JP5509533B2 - Hair cleanser and cleanser product - Google Patents

Description

The present invention relates to hair Kamiarai cleaning agent and detergent product foam quality is excellent.

  For cosmetics, shampoos, facial cleansers, body soaps, and other types of rinse-off cosmetics have a fine foam texture when applied to the hair and skin and foamed, providing a rich foam quality that is difficult to defoam. On the other hand, cosmetics that do not rinse away, such as hair foam agents, are finely shaped when they are discharged from a container, have shape retention, and quickly defoam when applied to hair etc. A suitable good foam quality is required.

  Furthermore, in hair cosmetics, since hair that has been dyed is faded by washing the hair, there is a need for a hair cosmetic that suppresses discoloration and maintains the hair color after dyeing. On the other hand, hair cosmetics using a special surfactant (see Patent Document 1: Japanese Patent Laid-Open No. 7-233303 and Patent Document 2: Japanese Patent Laid-Open No. 2002-275038) have been proposed. However, there are problems that the anti-fading effect is insufficient and the foam quality is lowered. From the above, there has been a demand for a hair cosmetic composition that has an excellent anti-fading effect and good foam quality.

  In skin cosmetics, elbows, arms, shins, and the like may become white (whitening) in a dry environment such as in winter due to elution of the stratum corneum in the skin after washing. In view of the above, a skin cosmetic that prevents such whitening of the skin and has good foam quality has been desired.

Japanese Patent Laid-Open No. 7-233303 JP 2002-275038 A JP 2007-161986 JP 7-315463 A

The present invention has been made in view of the above circumstances, and an object thereof is to provide a hair Kamiarai cleaning agent and detergent product foam quality is excellent. Furthermore, it aims at providing the thing which is excellent in the anti-fading effect of hair in the case of a hair cleaning agent, and excellent in the anti-whitening effect of skin in the case of a skin cleaning agent.

  As a result of intensive studies to achieve the above object, the present inventors have used (A) an amphoteric surfactant or an anionic surfactant in combination with a specific (B) acrylic acid polymer, and (A) / ( B) improves the foam quality by adjusting the mass ratio represented by B) to 0.1 to 50.0. Further, in the case of hair cosmetics, it has an excellent anti-fading effect on hair, and in the case of skin cosmetics, the skin It has been found that the effect of preventing whitening is excellent, and has led to the present invention.

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｒ²は水素原子又は−ＣＨ₂ＯＨ基を示し、Ａは酸素原子又は−ＮＨ−を示す。）

（式中、Ｒ³は水素原子又はメチル基を示し、Ｍは水素原子、アルカリ金属原子、アンモニウム又はアミンを示す。）
［２］．（Ａ）両性界面活性剤がカルボキシベタイン型両性界面活性剤である請求項［１］記載の毛髪洗浄剤、
［３］．（Ｂ）アクリル酸系ポリマーの重量平均分子量が３，０００〜１００，０００である［１］又は［２］記載の毛髪洗浄剤、
［４］．フォーマー容器と、このフォーマー容器に充填されてなる［１］〜［３］のいずれかに記載の毛髪洗浄剤とからなる毛髪洗浄剤製品を提供する。 Therefore, the present invention
[1]. (A) a surfactant selected from amphoteric surfactants, sulfate ester type anionic surfactants and N-acyl amino acid type anionic surfactants, and (B) a monomer represented by the following general formula (1) An acrylic acid-based polymer containing 70 to 95 mol% of units and 5 to 30 mol% of monomer units represented by the following general formula (2) as constituent units is contained, and the blending amount of component (A) is 5 The blending amount of the component (B) is 0.2 to 5% by mass, and the mass ratio represented by (A) / (B) is 0.1 to 50.0. hair Kamiarai cleaning agent which is characterized,

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or a —CH ₂ OH group, and A represents an oxygen atom or —NH—).

(In the formula, R ³ represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, an alkali metal atom, ammonium or an amine.)
[ 2 ]. (A) according to claim [1] amphoteric surfactant is a carboxybetaine type amphoteric surfactants SL placing hair Kamiarai cleaning agent,
[ 3 ]. (B) a weight average molecular weight of the acrylic acid polymer is 3,000 to 100,000 [1] or [2], wherein the hair Kamiarai cleaning agent,
[ 4 ]. A foamer container, to provide a hair Kamiarai purification agent product comprising a hair Kamiarai cleaning agent according to any of this to be filled in the former vessel [1] to [3].

  ADVANTAGE OF THE INVENTION According to this invention, the foam quality of cosmetics can be improved, Furthermore, the hair cosmetics excellent in the fading prevention effect of hair, and the skin cosmetics excellent in the skin whitening prevention effect can be provided.

  The cosmetic of the present invention comprises (A) an amphoteric surfactant or an anionic surfactant, and (B) 70 to 95 mol% of a monomer unit represented by the general formula (1), and the general formula (2). Cosmetics containing an acrylic acid-based polymer containing 5 to 30 mol% of monomer units represented as structural units, and having a mass ratio represented by (A) / (B) of 0.1 to 50.0 It is a fee.

(A) Amphoteric surfactants or anionic surfactants Amphoteric surfactants include carboxybetaine-type amphoteric surfactants such as coconut oil fatty acid amidopropyl betaine, lauric acid amidopropyl betaine, lauryl dimethylaminoacetic acid betaine, lauryl hydroxy sulfobetaine, such as sulfobetaine, aminocarboxylic acid types such as lauryl aminopropionic acid, 2-alkyl -N- carboxymethyl -N- hydroxyethyl imidazolinium betaine, N- coconut oil fatty acid acyl -N '- carboxyethyl - N '- hydroxyethyl ethylenediamine salt imidazolinium betaine type, such as, lecithin, and the like. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the anionic surfactant include sulfuric acid ester type anionic surfactants such as alkyl (preferably C10-16) sulfate, polyoxyethylene alkyl (preferably C10-16) ether sulfate, sulfonic acid type such as α-olefin sulfonate, N-acyl-N-methyltaurine salt, alkyl sulfosuccinate, N-acyl-N-methylglycine salt, N-acyl-N-methyl-β-alanine salt ( N-acyl (preferably C10-18) amino acid type such as N-lauroyl-N-methyl-β-alanine salt), N-acyl glutamate (N-coconut oil fatty acid acyl-L-glutamate etc.) Examples thereof include phosphoric acid ester types such as anionic surfactants, alkyl phosphates, and polyoxyethylene alkyl ether phosphates.

  Examples of the counter ion used for these surfactant salts include alkali metal salts such as sodium salt and potassium salt, and amine salts such as ammonium salt, triethanolamine salt and aminomethylpropanol salt.

  As the component (A), a surfactant selected from carboxybetaine type amphoteric surfactants, sulfate ester type anionic surfactants and N-acyl amino acid type anionic surfactants is preferable.

  Although the compounding quantity of (A) component is not specifically limited, In cosmetics, it is 0.01 mass% or more normally, 0.1-50 mass% is preferable, and 0.2-25 mass% is more. preferable. If the blending amount is less than 0.01% by mass, the intended effect may not be obtained. In the case of a rinsing-type hair cosmetic, 5 to 20% by mass is more preferable, in the case of a type of rinsing-free hair cosmetic, 0.2 to 1% by mass is more preferable, and in the case of a skin cosmetic. 0.2 to 10% by mass is more preferable.

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｒ²は水素原子又は−ＣＨ₂ＯＨ基を示し、Ａは酸素原子又は−ＮＨ−を示す。）

（式中、Ｒ³は水素原子又はメチル基を示し、Ｍは水素原子、アルカリ金属原子、アンモニウム又はアミンを示す。） (B) Acrylic acid-based polymer The monomer unit 70 to 95 mol% represented by the general formula (1) and the monomer unit 5 to 30 mol% represented by the general formula (2) are included as structural units. It is an acrylic acid polymer made of a copolymer, and can be used alone or in combination of two or more.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or a —CH ₂ OH group, and A represents an oxygen atom or —NH—).

(In the formula, R ³ represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, an alkali metal atom, ammonium or an amine.)

  Examples of the alkali metal atom include sodium atom, potassium atom, and amine include monoethanolamine, diethanolamine, triethanolamine and the like. When M is an alkali metal atom, ammonium or amine, -COOM forms a salt. To do.

  Examples of the monomer corresponding to the monomer unit represented by the general formula (1) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, 2, Examples include 3-dihydroxypropyl acrylate and 2,3-dihydroxypropyl methacrylate. Examples of the monomer corresponding to the monomer unit represented by the general formula (2) include acrylic acid, methacrylic acid, and salts thereof.

  The proportion of the monomer unit represented by the general formula (1) is 70 to 95 mol% in the acrylic acid polymer (in 100 mol% of all monomer units), preferably 75 to 85 mol%. The ratio of the monomer unit represented by (2) is 5 to 30 mol% in the acrylic acid polymer (in 100 mol% of all monomer units), and preferably 10 to 20 mol%. When the proportion of the monomer unit represented by the general formula (1) is less than 70 mol% and the proportion of the monomer unit represented by the general formula (2) exceeds 30 mol%, the desired effect cannot be obtained, When the proportion of the monomer unit represented by the general formula (1) exceeds 95 mol% and the proportion of the monomer unit represented by the general formula (2) is less than 5 mol%, the foam quality improving effect is obtained. Absent.

  Further, the acrylic acid polymer of the present invention may contain monomer units other than the monomer unit represented by the general formula (1) or (2) as long as the effects of the present invention are not impaired. it can. Examples of other monomer units include monomer units corresponding to nonionic monomers, amphoteric monomers, semipolar monomers, cationic monomers, and polysiloxane group-containing monomers. It is done. However, these monomers do not include monomers corresponding to the monomer units represented by the above (1) or (2). As for the ratio of monomer units other than the monomer unit represented by General formula (1) or (2), 0-15 mol% in an acrylic acid polymer is preferable. The acrylic acid polymer of the present invention may be a random copolymer or a block copolymer, and the acrylic acid polymer of the present invention comprises monomer units represented by the general formulas (1) and (2). An acrylic acid polymer comprising a copolymer as a unit is preferred.

  Examples of nonionic monomers include esters of alcohols having 1 to 22 carbon atoms and (meth) acrylic acid, amides of alkylamines having 1 to 22 carbon atoms and (meth) acrylic acid, ethylene glycol, 1 , 3-propylene glycol, etc. and (meth) acrylic acid monoesters, esters in which the monoester's hydroxyl group is etherified with methanol, ethanol, etc., (meth) acryloylmorpholine, etc. Examples of the body include betaine group-containing (meth) acrylic esters, betaine group-containing (meth) acrylamides, etc., and examples of semipolar monomers include amine oxide group-containing (meth) acrylic esters and amine oxide groups (Meth) acrylamide and the like, and examples of the cationic monomer include quaternary ammonia. Um group-containing (meth) acrylic esters, quaternary ammonium group-containing (meth) acrylamide and the like.

  The polysiloxane group-containing monomer is a compound having a polysiloxane structure and a structure capable of being covalently linked to an acrylic acid polymer. Such a structural unit has a high affinity with the silicone oil usually used together in the cosmetic composition, and serves to bind the silicone oil with other structural units in the acrylic acid-based polymer. In particular, it is considered that there is a function to increase the adsorption power of silicone oil to damaged hair and the like.

In addition, the ratio of each monomer unit in the acrylic acid polymer is the carbonyl group, amide bond, IR absorption of polysiloxane structure and various functional groups, and the methyl group or amide bond site of polydimethylsiloxane and adjacent to them. It can be measured by ¹ H-NMR such as methyl group and methylene group, or ¹³ C-NMR thereof.

The weight average molecular weight of the acrylic acid polymer is usually 3,000 to 1,000,000. If it is less than 3,000, the conditioning effect may be weakened, and if it exceeds 1,000,000, a feeling of adhesion may occur. The lower limit of the weight average molecular weight is preferably 10,000 or more, and the upper limit of the weight average molecular weight is preferably 400,000 or less, more preferably 200,000 or less, and more preferably 100,000 or less from the viewpoint of further increasing the smoothness after drying. More preferred is 50,000 or less.

  The weight average molecular weight of the acrylic acid polymer can be measured by gel permeation chromatography. Specifically, the apparatus: manufactured by Tosoh Corporation, SC8010, SD8022, RI8020, CO8011, PS8010, column: Wako Pure Chemical Industries, Ltd. Using Wakopak Co., Ltd. (Wakobeads G-50), developing solvent: water / methanol / acetic acid / sodium acetate = 6/4 / 0.3 / 0.41), polyethylene glycol can be obtained as a standard substance.

  The molecular weight of the acrylic acid polymer can be adjusted, for example, by controlling the degree of polymerization of the polymer. The molecular weight and viscosity can also be controlled by increasing or decreasing the addition amount of a crosslinking agent such as a polyfunctional acrylate. However, if a crosslinking agent is added as much as possible, the molecular weight and the viscosity are rapidly increased, and thus there are aspects that are difficult to control in industrial production. For this reason, it is preferable not to contain a crosslinking agent.

  The acrylic acid-based polymer of the present invention can be obtained in accordance with the method described in JP2007-161986. For example, after mixing monomers giving their respective structural units or their precursors and copolymerizing them by methods such as solution polymerization, suspension polymerization, emulsion polymerization, etc., addition of polysiloxane structure, condensation reaction as necessary It can manufacture by performing etc. In addition, the counter ion of the anionic monomer represented by the general formula (2) may be subjected to polymerization by substituting part or all of the anionic monomer other than hydrogen ion by a neutralization reaction before polymerization. Alternatively, after the other reaction, a part or all of the reaction may be replaced with a substance other than hydrogen ion by a neutralization reaction. These can be appropriately selected depending on the ease of synthesis. In addition, each monomer is mix | blended so that each monomer may become a specific molar ratio with respect to the total amount (100 mol%) of all the monomers. The proportion of the structural unit composed of each monomer in the copolymer of the present invention is the same as the blending amount of each monomer at the time of copolymerization.

  The polymerization reaction is preferably performed in a hydrophilic solvent. Examples of the hydrophilic solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, alcohol solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, and sec-butanol, water, and the like. Is mentioned. These may be used alone or in combination of two or more. Among these, it is preferable to use an alcohol solvent.

  As polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethyl) Valeronitrile), dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (1-cyclohexanecarbonitrile), 2,2 ′ -Azobis (2-methyl-N- (2-hydroxyethyl) -propionamide), 2,2'-azobis (2-amidinopropane) dihydrochloride, dimethyl 2,2'-azobis (2-methylpropionate) ), Benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, etc., persulfate, or redox thereof. Scan system and the like, can be used without particular limitation. The polymerization initiator is preferably used in the range of 0.01 to 5% by mass with respect to all monomers.

  The polymerization reaction can be performed, for example, in an inert gas atmosphere such as nitrogen or argon, preferably at 30 to 120 ° C, more preferably at 40 to 100 ° C, and usually for 1 to 30 hours. After completion of the polymerization, the produced copolymer may be isolated from the reaction solution by an appropriate means such as solvent distillation or addition of a poor solvent. This copolymer can be used as it is or after further purification, for example, in the production of cosmetics. Purification can be carried out by combining appropriate means such as reprecipitation, solvent washing, membrane separation and the like as necessary.

  (B) Although the compounding quantity of a component is not specifically limited, It is 0.01 mass% or more normally in cosmetics, 0.1-10 mass% is preferable, and 0.2-5 mass% is more. preferable. If the blending amount is less than 0.01% by mass, the intended effect may not be obtained.

  In the present invention, the mass ratio of the components (A) and (B) represented by (A) / (B) may be in the range of 0.1 to 50.0 in order to obtain the desired effect. Necessary, 0.1 to 35.0 is preferable. When (A) / (B) is less than 0.1, a preferable foam quality cannot be obtained, and when it exceeds 50.0, the foam quality improving effect cannot be sufficiently obtained, and the effect of preventing the fading of hair and the suppression of whitening of the skin are achieved. The effect cannot be obtained. In the case of a type of hair cosmetic to be washed away, 1.0 to 35.0 is more preferred, in the case of a type of hair cosmetic that is not washed away, 0.1 to 1.0 is more preferred, and in the case of skin cosmetics, 5 is preferred. 0.0 to 35.0 is more preferable.

  The cosmetic of the present invention includes, in addition to the above components, a cationic surfactant, a nonionic surfactant, a semipolar surfactant, and a component (B) as long as the effects of the present invention are not impaired depending on the purpose. Other polymer compounds, polyhydric alcohols, higher alcohols, silicones, lower alcohols, long chain fatty acids, ester oils, thickeners, fragrances, ultraviolet absorbers, fine particle powders, plant extracts, proteins and their derivatives, amino acids, Preservatives, colorants, pH adjusters, antioxidants, chelating agents, purified water and the like can be blended.

  When blending a fragrance in the cosmetic of the present invention, the fragrance used is the same as the fragrance and fragrance composition described in JP-A-2003-95895. When blending a fragrance composition, the fragrance composition is included in the cosmetic. It is suitable to mix | blend so that a thing may be 0.00001-50 mass%, More preferably, 0.0001-30 mass% is mix | blended.

  Examples of cosmetics include hair or skin cosmetics, and examples of washing-off type hair cosmetics include shampoos, rinse-in shampoos, pre-shampoos and other hair washing agents, washing-out type treatments, rinses, conditioners, etc. Examples of hair cosmetics that do not wash away include treatments that do not wash away, and styling agents. As such a cosmetic, it can be used as a foam agent that is filled in a former container and discharged in a foam form. Examples of the former container include a non-gas type foam discharge container and an aerosol container using a propellant and a pressure-resistant container, and a non-gas type foam discharge container is preferable. The non-gas type foam discharge container is not particularly limited as long as the cosmetic can be mixed with air and discharged in a foamed state. For example, a squeeze foamer that can discharge bubbles by squeezing the bottle body by hand. Examples thereof include a pump former container that can discharge bubbles by pushing down the container and the nozzle part, and can be appropriately selected according to the purpose. Examples of skin cosmetics include body soaps and facial cleansers.

  The cosmetic of the present invention can be prepared based on a conventional method, and can be obtained, for example, by mixing the component (A), the component (B), an optional component, and water (remainder). The obtained cosmetic can be appropriately filled in a container.

  The pH of the hair cosmetic of the present invention is preferably 3 to 7, and the pH of the skin cosmetic is preferably 4 to 11. Preferred pH adjusters include inorganic acid salts such as sodium hydroxide and sodium pyrophosphate, and organic acids such as glycolic acid and citric acid. In the present invention, the pH is measured at 25 ° C. using a HM-25R type pH meter manufactured by Toa Denpa Kogyo.

  The cosmetic of the present invention is particularly suitable for hair dyed hair because it has an effect of preventing discoloration of the hair dyed hair.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, unless otherwise specified, “%” of the composition represents “% by mass”, the ratio represents the mass ratio, and the amount of each component in the table is the amount converted into the pure amount unless otherwise specified. .

[Preparation example of polymer (1)]
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 100 parts by mass of ethanol, and 96.8 parts by mass of 2-hydroxyethylacrylamide and 3.2 parts of acrylic acid were added to the dropping funnel. And a monomer mixed solution consisting of 80 parts by mass of ethanol was charged, and the reactor was purged with nitrogen, and then heated to 80 ° C. Into the reactor, 1 part by mass of dimethyl 2,2′-azobis (2-methylpropionate) (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the monomer mixture was added over 2 hours. It was dripped. After the completion of the dropwise addition, the mixture was reacted for 6 hours and then cooled to obtain a polymer (1).

[Preparation examples of polymers (2) to (7)]
Polymers (2) to (7) were prepared in the same manner as the preparation method of the polymer (1) except that the monomer and the blending amount thereof were adjusted so as to be the structural units shown in Table 1. The weight average molecular weight is as follows: apparatus: manufactured by Tosoh Corporation, SC8010, SD8022, RI8020, CO8011, PS8010, column: Wako Pure Chemical Industries, Ltd. Wakopak (Wakobeads G-50), developing solvent: water / methanol / acetic acid / sodium acetate = 6/4 / 0.3 / 0.41), and polyethylene glycol was determined as a standard substance.

ＨＥＡＡ：２−ヒドロキシエチルアクリルアミド
ＧＬＭ：２，３−ジヒドロキシプロピルメタクリレート
ＡＡ：アクリル酸
ＭＡ：メタクリル酸

HEAA: 2-hydroxyethylacrylamide GLM: 2,3-dihydroxypropyl methacrylate AA: acrylic acid MA: methacrylic acid

[Examples 1-15, Comparative Examples 1-9]
According to the composition shown to Tables 2-4, the hair washing agent was prepared according to the conventional method. Each hair cleaning agent was evaluated as follows. The results are also shown in Tables 2-4. In addition, pH adjustment was performed at 25 degreeC using the HM-25R type | mold pH meter by Toa Denpa Kogyo.

<Anti-fading effect>
A black hair bundle having a length of 10 cm and a mass of 1 g was immersed in a model bleach solution having a composition 1 of 10 times mass at room temperature for 30 minutes. Thereafter, it was thoroughly washed with warm water and dried. Further, a commercial hair dye (Beauty Lab Hair Color (Stylish Brown); manufactured by Hoyu Co., Ltd.) was applied in the same amount as the mass of the hair bundle, wrapped in a wrap, and treated at room temperature for 30 minutes. Next, 10% POE (2) sodium lauryl ether sulfate of 1/10 mass of the hair bundle mass was applied, combed for 1 minute, rinsed with warm water for 1 minute, and dried to obtain an evaluation hair bundle. The color tone of the hair bundle was measured with a color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. and used as an initial value.
The evaluation hair bundle was wetted with water, 0.1 g of the sample hair cleaning agent was applied thereto, and the hair was combed for 1 minute to quickly adjust the whole hair bundle. Thereafter, it was rinsed with warm water for 1 minute and dried. After repeating this treatment 30 times, the color tone of the hair bundle was measured again with a color difference meter, and the color difference (ΔE *) from the initial value was determined. Note that this value and the visual impression have the following relationship.
ΔE * is 0 or more and less than 1.6: little change in color ΔE * is 1.6 or more and less than 2.5: slight color change ΔE * is 2.5 or more: color change (composition) 1) Model bleach solution Hydrogen peroxide 6%
Ammonia 2%
Sodium hydroxide adjusted to pH 10.5
Purified water balance
Total 100%

<Foam quality evaluation>
The sample hair cleanser was diluted 10 mass times with purified water (corresponding to the dilution factor at the time of shampooing), and this liquid was non-aerosol foamer pump (foam releasing pump container of FIG. ), The foam was picked up, and “feel” and “hardness of foam” of the foam were subjected to sensory evaluation based on the following evaluation criteria. A result is shown by the average value of evaluation of five evaluators.
[Evaluation criteria]
5 points: Good foam quality 4 points: Somewhat good foam quality 3 points: Somewhat bad foam quality 2 points: Bad foam quality 1 point: No foam

[Examples 16 to 26]
According to the compositions shown in Tables 5 and 6, shampoo compositions were prepared by the following preparation methods. About each shampoo composition, the anti-fading effect was implemented similarly to Example 1, and foam quality evaluation was implemented by the following evaluation. The results are also shown in Tables 5 and 6.
Table 5: Each component was stirred and mixed, and finally pH adjustment was performed using glycolic acid or citric acid to prepare a shampoo composition.
Table 6: With the component (a) heated to 80 ° C. and well stirred, purified water that was also heated to 80 ° C. was gradually added with stirring. The amount of purified water added at this time was 25% of the total amount of the composition. The mixed solution was cooled to 50 ° C. with stirring. Separately, the remaining components were mixed, and both solutions were mixed with stirring to prepare a shampoo composition.

<Foam quality evaluation>
Using a shampoo composition (the amount is appropriately selected according to the amount of hair), normal hair washing was performed, and the “feel” and “hardness of foam” of the foam were subjected to sensory evaluation based on the following evaluation criteria. A result is shown by the average value of evaluation of five evaluators.
[Evaluation criteria]
5 points: Good foam quality 4 points: Somewhat good foam quality 3 points: Somewhat bad foam quality 2 points: Bad foam quality 1 point: No foam

[Ratio Comparative Examples 10 to 12]
According to the composition shown in Table 7, a treatment foam was prepared according to a conventional method and filled into a non-aerosol foamer pump (foam discharge pump container of FIG. 1 described in JP-A-7-315463). Each treatment foam was evaluated as follows. The results are also shown in Table 7.

<Anti-fading effect>
The evaluation hair bundle was prepared and the initial value was measured in the same manner as in Example 1. 0.5 g of the sample treatment foam was applied to the evaluation hair bundle, passed through for 1 minute to quickly adjust the whole hair bundle, and then dried with a drier. Two hours after drying, the hair bundle was wetted with warm water, 0.1 g of 10% POE (2) sodium lauryl ether sulfate was applied, passed through for 1 minute, rinsed with warm water for 1 minute, and dried. This sample treatment foam application → drying → cleaning treatment was repeated 30 times, and then the color tone of the hair bundle was again measured with a color difference meter to obtain the color difference (ΔE *) from the initial value. Note that this value and the visual impression have the following relationship.
ΔE * is 0 or more and less than 1.6: little change in color ΔE * is 1.6 or more and less than 2.5: slight color change ΔE * is 2.5 or more: color change
<Foam quality evaluation>
From the non-aerosol foamer pump, 3 g of the treatment foam was discharged in the form of foam, and the sensory evaluation was performed on the “feel” and “hardness of the foam” based on the following evaluation criteria. A result is shown by the average value of evaluation of five evaluators.
[Evaluation criteria]
5 points: Good foam quality 4 points: Somewhat good foam quality 3 points: Somewhat bad foam quality 2 points: Bad foam quality 1 point: No foam

[ Reference Example 1 , Comparative Example 13]
In accordance with the composition shown in Table 8, a skin cleanser was prepared according to a conventional method. The obtained skin cleanser was filled into a non-aerosol foamer pump container described in JP-A-7-315463. The following evaluation was carried out for each skin cleanser. The results are also shown in Table 8.

<Skin whitening suppression effect>
From a non-aerosol foamer pump, 6 g of skin cleanser was discharged in the form of foam and washed from near the wrist to the upper part of the elbow. After wiping off the moisture so that it was pressed with a towel, it was rested in an environment of room temperature 23 ° C. and relative humidity 40%, and the skin whitening state of the elbow and forearm after 1 hour was evaluated according to the following criteria. The evaluation is performed by five evaluators who tend to have white arms in winter, and the result is shown as an average value of the evaluation of the five evaluators.
[Evaluation criteria]
5 points: no whitening at all 4 points: almost no whitening 3 points: slightly whitening 2 points: 1 point with significant whitening 1 point: severe whitening

<Foam quality evaluation>
The foam quality was evaluated in the same manner as in Comparative Example 10 .

The raw materials used in the above examples are shown below.

Claims (4)

(A) a surfactant selected from amphoteric surfactants, sulfate ester type anionic surfactants and N-acyl amino acid type anionic surfactants, and (B) a monomer represented by the following general formula (1) An acrylic acid-based polymer containing 70 to 95 mol% of units and 5 to 30 mol% of monomer units represented by the following general formula (2) as constituent units is contained, and the blending amount of component (A) is 5 The blending amount of the component (B) is 0.2 to 5% by mass, and the mass ratio represented by (A) / (B) is 0.1 to 50.0. hair Kamiarai cleaning agent, characterized.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or a —CH ₂ OH group, and A represents an oxygen atom or —NH—).

(In the formula, R ³ represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, an alkali metal atom, ammonium or an amine.) (A) Hair Kamiarai cleaning agent of amphoteric surfactants claim 1 Symbol placement carboxymethyl betaine type amphoteric surfactants. (B) Hair Kamiarai cleaning agent according to claim 1 or 2 wherein wherein the weight average molecular weight of the acrylic acid polymer is 3,000 to 100,000. A foamer container, hair Kamiarai purification agent product comprising a hair Kamiarai cleaning agent according to any one of claims 1 to 3 comprising filled in the foamer container.