaminess, and no squeaking during rinsing And the moist feeling after drying was evaluated. The results are also shown in Table 8.

Evaluation method of Examples 23-44
Method for Measuring Shampoo Composition Viscosity The shampoo composition viscosity was measured using a Brookfield viscometer according to the cosmetic raw material standard and the second method of the general test method.
<Measurement conditions> The rotor used was No. 3-4, rotor speed is 30rpm
<Measurement Method> The shampoo composition was kept at 25 ± 1 ° C., the rotor was gently inserted into the liquid and allowed to stand for 1 minute, and then the rotor was rotated to measure the viscosity after 10 revolutions.

Evaluation of long-term dispersion stability of liquid crystal structures <Method>
The prepared shampoo composition is stored for 1 month at 40 ° C, which is an unstable temperature (near the phase transition point) for the liquid crystal structure, and for 40 ° C for 3 months assuming that it is correlated with long-term storage at room temperature for 1 year or more. The uniform dispersibility was evaluated based on the following evaluation criteria by its appearance (no separation) and observation with a polarizing microscope. Preservation with time was performed by filling each of the containers (1) to (9) with a shampoo composition.
<Evaluation criteria>
◎: Very good ○: Good △: Normal ×: Bad

Evaluation of foaming and foam sliding of shampoo composition <Method>
Ten female panelists with short to semi-long hair dyed brownish were evaluated for foaming and slipping of the shampoo when the shampoo composition was used for 10 days based on the following scores. In the table, the total score of 10 people is represented by the following criteria.
In-bath products such as rinse conditioners used after shampooing and out-bath products such as styling agents and hair care agents were used as they were used daily.
<Score>
+2 points: Very good +1 point: Slightly good -1 point: Slightly bad -2 points: Very bad <Standard>
◎: Total score of 15 points or more ◎ to ○: 14 to 10 points ○: Total score is 9 to 5 points △: Total score is 4 to 0 points △ to ×: Total points are −1 to -4 points ×: Total Points are -5 points or less

Evaluation of squeaky feeling during shampoo rinsing Evaluation was performed in the same manner as in Example 1.
Evaluation of solubility A shampoo composition was prepared, and the state of the liquid immediately after the preparation was evaluated according to the following evaluation criteria.
<Evaluation criteria>
◎: No uniform precipitate or insoluble gelled product ○: Uniform and no precipitate, but slightly small gelled product △: No precipitate, but large amount of large gelled product ×: Precipitate Yes, or allow phase separation
A foamy creamy hair bundle of 10 g was moistened with water at 40 ° C. to contain 5 g of water. Next, 1 g of the shampoo composition was used to wash the hair bundle, and the creamy property of the foam during washing was compared with a control shampoo (without hydroxypropylmethylcellulose), and sensory evaluation was performed based on the following evaluation criteria.
<Evaluation criteria>
○: Clearly better than control shampoo △: Slightly better than control shampoo ×: Same as control shampoo

Moist feeling after drying 10 female panelists' hair is divided into 2 left and right parts, shampoo composition on one side and control shampoo (without hydroxypropyl methylcellulose) on each other 3ml each, shampooed and dried with dryer The smoothness after the evaluation was evaluated based on the following score. In the table, the total score of 10 people was represented by the following criteria.
<Score>
+2 points compared to control shampoo: Good +1 point: Slightly good 0 point: Equivalent -1 point: Slightly bad -2 point: Poor <Standard>
A: Superior to control shampoo (total score of 10 or more)
○: Slightly better than the control shampoo (total 5-9 points)
Δ: Same level as the control shampoo (total score is 4 to -4 points)
X: Inferior to control shampoo (total score is -5 points or less)

[Examples 45 to 50]
A shampoo composition having the following composition was prepared by the following method based on the description in Table 9, and evaluated for the absence of squeaking and -5 ° C storage stability based on the following evaluation criteria. The results are also shown in Table 9.
Composition of shampoo composition
Component of liquid crystal structure (A) Alkyltrimethylammonium chloride 2.0
(B) Behenyl alcohol 4.8
(C) Amidopropyl betaine laurate 15.0
(E) Lauryldimethylamine oxide 1.0
Dissolution improver for liquid crystal structure POE (10) behenyl ether 0.5
Palm oil fatty acid diethanolamide 3.0
Propylene glycol 2.0
(D) Bentonite 0.3
Other ingredients Hydroxypropyl methylcellulose 0.2
Diglucosyl gallic acid 0.5
Hydrolyzed wheat protein 1.5
Raffinose 0.5
(F) Dimethyl silicone (100,000 cSt) 1.5
Sodium benzoate 0.9
Methylchloroisothiazolinone / methylisothiazolinone solution
0.01
Yellow No. 203 0.0005
Red No. 106 0.0001
Citric acid monohydrate 0.46
Fragrance 0.5
Purified water balance
Total 100.0

[Production method]
Disperse water-swellable clay mineral in purified water (ion-exchanged water), add detersive surfactant, and heat and mix the components of the liquid crystal structure and the dissolution improver of the liquid crystal structure in advance. Add the product to T1 ° C. Thereafter, cooling is started when the entire liquid reaches T2 ° C. After cooling to about 40 ° C., other components were added, and the amount of citric acid was adjusted to prepare a shampoo composition with pH = 5.5.

The mixing tank used was a 20-liter vacuum emulsification pot (PVT-1-20 manufactured by Mizuho Industry Co., Ltd.). In the jacket cooling method, water at 15 to 20 ° C. was passed through the jacket of the vacuum emulsification kettle to cool. In the continuous partial quenching method using an external heat exchanger, pipes are connected via the content extraction port at the bottom of the vacuum emulsification pot, an external heat exchanger, and a transfer pump to emulsify the contents cooled by the external heat exchanger. The contents of the vacuum emulsification kettle were continuously circulated by connecting a pipe returning to the kettle to the raw material inlet at the top of the vacuum emulsification kettle. As an external heat exchanger, UX-005 (heat transfer area is 0.612 m ² ) manufactured by Nisaka Manufacturing Co., Ltd. was used. Adjust the amount of cooling water between the start and end of cooling so that 5-7 ° C cooling water enters the heat exchanger and the contents and cooling water come out of the heat exchanger at 20-35 ° C did. The time required for cooling to T2 to 38 ° C. was about 40 minutes by the jacket cooling method and 10 to 12 minutes by the continuous partial quenching method using an external heat exchanger.

  In addition, although the temperature change (T1 degreeC-> T2 degreeC) has arisen just before emulsification-cooling, the operation in the meantime is demonstrated. In Examples 45 to 47 and 49, only the steam heating by the jacket was stopped at the start of emulsification, and the composition of the contents was not changed (natural heat dissipation). On the other hand, in Example 48, the jacket heating was stopped, and the total amount of sodium benzoate to be added was changed to a 33% aqueous solution (the temperature of the aqueous sodium benzoate solution was about 15 ° C.) and added and stirred after emulsification. Further, in Example 50, the jacket heating was stopped, and 1/3 of amide amidopropyl betaine to be added was added and stirred after emulsification (the temperature of amidopropyl betaine laurate was about 15 ° C., and the remaining 2 / 3 is added before emulsification). As a result of measuring the crystallization temperature (T ° C.) of the shampoo composition of the example prepared by the above production method using a differential scanning calorimeter (DSC) (DSC6100, manufactured by Seiko Instruments), 74 ° C. there were. The measurement conditions were such that the sample amount was 31 mg of Example 45, 29 mg of Example 46, 32 mg of Example 47, 32 mg of Example 48, 33 mg of Example 49, 31 mg of Example 50, 31 mg of Example 50, and the heating rate was 1 ° C./min.

  In addition, after the shampoo composition thus obtained was produced (when cooled to about 45 ° C.), a small amount was taken out and quickly cooled to 5 ° C., and then in accordance with the cosmetic raw material standard, the second method of the general test method, Brookfield type The viscosity was measured using a viscometer (the rotor used was No. 3, the rotor rotation speed was 30 rpm and the value after 10 rotations). As a result, the shampoo compositions of Examples 46 to 48 had a viscosity of 1.2 to 1.3 Pa · s, indicating that cooling was performed efficiently. In addition, when disassembling and cleaning the used external heat exchanger, the heat transfer portion was observed, but no solid matter was observed due to cooling.

  The obtained shampoo composition was allowed to stand for 24 hours and kept at 25 ° C. ± 2 ° C., and the viscosity was measured in the same manner. As a result, Example 45: 3.2 Pa · s, Example 46: 2.4 Pa · s, Example 47: 2.6 Pa · s, Example 48: 2.4 Pa · s.

Evaluation of squeakiness at the time of shampoo rinsing Evaluate the squeakiness when rinsing with hot water after washing hair with shampoo composition by 10 women who are carrying hair color in their 20s and 40s. The following evaluation criteria are shown.
<Evaluation criteria>
◎: If 9 or more people do not respond ○: If 6-8 people do not respond △: If 3-5 people do not respond ×: Less than 2 panelists do not feel
-5 ° C Storage Stability Evaluation Shampoo composition was filled in each of the above containers (1) to (9) and stored for 1 month in a thermostat controlled at -5 ± 1 ° C, then 22-26 ° C. The whole shampoo composition was transferred into a petri dish or the like and the appearance was observed, and evaluated according to the following evaluation criteria.
<Evaluation criteria>
(Double-circle): In all the storage containers, layer separation and precipitation of a solid substance were not recognized.
○: Some glossiness derived from crystal precipitation was observed.
(Triangle | delta): There existed a thing in which precipitation of the solid substance of the level which can be recognized for a naked eye was recognized slightly.
X: Precipitation of many solids which can be recognized with the naked eye was recognized, or there existed what layer separation was recognized.

[Example 51]
A shampoo composition having the following composition was prepared in the same manner as in Example 46.
Composition Mass%
Behenyltrimethylammonium chloride 2.0
Behenyl alcohol 5.0
Monoglyceryl behenate (HLB4.3) 0.3
Behenyl ether (EO10) (HLB9) 0.3
Palm oil fatty acid diethanolamide 3.0
Amidopropyl betaine laurate 13.0
Alkyl (8-16) glucoside 1.0
Bentonite 0.3
Dimethylamine oxide laurate 1.0
Dimethyl silicone 1.8
Amino-modified silicone 0.2
Propylene glycol 5.0
Sodium benzoate 0.9
Arginine 0.5
Citric acid 0.5
Fragrance 0.5
Purified water balance
Total 100.0%
Property Viscosity 5Pa ・ s
Specific gravity 1.02 (25 ° C)
pH 5.8
Has thixotropic properties

  In the shampoo compositions of the above examples, a regular diffraction pattern was observed as a result of X-ray diffraction. When these were observed with a polarizing microscope, the tissue image showed optical anisotropy, and when the frozen and cleaved sample was observed with a cryo-scanning electron microscope, the thin layer was overlapped. It was recognized that the shampoo compositions of the examples obtained were those in which the liquid crystal structures were dispersed.

In the examples and comparative examples, the following were used.
* Stearyltrimethylammonium chloride: ARCARD T833 (manufactured by Lion Corporation)
Stearyltrimethylammonium chloride in accordance with cosmetic raw material standards (hereinafter abbreviated as “Ningyuan Group”), an aqueous solution having a pure content of about 33% (remaining 29% Nangxin anhydrous ethanol, 38% Ningen group purified water). In the table, the equivalent amount of stearyltrimethylammonium chloride is shown.
* Behenyl trimethyl ammonium chloride: ARCARD 22-80 (manufactured by Lion Corporation)
Behenyltrimethylammonium chloride conforming to the makeup base, pure solid of about 80%. The table shows the equivalent amount of behenyltrimethylammonium chloride.
See Supplement to Cosmetic Material Standard 2nd Edition.
This product is synthesized from erucic acid derived from rapeseed oil through a long chain amine. The alkyl chain length distribution of the long-chain amine is as follows.
C ₁₆ or less 2% or less C ₁₈ 6% or less C ₂₀ 6% or less C ₂₂ 87 to 93%
C ₂₄ 3% or less * Distearyldimethylammonium chloride: ARCARD 218P-75E (manufactured by Lion Corporation)
Distearyldimethylammonium chloride conforming to the makeup base and a paste with a pure content of about 75%. In the table, the amount corresponding to the pure content of distearyldimethylammonium chloride is shown. The alkyl (alkenyl) group of this product is a quaternary ammonium salt with C18F0: C18F1 = 75: 25.
* Lauric acid amidobutylguanidine solution: C12A4G (manufactured by Lion Corporation)
An aqueous solution with a pure content of about 32%. In the table, the amount corresponding to the pure content of lauric acid amide butyl guanidine solution is described.

* Cetyl alcohol: Lorol C16 (manufactured by Cognis Japan)
Compliant with Jeongwon group. The chain length distribution is generally as follows.
C ₁₄₀ 0-3%
C ₁₆ 95% or more C ₁₈ 0-5%
* Stearyl alcohol: Conol 30SS (manufactured by New Japan Science Co., Ltd.)
Conformity standard * Hardened rapeseed oil alcohol: Stenol 1822SR (manufactured by Cognis Japan Co., Ltd.)
The chain length distribution is generally as follows in accordance with the formulation standard for cosmetic varieties (hereinafter abbreviated as “cosmetic arrangement rules”).
C ₁₆ or less 1.5% or less C ₁₈ 40 to 46%
C ₂₀ 8-14%
C ₂₂ 42-48%
C ₂₄ 0.5% or less * Behenyl alcohol: LANETTE 22 (manufactured by Cognis Japan)
Conforms to Jeongwon, solid.
This product is derived from coconut oil, and its alkyl chain length distribution is as follows.
C ₁₆ 0.5% or less
C ₁₈ 5-15%
C ₂₀ 10-20%
C ₂₂ 70-80%
C ₂₄ 1% or less * Stearic acid: Stearic acid 100 (manufactured by Shin Nippon Rika Co., Ltd.)
Compliant with Jeongwon group.
* Monoglyceryl stearate: Riquemar S-100 (manufactured by Riken Vitamin Co., Ltd.)
Compliant with makeup regulations, white solid, mp62-68, HLB4.3.
* Monoglyceryl behenate: Riquemar B-100 (Riken Vitamin Co., Ltd.)
Compliant with makeup regulations, white solid, mp74-80, HLB4.2.
* Stearyl ether (EO11): EMALEX 611 (manufactured by Nippon Emulsion Co., Ltd.)
Compliant with makeup regulations, white wax, HLB11.
* Behenyl ether (EO10): EMALEX BHA-10 (manufactured by Nippon Emulsion Co., Ltd.)
Compliant with makeup regulations, white wax, HLB9.
* Solid paraffin (EO10): Solid paraffin (Nippon Seiki Co., Ltd.)
Compliant with the high melting point paraffin.
* Ethylene glycol distearate: Genapol PMS (manufactured by Clariant Japan)
This is an ethylene glycol distearate conforming to the makeup regulations and the mixing ratio of C ₁₆ and C ₁₈ is 6: 4.
In order to improve the dispersibility in the shampoo, the blending method of the raw material in the shampoo is preliminarily 20% POE alkyl ether sodium sulfate aqueous solution, coconut oil fatty acid diethanolamide 25% with respect to a mass ratio of 25% of the raw material. A dispersion was prepared by mixing 30% water at about 80 ° C., and the dispersion was added to the shampoo solution.
* Coconut oil fatty acid diethanolamide: CDE-100 (manufactured by Kawaken Fine Chemical Co., Ltd.) was used.
Conforms to the makeup base coconut oil fatty acid diethanolamide.
* POE (20) hydrogenated castor oil: CW-20-90 (Aoki Yushi Kogyo Co., Ltd.)
A polyoxyethylene hydrogenated castor oil based on the makeup base, an aqueous solution with a pure content of about 90%. In the table, the equivalent amount of POE (20) hydrogenated castor oil is shown.

* Polyoxyethylene lauryl ether sulfate Na: Sodium POE alkyl ether sulfate (manufactured by Lion Corporation)
A polyoxyethylene alkyl (12, 13) ether sodium sulfate solution (3E.O.) in accordance with the makeup regulations and an aqueous solution having a pure content of about 27%. In the table, the equivalent amount of pure POE alkyl ether sodium sulfate is shown.
* Sodium tetradecene sulfonate: sodium tetradecene sulfonate (manufactured by Lion Corporation)
An aqueous solution containing sodium hydroxyalkane sulfonate with a pure content of about 35%, which is a sodium tetradecene sulfonate solution conforming to the cosmetic regulations. In the table, the amount corresponding to the pure content of sodium tetradecenesulfonate was described.
* Lauric acid amidopropyl betaine: Enacol N30B (manufactured by Lion Corporation)
An aqueous solution of approximately 30% pure lauric acid amidopropyl betaine solution that conforms to the cosmetic regulations. In the table, the amount corresponding to the pure content of amidopropyl betaine laurate is shown.
* Lauryldimethylaminoacetic acid betaine: Obazoline LB-SF (manufactured by Toho Chemical Industry Co., Ltd.)
An aqueous solution with a purity of about 35% based on Jeongwon. In the table, the equivalent amount of pure lauryldimethylaminoacetic acid betaine is shown.
* Laurylhydroxysulfobetaine: Anhithol 20HD (manufactured by Kao Corporation)
An aqueous solution of about 30% pure lauryl hydroxysulfobetaine solution according to the cosmetic regulations. In the table, the equivalent amount of pure lauryl hydroxysulfobetaine is shown.
* Alkylpoly (8-16) glucoside: PLANTACARE 818UP (manufactured by Cognis Japan)
Alkyl poly (8-16) glucoside according to the cosmetic regulations and a liquid with a pure content of about 52%. In the table, the amount corresponding to the pure content of alkylpoly (8-16) glucoside is shown.
This product is derived from coconut oil, and its alkyl chain length distribution is as follows.
C ₈ 24-30%
C ₁₀ 15-22%
C ₁₂ 37-42%
C ₁₄ 12-18%
C ₁₆ 4% or less

* Bentonite: Kunipia F (Kunimine Industry Co., Ltd.)
Compliant with Jeongwon group.
* Synthetic bentonite: Smecton SA (Kunimine Industry Co., Ltd.)
Compliant with Jeongwon
* Lauryldimethylamine oxide: Aromox DM12D-W (manufactured by Lion Corporation)
A lauryl dimethylamine oxide solution that conforms to the makeup regulations and an aqueous solution having a pure content of about 33%. In the table, the equivalent amount of lauryl dimethylamine oxide is shown.
* Dimethyl silicone (100,000 cSt): Rheoflow DMS-55 (manufactured by Lion Corporation), refractive index 1.404
Highly polymerized methylpolysiloxane having a viscosity of 100,000 cSt and an average molecular weight of about 130,000 according to the cosmetic regulations is mechanically applied with POE (15) cetyl ether according to the cosmetic raw material standards (hereinafter referred to as “Morning basic group”). Emulsified and dispersed in water, dimethyl silicone concentration is about 55%. The average particle diameter of dimethyl silicone in the aqueous dispersion is about 0.5 μm. The table shows the equivalent amount of dimethyl silicone.
* Dimethyl silicone (1000000 cSt): BY22-050A (manufactured by Toray Dow Corning), refractive index 1.404
* Dimethyl silicone (10000000 cSt): BY22-055 (manufactured by Toray Dow Corning Co., Ltd.), refractive index 1.400
* Amino-modified silicone: SM8704C (manufactured by Dow Corning Toray)
Amodimethicone aqueous dispersion conforming to cosmetic regulations and concentration of amino-modified silicone is about 40%. The average particle size of the amino-modified silicone in the aqueous dispersion is about 0.1 μm. The table shows the equivalent amount of amino-modified silicone. Refractive index 1.405
* Polyether-modified silicone (polyoxyethylene / methylpolysiloxane copolymer): SH3775M (manufactured by Dow Corning Toray Co., Ltd.), refractive index 1.423
Compliant with makeup regulations.
* Cationized cellulose: XE-511K (manufactured by Lion Corporation)
Conforms to O- [hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose chloride.
* Hydroxypropyl cellulose: HPC-SL (manufactured by Nippon Soda Co., Ltd.)
* Hydroxypropyl methylcellulose (1): Metroze 60SH-4000 (manufactured by Shin-Etsu Chemical Co., Ltd.), 29% by mass of methoxy group, 10% by mass of hydroxypropoxy group, 20 ° C., viscosity of 2% aqueous solution 4000 mPa · s
* Hydroxypropyl methylcellulose (2): Metroze 60SH-10000 (Shin-Etsu Chemical Co., Ltd., 29% by mass of methoxy group, 10% by mass of hydroxypropoxy group, 20 ° C., viscosity of 2% aqueous solution 10000 mPa · s
* Hydroxypropyl methylcellulose (3): Metroze 60SH-1500 (Shin-Etsu Chemical Co., Ltd.), 29% by mass of methoxy group, 10% by mass of hydroxypropoxy group, 20 ° C., 2% viscosity of aqueous solution 1500 mPa · s
* Hydroxypropyl methylcellulose (4): Metroze 65SH-400 (Shin-Etsu Chemical Co., Ltd., 29% by mass of methoxy group, 6% by mass of hydroxypropoxy group, 20 ° C., viscosity of 2% aqueous solution 400 mPa · s
* Xanthan gum: Monato gum DA (manufactured by Kelco)
* Highly polymerized PEG (polyethylene glycol): Polyox WSR 60K-CG (manufactured by Union Carbide Corp.)
* PEG (polyethylene glycol) distearate (150EO): EMALEX 6300 DI-ST (manufactured by Nippon Emulsion Co., Ltd.)
* Dimethyldiallylammonium chloride / acrylamide copolymer: Kayaacrylic resin MN-50 (manufactured by Nippon Kayaku Co., Ltd.)
A dimethyldiallylammonium chloride / acrylamide copolymer solution that conforms to the cosmetic regulations and is an aqueous solution with a pure content of about 5.5%.
The charging ratio of monomeric dimethyldiallylammonium chloride and acrylamide is about 1: 1. The table shows the equivalent amount of dimethyldiallylammonium chloride / acrylamide copolymer.

* Propylene glycol: Propylene glycol (Asahi Glass Co., Ltd.)
* Sorbitol: D-sorbite liquid (manufactured by Towa Kasei Kogyo Co., Ltd.)
An aqueous solution of approximately 60% pure sorbite solution that conforms to the makeup base. In the table, the equivalent amount of sorbitol is shown.
* Hydrolyzed collagen solution: Promois W-52 (manufactured by Seiwa Kasei Co., Ltd.)
Compliant with makeup regulations.
* Hydrolyzed silk fluid: Promois Silk 1000 (manufactured by Seiwa Kasei Co., Ltd.)
Compliant with makeup regulations.
* Hydrolyzed wheat protein: Clopepeptide W (manufactured by Croda Japan Co., Ltd.), GLUADIN WLM (manufactured by Cognis Japan Co., Ltd.)
Compliant with makeup regulations.
* Hydrolyzed wheat peptide A: GLUADIN WLM (manufactured by Cognis Japan), molecular weight 500
* Hydrolyzed wheat peptide B: GLUADIN W20 (manufactured by Cognis Japan Co., Ltd.), molecular weight 2000-5000
* Yellow No. 5: Yellow No. 5 (manufactured by Daiwa Kasei Co., Ltd.)
* Yellow No. 203: Quinoline Yellow WS-G (Chuo Synthetic Chemical Co., Ltd.)
* Red No. 106: Red No. 106 (manufactured by Hatake Kasei Co., Ltd.)
* Brown 201: Brown 201 (Made by Kasei Kasei Co., Ltd.)
* Green No. 3: Green No. 3 (Made by Kasei Chemical Co., Ltd.)
* Green 201: Green 201 (manufactured by Koyo Chemical Co., Ltd.)
* Methylparaben: (Yoshitomi Fine Chemical Co., Ltd.)
Compliant with Jeongwon group.
* Sodium benzoate: Sodium benzoate (BfGoodrich Kalama Inc.) based on the makeup base
* Methylchloroisothiazolinone, methylisothiazolinone KATHON CG (manufactured by Rohm and Haas Japan Co., Ltd.) conforming to cosmetic regulations. In the table, the blending amount of this liquid is described.
* Glycine: (Ajinomoto Co., Inc.)
Compliant with Jeongwon group.
* Arginine: (Ajinomoto Co., Inc.)
Compliant with Jeongwon group.
* Glutamic acid: (Ajinomoto Co., Inc.)
Dietary compliance.
* Citric acid: Ketchho Quesan L (Fuso Chemical Co., Ltd.) conforming to the base of citric acid and monohydrate
* Pyrrolidone carboxylic acid: (Ajinomoto Co., Inc.)
Compliant with Jeongwon group.
* Phosphoric acid: (Pure Chemical Co., Ltd.)
* Triisopropanolamine: (Mitsui Chemicals Fine Co., Ltd.)

* Fragrance The following fragrance was used.
mass%
Lemon oil 5%
10% sweet orange oil
Geranium oil 3%
Lavender oil 6%
Sandalwood oil 1%
Lilianal 5%
Nopylacetate 1%
Linalool 2%
Benzylbenzoate 2%
Benzyl salicylate 3%
β-ionone 2%
Methyl ionone 3%
Helional 2%
Hedion 8%
Iso E Super 3%
cis-3-hexenol 0.3%
Ligandlar 0.3%
Triplar 0.4%
Cyclamenaldehyde 1.5%
Hexylcinnamic aldehyde 6%
Belt fix 3%
Galaxolide 5%
Tonalid 6%
Vendor lid 1%
Vacdanol 0.5%
Cashmelan 2%
Musk T 1%
3% fruit base
Rose base 3%
Jasmine base 1%
Muge base 3%
Amber base 1%
Nonanal 10% dipropylene glycol solution 2%
Decanal 10% dipropylene glycol solution 1%
Methyl nonylaldehyde 10% dipropylene glycol solution 2%
Dipropylene glycol balance <br/> Total 100%

It is a block diagram which shows suitable embodiment of the apparatus used for the continuous partial quenching method which concerns on this invention. It is a chart when DSC measurement is performed for a shampoo composition having a typical composition.

Claims (10)

(A) 0.5 to 6% by mass of a cationic surfactant selected from alkyl quaternary ammonium salts represented by the following general formula (1) and guanidine derivatives represented by the following general formula (2) or salts thereof When,

(Wherein R ¹ , R ² , R ³ , and R ⁴ each represents an alkyl group, a hydroxyalkyl group, an alkenyl group, a polyalkylene oxide group, or a benzyl group, and R ¹ , R ² , R ³ , and R one or two alkyl groups of 10 to 24 carbon atoms of ^4, a hydroxyalkyl group or an alkenyl group and the remainder is a methyl group, an ethyl group, a benzyl group, or _{- (C 2 H 4 O)} q -H Or a polyalkylene oxide group represented by — (C ₃ H ₆ O) _r —H (where q and r are each an integer of 1 to 5), and these may be the same or different from each other. Z ^- represents an anion.)

(Wherein R ⁵ is a linear or branched alkyl group or alkenyl group having 1 to 21 carbon atoms, A is a linear or branched alkylene group or alkenylene group having 1 to 10 carbon atoms, and t is 1 And when t is 2 or more, A in each block may be different from each other.
(B ′) an oil content of 1.2 to 7.5% by mass that forms a liquid crystal structure alone with the component (A) selected from a linear alcohol having 16 to 22 carbon atoms and a fatty acid having 16 to 22 carbon atoms;
(B ″) an oil component selected from a condensate of an alcohol having 8 to 22 carbon atoms and a polyhydric alcohol and a condensate of a fatty acid having 8 to 24 carbon atoms and a polyhydric alcohol (except for those less than HLB4) When,
(C) An amphoteric surfactant or, if necessary, an anionic surfactant is contained, and (B ′) / [(A) + (B ′)] (mass ratio) is 0.35 to 0. 90, the compounding amount of the amphoteric surfactant and the anionic surfactant exceeds 2% by mass, provided that the anionic surfactant is less than 5% by mass, and the components (A) and (B ′) A shampoo composition characterized in that a liquid crystal structure formed from is dispersed in the composition.   The shampoo composition according to claim 1, wherein the liquid crystal structure has an average particle size of less than 20 µm.   The shampoo composition according to claim 1 or 2, further comprising (D) 0.01% by mass or more of a water-swellable clay mineral.   Furthermore, (E) amine oxide is contained, The shampoo composition of any one of Claims 1-3 characterized by the above-mentioned.   The shampoo composition according to any one of claims 1 to 4, further comprising (F) a silicone derivative having a refractive index of less than 1.46. Furthermore, as the (G) viscosity imparting agent, the following formula

(In the formula, the molecular terminal and R represent a hydrogen atom, a methyl group or a hydroxypropyl group.)
A methoxy group of 25 to 35% by mass and a hydroxypropoxy group of 5 to 15% by mass (provided that the total of the hydroxyl group, methoxy group and hydroxypropoxy group is 100% by mass). 6. The shampoo composition according to claim 1, comprising hydroxypropylmethylcellulose having a viscosity of 2 mass% aqueous solution at 20 ° C. of 2100 to 35000 mPa · s.   The shampoo composition according to any one of claims 1 to 6, wherein the shampoo composition is for colored hair.   A method for producing a shampoo composition, in which a liquid crystal structure formed with the components (A) and (B ′) as constituents is dispersed in an aqueous phase containing the component (C), the liquid crystal structure (A), (B ′) and the above component (B ″) are mixed with the aqueous phase containing the component (C) at a temperature equal to or higher than the crystallization temperature of the body component, and the resulting mixture is crystallized at the crystallization temperature. It cools from the above temperature, The manufacturing method of the shampoo composition of Claim 1 characterized by the above-mentioned.   9. The mixture is cooled from a temperature equal to or higher than a crystallization temperature by continuously extracting a part of the mixture, quenching the mixture, and returning the quenched product to the mixture. The manufacturing method as described.   Furthermore, the manufacturing method of Claim 8 or 9 including the process of mixing the (D) clay mineral disperse | distributed or swollen in water with the water phase containing (C) component.

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