JP4129645B2 - Shampoo composition - Google Patents

Description

  The present invention relates to a shampoo composition, and more particularly to a shampoo composition that can suppress a squeaky sensation during hair washing and can improve the finished feel of the hair after washing and drying.

  Hair that has been damaged by coloring or the like is more easily adsorbed with calcium in tap water than normal hair. For this reason, it is said that the softness and smoothness of the hair is easily reduced after the hair is washed and dried, and the accumulation of calcium in the hair is one of the factors that deteriorate the hair feel. Furthermore, the damaged hair has a problem that the hair is more squeaky than normal hair even during shampooing, and the cuticle is easily peeled off.

  As a method for removing the calcium salt adsorbed on the hair, a technique of blending a chelating agent in a shampoo has been proposed (see, for example, Patent Document 1: Japanese Patent Laid-Open No. 63-150213). However, in this method, although the softness and smoothness of the hair after washing and drying are improved, a further improvement effect is desired, and the suppression of squeaky feeling during washing is insufficient.

  On the other hand, as a method for suppressing the squeaky feeling during hair washing, a method of blending a cationic polymer compound in the composition in a shampoo based on a washing base such as an anionic surfactant is common. In addition, by forming and dispersing a liquid crystal structure composed mainly of a cationic surfactant and solid oil at room temperature in the shampoo composition, the liquid crystal is adsorbed to the hair when it is rinsed to give smoothness. (For example, refer patent document 2,3: Unexamined-Japanese-Patent No. 2001-181145, international publication 2004/045568 pamphlet).

  However, for hair damaged by repeated coloring or the like, it has been desired to further suppress the squeaky feeling at the time of shampooing and to improve the finished feel of the hair after shampooing and drying.

Japanese Patent Laid-Open No. 63-150213 JP 2001-181145 A International Publication No. 2004/045568 Pamphlet

  This invention is made | formed in view of the said situation, and it aims at providing the shampoo composition which can suppress the squeak feeling at the time of hair washing, and can improve the finishing touch of the hair after hair washing drying.

  As a result of intensive studies to achieve the above object, the present inventor has found that (A) a cationic surfactant selected from stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, and amidobutylguanidine acetate. (B) The content of the anionic surfactant in the shampoo composition containing a solid oil component at room temperature selected from stearyl alcohol, behenyl alcohol, hardened rapeseed oil alcohol, and myristyl alcohol is less than 5% by mass. (C) By using hydroxyethane diphosphonic acid in combination, the liquid crystal structure formed mainly of the component (A) and the component (B) is dispersed in the composition to form a shampoo composition. Damage due to coloring, etc. Knowledge that drastically improves squeezing of shampooed hair and suppresses peeling of the cuticle while removing residual calcium to suppress squeaky sensation at the time of shampooing and improve the finish of the hair after it has been dried. However, the present invention has been achieved.

Therefore, the present invention
[1]. Cationic surfactant selected from stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, and lauric acid amide butyl guanidine acetate, (B) selected from stearyl alcohol, behenyl alcohol, hardened rapeseed oil alcohol, and myristyl alcohol A solid oil component at room temperature and (C) hydroxyethanediphosphonic acid, and an anionic surfactant content of less than 5% by mass, comprising mainly the component (A) and the component (B). Provided is a shampoo composition in which a liquid crystal structure formed as a component is dispersed in the composition.

  ADVANTAGE OF THE INVENTION According to this invention, the shampoo composition which suppresses the squeak feeling at the time of hair washing and improves the finishing touch of the hair after hair washing drying can be provided.

  The component (A) is a cationic surfactant and is not particularly limited as long as it can be blended into a shampoo composition, and may be used alone or in combination of two or more. it can. As the cationic surfactant, for example, an alkyl quaternary ammonium salt represented by the following general formula (1) 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、−（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シド基であり、これらは互いに同一であっても異なっていてもよい。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, — (C ₃ H ₆ O) _r —H (where q and r are each an integer of 1 to 5), and these 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. Of these, the hydrochloride and bromate forms are preferred.

  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.

  Moreover, the guanidine derivative represented by following General formula (2) or its salt can also be used suitably as a cationic surfactant.

（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。）

(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, citrate 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 used.

  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, 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、より好ましくは１３〜２２の脂肪酸残基であり、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. 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 diethylaminopropylamide, dimethylaminopropyl amides behenic acid. Among these, stearic acid dimethylaminopropylamide, stearic acid diethylaminoethylamide, behenic acid diethylaminoethylamide, and behenic acid dimethylaminopropylamide are preferably used.

  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 1 type individually or in combination of 2 or more types.

  Although the compounding quantity of the cationic surfactant of (A) component of this invention is not restrict | limited in particular, 0.05-7 mass% is preferable in the shampoo composition of this invention. If the blending amount is too small, there may be a case where sufficient smoothness and flexibility cannot be imparted to the hair during rinsing. On the other hand, if the amount is too large, the hair may become sticky.

  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 thereof is set to 0.00 in the shampoo composition. The range of 05-6 mass% is preferable, More preferably, it is 0.5-4 mass%.

  When an amino acid 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 to 5% by mass in the shampoo composition, more Preferably it is 0.3-3 mass%.

  When mix | blending an amidoamine type surfactant, the compounding quantity is 0.1-7 mass% in a shampoo composition, More preferably, it is 0.5-5 mass%.

  The component (B) is an oil component that is solid at normal temperature, and the type thereof is not particularly limited as long as it can be blended into the shampoo composition, and these may be used alone or in appropriate combination of two or more. it can. In addition, normal temperature means 20-30 degreeC. Specifically, higher alcohols such as cetostearyl alcohol, cetyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnervir alcohol, ceryl alcohol, cholesterol, phytosterol, hexaglycerin monostearate, decaglycerin tristearate, mono Diglyceryl stearate, monoglyceryl monostearate, hexaglycerin hexastearate, hexaglycerin octastearate, hexaglycerin triisostearate, hexaglycerin pentastearate, decaglycerin pentastearate, decaglycerin decastearate, pentabehenic acid Decaglycerin, pentaglycerin trioleate, pentaglycerin tristearate, tribehenine Polyglycerin fatty acids such as pentaglycerin, tetrabehenic acid pentaglycerin, pentabehenic acid pentaglycerin, dibehenic acid triglycerin, tribehenic acid triglycerin, tetrabehenic acid triglycerin, hexastearic acid pentaglycerin, tristearic acid tetraglycerin, pentastearic acid tetraglycerin Examples thereof include petroleum waxes such as esters, paraffin wax and microcrystalline wax, plant waxes such as carnauba wax and candelilla wax, beeswax and ceresin.

  Among these, in the component (A) and the composition, an oil component capable of forming a liquid crystal structure alone is preferable, and specific examples include higher alcohols having a melting point of 45 ° C. or higher, more preferably 45 to 75 ° C.

  Examples of the higher alcohol having a melting point of 45 ° C. or higher include alcohols having a linear alkyl group or alkenyl group having 14 to 26 carbon atoms, and specifically include cetostearyl alcohol, cetyl alcohol, stearyl alcohol, arachi Suitable examples include alcohol, behenyl alcohol, carnervir alcohol, and seryl alcohol. A higher alcohol having a melting point of less than 45 ° C can be used in combination, but in this case, the melting point of the higher alcohol mixture is preferably 45 ° C or more.

  In the shampoo composition of the present invention, it is preferable that a liquid crystal structure formed mainly of the component (A) and the component (B) is dispersed in the composition. In forming the liquid crystal structure, the ratio of the component (A) to the component (B) is important. The mass ratio of the component (A) and the component (B) in the shampoo composition is preferably (B) / [(A) + (B)], preferably 0.35 to 0.90, more preferably 0.5. ~ 0.90. When the mass ratio is less than 0.35 or exceeds 0.90, the squeeze improvement at the time of rinsing may be weak.

The most preferable combination of the component (A) and the component (B) includes the following.
(I) (B) / [(A) + (B)] = in the combination of (A) a C ₁₆ -C ₂₂ monoalkyl cationic surfactant and (B) a higher alcohol of C ₁₆ -C ₂₂ 0.6-0.8
(Ii) (B) / [(A) + (B)] = 0 in the combination of (A) a C ₁₆ -C ₂₂ dialkyl cationic surfactant and (B) a higher alcohol of C ₁₆ -C ₂₂ .5 to 0.7

  (B) As for the compounding quantity of a component, 0.5-10 mass% is preferable normally in a shampoo composition, More preferably, it is 2-10 mass%. When the blending amount is less than 0.5% by mass, the feeling of use may be insufficient, while when it exceeds 10% by mass, the temporal stability of the composition may be deteriorated.

  The component (C) is a metal sequestering agent, and the type thereof is not particularly limited as long as it can be blended in the shampoo composition, and can be used alone or in combination of two or more. Examples of the sequestering agent include hydroxyethanediphosphonic acid and its salt, aminocarboxylic acid and its salt, phosphate, hydroxycarboxylic acid and its salt, ethylenediaminetetraacetic acid and its salt, dihydroxyethylglycine and its salt, tartaric acid, Examples include succinic acid, gluconic acid, sodium polyphosphate, sodium metaphosphate, and the like. Among these, hydroxyethane diphosphonic acid and its salt, aminocarboxylic acid and its salt, phosphate, hydroxycarboxylic acid and its salt are preferable, and hydroxyethane diphosphonic acid (HEDP) is particularly preferable.

  (C) As for the compounding quantity of a component, 0.01-5 mass% is preferable in a shampoo composition, More preferably, it is 0.1-1 mass%.

  In addition to the cationic surfactant, the shampoo composition of the present invention can contain a detersive surfactant such as an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant. These can be used individually by 1 type or in combination of 2 or more types.

  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-arginate are preferred.

  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 alkanolamide, fatty acid monoethanolamide, sucrose fatty acid ester, alkyl glycoside, alkyl glyceryl glycoside, methyl glucoside fatty acid ester and the like.

  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.

  The blending amount of the detersive surfactant is preferably 2% by mass or more, and more preferably 10% by mass or more. Although the upper limit of the compounding amount of the detersive surfactant is not particularly limited, it is usually 30% by mass. In this, content of an anionic surfactant is less than 5 mass%, More preferably, it is 2 mass% or less, and an anionic surfactant does not need to be contained in a shampoo composition. By setting the amount of the anionic surfactant within this range, the effect of using the components (A), (B) and (C) together is enhanced, and the dispersion stability of the formed liquid crystal structure is improved.

  The shampoo composition of the present invention is generally used in the shampoo composition as necessary, in addition to the above essential components, detersive surfactant and purified water, as long as the effects of the present invention are not impaired. It is possible to mix various additive components.

  As various additive components, for example, inorganic salts such as silicone compounds, polyols, sodium chloride and sodium sulfate, organic salts, humectants such as propylene glycol, tonic agents, solubilizers, antioxidants such as BHT and α-tocopherol, Bactericides such as triclosan and trichlorocarban, UV absorbers, antioxidants, protein derivatives, animal and plant extracts, antidandruff agents such as piroctone olamine and zinc pyrithione, anti-inflammatory agents such as dipotassium glycyrrhizinate, benzoic acid and its salts , Parabens, preservatives such as caisson CG, pH adjusters such as citric acid and triethanolamine, pearlizing agents such as ethylene glycol difatty acid esters, emulsions, hydrotropes, lower alcohols, vitamins, volatile oils , Hydrophobic solvent, dilutable solvent, pigment, fragrance, etc. can be added arbitrarilyThese additive components can be used singly or in appropriate combination of two or more, and can be blended as long as the effects of the shampoo composition of the present invention are not impaired.

  The type of the silicone compound is not particularly limited, and those normally 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.

In addition, although the viscosity etc. in particular are not restrict | limited for these silicone compounds, Usually, the viscosity in 25 degreeC is 1-20,000,000 mm < ² > / s, Preferably it is 30-100,000,000 mm < ² >. / S is preferably used.

  Further, as the silicone compound, those obtained by emulsifying the silicone compound with a surfactant and emulsifying it can also be used. In addition, there is no restriction | limiting in particular in an emulsifier and the emulsification method, and such an emulsion can be used variously.

  Examples of the fragrance and fragrance composition used in the present invention include the fragrance components described in paragraph numbers [0021] to [0035] of JP-A-2003-300121, the fragrance solvent described in [0050], and the like. . The amount of the perfume solvent used is 0.1 to 99% by mass, preferably 1 to 50% by mass in the perfume composition.

  Examples of the fragrance stabilizer include dibutylhydroxytoluene, butylhydroxyanisole, vitamin E and its derivatives, catechin compounds, flavonoid compounds, polyphenol compounds and the like, and 0.0001 to 10% by mass is added to the fragrance composition. However, 0.001-5 mass% is preferably blended. Among these, a preferable stabilizer is dibutylhydroxytoluene.

  The fragrance composition is a mixture composed of the above fragrance components, a solvent, a fragrance stabilizer and the like. Such a fragrance composition is blended in the composition of the present invention in an amount of 0.005 to 40% by mass, preferably 0.01 to 10% by mass in the shampoo composition.

  In the shampoo composition of the present invention, it is preferable that a liquid crystal structure formed mainly of the component (A) and the component (B) is dispersed in the composition. Dispersion of the liquid crystal structure in the composition improves the squeak during shampoo rinsing, particularly the intense squeaky feeling of colored hair. “Forming as a main component” means that the liquid crystal structure is formed of the component (A) and the component (B), but in addition to these 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.

  The shampoo composition of this invention can be prepared according to the method as described in Unexamined-Japanese-Patent No. 2001-311099. More specifically, an aqueous phase containing a detersive surfactant and (C) a sequestering agent, (A) a cationic surfactant and (B) a solid oil at room temperature to the melting point of the component (B) A method of mixing the oil phases dissolved together at 40 to 85 ° C. and cooling the resulting mixture is preferred.

  Examples of the container of the shampoo composition of the present invention include aluminum laminate 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, laminate 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 for the bottle, polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyvinyl chloride, ethylene-vinyl alcohol resin, acrylonitrile / styrene resin, ABS resin, polyamide, etc., glass, etc. can be used in combination with a charcoal layer or two or more layers. .

  The method of using the shampoo composition of the present invention is not particularly limited, and a normal dose of the shampoo composition can be used according to a conventional method.

  EXAMPLES Hereinafter, although an Example, a reference example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, unless otherwise specified, “%” in the composition represents mass%.

[Examples 1-5, Reference Examples 1-5, Comparative Examples 1-10]
Shampoo compositions having the compositions shown in Tables 1 to 4 were prepared by the following production method. The obtained shampoo composition was evaluated by the following method. The results are also shown in Tables 1-4.

Manufacturing method [1]. The oil-soluble components (A) and (B) were dissolved by heating at 45 to 80 ° C. to prepare an oil phase.
[2]. The component (C), the detersive surfactant and other components were stirred and dissolved in purified water at room temperature to 80 ° C. to prepare an aqueous phase.
[3]. Add the oil phase obtained in [1] to the aqueous phase obtained in [2], stir and mix with a paddle mixer at a temperature of 40 to 80 ° C., gradually cool to room temperature while stirring, and adjust the pH as necessary. The shampoo composition was obtained by adjusting.

  In the shampoo compositions of Examples 1 to 5 and Reference Examples 1 to 5 prepared by the above production method, regular diffraction patterns were 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 cryoscanning electron microscope, the thin layers were overlapped. From this, it was recognized that the shampoo compositions of Examples 1 to 5 and Reference Examples 1 to 5 were those in which the liquid crystal structures were dispersed.

Evaluation method and evaluation criteria [1]. A feeling of squeak when shampooing
<Method>
Evaluation was performed on 10 female panelists with short to semi-long hair dyed brown. A panelist used the shampoo composition for 10 days, and evaluated the squeaky feeling during rinsing based on the following score. In the table, the total score of 10 people is shown by the following evaluation criteria. In-bath products such as rinse / conditioner used after shampooing and out-bath products such as styling agents and hair care agents were used as they were everyday.

<Score>
+2 points: Very good, +1 point: Somewhat good, -1 point: Somewhat bad, -2 point: Very bad
<Evaluation criteria>
No squeak when shampoo rinse ◎: Total score is 15 or more ◎ ~ ○: 14 to 10 points ○: Total score is 9 to 5 points △: Total score is 4 to 0 points Δ ~ ×: Total score is -1 -4 points x: The total score is -5 points or less

[2]. Evaluation of calcium removal effect by shampoo
<Method>
A hair bundle (length 30 cm, 10 g) of damaged hair (perm once, bleach 2 times) was repeatedly washed with 1 g of shampoo composition 7 times. The amount of residual calcium in the hair after this hair washing treatment was quantified. The amount of calcium remaining in the hair was measured by adding an acid to the hair collected in a certain amount to hydrolyze it, and analyzing this by ICP emission analysis. From the obtained amount of calcium, the calcium residual rate was converted with the amount of calcium in the blank hair before the hair washing treatment as 100%. The correlation between the remaining amount of calcium and the softness of the hair has been confirmed, and the parentheses in the parentheses in the following evaluation criteria indicate the sensory evaluation level of the softness with respect to the blank hair.
<Evaluation criteria>
Calcium remaining rate (softness of hair)
A: Less than 70% (feels softer than blank hair)
○: Less than 70 to 100% (feels slightly softer than blank hair)
Δ: 100% (softness does not change compared to blank hair)
×: More than 100% (feels harder than blank hair)

The shampoo compositions obtained in the above examples, reference examples and comparative examples were filled in the following containers. 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: Material PP Cap: Material PP
<2> Bottle: Material HDPE Cap: Material PP
<3> Bottle: 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: HDPE Dispenser: Materials PP, PE and SUS304
<7> Bottle: PET Dispenser: Materials PP, PE and SUS304
<8> Bottle part: PP / HDPE Dispenser part: Material used PP, PE and SUS304
<Pouch container>
<9> Material Aluminum-deposited polyethylene pouch

  Hereinafter, shampoo compositions having the compositions shown in Examples 6 to 8 were prepared in the same manner as in Example 1. The same evaluation was performed by X-ray diffraction and the like in the same manner as in Example 1. All of the shampoo compositions of Examples 6 to 8 were found to have a liquid crystal structure dispersed therein, and good results were obtained with respect to the absence of squeaking and the calcium residual ratio during rinsing.

[Example 6]
Composition Mass%
Behenyltrimethylammonium chloride 2.5
Behenyl alcohol 6.0 Hydroxyethane diphosphonic acid 0.1
Amidopropyl betaine laurate 12.0
Lauric acid amidopropyl hydroxysulfobetaine * 53 2.0
Acyl glutamic acid triethanolamine * 54 0.5
Lauryldimethylamine oxide 1.0
POE (2) Lauric acid monoethanolamide 3.0
Behenyl ether (10EO) 0.3
Polyethylene glycol monostearate * 55 0.2
Glyceryl monolaurate * 56 1.0
Bentonite 0.3
Dimethyl silicone emulsion * 57 1.0
Amino-modified silicone (SM8704C) 0.2
Sodium benzoate 1.0
Ethylene glycol distearate 2.0
Arginine 0.5
Propylene glycol 10.0
Polyethylene glycol * 58 3.0
Plant mixed extract A * 59 0.3
Plant mixed extract B * 60 0.3
Birch extract * 61 0.3
Yellow No. 203 0.001
Yellow No. 5 0.002
Fragrance A 0.5
Citric acid 0.45
Total 100.0

[Example 7]
Composition Mass%
Behenyltrimethylammonium chloride 2.5
Behenyl alcohol 5.0
Sodium polyphosphate 0.5
Amidopropyl betaine laurate 8.0
Lauryldimethylaminoacetic acid betaine 4.0
Lauryl dihydroxyethylamine oxide 1.0
Glyceryl monolaurate * 56 2.0
Dimethyl silicone emulsion * 57 1.0
Hydroxypropyl methylcellulose 0.1
Bentonite 0.3
Piroctone olamine * 62 0.3
Sodium benzoate 0.7
Trimethylglycine * 63 0.5
Glycerin 1.0
Dibutylhydroxytoluene 0.01
Oxybenson 0.1
Yellow No. 203 0.001
Yellow No. 5 0.002
Fragrance B 0.5
Citric acid 0.5
Total 100.0

[Example 8]
Composition Mass%
Behenyltrimethylammonium chloride 1.5
Behenic acid dimethylaminopropylamide 1.0
Behenyl alcohol 6.0
Edetic acid disodium 0.5
Amidopropyl betaine laurate 12.0
Sodium POE alkyl sulfosuccinate * 64 0.5
Lauryldimethylamine oxide 1.0
Glyceryl monolaurate 2.0
Dimethyl silicone emulsion * 57 1.0
Cationized guar gum * 65 0.1
Sodium benzoate 0.7
2-ethylhexyl methoxycinnamate * 66 0.5
Glycerin 1.0
Dibutylhydroxytoluene 0.01
Oxybenson 0.1
Glycolic acid * 67 0.5
Citric acid 0.5
Fragrance C 0.5
Total 100.0

In addition, the following were used for Examples 1-8, Reference Examples 1-5, and Comparative Examples 1-10.
* 1 Stearyl trimethyl ammonium 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.
* 2 Behenyltrimethylammonium 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 * 3 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 having C ₁₈ F ₀ : C ₁₈ F ₁ = 75: 25.
* 4 Lauric acid amidobutyl guanidine 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.
* 5 Stearyl alcohol: Conol 30SS (manufactured by New Japan Science Co., Ltd.)
Conformity standard * 6 Behenyl alcohol: LANETTE 22 (manufactured by Cognis Japan Co., Ltd.)
Jeongwon based, 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 * 7 Cured 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 * 8 Myristyl alcohol: Conol 1495 (manufactured by Shin Nippon Rika Co., Ltd.)
* 9 Lauryl alcohol: Conol 20L (manufactured by Shin Nippon Rika Co., Ltd.)
Compliant with Jeongwon group.
* 10 Oleyl alcohol: Angersol 90NR (manufactured by Shin Nippon Rika Co., Ltd.)
* 11 Hydroxyethane diphosphonic acid: Ferriox 115 (manufactured by Lion Corporation)
* 12 Edetate disodium: Dissolvin NA2 (manufactured by Akzo Nobel)
* 13 Sodium polyphosphate: Sodium polyphosphate (manufactured by Iwase Cospha)
* 14 Succinic acid: Succinic acid (manufactured by Iwase Cospha)
* 15 Monoglyceryl stearate: Riquemar S-100 (Riken Vitamin Co., Ltd.)
Compliant with makeup regulations, white solid, mp62-68, HLB4.3.
* 16 Monoglyceryl behenate: Riquemar B-100 (manufactured by Riken Vitamin Co., Ltd.)
Compliant with makeup regulations, white solid, mp74-80, HLB4.2.
* 17 Stearyl ether (EO11): EMALEX 611 (manufactured by Nippon Emulsion Co., Ltd.)
Compliant with makeup regulations, white wax, HLB11.
* 18 Behenyl ether (EO10): EMALEX BHA-10 (manufactured by Nippon Emulsion Co., Ltd.)
Compliant with makeup regulations, white wax, HLB9.
* 19 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.
* 20 Ethylene glycol distearate: Genapol PMS (manufactured by Clariant Japan Co., Ltd.)
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 composed of 25% POE alkyl ether sodium sulfate aqueous solution, coconut oil fatty acid diethanolamide 25% and 25% by mass 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.
* 21 Sodium polyoxyethylene lauryl ether sulfate: Sodium POE alkyl ether sulfate (manufactured by Lion Corporation)
A polyoxyethylene alkyl (carbon number 12, 13) ether sodium sulfate solution (3EO) that complies with the makeup regulations and an aqueous solution with a pure content of about 27%. In the table, the equivalent amount of pure POE alkyl ether sodium sulfate is shown.
* 22 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.
* 23 Laminic acid amidopropyl betaine: Enagicol L30B (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.
* 24 Lauryldimethylaminoacetic acid betaine: Obazoline LB-SF (manufactured by Toho Chemical Industry Co., Ltd.)
An aqueous solution with a pure content of about 35%, which conforms to the makeup base. In the table, the equivalent amount of pure lauryldimethylaminoacetic acid betaine is shown.
* 25 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.
* 26 Alkyl (carbon number 8-16) glucoside: PLANTACARE 818UP (manufactured by Cognis Japan Co., Ltd.)
Alkyl (carbon number 8-16) glucoside conforming to makeup regulations and liquid with a pure content of about 52%. In the table, the equivalent amount of pure alkyl (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 * 27 Bentonite: Kunipia F (Kunimine Industries Co., Ltd.)
Compliant with Jeongwon group.
* 28 Synthetic bentonite: Smecton SA (Kunimine Industry Co., Ltd.)
Compliant with Jeongwon group.
* 29 Hydroxypropyl cellulose: HPC-SL (Nippon Soda Co., Ltd.)
* 30 Xanthan gum: Monato gum DA (manufactured by Kelco)
* 31 Highly polymerized polyethylene glycol: Polyox WSR 60K-CG (manufactured by Union Carbide Corp.)
* 32 Polyethylene glycol distearate (150EO): EMALEX 6300 DI-ST (manufactured by Nippon Emulsion Co., Ltd.)
* 33 Dimethyl silicone: Leoflow DMS-55 (manufactured by Lion Corporation)
A highly polymerized methylpolysiloxane having a viscosity of 100,000 mm ² / s and an average molecular weight of about 130,000 in accordance with the cosmetic regulations is machined with POE (15) cetyl ether in accordance with the cosmetic raw material standards (hereinafter referred to as “the cosmetic base”). An aqueous dispersion emulsified and dispersed by force. The concentration of dimethyl silicone 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.
* 34 Polyoxyethylene / methylpolysiloxane copolymer: SH3775M (manufactured by Toray Dow Corning Silicone Co., Ltd.)
Compliant with makeup regulations.
* 35 Amino-modified silicone: SM8704C (Toray Dow Corning Silicone Co., Ltd.)
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.
* 36 Cation-modified silicone: X-52-2380 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 37 Coconut oil fatty acid diethanolamide: CDE-100 (manufactured by Kawaken Fine Chemical Co., Ltd.)
Conforms to the makeup base coconut oil fatty acid diethanolamide.
* 38 Polyoxyethylene (2) lauric acid monoethanolamide: Amidette 2L-Y (manufactured by Kawaken Fine Chemical Co., Ltd.) was used.
* 39 Cationized cellulose: XE-511K (manufactured by Lion Corporation)
Conforms to O- [hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose chloride.
* 40 Dimethyldiallylammonium chloride / acrylamide copolymer: Kayaacrylic resin MN-50 (manufactured by Nippon Kayaku Co., Ltd.)
A dimethyldiallylammonium chloride / acrylamide copolymer solution according to the makeup regulations, 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.
* 41 Propylene glycol: Propylene glycol (Asahi Glass Co., Ltd.)
* 42 Sorbitol: D-Sorbit liquid (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.
* 43 Hydrolyzed wheat protein solution: Clopepeptide W (manufactured by Croda Japan Co., Ltd.), GLUADIN WLM (manufactured by Cognis Japan Co., Ltd.)
Compliant with makeup regulations.
* 44 Diglucosyl gallic acid: Diglucosyl gallic acid (manufactured by Mitsui Chemicals, Inc.)
* 45 Methyl paraben: Methyl paraben (manufactured by Yoshitomi Fine Chemical Co., Ltd.)
Compliant with Jeongwon group.
* 46 Sodium benzoate: Sodium benzoate (BFGoodrich Kalama Inc.)
Compliant with Jeongwon group.
* 47 Methylchloroisothiazolinone, methylisothiazolinone solution: KATHON CG (manufactured by Rohm and Haas Japan Co., Ltd.)
Compliant with makeup regulations. In the table, the blending amount of this liquid is described.
* 48 Arginine: Arginine (Ajinomoto Co., Inc.)
Compliant with Jeongwon group.
* 49 Yellow No. 203: Quinoline Yellow WS-G (Chuo Synthetic Chemical Co., Ltd.)
* 50 Red 106: Red 106 (Made by Kasei Kasei Co., Ltd.)
* 51 Green No.3: Green No.3 (manufactured by Hatake Kasei Co., Ltd.)
* 52 Citric acid: Ketchou Quesan L (manufactured by Fuso Chemical Industry Co., Ltd.)
Conforms to Chengyuan group citric acid monohydrate.
* 53 Lauric acid amidopropyl hydroxysulfobetaine: Softazoline LSB (manufactured by Kawaken Fine Chemical Co., Ltd.)
An aqueous solution with a pure content of about 30%. The compounding amount described is a pure equivalent amount.
* 54 Acylglutamate triethanolamine: Amisoft CT-12 (Ajinomoto Co., Inc.)
* 55 Polyethylene glycol monostearate: Emalex 6300M-ST (manufactured by Nippon Emulsion Co., Ltd.)
* 56 Glyceryl monolaurate: MONOMULS 90-L12 (manufactured by Cognis Japan)
* 57 Dimethyl silicone emulsion: An aqueous dispersion of dimethicone in which a viscosity of 10 million / 4 million / 1,000 mm ² / s is mixed in a ratio of 15/15/70 mass%. The average particle diameter of dimethyl silicone in the aqueous dispersion is about 0.5 μm. The compounding amount described is the amount corresponding to the pure component of the total amount of dimethicone.
* 58 Polyethylene glycol: PEG300 (manufactured by Lion Corporation)
* 59 Plant mixed extract A: Falco Rex BX44 (manufactured by Ichimaru Falcos)
This mixed liquid is a 1,3-BG aqueous solution containing hypericum extract, chamomile extract, linden extract, ginseng extract, cornflower extract and roman chamomile extract.
* 60 Mixed plant extract B: Falco Rex BX46 (manufactured by Ichimaru Falcos)
This mixed solution is a 1,3-BG aqueous solution containing horsetail extract, hop extract, pine extract, lemon extract and rosemary extract.
* 61 Birch extract: Birch extract (C) (Ichimaru Falcos Co., Ltd.)
Compliant with makeup regulations.
* 62 Piroctone Olamine: Octopirox (manufactured by Clariant Japan Co., Ltd.)
* 63 Trimethylglycine: Trimethylglycine (Ajinomoto Co., Inc.)
* 64 Sodium POE alkylsulfosuccinate: Viewlite ESS (manufactured by Sanyo Chemical Co., Ltd.)
* 65 Cationized guar gum: Labor gum CG-M6L (Dainippon Pharmaceutical Co., Ltd.)
* 66 2-ethylhexyl methoxycinnamate: Neo Heliopan AV (manufactured by Haamann & Reimer)
* 67 Glycolic acid: Gripure 70 (manufactured by DuPont)

  The fragrance | flavors AD used for the Example, the reference example, and the comparative example are as follows.

Claims (1)

  (A) a cationic surfactant selected from stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, and lauramidobutylguanidine acetate, (B) stearyl alcohol, behenyl alcohol, hardened rapeseed oil alcohol, and myristyl An oil component that is solid at room temperature selected from alcohol, and (C) hydroxyethanediphosphonic acid, the content of an anionic surfactant is less than 5% by mass, and the components (A) and (B) A shampoo composition in which a liquid crystal structure formed mainly as a main component is dispersed in a composition.