JP5502408B2 - Shampoo composition - Google Patents

Description

  The present invention prevents “entanglement at the time of shampooing” of hair damaged by repeated coloring, permanents, and excessive dryer drying, and eliminates “pasting after drying” and reduces “skin rustling”. It relates to a shampoo composition that can be made.

In recent years, there has been an increase in the number of women who perform chemical treatments such as coloring and perm, so that the hair is damaged, especially with wet hair, `` hairs tend to get tangled together '', and hair and split ends are likely to occur. I am worried about the dryness of hair after drying. In addition, the scalp is damaged by external stimuli such as drying, ultraviolet rays, and drugs used for coloring, and “scaling of the scalp” is felt.
As a means to solve such problems, by adding a cationic surfactant or higher alcohol, which is a rinse component, to the shampoo composition, the liquid crystal structure adsorbs to the hair and expresses smoothness when rinsing the hair. However, various techniques for suppressing the dryness of hair after drying and giving a smooth feel have been proposed.

  As such a shampoo composition, for example, a liquid crystal dispersion detergent composition comprising a cationic surfactant, a higher alcohol and a polyglycerin fatty acid ester (see Patent Document 1), a detergent composition such as an amphoteric surfactant, a cationic surfactant And a shampoo composition containing an oil for forming a liquid crystal structure (see Patent Document 2), a silicone compound, a poorly water-soluble liquid crystal structure, and a detersive surfactant containing an amphoteric surfactant (Patent Document 3) Etc.) have been proposed.

  However, each of the above prior art documents contains a preservative (paraben, benzoic acid or a salt thereof, etc.) in order to obtain long-term storage stability of the preparation, and therefore, for people with weak skin or people with dry skin. It is known that the stimulation is too strong and may cause skin disorders such as contact dermatitis and allergies (see Non-Patent Document 1). In addition, the effect of preventing “entanglement at the time of shampooing” of hair damaged by repeated coloring, perm, and excessive drying of the hair, eliminating “pasting after drying”, and reducing the “background scalp” It is not sufficient, and the current situation is that further improvement and development are desired.

JP 2001-311099 A JP 2004-292387 A JP 2004-262805 A

Ritsuko Hayakawa, “Contact Dermatitis”, Treatment, published January 1, 1996, Vol. 78, no. Special issue, p. 1461-1463

  An object of the present invention is to solve the conventional problems and achieve the following objects. In other words, the present invention prevents “entanglement at the time of shampooing” of hair damaged by repeated coloring, permanents, and excessive dryer drying, eliminates “pasting after drying”, and reduces “skin rustling”. It is an object of the present invention to provide a shampoo composition that is excellent in preservative power even if it contains no preservative (paraben, benzoic acid or its salt, etc.).

As a result of intensive studies by the present inventors in order to solve the above problems, (A) a cationic surfactant, (B) a long-chain aliphatic alcohol having 12 to 24 carbon atoms, and (C) 10 masses of an amphoteric surfactant. % To 30% by mass and (D) 8% to 30% by mass of glycerin, and the mass ratio of the component (C) to the component (D) [(D) / ((C) + (D)) ] From 0.30 to 0.70, from these synergistic effects, even if no preservative (paraben, benzoic acid or its salt, etc.) is added, it has excellent antiseptic power, prevents entanglement during hair washing, after drying It was found that a shampoo composition excellent in the lack of roughness and excellent in long-term storage stability of the preparation can be obtained.
Furthermore, it has been found that the effect of suppressing scuffing of the background is dramatically improved, preferably by adding an alkylamine oxide as component (E).

ただし、前記一般式（１）中、Ｒ^３及びＲ^４の少なくとも１つは、炭素数１２〜２８の直鎖又は分岐鎖のアルキル基又はアルケニル基である。Ｒ^３及びＲ^４のどちらか一方は、メチル基又はエチル基であり、これらは互いに同一であっても異なっていてもよい。Ｒ^５及びＲ^６は、メチル基又はエチル基である。Ｚ⁻は、アニオンを表す。
＜４＞ （Ｂ）成分の長鎖脂肪族アルコールの炭素数が１６〜２２である前記＜１＞から＜３＞のいずれかに記載のシャンプー組成物である。 The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> (A) Cationic surfactant, (B) Long chain aliphatic alcohol having 12 to 24 carbon atoms, (C) Amphoteric surfactant 10% by mass to 30% by mass, and (D) Glycerol 8% by mass Containing 30% by weight,
The shampoo composition, wherein a mass ratio [(D) / ((C) + (D))] of the component (C) and the component (D) is 0.30 to 0.70. .
<2> Further contains (E) alkylamine oxide 0.3 mass% to 5 mass%,
(D) It is a shampoo composition as described in <1> whose mass ratio [(D) / (E)] of the said (E) component is 5-40.
<3> The shampoo composition according to any one of <1> to <2>, wherein the cationic surfactant as the component (A) is a compound represented by the following general formula (1).

However, in the general formula (1), at least one of R ³ and R ⁴ is a linear or branched alkyl group or alkenyl group having 12 to 28 carbon atoms. One of R ³ and R ⁴ is a methyl group or an ethyl group, and these may be the same as or different from each other. R ⁵ and R ⁶ are a methyl group or an ethyl group. Z ⁻ represents an anion.
<4> The shampoo composition according to any one of <1> to <3>, wherein the long-chain aliphatic alcohol of component (B) has 16 to 22 carbon atoms.

  According to the present invention, various problems in the past can be solved, preventing entanglement of hair damaged by repeated coloring, permanents, and excessive dryer drying, and eliminating `` pasting after drying '' At the same time, it is possible to reduce the “background scalp”, and it is possible to provide a shampoo composition having an excellent antiseptic power even if a preservative (paraben, benzoic acid or a salt thereof, etc.) is not added.

  The shampoo composition of the present invention contains (A) a cationic surfactant, (B) a long-chain aliphatic alcohol, (C) an amphoteric surfactant, and (D) glycerin, (E) an alkylamine oxide, It contains other components as necessary.

<(A) Cationic surfactant>
The cationic surfactant of the component (A) is not particularly limited as long as it can be blended in the shampoo composition, and may be used alone or in combination of two or more. Among these, a cationic surfactant having a hydrocarbon group having 12 or more carbon atoms is preferable.
The hydrocarbon group having 12 or more carbon atoms may be divided by a functional group such as —O—, —CONH—, and —COO—, and the carbon number of 12 includes —CONH—, —COO—, and the like. Contains the carbon number of the functional group.

  The cationic surfactant of the component (A) is usually contained in the form of a salt, specifically, inorganic salts such as hydrochloride, bromate, sulfate, phosphate, etc .; glycolate, acetate And organic acid salts such as lactate, succinate, tartrate, citrate, acidic amino acid salt, higher fatty acid salt, pyroglutamate and p-toluenesulfonate.

  The cationic surfactant having a hydrocarbon group having 12 or more carbon atoms is not particularly limited as long as it can be blended in a shampoo composition, and can be appropriately selected according to the purpose. ) Quaternary ammonium salt, (2) quaternary ammonium salt containing 1 to 3 ester groups in the molecule, (3) amidoamine type surfactant, (4) amine type surfactant, (5) guanidine derivative Or a salt thereof, (6) an amino acid cationic surfactant, and the like.

前記一般式（１）において、Ｒ^３及びＲ^４の少なくとも１つは、炭素数１２〜２８、好ましくは１６〜２４、より好ましくは炭素数２２の直鎖又は分岐鎖のアルキル基又はアルケニル基であり、直鎖アルキル基が特に好ましい。Ｒ^３及びＲ^４のどちらか一方は、メチル基又はエチル基であってもよく、これらは互いに同一であっても異なっていてもよい。
Ｒ^５及びＲ^６は、いずれもメチル基又はエチル基である。
Ｚ⁻は、アニオンを表し、例えば、ＣＨ_３ＳＯ_４ ⁻、Ｃ_２Ｈ_５ＳＯ_４ ⁻、Ｃｌ⁻、Ｂｒ⁻等が挙げられる。 -Quaternary ammonium salt-
As said quaternary ammonium salt, the compound represented by following General formula (1) is suitable.

In the general formula (1), at least one of R ³ and R ⁴ is a linear or branched alkyl group or alkenyl group having 12 to 28 carbon atoms, preferably 16 to 24 carbon atoms, more preferably 22 carbon atoms. And straight chain alkyl groups are particularly preferred. Either one of R ³ and R ⁴ may be a methyl group or an ethyl group, and these may be the same as or different from each other.
R ⁵ and R ⁶ are both methyl groups or ethyl groups.
Z ⁻ represents an anion, and examples thereof include CH ₃ SO ₄ ⁻ , C ₂ H ₅ SO ₄ ⁻ , Cl ⁻ and Br ⁻ .

  Examples of the quaternary ammonium salt represented by the general formula (1) include behenyltrimethylammonium chloride and dibehenyldimethylammonium chloride.

前記一般式（２）において、Ｒ^７は、炭素数１２〜２６であり、エステル基を１つ含む直鎖又は分岐鎖のアルキル基又はアルケニル基である。
Ｒ^８は、メチル基、エチル基、又は炭素数１〜４のヒドロキシアルキル基を示し、該Ｒ^８は、互いに同一であっても異なっていてもよい。
Ｘ⁻は、アニオンを示し、例えばＣＨ_３ＳＯ_４ ⁻、Ｃ_２Ｈ_５ＳＯ_４ ⁻、Ｃｌ⁻、Ｂｒ⁻等が挙げられる。 -Quaternary ammonium salt containing 1 to 3 ester groups in the molecule-
Examples of the quaternary ammonium salt containing one ester group in the molecule include compounds represented by the following general formula (2).

In the general formula (2), R ⁷ is a linear or branched alkyl group or alkenyl group having 12 to 26 carbon atoms and including one ester group.
R ⁸ represents a methyl group, an ethyl group, or a hydroxyalkyl group having 1 to 4 carbon atoms, and R ⁸ may be the same as or different from each other.
Among X ^- denotes an anion, for example, _{^{CH 3 SO 4 -, C 2}} H 5 SO 4 -, Cl -, Br - , and the like.

前記一般式（３）において、Ｒ^９は、直鎖又は分岐鎖の炭素数９〜２３のアルキル基又はアルケニル基を示し、該Ｒ^９としては、直鎖の炭素数１３〜２１のアルキル基又はアルケニル基が好ましい。具体的には、ステアリン酸、パルミチン酸、ミリスチン酸、オレイン酸、エライジン酸等の脂肪酸からカルボキシル基を除いた残基であることが好ましい。 The quaternary ammonium salt containing one ester group in the molecule is preferably a compound represented by the following general formula (3).

In the general formula (3), R ⁹ represents a linear or branched alkyl group or alkenyl group having ^{9 to} 23 carbon atoms, and as R ⁹ , the linear alkyl group having 13 to 21 carbon atoms or Alkenyl groups are preferred. Specifically, a residue obtained by removing a carboxyl group from a fatty acid such as stearic acid, palmitic acid, myristic acid, oleic acid, and elaidic acid is preferable.

前記一般式（４）において、Ｒ^７、Ｒ^８、及びＸ⁻は、前記一般式（２）と同じ意味を示す。Ｒ^７及びＲ^８は、それぞれ互いに同一であっても異なっていてもよい。 Examples of the quaternary ammonium salt containing two ester groups in the molecule include compounds represented by the following general formula (4).

In the said General formula (4), R < ⁷ >, R < ⁸ > and X < ^- > show the same meaning as the said General formula (2). R ⁷ and R ⁸ may be the same as or different from each other.

前記一般式（５）において、Ｒ^９は、前記一般式（３）と同じ意味を示す。Ｒ^９は互いに同一であっても異なっていてもよく、直鎖の炭素数１３〜２１のアルキル基又はアルケニル基が好ましい。具体的には、ステアリン酸、パルミチン酸、ミリスチン酸、オレイン酸、エライジン酸等の脂肪酸からカルボキシル基を除いた残基であることが好ましい。 The quaternary ammonium salt containing two ester groups in the molecule is preferably a compound represented by the following general formula (5).

In the general formula (5), R ⁹ has the same meaning as in the general formula (3). R ⁹ may be the same as or different from each other, and is preferably a linear alkyl group or alkenyl group having 13 to 21 carbon atoms. Specifically, a residue obtained by removing a carboxyl group from a fatty acid such as stearic acid, palmitic acid, myristic acid, oleic acid, and elaidic acid is preferable.

前記一般式（６）において、Ｒ^７、Ｒ^８、及びＸ⁻は、前記一般式（２）と同じ意味を示す。Ｒ^７は、互いに同一であっても異なっていてもよい。 Examples of the quaternary ammonium salt containing three ester groups in the molecule include compounds represented by the following general formula (6).

In the said General formula (6), R < ⁷ >, R < ⁸ > and X < ^- > show the same meaning as the said General formula (2). R ⁷ may be the same as or different from each other.

前記一般式（７）において、Ｒ^９は、前記一般式（３）と同じ意味を示す。Ｒ^９は、互いに同一であっても異なっていてもよく、直鎖の炭素数１３〜２１のアルキル基又はアルケニル基が好ましい。具体的には、ステアリン酸、パルミチン酸、ミリスチン酸、オレイン酸、エライジン酸等の脂肪酸からカルボキシル基を除いた残基であることが好ましい。 The quaternary ammonium salt containing three ester groups in the molecule is preferably a compound represented by the following general formula (7).

In the general formula (7), R ⁹ has the same meaning as in the general formula (3). R ⁹ may be the same as or different from each other, and is preferably a linear alkyl group or alkenyl group having 13 to 21 carbon atoms. Specifically, a residue obtained by removing a carboxyl group from a fatty acid such as stearic acid, palmitic acid, myristic acid, oleic acid, and elaidic acid is preferable.

R ⁹ is a residue obtained by removing a carboxyl group from a fatty acid having 10 to 24 carbon atoms, and is a group derived from any of a saturated fatty acid, an unsaturated fatty acid, a linear fatty acid, and a branched fatty acid. In the case of an unsaturated fatty acid, a cis isomer and a trans isomer are present, and the mass ratio (cis / trans) is preferably 25/75 to 80/20, more preferably 40/60 to 80/20.
Examples of the fatty acid used as R ⁹ include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodinated 10-60), and partial water. Examples include soy beef tallow fatty acid (iodine value of 10 to 60). Among these, oleic acid, elaidic acid, linoleic acid, and stearic acid are particularly preferable.
A predetermined amount of stearic acid, palmitic acid, myristic acid, oleic acid and elaidic acid derived from plants is combined, and the ratio (saturated / unsaturated) is 95/5 to 50/50 (mass / mass), and the cis / trans mass The ratio is preferably 40/60 to 80/20, the ratio of 18 carbon atoms is preferably 60% by mass or more, the fatty acid having 20 carbon atoms is 2% by mass or less, and the fatty acid having 22 carbon atoms is 1 mass. It is preferable to use a fatty acid composition adjusted to be not more than%.
The quaternary ammonium salt containing 1 to 3 ester groups in the molecule is obtained by condensation reaction of the fatty acid composition or fatty acid methyl ester composition with triethanolamine, followed by a quaternizing reagent such as dimethyl sulfate. It can be synthesized by a quaternization reaction.
Incidentally, the ^R 7 in the general formula (2) to (7) ^in, R 8, ^{R 9} and X ^- is, ^R 7 in the other formula (2) to ^(7), R 8, ^{R 9} and X ^- and they are each independently.

前記一般式（８）において、Ｒ^１０は、炭素数１１〜２７が好ましく、より好ましくは１５〜２３、更に好ましくは炭素数２１の直鎖又は分岐鎖のアルキル基又はアルケニル基である。
Ｒ^１１は、炭素数１〜４のアルキル基であり、メチル基又はエチル基が好ましい。
ｎは、２〜４の整数を示す。 -Amidoamine type surfactant-
Examples of the amidoamine type surfactant include compounds represented by the following general formula (8).

In the general formula (8), R ¹⁰ is preferably a linear or branched alkyl or alkenyl group having 11 to 27 carbon atoms, more preferably 15 to 23 carbon atoms, and still more preferably 21 carbon atoms.
R ¹¹ is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group.
n shows the integer of 2-4.

Examples of the amidoamine surfactant represented by the general formula (8) include stearic acid diethylaminoethylamide, stearic acid dimethylaminoethylamide, palmitic acid diethylaminoethylamide, coconut oil fatty acid diethylaminopropylamide, and palmitic acid dimethylaminoethyl. Amides, myristic acid diethylaminoethylamide, myristic acid dimethylaminoethylamide, behenic acid diethylaminoethylamide, behenic acid dimethylaminoethylamide, stearic acid diethylaminopropylamide, stearic acid dimethylaminopropylamide, palmitic acid diethylaminopropylamide, palmitic acid dimethyl Aminopropylamide, myristic acid diethylaminopropylamide, myristic acid dimethylaminopro Ruamido, behenic acid diethylaminopropylamide, behenic acid dimethylaminopropylamide, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, stearic acid dimethylaminopropylamide, stearic acid diethylaminoethylamide, behenic acid diethylaminoethylamide, and behenic acid dimethylaminopropylamide are particularly preferable.
These surfactants are usually contained in the above-described various salt forms, and acidic amino acid salts, citrates, and hydrochlorides are preferable. In addition, the salt used for neutralization may use together 1 type, or 2 or more types.

-Amine type surfactant-
Examples of the amine-type surfactant include stearoxypropyldimethylamine.

ただし、前記一般式（９）中、Ｒ^１２は、炭素数１１〜２７が好ましく、より好ましくは１１〜２１の直鎖又は分岐鎖のアルキル基又はアルケニル基である。Ａは、炭素数１〜１０の直鎖状もしくは分岐鎖状のアルキレン基又はアルケニレン基である。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は互いに異なっていてもよい。 -Guanidine derivative or salt thereof-
As said guanidine derivative or its salt, the compound represented by following General formula (9) is mentioned.

In the general formula ^{(9), R 12} is preferably 11-27 carbon atoms, more preferably a straight-chain or branched alkyl or alkenyl group of 11 to 21. A is a C1-C10 linear or branched alkylene group or alkenylene group. t is an integer of 1 to 5, and when t is 2 or more, A in each block may be different from each other.

Examples of ^{R 12,} for example _{C 11 H 23 -, 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 — and the like. A as a substituent in the general formula (9) is preferably a linear or branched alkylene group or alkenylene group having 1 to 10 carbon atoms, more preferably 2 to 6, for example, methylene group, ethylene Group, propylene group, butylene group, pentylene group, hexylene group, isopropylene group, 2-pentenyl group, 2-ethylbutylene group and the like.
The guanidine derivative represented by the general formula (9) is usually contained in the above-described various salt forms, and in the form of hydrochloride, bromate, acetate, glycolate, citrate, or acidic amino acid salt. preferable.

-Amino acid-based cationic surfactant-
Examples of the amino acid cationic surfactants include mono-N-long chain (C12-22) acyl basic amino acid lower (C1-8) alkyl ester salts.
Examples of basic amino acids constituting the amino acid cationic surfactant include natural amino acids such as ornithine, lysine and arginine. A synthetic amino acid such as α, γ-diaminobutyric acid can also be used. These may be optically active or racemic.
The acyl group is a saturated or unsaturated higher fatty acid residue having 12 to 22 carbon atoms. These may be natural or synthesized, for example, natural mixtures such as single fatty acid residues such as lauroyl group, myristoyl group, palmitoyl group, stearoyl group, coconut oil fatty acid residue, beef tallow higher fatty acid residue, etc. And higher fatty acid residues.

  Examples of the lower alkyl ester include methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester and the like. The lower alkyl ester is usually blended in the form of a salt, specifically, inorganic salts such as hydrochloride, bromate, sulfate, phosphate, etc .; glycolate, acetate, lactate, succinic acid And organic acid salts such as salts, tartrate, citrate, acidic amino acid salt, higher fatty acid salt, pyroglutamate and p-toluenesulfonate. Among these, hydrochloride, L- or DL-pyrrolidone carboxylate, and acidic amino acid salt are particularly preferable.

  Among these cationic surfactants of the component (A), the quaternary ammonium salt represented by the general formula (1) is preferable, and behenyltrimethylammonium chloride is particularly preferable in that it can provide no dryness after drying.

  The content of the cationic surfactant of the component (A) (the total content when two or more are used) is not particularly limited and can be appropriately selected according to the purpose, and is based on the total amount of the shampoo composition. 1 mass% to 3 mass% is preferable. When the content is less than 1% by mass, the hair may not be entangled in wet hair and the hair may not be dry after drying. When the content exceeds 3% by mass, the hair is sticky. Such a weight may be generated, and the lack of smoothness may be reduced.

<(B) Long chain aliphatic alcohol having 12 to 24 carbon atoms>
The long chain aliphatic alcohol having 12 to 24 carbon atoms as the component (B) can form a liquid crystal structure alone with the cationic surfactant as the component (A) in the shampoo composition. Particularly preferred.
When the number of carbon atoms is less than 12, skin irritation may occur and it may be difficult to form a liquid crystal structure with a cationic surfactant. When the number of carbon atoms exceeds 24, the melting point becomes high and the system is difficult to dissolve. It may be difficult to form a structure.

Examples of the long chain aliphatic alcohol having 12 to 24 carbon atoms as the component (B) include higher alcohols represented by the following general formula (10).
R ¹³ -OH ··· general formula (10)
However, in the general formula (10), R ¹³ is an aliphatic hydrocarbon group having 12 to 24 carbon atoms, preferably a linear or branched alkyl group or alkenyl group having 16 to 22 carbon atoms, more preferably. Is a linear alkyl group having 16 to 22 carbon atoms.

  Examples of the long-chain aliphatic alcohol represented by the general formula (10) include myristyl alcohol, cetyl alcohol, stearyl alcohol, 2-hexyldecyl alcohol, cetostearyl alcohol, stearyl alcohol, isostearyl alcohol, octyldodecyl alcohol, and arachi. Examples include alcohol, behenyl alcohol, hydrogenated rapeseed oil alcohol, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, carnervir alcohol, seryl alcohol, cholesterol, phytosterol, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, linear alcohols having 16 to 22 carbon atoms (cetyl alcohol, stearyl alcohol, behenyl alcohol, etc.) are preferable from the viewpoint of high-temperature stability, and behenyl alcohol having 22 carbon atoms is the cationic interface of (A). Since it is easy to form a liquid crystal structure with an activator and to be easily adsorbed to the hair, it is particularly preferable from the viewpoint of the dryness of the hair after drying.

  There is no restriction | limiting in particular in content of the long-chain aliphatic alcohol of the said (B) component, According to the objective, it can select suitably, 0.5 mass%-10 mass% with respect to the said shampoo composition whole quantity are 0.5 mass%-10 mass%. Preferably, 2% by mass to 10% by mass is more preferable from the viewpoints of no entanglement of hair in wet hair and no looseness of hair after drying. When the content is less than 0.5% by mass, there may be no entanglement of hair in wet hair, and there may be no dryness of hair after drying. Storage stability may deteriorate.

  In the present invention, the mass ratio [(A) / (B)] of the cationic surfactant of the component (A) and the long-chain aliphatic alcohol having 12 to 24 carbon atoms of the component (B) is 1 / It is preferable that it is 1-1 / 4. If the mass ratio [(A) / (B)] exceeds 1/1, it may not be possible to impart no entanglement of hair in wet hair and no looseness of hair after drying. On the other hand, if the mass ratio [(A) / (B)] is less than ¼, it is not possible to impart no hair entanglement in wet hair and no dryness of hair after drying. , Long-term storage stability may deteriorate.

<(C) Amphoteric surfactant>
The amphoteric surfactant of the component (C) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkylbetaine activators, amide betaine activators, sulfobetaine activators, hydroxysulfone activators. Examples include betaine activators, amide sulfobetaine activators, phosphobetaine activators, imidazolinium betaine activators, aminopropionic acid activators, amino acid activators, and the like. Among these, alkylbetaine surfactants are particularly preferable.
Examples of the alkylbetaine surfactant include 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-carboxy. And methyl-N-hydroxyethyl imidazolinium betaine. These may be used individually by 1 type and may use 2 or more types together. Among these, amidopropyl betaine laurate improves bubbling, and bubbles spread to the hair, so there is no “entanglement at the time of shampooing”, and it also has an antiseptic power against E. coli, staphylococci and fungi. This is particularly preferable.

  The content of the amphoteric surfactant of the component (C) is 10% by mass to 30% by mass, and preferably 14% by mass to 24% by mass with respect to the total amount of the shampoo composition. When the content is less than 10% by mass, foaming of the main purpose as shampoo performance is reduced, so that foam does not flow in the hair, there is no entanglement of hair in wet hair, and there is no looseness of hair after drying. Is not sufficient, and the antiseptic power of Escherichia coli, staphylococci and fungi may be reduced. On the other hand, when the content exceeds 30% by mass, the dispersibility of the cationic surfactant as the component (A) and the long-chain aliphatic alcohol having 12 to 24 carbon atoms as the component (B) decreases, and the shampoo composition Since the uniformity of the product cannot be ensured, the increase in the viscosity of the preparation may not exhibit the effect of imparting no tangling of the hair in wet hair and no looseness of the hair after drying.

<(D) Glycerin>
The glycerin may be derived from a plant or synthesized.
Content of the said glycerol is 8-30 mass% with respect to the said shampoo composition whole quantity, and 12 mass%-25 mass% are more preferable. When the content is less than 8% by mass, the effect of imparting dryness to the hair after drying is not sufficient, and the antiseptic power of Escherichia coli, staphylococci and fungi may be reduced in terms of antiseptic power. If it exceeds 30% by mass, it may cause the hair to become sticky and reduce the roughness.

  The mass ratio [(D) / ((C) + (D)] of the component (C) and the component (D) is 0.30 to 0.70, and is 0.40 to 0.60. However, the mass ratio [(D) / ((C) is preferred from the viewpoints of no entanglement of hair in wet hair, no dryness of hair after drying, suppression of rusting of the skin, long-term storage stability, and antiseptic properties against mold. ) + (D)] is less than 0.30, the moisturizing effect of the glycerin (D) component is not sufficient, so that there is no entanglement of the hair in wet hair, and no dryness of the hair after drying. If the mass ratio [(D) / ((C) + (D)] exceeds 0.70, the glycerin as the component (D) may be reduced. As the ratio increases, it causes the hair to become sticky and the lack of smoothness decreases. The mass ratio [(D) / ((C) + (D)] is obtained by rounding off the third decimal point. .

<(E) Alkylamine Oxide>
In the shampoo composition of the present invention, by further containing the alkylamine oxide as the component (E), the effect of suppressing scuffing on the background is dramatically improved.
Examples of the alkylamine oxide of the component (E) include decyl dimethylamine oxide, lauryl dimethylamine oxide, myristyl dimethylamine oxide, and the like. Among these, lauryldimethylamine oxide is particularly preferable in terms of the effect of suppressing scuffing of the background.
The number of carbon atoms of the alkylamine oxide as the component (E) is preferably 8 to 18 and more preferably 10 to 14 from the viewpoint of the effect of reducing background scuff.
The content of the alkylamine oxide as the component (E) is preferably 0.3% by mass to 5% by mass and more preferably 0.3% by mass to 3% by mass with respect to the total amount of the shampoo composition. If the content is less than 0.3% by mass, the effect of suppressing scalp on the background may not be sufficient, and if it exceeds 5% by mass, an excessive amount of alkylamine oxide remains on the background. Kayumi may come out.

  The mass ratio [(D) / (E)] of the component (D) and the component (E) is preferably 5 to 40. From the viewpoints of the effect of suppressing rusting of the background, antiseptic effect, and long-term storage stability, 6 -36 is more preferable. When the mass ratio [(D) / (E)] is less than 5, the ratio of the alkylamine oxide of the component (E) is high with respect to the total amount of glycerin and alkylamine oxide which are moisturizers, so It may come out. On the other hand, when the mass ratio [(D) / (E)] exceeds 40, the ratio of the alkylamine oxide of the component (E) to the total amount of glycerin and alkylamine oxide as a moisturizing agent decreases, and the background The effect of suppressing kayaking may also be reduced.

-Other ingredients-
The shampoo composition of the present invention is widely used for general shampoo compositions in addition to the components (A) to (D), preferably (E), as long as the object of the present invention is not impaired. Various additive components can be blended as necessary. These components include: silicone compounds such as dimethylpolysiloxane, polyether-modified silicone, and amino-modified silicone; hydrocarbons such as liquid paraffin and squalane; esters such as isopropyl myristate; vegetable oils such as camellia oil, almond oil, jojoba oil Nonionic surfactants such as polyoxyethylene alkyl ether, glycerin fatty acid ester, sucrose fatty acid ester and polyglycerin fatty acid ester; gallic acid derivatives; amino acids such as glycine, serine and arginine; pyrrolidone carboxylic acid or salt, herbal medicine, Anti-inflammatory agents such as vitamins, dipotassium glycyrrhizinate and glycyrrhetinic acid; antidandruff agents such as piroctone olamine and zinc pyrithione; bactericides such as isopropylmethylphenol and triclosan; tar dyes, UV absorbers, acids Inhibitors, solvents such as ethanol, anionic polymers such as acrylic acid polymers, nonionic polymers such as vinylpyrrolidone polymers, amphoteric polymers such as diallyldimethylammonium chloride / acrylic acid, cationized cellulose, cationized guar gum, etc. Cationic polymers of the following: inorganic powders such as anhydrous silica and magnesia silica; organic powders such as nylon and polyethylene. These may be used individually by 1 type and may use 2 or more types together.

As the fragrance and fragrance composition used in the shampoo composition of the present invention, the fragrance components described in paragraph numbers [0021] to [0035] of JP-A No. 2003-300121, and further described in paragraph number [0050] Perfume solvents and the like. In the present invention, the “perfume composition” means a mixture comprising the above-described perfume ingredients, a solvent, a perfume stabilizer and the like.
0.1 mass%-99 mass% are preferable with respect to the said fragrance | flavor composition whole quantity, and, as for content of the said solvent for fragrance | flavors, 1 mass%-50 mass% are more preferable.
Examples of the fragrance stabilizer include dibutylhydroxytoluene, butylhydroxyanisole, vitamin E or derivatives thereof, catechin compounds, flavonoid compounds, polyphenol compounds, and the like. Among these, dibutylhydroxytoluene is particularly preferable.
As for content of the said fragrance | flavor stabilizer, 0.0001 mass%-10 mass% are preferable with respect to the said fragrance | flavor composition whole quantity, and 0.001 mass%-5 mass% are more preferable.
0.005 mass%-40 mass% are preferable with respect to the said shampoo composition whole quantity, and, as for content of the said fragrance | flavor composition, 0.01 mass%-10 mass% are more preferable.

  The shampoo composition of the present invention is prepared by mixing and dissolving the component (C) and the component (D), preferably a water-soluble component containing the component (E) in a hot water bath at 80 ° C. The oil phase containing the component (A) and the component (B) is added to the aqueous phase and mixed uniformly. Then, it can prepare by adding a silicone emulsion and cooling to room temperature, further stirring. There is no restriction | limiting in particular as an apparatus used for the said stirring, According to the objective, it can select suitably, For example, a stirring bar, a stirring blade, etc. are mentioned.

-PH-
There is no restriction | limiting in particular as pH of the said shampoo composition, Although it can select suitably according to the objective, 5.0-6.0 are preferable at 25 degreeC.
The pH can be measured, for example, at 25 ° C. using a pH meter (HM-30G, manufactured by Toa DKK Corporation) of the shampoo composition diluted 10 times with purified water.
The pH of the shampoo composition can be adjusted using a desired pH adjuster. The pH adjuster is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include citric acid, succinic acid, 2-amino-2-methyl-1-propanol, and monoethanolamine. .

-Viscosity-
There is no restriction | limiting in particular as a viscosity of the shampoo composition of this invention, Although it can select suitably according to the objective, 1 Pa * s-30 Pa * s are preferable at 25 degreeC.
The viscosity can be measured, for example, using a viscometer (manufactured by TOKIMEC, BM type viscometer, No. 4 rotor) at 30 rpm, 20 seconds, and 25 ° C.

-Application-
The shampoo composition of the present invention prevents entanglement of hair damaged by repeated coloring, perm, and excessive dryer drying, eliminates `` passiness after drying '', and `` scalp scalp '' Because it is excellent in preservative power even if it contains no preservatives (paraben, benzoic acid or its salt, etc.), it is suitable for shampoos for skin cleansing, shampoos for damage care, mild shampoos, rinse-in shampoos, etc. Can be used.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Examples 1-24 and Comparative Examples 1-8)
-Preparation of shampoo composition-
According to the composition shown in Table 1 (unit: mass%), shampoo compositions of Examples 1 to 24 and Comparative Examples 1 to 8 were prepared by a conventional method. Specifically, in a hot water bath at 80 ° C., the water-soluble component containing the component (C), the component (D), and the component (E) as necessary was mixed and dissolved to obtain an aqueous phase. To this aqueous phase, an oil phase containing the components (A) and (B) was added and mixed uniformly. Thereafter, a silicone emulsion was added and further cooled to room temperature with stirring. The pH was adjusted using citric acid as a pH adjuster.
Each obtained shampoo composition was diluted 10 times with purified water, and the pH was measured at 25 ° C. using a pH meter (manufactured by Toa DKK Corporation, HM-30G). The results are shown in Table 1.

<Sensory evaluation>
The sensory evaluation was performed as follows for “no entanglement of hair in wet hair”, “no looseness of hair after drying”, and “no scalp on the skin”. The results are shown in Table 1.
[Sensory evaluation method]
Women in their 30s and 40s who have performed chemical treatments such as coloring and perm within 3 months, entangled the hair at the time of shampooing, feels rustiness of the hair after washing and drying with a hair dryer, and also feels the scalp of the skin 30 By name, each shampoo composition was used for 7 days and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: 27 or more out of 30 respondents are good ◎ to ○: 24 or more out of 30 respondents are good ○: 15 to 23 out of 30 respondents are good △: Good Number of respondents 5 to 14 out of 30 ×: Less than 5 respondents answered good. In the above evaluation criteria, “good” means “no hair entanglement in wet hair” for each evaluation item. Means "no dry hair after drying" and "no scalp on the skin".

<Evaluation method of long-term storage stability>
About 40 mL of each shampoo composition was filled in 50 mL of glass vial bottle, stored at 40 ° C. for 6 months, and the appearance of each shampoo composition was visually determined according to the following criteria. The results are shown in Table 1.
〔Evaluation criteria〕
◎: No change in appearance, no separation is observed ○: Appearance is partially non-uniform in color tone, but no separation is observed △: Very little separation is observed ×: Separation is recognized Be

<Evaluation of preservative power of shampoo composition>
As a test bacterium, Escherichia coli NBRC3972 and Staphylococcus aureus NBRC13276 were used. These were all obtained from the National Institute of Technology and Evaluation (NITE).
As the fungus, Paecilomyces variotii (derived from the environment) was used.
Each of these test bacteria was cultured in an optimum medium, and a bacterial suspension was prepared so as to be about 10 ⁸ to 10 ⁹ cells / mL.
0.2 mL of the bacterial suspension was added to 20 g of the evaluation sample and mixed well to prepare an evaluation sample solution, and then the bacteria were stored at 20 ° C. and the fungi were stored at 25 ° C. in the dark.
Next, after 1 day, 4 days, 7 days, 14 days, and 28 days after storage, 1 g of the evaluation sample solution is aseptically collected and placed in 9 mL of lecithin / polysorbate 80-added soybean / casein / digest liquid medium. Diluted and mixed. Take 1 mL and 0.1 mL of the solution obtained by dilution and mixing in petri dishes, and mix with bacteria in lecithin / polysorbate 80-added soybean / casein / digest agar and fungi in lecithin / polysorbate 80+ glucose / pepton agar. It was. Bacteria were cultured at 30 ° C. for 4 days, and fungi were cultured at 25 ° C. for 7 days, and the number of surviving bacteria in the sample was measured.
The determination was made according to the following criteria based on the number of days until the added bacteria or fungi were below the detection limit (10 cells / g or less). The results are shown in Table 1.
〔Evaluation criteria〕
◎: within 7 days the detection limit was reached (10 cells / g or less), and the added bacteria were killed. ○: within 8-14 days, the detection limit was reached (10 cells / g or less), and the added bacteria. △: More than 14 days to fall below the detection limit (10 / g or less) ×: No added bacteria killed

Below, the specific Example which applied the shampoo composition of this invention to actual shampoo is shown. In addition, the shampoo of the following Example was prepared according to each composition.
When the following Examples 25 to 27 were evaluated in the same manner as in Examples 1 to 24, all showed excellent effects.

(Example 25)
-Shampoo-
・ Behenyltrimethylammonium chloride 2.5% by mass
・ Behenyl alcohol 6.0% by mass
・ 14% by mass of amidopropyl betaine laurate
・ Glycerin 15% by mass
・ Lauryldimethylamine oxide 1% by mass
・ Polyoxyethylene lauryl sulfate Na 1% by mass
・ Polyoxyethylene behenyl ether 0.2% by mass
・ Smectite 0.3% by mass
・ Highly polymerized amino-modified silicone emulsion 3% by mass
・ Amino-modified silicone emulsion 0.5% by mass
・ Hydroxypropyl methylcellulose 0.1% by mass
・ Hydroxyethane diphosphonic acid 0.1% by mass
・ Polyoxyethylene cetostearyl hydroxymyrstyrene ether 0.35% by mass
-Fragrance B 0.5% by mass
・ Citric acid
・ Purified water balance
Total 100% by mass
Mass ratio [(D) / ((C) + (D))] = 0.52
Mass ratio [(D) / (E)] = 15
pH 5.3 (25 ° C.), viscosity 8.0 Pa · s (25 ° C.)
<Evaluation results>
No entanglement in wet hair: ◎
No dry hair after drying: ◎
Nasty Kayumi: ◎
Long-term storage stability: ○
Antiseptic effect (staphylococci, Escherichia coli, mold): ◎

(Example 26)
-Shampoo-
・ Behenyltrimethylammonium chloride 2.5% by mass
・ Behenyl alcohol 6.0% by mass
・ 10% by weight of lauric acid amidopropyl betaine
-Palm oil fatty acid amidopropyl betaine 5% by mass
・ Glycerin 15% by mass
・ Lauryldimethylamine oxide 2% by mass
・ Polyoxyethylene lauryl sulfate Na 1% by mass
・ Polyoxyethylene behenyl ether 0.2% by mass
・ Smectite 0.3% by mass
・ Highly polymerized amino-modified silicone emulsion 2% by mass
・ Dimethyl silicone emulsion 1% by mass
・ Hydroxypropyl methylcellulose 0.1% by mass
・ Hydroxyethane diphosphonic acid 0.1% by mass
・ Polyoxyethylene cetostearyl hydroxymyrstyrene ether 0.8% by mass
-Fragrance C 0.5% by mass
・ Citric acid appropriate amount ・Purified water balance
Total 100% by mass
Mass ratio [(D) / ((C) + (D))] = 0.50
Mass ratio [(D) / (E)] = 7.5
pH 5.3 (25 ° C.), viscosity 20 Pa · s (25 ° C.)
<Evaluation results>
No entanglement in wet hair: ◎
No dry hair after drying: ◎
Nasty Kayumi: ◎
Long-term storage stability: ○
Antiseptic effect (staphylococci, Escherichia coli, mold): ◎

(Example 27)
-Shampoo-
・ Behenyltrimethylammonium chloride 2.5% by mass
・ Behenyl alcohol 6.0% by mass
・ 15% by mass of amidopropyl betaine laurate
・ Glycerin 12% by mass
・ Lauryldimethylamine oxide 1% by mass
・ Polyoxyethylene lauryl sulfate Na 2% by mass
・ Polyoxyethylene behenyl ether 0.2% by mass
・ Smectite 0.3% by mass
・ Highly polymerized amino-modified silicone emulsion 5% by mass
・ Amino-modified silicone emulsion 0.5% by mass
・ Hydroxypropyl methylcellulose 0.05% by mass
・ Hydroxyethane diphosphonic acid 0.1% by mass
・ Polyoxyethylene cetostearyl hydroxymyrstyrene ether 0.2% by mass
-Fragrance D 0.5% by mass
・ Citric acid appropriate amount ・Purified water balance
Total 100% by mass
Mass ratio [(D) / ((C) + (D))] = 0.44
Mass ratio [(D) / (E)] = 12
pH 5.3 (25 ° C.), viscosity 5.0 Pa · s (25 ° C.)
<Evaluation results>
No entanglement in wet hair: ◎
No dry hair after drying: ◎
Nasty Kayumi: ◎
Long-term storage stability: ○
Antiseptic effect (staphylococci, Escherichia coli, mold): ◎

In addition, the specific content of the material used in Examples 1-27 and Comparative Examples 1-8 is as showing below.

  The shampoo composition of the present invention prevents entanglement of hair damaged by repeated coloring, perm, and excessive dryer drying, eliminates `` passiness after drying '', and `` scalp scalp '' Because it is excellent in preservative power even if it contains no preservatives (paraben, benzoic acid or its salt, etc.), it is suitable for shampoos for skin cleansing, shampoos for damage care, mild shampoos, rinse-in shampoos, etc. Can be used.

Claims (6)

(A) Quaternary ammonium salt represented by the following general formula (1) , (B) C12-24 long chain aliphatic alcohol, (C) lauric acid amidopropyl betaine, lauryldimethylaminoacetic acid betaine, palm Amphoteric surfactant which is at least one selected from oil fatty acid amidopropyl betaine, coconut oil fatty acid dimethylaminoacetic acid betaine, lauryl hydroxysulfobetaine, and 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine 10% to 30% by weight, and (D) glycerin 8% to 30% by weight,
The shampoo composition, wherein a mass ratio [(D) / ((C) + (D))] of the component (C) and the component (D) is 0.30 to 0.70.

In the general formula (1), at least one of R ³ and R ⁴ is a linear or branched alkyl group having 12 to 28 carbon atoms or an alkenyl group, and one of R ³ and R ⁴ is May be a methyl group or an ethyl group, and these may be the same or different. R ⁵ and R ⁶ are both methyl groups or ethyl groups. Z ⁻ represents an anion. Furthermore (E) decyl dimethyl amine oxide, containing lauryl dimethyl amine oxide, and an alkyl dimethyl amine oxide 0.3 wt% to 5 wt% of at least one selected from myristyl dimethyl amine oxide,
The shampoo composition according to claim 1, wherein a mass ratio [(D) / (E)] of the component (D) and the component (E) is 5 to 40. (B) Long chain aliphatic alcohol having 12 to 24 carbon atoms is myristyl alcohol, cetyl alcohol, stearyl alcohol, 2-hexyldecyl alcohol, cetostearyl alcohol, isostearyl alcohol, octyldodecyl alcohol, aralkyl alcohol, behenyl alcohol, curing The shampoo composition according to any one of claims 1 to 2, which is at least one selected from rapeseed oil alcohol, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, carnervir alcohol, and seryl alcohol. The shampoo composition according to any one of claims 1 to 3, wherein the content of the component (A) is 1% by mass to 3% by mass, and the content of the component (B) is 0.5% by mass to 10% by mass. object. (A) component is a quaternary ammonium salt selected from behenyltrimethylammonium chloride and stearyltrimethylammonium chloride, (B) a long-chain aliphatic alcohol selected from behenyl alcohol, cetyl alcohol, and hardened rapeseed oil alcohol, The component (C) is an alkylbetaine amphoteric surfactant selected from lauric acid amidopropyl betaine and coconut oil fatty acid amidopropyl betaine, and (E) component is lauryldimethylamine oxide. A shampoo composition as described. The shampoo composition according to any one of claims 1 to 5, wherein the shampoo composition is used for any one of a background cleansing shampoo, a damage care shampoo, a mild shampoo, and a rinse-in shampoo.