WO2020166190A1

WO2020166190A1 - Hair detergent composition

Info

Publication number: WO2020166190A1
Application number: PCT/JP2019/048807
Authority: WO
Inventors: 翔鈴木; ほたか浅野; 俊輔廣島; 泉大石; 英輔稲垣
Original assignee: ライオン株式会社
Priority date: 2019-02-15
Filing date: 2019-12-12
Publication date: 2020-08-20
Also published as: CN113423378A; JPWO2020166190A1; JP7340550B2; KR20210126554A

Abstract

A hair detergent composition which comprises (A) a carboxylic acid salt type anionic surfactant, (B) an amphoteric surfactant, (C) at least one cationic polymer selected from among dimethyldiallylammonium chloride polymers and dimethyldiallylammonium chloride/acrylic acid copolymers, (D) an azole antifungal agent, and (E) at least one substance selected from the group consisting of rosemary extracts, phenoxyethanol, and swertia herb extracts, wherein the dimethyldiallylammonium chloride/acrylic acid copolymers in the component (C) are each one in which the molar proportion of structural units derived from dimethyldiallylammonium chloride is 65 mol% or higher.

Description

Hair cleansing composition

The present invention relates to a hair cleansing composition.

Since an azole antifungal agent such as miconazole has an antibacterial effect against Malassezia bacterium, which is one of the indigenous bacteria of the scalp, a hair cleansing composition containing the azole antifungal agent as an antidandruff agent is commercially available. ing.
However, there is a problem in that the stability of the azole antifungal agent with time may deteriorate due to coexisting components such as a surfactant in the hair cleansing composition.

For this problem, some means for keeping the azole antifungal agent in the hair cleansing composition stable have been reported (see, for example, Patent Document 1).
However, in the conventional hair cleansing composition containing an azole antifungal agent, the active ingredient (the azole antifungal agent) is washed out during rinsing, and the expected effect on the skin and hair can be obtained. There was a problem that it was difficult.

In order to solve this problem, as one of the methods for retaining the active ingredient, a method using a technique of retaining the active ingredient by the hydrophobic interaction of the surfactant and the coacervation of the cationic polymer can be considered.
However, the coacervate of the surfactant and the cationic polymer is also often flowed at the time of rinsing, and there is a problem that it is not possible to obtain the retention property to the extent that the effect of the active ingredient can be sufficiently obtained. There was (see Patent Document 2).

Therefore, there is still provided a hair cleansing composition which has excellent retention of the azole antifungal agent, can sufficiently obtain the effect thereof, and can maintain the stability of the azole antifungal agent. At present, there is a strong demand for rapid development.

JP, 2014-47165, A JP, 2007-277227, A

The present invention aims to solve the above-mentioned problems in the past and achieve the following objects. That is, it is an object of the present invention to provide a hair cleansing composition which is excellent in the effect of improving dandruff and itch and has excellent storage stability at high temperatures.

As a result of intensive studies to achieve the above object, the present inventors have found that (A) a carboxylate type anionic surfactant, (B) an amphoteric surfactant, and (C) dimethyldiallylammonium chloride. From a polymer and at least one cationic polymer selected from dimethyldiallylammonium chloride-acrylic acid copolymer, (D) an azole antifungal agent, and (E) rosemary extract, phenoxyethanol, and assembly extract At least one selected from the group consisting of dimethyldiallylammonium chloride-acrylic acid copolymer (C), wherein the molar ratio of structural units derived from dimethyldiallylammonium chloride is 65 mol% or more. The present inventors have found that a hair cleansing composition has an excellent effect of improving dandruff and itchiness, and also has excellent storage stability at high temperatures, and has completed the present invention.

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,
(A) a carboxylate type anionic surfactant,
(B) an amphoteric surfactant,
(C) at least one cationic polymer selected from dimethyldiallylammonium chloride polymer and dimethyldiallylammonium chloride-acrylic acid copolymer;
(D) an azole antifungal agent,
(E) at least one selected from the group consisting of rosemary extract, phenoxyethanol, and assembly extract,
The hair cleansing composition is characterized in that the dimethyldiallylammonium chloride-acrylic acid copolymer as the component (C) has a molar ratio of structural units derived from dimethyldiallylammonium chloride of 65 mol% or more.

ADVANTAGE OF THE INVENTION According to this invention, the said various problems in the past are solved, the said objective is achieved, the dandruff and the itch improvement effect are excellent, and the hair cleansing composition excellent in the storage stability in high temperature is provided. be able to.

(Hair cleaner composition)
The hair cleansing composition of the present invention comprises (A) a carboxylate type anionic surfactant, (B) an amphoteric surfactant, (C) a cationic polymer, and (D) an azole antifungal agent. And (E) at least one selected from the group consisting of rosemary extract, phenoxyethanol, and assembly extract, and, if necessary, further contains other components.

<(A) Carboxylate type anionic surfactant>
The carboxylic acid salt type anionic surfactant as the component (A) can be contained in order to improve the effect of improving dandruff and itch.

The component (A) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethercarboxylic acid type surfactants and amino acid type surfactants. These may be used alone or in combination of two or more. Among these, ethercarboxylic acid type surfactants are preferable.

<< Ether carboxylic acid type surfactant >>
The ethercarboxylic acid type surfactant is appropriately selected depending on the intended purpose without any limitation, and examples thereof include compounds represented by the following general formula (A1) or (A2). The ethercarboxylic acid type surfactants may be used alone or in combination of two or more.

In the general formulas (A1) and (A2), R ² represents a linear or branched alkyl or alkenyl group, or a phenyl group substituted with a linear or branched alkyl or alkenyl group. The carbon number of R ² is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 to 14 and more preferably 11 to 13 from the viewpoint of the effect of improving dandruff and itch.

In the general formula (A1), R ³ represents an alkylene group. The carbon number of R ³ is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2 to 4, and more preferably 2. The R ^{3 s} may be the same as or different from each other.

In the general formula (A1), o represents the average number of moles of alkylene oxide added. The average number of moles of alkylene oxide added is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 10 and more preferably 3 to 6 from the viewpoint of the effect of improving dandruff and itch. ..

In the general formulas (A1) and (A2), M ¹ represents a hydrogen atom, an alkali metal, an alkaline earth metal, an alkanolamine, ammonium or a basic amino acid. Among these, alkali metals are preferable, and sodium is more preferable.

Specific examples of the ether carboxylic acid type surfactant represented by the general formula (A1) or (A2) include polyoxyethylene alkyl ether acetate such as polyoxyethylene lauryl ether acetate and lauryl glycol acetate. Such alkyl glycol acetates and the like can be mentioned. Among these, the ethercarboxylic acid type surfactant is preferably polyoxyethylene alkyl ether acetate in terms of the effect of improving dandruff and itch.

The ethercarboxylic acid type surfactant may be appropriately synthesized or may be a commercially available product.
Examples of commercial products of the ether carboxylic acid type surfactants include Enadicol EC-30 (sodium polyoxyethylene lauryl ether acetate, manufactured by Lion Corporation), Beaulite LCA-25F (sodium polyoxyethylene lauryl ether acetate), Beaulite LCA (sodium polyoxyethylene lauryl ether acetate), Beaulite LCA-30D (sodium polyoxyethylene lauryl ether acetate), Beaulite LCA-H (polyoxyethylene lauryl ether acetate), Beaulite LCA-25NH (laureth- 4 carboxylic acid), Beaulite SHAA (sodium lauryl glycol carboxylate) (above, Sanyo Kasei Co., Ltd.), Kao Akipo RLM-45 NV (polyoxyethylene lauryl ether sodium acetate (average number of moles of ethylene oxide (EO) added): 4.5)), Kao Akipo RLM-100NV (sodium polyoxyethylene(10) lauryl ether acetate (average number of moles of EO added: 10)) (above, manufactured by Kao Corporation) and the like.

<<Amino acid type surfactant>>
The amino acid type surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds represented by general formula (A3) shown below. The amino acid type surfactants may be used alone or in combination of two or more.

In the general formula (A3), R ² represents a linear or branched alkyl group or alkenyl group, or a phenyl group substituted with a linear or branched alkyl group or alkenyl group. The carbon number of R ² is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 to 23, more preferably 8 to 18.

In the general formula (A3), R ⁴ represents a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, the number of carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 3.

In the general formula (A3), R ⁵ and R ⁶ represent a hydrogen atom or —(CH ₂ ) _m —COOM ² . The R ⁵ and the R ⁶ may be the same or different from each other.

In the general formula (A3), m and n are numbers from 0 to 20. The m and n may be the same or different from each other.

In the general formula (A3), M ¹ and M ² represent a hydrogen atom, an alkali metal, an alkaline earth metal, an alkanolamine, ammonium or a basic amino acid. The M ¹ and the M ² may be the same as or different from each other.

The amino acid structure of the hydrophilic part of the amino acid type surfactant is not particularly limited and may be appropriately selected depending on the intended purpose, but glycine, glutamic acid, methylalanine and the like are preferable.

Specific examples of the amino acid type surfactant represented by the general formula (A3) include N-acyl-glycine such as N-cocoyl-glycine potassium (N-coconut oil fatty acid acylglycine potassium) or a salt thereof; N- N-acyl-N-carboxyethyl-glycine such as myristoyl-N-carboxyethyl-glycine sodium or a salt thereof; sodium N-myristoyl-L-glutamate, potassium N-myristoyl-L-glutamate, N-lauroyl-L-glutamic acid Sodium, sodium myristoylmethylaminoacetate, potassium N-coconut oil fatty acid acyl-L-glutamate, sodium N-coconut oil fatty acid acyl-L-glutamate, sodium N-palm fatty acid acyl-L-glutamate, N-stearoyl-L-glutamic acid N-acyl glutamic acid such as sodium or a salt thereof; N-acyl aspartic acid such as N-lauroyl aspartic acid, N-myristoyl aspartic acid, N-palmitoyl aspartic acid or a salt thereof; N-lauroyl-N-methyl-β-alanine Potassium, N-lauroyl-N-methyl-β-alanine triethanolamine, sodium lauroylmethyl-β-alanine, sodium myristoylmethyl-β-alanine, sodium coconut oil fatty acid methylalanine sodium, N-coconut oil fatty acid acyl-DL-alanine N-acyl-N-methyl-β-alanine such as triethanolamine or salt thereof; sodium cocoylalanine, N-cocoyl-β-alanine N-acyl-β-alanine such as triethanolamine or salt thereof; coconut oil fatty acid Examples thereof include N-acyl sarcosine such as sarcosine triethanolamine and salts thereof. Among these, the amino acid type surfactants are preferably N-acyl sarcosine salts, N-acyl alanine salts, N-acyl glutamate salts, N-acyl aspartate salts and the like from the viewpoint of the effect of improving dandruff and itch.

The amino acid type surfactant may be appropriately synthesized or may be a commercially available product.
Examples of commercially available amino acid type surfactants include Amisoft (registered trademark) CS-11 (N-myristoyl-L-sodium glutamate), Amisoft (registered trademark) CS-22 (N-coconut oil fatty acid acyl-L). -Sodium glutamate solution), Amisoft (registered trademark) LS-11 (N-lauroyl-L-glutamate sodium), Amisoft (registered trademark) MS-11 (N-myristoyl-L-glutamate sodium), Amisoft (registered trademark) HS -11P (N-stearoyl-L-glutamate sodium), Amisoft (registered trademark) HS-11P (F) (sodium N-stearoyl-L-glutamate), Amisoft (registered trademark) HS21 (N-stearoyl-L-glutamate diester) Sodium), Amylite (registered trademark) ACS-12 (sodium cocoyl alanine) (above, manufactured by Ajinomoto Healthy Supply Co., Ltd.), Amino Surfact (registered trademark) AMMS-P1 (sodium N-myristoyl-L-glutamate) (Asahi Kasei Chemicals) NIKKOL sarcosinate MN (sodium myristoylmethylaminoacetate), NIKKOL alaninate LN-30 (sodium lauroylmethyl-β-alanine solution) (produced by Nikko Chemicals Co., Ltd.), alanone ACE (coconut oil fatty acid methylalanine sodium) Liquid), alanone AME (myristoylmethyl-β-alanine sodium liquid), alanone ALE (lauroylmethyl-β-alanine sodium liquid) (above, manufactured by Kawaken Fine Chemicals Co., Ltd.), Enadicol L-30AN (lauroylmethyl-β-alanine) Sodium solution) (manufactured by Lion Corporation), Softyl AT-L (sodium lauroylmethyl-β-alanine solution) (manufactured by NOF Corporation) and the like.

The content of the component (A) is not particularly limited and may be appropriately selected depending on the intended purpose, but from the viewpoint of the effect of improving dandruff and itch, it is 1 relative to the total amount of the hair cleaning composition. Mass% to 20 mass% is preferable, and 5 mass% to 11 mass% is more preferable. When the content of the component (A) is 1% by mass to 20% by mass, the effect of improving dandruff and itch is good.

<(B) Amphoteric surfactant>
The amphoteric surfactant as the component (B) can be contained in order to improve the effect of improving dandruff and itch.

The component (B) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include betaine-type amphoteric surfactants and amino acid-type amphoteric surfactants. These may be used alone or in combination of two or more. Among these, betaine-type amphoteric surfactants are preferable from the viewpoint of the effect of improving dandruff and itch.

The betaine-type amphoteric surfactant is not particularly limited and may be appropriately selected depending on the purpose, for example, alkylbetaine-type amphoteric surfactant, amidobetaine-type amphoteric surfactant, sulfobetaine-type amphoteric surfactant. Agents, hydroxysulfobetaine type amphoteric surfactants, amidosulfobetaine type amphoteric surfactants, phosphobetaine type amphoteric surfactants, imidazolinium betaine type amphoteric surfactants, and the like. These may be used alone or in combination of two or more.

The alkylbetaine-type amphoteric surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include lauryldimethylaminoacetic acid betaine, coconut oil alkylbetaine and stearyldimethylaminoacetic acid betaine.

The amidobetaine-type amphoteric surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples include lauric acid amidopropyl betaine, coconut oil fatty acid amidopropyl betaine, and palm kernel oil fatty acid amidopropyl betaine. Is mentioned.

The sulfobetaine-type amphoteric surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, lauryl hydroxysulfobetaine, lauramidopropyl hydroxysultaine, coconut oil fatty acid dimethylaminohydroxysulfobetaine, etc. Is mentioned.

The hydroxysulfobetaine-type amphoteric surfactant is not particularly limited and may be appropriately selected depending on the purpose, for example, coconut oil fatty acid dimethylaminohydroxysulfobetaine, lauryldimethylaminohydroxysulfobetaine, laurylhydroxysulfobetaine. And so on.

The amidosulfobetaine-type amphoteric surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkylamidopropyl betaine. Examples of the alkylamidopropyl betaine include coconut oil fatty acid amidopropyl betaine (cocamidopropyl betaine), lauric acid amidopropyl betaine, and isostearamidopropyl betaine.

The phosphobetaine-type amphoteric surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkylhydroxyphosphobetaine. Examples of the alkyl hydroxyphosphobetaine include lauryl hydroxyphosphobetaine, myristyl hydroxyphosphobetaine, stearyl hydroxyphosphobetaine, and the like.

The imidazolinium betaine-type amphoteric surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium and N- Examples include coconut oil fatty acid acyl-N′-carboxymethyl-N′-hydroxyethylethylenediamine sodium, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and the like.

Among these, the component (B) is preferably an alkylbetaine-type amphoteric surfactant, an amidobetaine-type amphoteric surfactant, an imidazolinium-betaine-type amphoteric surfactant, etc. from the viewpoint of the effect of improving dandruff and itching. Lauryl dimethylamino acetic acid betaine, lauric acid amidopropyl betaine, coconut oil fatty acid amidopropyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and the like are more preferable.

As the component (B), those appropriately synthesized may be used, or commercially available products may be used.
Examples of commercially available products of the component (B) include Enadicol L-30B (lauric acid amidopropyl betaine solution) (manufactured by Lion Corporation), Amhithol 20AB (lauric acid amidopropyl betaine), and Amhithol 55AB (cocamidopropyl betaine). , Amphitol 20YB (2-alkyl-N-carboxymethyl-N-hydroxyetherimidazolinium betaine), Amphitol 20BS (lauryl betaine) (above, manufactured by Kao Corporation), Levon 2000L (lauric amide propyl betaine solution), Levon 2000 (coconut oil fatty acid amidopropyl betaine solution), levon CIB (2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine), levon 105 (2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazo) Rinium betaine) (above, manufactured by Sanyo Kasei Co., Ltd.), softazoline LPB (lauric acid amide propyl betaine solution), softazoline CPB (coconut oil fatty acid amide propyl betaine solution), softazoline CPB-R (coconut oil fatty acid amide propyl betaine solution) ), softazoline CH (2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine), softazoline CH-R (2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine) (above, Kawaken Fine Chemicals Co., Ltd.), Anforex 30S (2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine), Anforex 35N (2-alkyl-N-carboxymethyl-N-hydroxyethylimidazole) Nibetain), Ampholex 50 (2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine), Ampholex K-80 (2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine) ) (Manufactured by Miyoshi Yushi Co., Ltd.), NIKKOL AM-101 (2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine), NIKKOL AM-301 (betaine lauryldimethylaminoacetate) (above, Nikko Chemicals stock) Company made) etc.

The content of the component (B) is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of the effect of improving dandruff and itch, it is 1 relative to the total amount of the hair cleaning composition. The content is preferably 20% by mass to 20% by mass, more preferably 2.5% by mass to 10% by mass. When the content of the component (B) is 1% by mass to 20% by mass, the effect of improving dandruff and itch is good.

<Mass ratio [(A)/(B)]>
The mass ratio of the content (mass %) of the component (A) to the content (mass %) of the component (B) represented by [(A)/(B)] is not particularly limited. It can be appropriately selected according to the purpose, but from the viewpoint of the effect of improving dandruff and itch, 0.8 to 16 is preferable, and 1 to 8 is more preferable. When the mass ratio is 0.8 to 16, the effect of improving dandruff and itch is good.

<(C) Cationic Polymer>
The cationic polymer of the component (C) is at least one selected from a dimethyldiallylammonium chloride polymer and a dimethyldiallylammonium chloride-acrylic acid copolymer, in order to improve the effect of improving dandruff and itch. Can be included.

The dimethyldiallylammonium chloride-acrylic acid copolymer in the component (C) has a molar ratio of structural units derived from dimethyldiallylammonium chloride of 65 mol% or more, and is represented by the following general formula (C1). It

However, in the said general formula (C1), n and m show the molar ratio (mol%) of each structural unit, it is n+m=100 and said m is 65 mol% or more.

The molar ratio of the structural units derived from dimethyldiallylammonium chloride in the dimethyldiallylammonium chloride-acrylic acid copolymer of the component (C) is 65 mol% or more from the viewpoint of the effect of improving dandruff and itch. And is preferably 95 mol% or more. If the molar ratio is less than 65 mol %, the effect of improving dandruff and itch cannot be felt.
The dimethyldiallylammonium chloride-acrylic acid copolymers may be used alone or in combination of two or more.

The molar ratio of each structural unit in the dimethyldiallylammonium chloride-acrylic acid copolymer of the component (C) can be determined by measurement by nuclear magnetic resonance (NMR) under the following measurement conditions.
[Measurement condition]
Solvent: Heavy water (D ₂ O)
Measuring device: JNM-LA300 (300 MHz, manufactured by JEOL Ltd.)

The weight average molecular weight of the cationic polymer of the component (C) is appropriately selected depending on the intended purpose without any limitation, but it is preferably 10,000 to 1,000,000, and preferably 15,000 to 450. 1,000 is more preferable.
The weight average molecular weight of the cationic polymer as the component (C) is, for example, SEC-MALLS-RI system (measurement condition: column: TSK gel α series α-M column 30 cm manufactured by Tosoh Corporation, solvent: 0.3 M aqueous solution of sodium nitrate). Can be measured at.

The viscosity of the solution of the cationic polymer as the component (C) having a solid content of 30% by mass to 44% by mass at 25°C is not particularly limited and may be appropriately selected depending on the intended purpose, but is 10 mPa·s. ˜15,000 mPa·s is preferable, and 20 mPa·s to 12,000 mPa·s is more preferable.
The viscosity can be measured using, for example, a Brookfield viscometer LVF (manufactured by Brookfield).

As the cationic polymer as the component (C), those appropriately synthesized may be used, or commercially available products may be used. Examples of the commercially available products include the following.
MERQUAT 100 (dimethyldiallylammonium chloride polymer, manufactured by Lubrizol Co., solid content 39 mass% to 44 mass%, viscosity at 25° C.: 8,000 mPa·s to 12,000 mPa·s, weight average molecular weight: 150,000). The viscosity was measured by using a Brookfield viscometer LVF (manufactured by Brookfield) at 25° C. at spindle No. It can be measured using a rotor of 3 and a condition of 6 revolutions/minute.

Mercoat 295 (dimethyldiallylammonium chloride-acrylic acid copolymer, manufactured by Lubrizol, viscosity of solid content 35% by mass to 40% by mass at 25° C.: 3,500 mPa·s to 9,000 mPa·s, weight average molecular weight : 190,000, n:m=5:95 (molar ratio) in the general formula (C1), and the molar ratio of structural units derived from dimethyldiallylammonium chloride is 95 mol%). The viscosity was measured using a Brookfield viscometer LVF (manufactured by Brookfield) at 25° C. at spindle No. 4 rotors can be used and it can measure at the conditions of 30 rotations/minute.

Mercoat 280 (dimethyl diallyl ammonium chloride-acrylic acid copolymer, manufactured by Lubrizol Co., solid content 39% by mass to 43% by mass at 25° C. viscosity: 3,000 mPa·s to 6,000 mPa·s, weight average molecular weight : 450,000, n:m=35:65 (molar ratio) in the general formula (C1), and the molar ratio of structural units derived from dimethyldiallylammonium chloride is 65 mol%). The viscosity was measured using a Brookfield viscometer LVF (manufactured by Brookfield) at 25° C. at spindle No. 4 rotors can be used and it can measure at the conditions of 60 rotations/minute.

The content of the component (C) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1% by mass to 5% by mass with respect to the total amount of the hair cleaning composition. , 0.3 mass% to 2 mass% is more preferable, and 0.5 mass% to 1 mass% is particularly preferable. When the content of the component (C) is 0.1% by mass to 5% by mass, the effect of improving dandruff and itch is good.

<(D) azole antifungal agent>
The azole antifungal agent of the component (D) can be contained in order to improve the effect of improving dandruff and itch.

The component (D) is appropriately selected depending on the intended purpose without any limitation, provided that it is an azole antifungal agent. For example, miconazole, clotrimazole, econazole, thioconazole, oxyconazole, bifonazole. , Lanoconazole, luliconazole, isoconazole, ketoconazole, fluconazole, itraconazole, neticonazole, sulconazole, phosfluconazole, voriconazole, croconazole, or salts thereof. These may be used alone or in combination of two or more.
The salts are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include nitrates and hydrochlorides.
Among these, the component (D) is preferably miconazole and/or a salt thereof, and more preferably miconazole nitrate, from the viewpoint of the effect of improving dandruff and itch.

As the component (D), those synthesized appropriately may be used, or commercially available products may be used. Examples of the commercially available product include miconazole nitrate (manufactured by Nagase & Co., Ltd.) and the like.

The content of the component (D) is not particularly limited and may be appropriately selected depending on the intended purpose, but from the viewpoint of the effect of improving dandruff and itchiness, and storage stability at high temperatures, the hair cleansing composition The amount is preferably 0.1% by mass to 1% by mass, more preferably 0.5% by mass to 1% by mass, based on the total amount of the product. When the content of the component (D) is 0.1% by mass or more, the effect of improving dandruff and itching is good, and when it is 1% by mass or less, the high temperature storage stability is good.

<(E) At least one selected from the group consisting of rosemary extract, phenoxyethanol, and assembly extract>
At least one selected from the group consisting of rosemary extract, phenoxyethanol, and assembly extract as the component (E) can be contained in order to improve high temperature storage stability. Among these, the component (E) is preferably rosemary extract, phenoxyethanol and the like, and phenoxyethanol is more preferable from the viewpoint of storage stability at high temperature.

The component (E) may be appropriately synthesized or may be a commercially available product. Examples of the commercially available products include Newpol EFP (phenoxyethanol, manufactured by Sanyo Kasei Co., Ltd.), Leomile WL (rosemary extract, manufactured by Toyoda Fragrance Co., Ltd.), assembly extract liquid ET (assembly extract), assembly extract liquid SS ( Assembly extract) (above, manufactured by Maruzen Pharmaceutical Co., Ltd.) and the like.

The content of the component (E) is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of storage stability at high temperature, it is 0.1% based on the total amount of the hair cleaning composition. The mass% to 2 mass% is preferable, and the mass% to 1 mass% is more preferable. When the content of the component (E) is 0.1% by mass to 2% by mass, the high temperature stability is good.

<Other>
The other components in the hair cleansing composition are not particularly limited as long as they do not impair the effects of the present invention, and can be appropriately selected from the components used in ordinary hair cleansing compositions. , Solvents (purified water, etc.), surfactants other than the components (A) and (B), oils, thickeners such as carboxymethyl cellulose, hydroxyethyl cellulose, citric acid, chelating agents (ethylenediaminetetraacetic acid (EDTA)) Etc.), opacifying agents (ethylene glycol diisostearate, fish scales, mica flakes, etc.), pigments, preservatives, antifungal agents, cooling agents, fragrances, and fragrance compositions. Among these, the hair cleansing composition preferably contains purified water.

Examples of the surfactant other than the component (A) and the component (B) include compounds represented by the following general formula (1).

In the general formula (1), R ¹ represents a linear or branched alkyl group or an alkenyl group, but a linear or branched alkyl group is preferable, and a linear alkyl group is more preferable.
The carbon number of R ¹ is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 8 to 18, and more preferably 11 to 13.

In the general formula (1), R ² and R ³ each independently represent a linear or branched alkyl group or a hydroxyalkyl group, and a linear or branched alkyl group is preferable, and a linear alkyl group is preferable. An alkyl group is more preferable, and a methyl group is particularly preferable.
In the general formula (1), R ² and R ³ may be the same as or different from each other.
The carbon number of R ² is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 3.
The carbon number of R ³ is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 3.

Among these, the compound represented by the general formula (1) is preferably an alkyldimethylamine oxide in which the alkyl chain length of R ^{1 in} the general formula (1) is 8 to 18, and the compound represented by the general formula (1) is Alkyl dimethylamine oxide having an alkyl chain length of R ¹ of 11 to 13 is more preferable.

As the compound represented by the general formula (1), those appropriately synthesized may be used, or commercially available products may be used.
Examples of the commercially available products include Unisafe A-LM (lauryldimethylamine oxide), Unisafe A-LMR (lauryldimethylamine oxide), Unisafe A-LE (dihydroxyethyllaurylamine oxide), Unisafe A-SM (stearyldimethylamine) Oxide) (above, NOF Corporation), Amphitol 20N (lauryldimethylamine oxide, manufactured by Kao Corporation), Sophthamine L (lauryldimethylamine oxide, manufactured by Toho Chemical Industry Co., Ltd.), Genaminox K-12 (lauryldimethyl). Amine oxide), genaminox KC (cocoamine oxide) (all manufactured by Clariant Japan Co., Ltd.), adecamine LDM (lauryldimethylamine oxide, manufactured by ADEKA Co., Ltd.), AX agent CS (lauryldimethylamine oxide), Cadenax DM12D-W (Lauryl dimethylamine oxide) (above, manufactured by Lion Specialty Chemicals Co., Ltd.), Standamox C1214 (lauryl dimethylamine oxide, manufactured by Cognis (BASF)), and the like.

The content of the other components is not particularly limited as long as the effect of the present invention is not impaired, and can be appropriately selected according to the purpose. The hair cleansing composition has the above general formula (1). When the compound represented is contained, the content thereof is preferably 0.1% by mass to 4% by mass, more preferably 0.4% by mass to 4% by mass, based on the total amount of the hair cleansing composition. ..

-High temperature storage stability-
The hair cleansing composition of the present invention is excellent in high-temperature stability, and is advantageous in that the effect of the component (D) can be sufficiently obtained.
The high-temperature stability can be confirmed on the basis of the quantitative value obtained by performing an accelerated test on the hair cleaning composition and quantifying the content of the component (D) before and after the accelerated test.
The method described in the following examples can be used for the acceleration test and the method for quantifying the content of the component (D).

-Production method-
The method for producing the hair cleansing composition of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the component (A), the component (B) and the component (C). , The component (D), the component (E), and further, if necessary, the other components are mixed and dissolved to produce the composition.
The hair cleansing composition may be manufactured using an apparatus. The device is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a stirring device having a shearing force and equipped with a stirring blade capable of mixing the whole.
The stirring blade is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a propeller, a turbine, and a disper.

-Use-
Since the hair cleansing composition of the present invention has an excellent effect of improving dandruff and itchiness and excellent storage stability at high temperatures, it can be widely used in shampoos, rinse-in shampoos, conditioning shampoos, treatment-in shampoos and the like. it can.

The following is a more detailed description based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

The content of each component described in Examples and Comparative Examples is shown by "mass %", and all values are values converted to pure content. In addition, the mass ratio [(A)/(B)] of the content (mass %) of the component (A) to the content (mass %) of the component (B) is rounded to one decimal place. , Obtained to the first decimal place and described.

(Examples 1-29 and Comparative Examples 1-9)
Hair cleansing compositions having the compositions and contents shown in Tables 1 to 4 below were prepared by the following method.
Specifically, the component (A) or the comparative component of the component (A), the component (B), the comparative component of the component (C) or the component (C), the component (D), the component (E) or the component (E). Comparative hair ingredients and purified water as common ingredients were mixed and dissolved to prepare respective hair cleansing compositions of Examples and Comparative Examples.

The prepared hair cleansing compositions of Examples 1 to 29 and Comparative Examples 1 to 9 were evaluated for "an dandruff and itch improvement effect" and "high temperature storage stability" as follows. The results are shown in Tables 1 to 4 below.

<Effect of dandruff and itching>
Twenty male professional panelists aged 20 to 30 who feel dandruff and itchiness when the scalp is dry use the hair cleansing composition of each of the Examples and Comparative Examples at a normal usage amount (3 g), and 1 The hair was washed once and for 7 days. The "effect of improving dandruff and itchiness" after using each hair cleaning composition for 7 days as compared with that before using each hair cleaning composition was evaluated according to the following evaluation criteria.
-Evaluation criteria for "effect of improving dandruff and itch"-
5 points: 17 or more people out of 20 who answered "I have an actual effect of improving dandruff and itching" 4 points: 13 people out of 20 who answered "I actually felt an effect of improving dandruff and itching" 16 people or less 3 points: 9 people or more and 12 people or less out of 20 who answered "I have an actual effect of improving dandruff and itch" 2 points: "I have an actual effect of improving dandruff and itch" Number of respondents is 5 to 8 out of 20 1 point: 4 or less out of 20 responding that "there is a feeling of improvement effect on dandruff and itch" In addition, 3 points or more in the above evaluation criteria It shall have the effect of improving dandruff and itching.

<High temperature storage stability>
An acceleration test was performed on each of the hair wash compositions of Examples and Comparative Examples by the following method.
Specifically, it is placed in a container (SV-50A, manufactured by Niden Rika Glass Co., Ltd.) that does not adsorb miconazole nitrate as the component (D) and does not evaporate water, and put it in a thermo-hygrostat at a temperature of 50° C. and a relative humidity of 40%. Stored for 1 month.
After storage for 1 month, each hair cleansing composition was sampled, and the content of the active ingredient (miconazole nitrate) before and after the accelerated test was quantified by a high performance liquid chromatograph (HPLC) method under the following measurement conditions. ..
The ratio (%) of the quantitative value of the content of the active ingredient after the acceleration test to the quantitative value of the content of the active ingredient before the acceleration test (hereinafter, may be referred to as “initial value”) is as follows. "High temperature storage stability" was evaluated according to the following evaluation criteria, which was obtained based on the formula (1).
Ratio (%) of the content of the active ingredient after the acceleration test to the initial value=(quantitative value of the content of the active ingredient after the acceleration test)/(quantitative value of the content of the active ingredient before the acceleration test)×100 ..Formula (1)
[HPLC measurement conditions]
・Apparatus High-pressure pump: LC-20AD (Shimadzu Corporation)
Autosampler: SIL-20A (manufactured by Shimadzu Corporation)
Column oven: CTO-20A (Shimadzu Corporation)
UV detector: SPD-M20A (manufactured by Shimadzu Corporation) (measurement wavelength: 230 nm)
・Column: Octadecylsilylated silica gel column (GL Science Co., Ltd.)
・Column temperature: 40℃
-Mobile phase: mixed solution of methanol/0.05 mol/L ammonium dihydrogen phosphate solution (4/1 (volume ratio))
・Flow rate: 1.3 mL/min ・Injection volume: 10 μL
-Evaluation criteria for "high temperature storage stability"-
⊚: The ratio of the content of the active ingredient after the acceleration test to the initial value is 98% or more. ◯: The ratio of the content of the active ingredient after the acceleration test to the initial value is 95% or more and less than 98%. ×: After the acceleration test The ratio of the content of the active ingredient to the initial value is less than 95%. In the above evaluation criteria, “⊚” or “◯” has “high temperature storage stability”.

From the results of the above Examples and Comparative Examples, in the hair cleansing compositions of Examples 1 to 29, the carboxylic acid salt type of the (A) component containing the azole antifungal agent of the (D) component was used. A highly hydrophobic coacervate composed of an anionic surfactant, the (B) amphoteric surfactant, and the cationic polymer of the (C) component is produced, and the coacervate precipitates during rinsing and is applied to the hair and scalp. It was considered that the close contact exerts an excellent antibacterial effect and an excellent effect of improving dandruff and itch.

The details of each component used in the above Examples and Comparative Examples are shown in Table 5 below.

Examples of aspects of the present invention include the following.
<1> (A) a carboxylate-type anionic surfactant,
(B) an amphoteric surfactant,
(C) at least one cationic polymer selected from dimethyldiallylammonium chloride polymer and dimethyldiallylammonium chloride-acrylic acid copolymer;
(D) an azole antifungal agent,
(E) at least one selected from the group consisting of rosemary extract, phenoxyethanol, and assembly extract,
The hair cleansing composition is characterized in that the dimethyldiallylammonium chloride-acrylic acid copolymer as the component (C) has a molar ratio of structural units derived from dimethyldiallylammonium chloride of 65 mol% or more.
<2> In the above <1>, the mass ratio of the content of the component (A) to the content of the component (B) represented by [(A)/(B)] is 0.8 to 16. The hair cleansing composition described in
<3> From <1> to <2>, wherein the content of the component (A) is 5% by mass to 11% by mass, and the content of the component (B) is 2.5% by mass to 10% by mass. The hair cleansing composition according to any one of 1.
<4> The hair cleaning composition according to any one of <1> to <3>, wherein the content of the component (C) is 0.3% by mass to 2% by mass.

Since the hair cleansing composition of the present invention has an excellent effect of improving dandruff and itchiness and excellent storage stability at high temperatures, it can be suitably used for shampoos, rinse-in shampoos, conditioning shampoos, treatment-in shampoos and the like. is there.

Claims

(A) a carboxylate type anionic surfactant,
(B) an amphoteric surfactant,
(C) at least one cationic polymer selected from dimethyldiallylammonium chloride polymer and dimethyldiallylammonium chloride-acrylic acid copolymer;
(D) an azole antifungal agent,
(E) at least one selected from the group consisting of rosemary extract, phenoxyethanol, and assembly extract,
A hair cleansing composition, wherein the molar ratio of the structural unit derived from dimethyldiallylammonium chloride in the dimethyldiallylammonium chloride-acrylic acid copolymer as the component (C) is 65 mol% or more.
The mass ratio of the content of the component (A) to the content of the component (B) represented by [(A)/(B)] is 0.8 to 16. Hair cleansing composition.
The content of the component (A) is 5% by mass to 11% by mass, and the content of the component (B) is 2.5% by mass to 10% by mass. Hair cleansing composition.
The hair cleansing composition according to any one of claims 1 to 3, wherein the content of the component (C) is 0.3% by mass to 2% by mass.