JP2020143002A - Cosmetic composition and hair cleanser - Google Patents

Abstract

To provide a cosmetic composition having excellent residual property of a water soluble anti-dandruff agent after washing.SOLUTION: There is provided a cosmetic composition comprising an acid (A), a surfactant (C), a cationic copolymer (D) and a water-soluble anti-dandruff agent (E), more preferably comprises a vinyl chloride-based copolymer (A) having a structural unit derived from a vinyl-based monomer having a hydrophilic group represented by the following (formula 1) and having a structural unit derived from a vinyl-based monomer having a hydrophobic group represented by the following (formula 2). CH2=C(R1)-COO-(CH2)m-N+R2R3R4 (Formula 1) (R1 represents a hydrogen atom or a methyl group, R2 and R3 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R4 represents CH2COO- or O- group, m represents 1 to 4) CH2=C(R5)-COOR6 (Formula 2) (R5 represents a hydrogen atom or a methyl group, R6 represents a linear, branched or cyclic alkyl group or aromatic group having 1 to 40 carbon atoms.)SELECTED DRAWING: Figure 2

Description

The present invention relates to cosmetic compositions and hair cleansers containing water-soluble antidandruff agents.

It is well known that an antidandruff agent such as zinc pyrithione salt is added to a cosmetic composition. When an anti-dandruff agent is added to a hair cleansing agent such as shampoo, the occurrence of dandruff can be effectively suppressed. This anti-dandruff effect is greatly affected by the persistence on the scalp and hair after washing, and the greater the persistence, the better the anti-dandruff effect. Therefore, in the case of an anti-dandruff agent that does not dissolve in a hair cleaning agent such as shampoo, such as zinc pyrithione salt, it easily remains on the scalp and hair after cleaning, and is excellent in the effect of preventing dandruff. On the other hand, water-soluble anti-dandruff agents (for example, piroctone olamine, cleanbazole, etc.) that are easily dissolved in an aqueous solution of a surfactant such as shampoo have a high anti-dandruff effect on the drug itself, but are used for cleaning containing a large amount of surfactant. Since it is highly soluble in the agent, it does not easily remain on the scalp and hair after washing, and as a result, there is a problem that the original anti-dandruff effect cannot be exhibited.

Patent Documents 1 to 3 report shampoo compositions in which a specific cationic copolymer is blended to enhance the persistence of an antidandruff agent.

Special Table 2005-524689 Japanese Unexamined Patent Publication No. 2010-2156-169 Korean Publication No. 10-2009-0120955

However, Patent Document 1 and Patent Document 2 aim to leave a poorly water-soluble dispersion such as zinc pyrithione salt on hair, and no study has been made on a water-soluble antidandruff agent. Further, the persistence of the water-soluble antidandruff agent of Patent Document 3 is not sufficient, and it is extremely difficult to effectively leave the water-soluble antidandruff agent on the scalp or hair.

As a method of overcoming this problem, it is conceivable to add a large amount of a water-soluble antidandruff agent such as piroctone olamine to the hair cleansing agent, but the hair cleansing agent such as shampoo has an upper limit and also has an upper limit. , There is a concern that a large amount of water-soluble antidandruff-containing waste liquid may be generated after the use of the hair cleansing agent, which may cause environmental pollution.

The present invention is intended to solve the above problems, enhances the persistence of the water-soluble anti-dandruff agent after washing, and exhibits a sufficient anti-dandruff effect only by using a small amount of the water-soluble anti-dandruff agent. It is an object of the present invention to provide a cosmetic composition and a hair cleansing agent which can be used.

As a result of diligent studies in view of the above problems, the present inventors have identified an acid (B) or an acid in addition to the surfactant (C), the cationic copolymer (D) and the water-soluble anti-fluff agent (E). It has been found that the water-soluble anti-fluffing agent (E) exhibits a high residual effect by containing the vinyl-based copolymer (A) of the above, and the present invention has been completed.

That is, the gist of the present invention lies in the following [1] to [9].

[1] A cosmetic composition containing an acid (B), a surfactant (C), a cationic copolymer (D), and a water-soluble antidandruff agent (E).

[2] Further, a structural unit derived from a vinyl-based monomer having a hydrophilic group represented by the following (Formula 1) and a vinyl-based monomer having a hydrophobic group represented by the following (Formula 2) are derived. The cosmetic composition according to [1], which contains a vinyl-based copolymer (A) having the structural unit of.
CH ₂ = C (R ¹ ) -COO- (CH ₂ ) _m- N ⁺ R ² R ³ R ⁴ (Equation 1)
(In (Equation 1), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents CH ₂ COO ⁻ or O. ^- group .m is an integer from 1 to 4).
CH ₂ = C (R ⁵ ) -COOR ⁶ (Equation 2)
(In (Formula 2), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a linear, branched or cyclic alkyl group or aromatic group having 1 to 40 carbon atoms.)

[3] The vinyl-based copolymer (A) is a (methacryloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer, a (ethyl betaine methacrylate / acrylate) copolymer, (acrylate / lauryl acrylate / stearyl acrylate / methacrylic acid). The cosmetic composition according to [2], which is one or more selected from the group consisting of an ethylamine oxide) copolymer and an acrylates / stearyl acrylate / ethylamine methacrylate) copolymer.

[4] The cosmetic according to any one of [1] to [3], wherein the acid (B) is an organic acid and is contained in a molar ratio of 1.8 or more with respect to the water-soluble antidandruff agent (E). Composition.

[5] The cationic copolymer (D) is a cationized guar, polyquaternium-10, polyquaternium-73, a (propyltrimonium chloride acrylamide / dimethylacrylamide) copolymer, and (ethyltrimonium methacrylate / hydroxyethylacrylamide). ) The cosmetic composition according to any one of [1] to [4], which is one kind or two or more kinds selected from the group consisting of copolymers.

[6] The cosmetic composition according to any one of [2] to [5], which contains 0.01% by mass or more of the vinyl copolymer (A).

[7] The cosmetic composition according to any one of [1] to [6], which contains one or both of an anionic surfactant and an amphoteric surfactant as the surfactant (C).

[8] The cosmetic composition according to any one of [1] to [7], wherein the water-soluble antidandruff agent (E) is piroctone olamine.

[9] A hair cleansing agent comprising the cosmetic composition according to any one of [1] to [8].

According to the present invention, the water-soluble anti-dandruff agent after washing is made to have an excellent anti-dandruff effect by enhancing the residual property on the scalp and hair and effectively exerting the original anti-dandruff effect of the water-soluble anti-dandruff agent. A material composition and a hair cleansing agent can be provided.

It is a graph which shows the adsorption promotion rate of Comparative Examples 1-6. It is a graph which shows the adsorption promotion rate of Comparative Example 1 and Examples 1-5. It is a graph which shows the adsorption promotion rate of Comparative Example 1 and Examples 1, 6 to 15.

Hereinafter, embodiments of the present invention will be described in detail, but the description of the constituent elements described below is a typical example of the embodiments of the present invention, and the present invention is not limited to these contents. ..

In addition, in this specification, "polymer" includes not only a synthetic polymer but also a polymer derived from a natural product. Further, (meth) acrylate is a general term for acrylate and methacrylate.
Further, in the present specification, "~" is used in the meaning of including the numerical values before and after it as the lower limit value and the upper limit value.

[Cosmetic composition]
The cosmetic composition of the present invention means any cosmetic used on hair and skin, for example, shampoo, conditioner, conditioner, treatment, hair dye, permant, out bath treatment, hair pack, hair. Widely used so-called cosmetics such as sprays, hair foams, styling products, body shampoos, makeup cleansing, hand soaps, emulsions, lotions, lotions, creams, beauty liquids, sunscreens, foundations, lipsticks, mascara, eye shadows, and hair removers. It includes. In addition, the usage pattern may include those that are applied to the skin, hair, etc. and thoroughly blended and then rinsed (rinsed), those that are not rinsed, and the like.

The cosmetic composition of the present invention is particularly preferably used for hair, and the hair cleansing agent comprising the cosmetic composition of the present invention is preferable because it has an excellent anti-dandruff effect. Here, the hair cleansing agent refers to a hair cleanser that is applied to the hair or scalp to wash it off, and examples thereof include shampoo, conditioner, conditioner, and treatment. According to the present invention, the anti-dandruff effect is improved because the amount of the anti-dandruff agent that exerts the anti-dandruff effect adsorbed on the hair or scalp is improved.

Generally, when diluting shampoo with water for the purpose of smoothing the feel when washing shampoo from hair, water-insoluble precipitates composed of cationic polymers and surfactants (hereinafter referred to as complex) It is necessary to devise the composition of the polymer and the hair cosmetic so that (sometimes referred to as) is produced.

As a method of adsorbing a large amount of zinc pyrithione salt, which is a sparingly soluble antidandruff agent, on the hair, (1) incorporating the zinc pyrithione salt into the above complex, (2) adsorbing a large amount of the above complex on the hair at the time of rinsing can be considered. ..

As a specific method (1) (a method of incorporating a large amount of zinc pyrithione salt into a complex), it is effective to enhance the interaction of the copolymer with zinc ions, which are constituents of the zinc pyrithione salt, for example. It is considered preferable that a large amount of a hydroxyl group having a chelating effect is contained as a constituent unit of the cationic copolymer.

Further, as the specific method (2) (a method of adsorbing a large amount of complex to the hair during rinsing), the copolymer has an appropriate amount of cationic groups, has structural flexibility, and has an affinity weight. For example, the coalescence has a structure having a high affinity for the hair surface. In order for the precipitate to satisfy these conditions, for example, the amount of cationic groups should be controlled by the amount of the structural unit of the polymer, and an acrylic resin should be added to the main chain of the copolymer to give flexibility to the structure. It is conceivable to use it or to incorporate a structure having hydrogen bonding property such as an amide group in order to enhance the affinity for hair.

However, since the water-soluble antidandruff agent itself is washed away during washing, the agents cannot be sufficiently left on the scalp and hair by the above methods (1) and (2).
In view of the above, the present inventor has repeatedly studied, and the acid (B), preferably the acid (B), and the specific vinyl copolymer (A) having a predetermined ratio or more with respect to the water-soluble antidandruff agent (E). By coexisting with the above, the solubility of the water-soluble antidandruff agent (E) in water such as an aqueous shampoo solution can be reduced, and the persistence of the water-soluble antidandruff agent (E) on the hair and scalp is effective. I found that it can be enhanced to.

That is, the cosmetic composition of the present invention preferably contains an acid (B), a surfactant (C), a cationic copolymer (D), and a water-soluble antifocal agent (E). Is a vinyl-based monomer containing an acid (B) in a molar ratio of 1.0 or more with respect to the water-soluble anti-fluffing agent (E), and preferably further having a hydrophilic group represented by the following (Formula 1). It contains a vinyl-based copolymer (A) having a derived structural unit and a structural unit derived from a vinyl-based monomer having a hydrophobic group represented by the following (formula 2).
CH ₂ = C (R ¹ ) -COO- (CH ₂ ) _m- N ⁺ R ² R ³ R ⁴ (Equation 1)
(In (Equation 1), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents CH ₂ COO ⁻ or O. ^- group .m is an integer from 1 to 4).
CH ₂ = C (R ⁵ ) -COOR ⁶ (Equation 2)
(In (Formula 2), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a linear, branched or cyclic alkyl group or aromatic group having 1 to 40 carbon atoms.)

Hereinafter, each component will be described.

<Vinyl copolymer (A)>
The vinyl-based copolymer (A) used in the present invention has a structural unit derived from a vinyl-based monomer having a hydrophilic group represented by the following (formula 1) and a hydrophobicity represented by the following (formula 2). It has a structural unit derived from a vinyl-based monomer having a group.
CH ₂ = C (R ¹ ) -COO- (CH ₂ ) _m- N ⁺ R ² R ³ R ⁴ (Equation 1)
(In (Equation 1), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents CH ₂ COO ⁻ or O. ^- group .m is an integer from 1 to 4).
CH ₂ = C (R ⁵ ) -COOR ⁶ (Equation 2)
(In (Formula 2), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a linear, branched or cyclic alkyl group or aromatic group having 1 to 40 carbon atoms.)

Examples of the vinyl-based monomer having a hydrophilic group represented by the above (formula 1) include betaine-based or amine oxide-based (meth) acrylic-based monomers, and specifically, dimethylaminoethyl methacrylate. Methyl chloride salts or derivatives (eg, methacryloyloxyethyl carboxybetaine or ethyl methacrylate carboxybetaine, ethyl methacrylate amine oxide) and the like can be mentioned.
The vinyl-based copolymer (A) may contain only one type of structural unit derived from a vinyl-based monomer having these hydrophilic groups, or may contain two or more types.

Examples of the vinyl-based monomer having a hydrophobic group represented by the above (formula 2) include methyl (meth) acrylate, ethyl (meth) acrylate, 3-methoxyethyl (meth) acrylate, propyl (meth) acrylate, and i. -Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate , Stearyl (meth) acrylate, 2-phenylethyl (meth) acrylate, benzyl (meth) acrylate, tetradecyl (meth) acrylate and the like. Of these, as the vinyl-based monomer having a hydrophobic group, an alkyl (meth) acrylate having a linear or branched alkyl group is preferable.
The vinyl-based copolymer (A) may contain only one type of structural unit derived from a vinyl-based monomer having these hydrophobic groups, or may contain two or more types.

The content of the structural unit derived from the vinyl-based monomer having a hydrophilic group in the vinyl-based copolymer (A) is preferably 10 to 80% by mass, particularly preferably 15 to 75% by mass. If the content of the structural unit derived from the vinyl-based monomer having a hydrophilic group in the vinyl-based copolymer (A) is not more than the above upper limit, it is too hydrophilic and will not be washed away during rinsing. If there is, the affinity with the water-soluble antidandruff agent (E) becomes good, and a residual effect on the scalp or hair can be obtained.

Further, the content of the structural unit derived from the vinyl-based monomer having a hydrophobic group in the vinyl-based copolymer (A) is preferably 5 to 85% by mass, particularly preferably 10 to 80% by mass. If the content of the structural unit derived from the vinyl-based monomer having a hydrophobic group in the vinyl-based copolymer (A) is not more than the above upper limit, it is too hydrophobic and is uniformly blended in a water-based cosmetic composition such as shampoo. If it is more than the above lower limit, it is too hydrophilic and it is prevented from being washed away at the time of rinsing.

The weight average molecular weight of the vinyl copolymer (A) is preferably 5000 to 2000000, particularly preferably 1000 to 20000. When the weight average molecular weight is at least the above lower limit, irritation to the skin or the like is reduced, and when it is at least the above upper limit, discomfort is less likely to occur when remaining on the hair or scalp, which is preferable.

Here, the weight average molecular weight of the vinyl-based copolymer (A) is measured by gel permeation chromatography (for example, water / methanol / acetic acid / sodium acetate is used as the developing solvent), and polyethylene glycol is used as a standard substance. Can be determined by using. The same applies to the weight average molecular weight of the cationic copolymer (D) described later.

Specific examples of the vinyl-based copolymer (A) include (methacryloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer, (ethyl betaine methacrylate / acrylates) copolymer, and (acrelites / lauryl acrylate / stearyl acrylate / methacrylic acid). Ethylamine oxide) copolymer, acrylates / stearyl acrylate / ethylamine methacrylate) copolymer and the like can be used.

A commercially available product can be used as the vinyl-based copolymer (A), and examples of the commercially available vinyl-based copolymer (A) include (methacryloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer and (methacryl). Examples of the ethyl betaine acid / acrylates) copolymer include polymers of the Yukaformer series manufactured by Mitsubishi Chemical Co., Ltd., and AMPHOSET, 104D, R205S, 510, SM, FH, 301, 202, WPS, 120D and the like can be used. it can. Examples of the (Acrylate / Lauryl acrylate / Stearyl acrylate / Ethylamine methacrylate) copolymer and the Acrylate / Stearyl acrylate / Ethylamine methacrylate) copolymer include polymers of the Diaformer series manufactured by Mitsubishi Chemical Corporation. Z-712, Z631, Z651, Z632 and the like can be used.

Only one kind of these vinyl-based copolymers (A) may be used, or a plurality of kinds may be used.

By having an amphoteric site, the vinyl-based copolymer (A) has an action of enhancing the persistence of the water-soluble antidandruff agent (E) after washing in the presence of the acid (B) described later. The vinyl-based copolymer (A) is not an essential component in the cosmetic composition of the present invention, but the cosmetic composition of the present invention contains the vinyl-based copolymer (A), so that it is water-soluble. The persistence of the dandruff agent (E) can be enhanced more effectively.

The content of the vinyl-based copolymer (A) in the cosmetic composition of the present invention is 5.0% by mass or less, for example, 0.01 to 2.0% by mass, particularly 0.1 to 1.5% by mass. %, Especially preferably 0.2 to 1.0% by mass. When the content of the vinyl-based copolymer (A) is at least the above lower limit, the effect of improving the persistence of the water-soluble antidandruff agent (E) can be effectively obtained. If the mass% of the vinyl copolymer (A) is not more than the above upper limit, there is no discomfort to the scalp or hair.

<Acid (B)>
The cosmetic composition of the present invention contains an acid (B).
Examples of the acid (B) include glycolic acid, lactic acid, tartronic acid, glyceric acid, hydroxybutyric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, γ-hydroxybutyric acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitrate, Leucic acid, mevalonic acid, salicylic acid, cleosortic acid, vanillic acid, syring acid, pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentidic acid, orseric acid, gallic acid, formic acid, acetic acid, gluconic acid, maleic acid, phthalic acid, alginic acid. Organic acids such as are preferable, and a copolymer containing acrylic acid or the like may be used as long as it functions as an acid.

Of these, the acid (B) is preferably an organic acid from the viewpoint of blending into a cosmetic composition, and among the organic acids, hydroxycarboxylic acids such as citric acid, lactic acid, and gluconic acid are water-soluble antifuke agents ( It is preferable from the viewpoint of compatibility with E) and / or the vinyl-based copolymer (A). Particularly preferred is citric acid.

The cosmetic composition of the present invention may contain only one of these acids (B), or may contain two or more of these acids (B).

The acid (B) has a molar ratio (acid (B) / water-soluble antidandruff agent (E) molar ratio) of 1.8 to 30, particularly 2 to the water-soluble antidandruff agent (E) in the cosmetic composition. It is preferably contained in the cosmetic composition of the present invention so as to be 0 to 20, particularly 5.0 to 15. If the content of the acid (B) is in the range below the above upper limit and above the above lower limit, it is water-soluble due to the action of affinity with the water-soluble antidandruff agent (E) and / or the vinyl-based copolymer (A). The persistence of the anti-dandruff agent (E) can be enhanced.

<Surfactant (C)>
The cosmetic composition of the present invention contains a surfactant (C).
As the surfactant, a hydrophilic nonionic surfactant or a lipophilic nonionic surfactant, which will be described later, can be used, but one of an anionic surfactant (c1) and an amphoteric surfactant (c2). Or both are preferably included. As the surfactant (C), any anionic surfactant (c1) and amphoteric surfactant (c2) that can be blended in cosmetics can be used in any combination.

The anionic surfactant (c1) is effective for cleaning hair and scalp. As the anionic surfactant (c1), those blended as a cleaning agent in cosmetics for cleaning can be used, and specifically, fatty acid salts, alkyl sulfates, polyoxyethylene alkyl ether sulfates, N. -Acyl amino acid salt, N-acyl taurine salt and the like can be mentioned. As the fatty acid of the fatty acid salt, for example, one or more selected from lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, isostearic acid and the like can be used. Examples of the alkyl group of the alkyl sulfate and the polyoxyethylene alkyl ether sulfate include a lauryl group, a myristyl group, a palmityl group, a stearyl group, an oleyl group, a linolyl group, an isostearyl group and the like. Examples of the N-acyl group in the N-acyl amino acid salt and the N-acyl taurine salt include N-lauroyl group, N-myristoyl group, N-palmitoyl group, N-stearoyl group, N-oleoyl group and N-cocoyl. A group or the like may be mentioned, and a methyl group or the like may be added to N in the N-acyl group. Examples of amino acids in the N-acylamino acid salt include glutamic acid, aspartic acid, alanine, sarcosine, glycine and the like.

The fatty acid salt, alkyl sulfate, polyoxyethylene alkyl ether sulfate, N-acyl amino acid salt, and N-acyl taurine salt of the anionic surfactant (c1) can be, for example, alkali metal salts. As the alkali metal, for example, potassium or sodium is preferable.

Specific examples of such anionic surfactant (c1) include coconut oil fatty acid sodium, coconut oil fatty acid triethanolamine, sodium lauryl sulfate, polyoxyethylene lauryl ether sulfate sodium, coconut oil fatty acid sarcosine, and N-lauroyl. Examples thereof include sarcosine sodium, N-lauroylmethyl-β-alanine sodium, N-acylmethyltaurine sodium, fatty acid allylglutamate sodium, coconut oil fatty acid acylglutamate triethanolamine, lauroyl glutamate and the like.

Only one kind of these anionic surfactants (c1) may be used, or two or more kinds may be used.

The amphoteric surfactant (c2) is effective in cleaning hair and scalp. Examples of the amphoteric surfactant (c2) include a glycine-type amphoteric surfactant as an amino acid-type amphoteric surfactant, an aminopropionic acid-type amphoteric surfactant, and an aminoacetate betaine-type amphoteric surfactant as a betaine-type amphoteric surfactant. There are sulfobetaine type amphoteric surfactants and the like. Specifically, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, undecyl hydroxyethyl imidazolinium betaine sodium, alkyldiaminoethyl glycine hydrochloride, N-palm oil fatty acid acyl-N'- Carboxyethyl-N'-hydroxyethylethylenediamine sodium, N-palm oil fatty acid acyl-N'-carboxyethoxyethyl-N'-carboxyethylethylenediamine disodium, N-palm oil fatty acid acyl-N'-carboxymethoxyethyl-N' -Carboxymethylethylenediamine disodium, palm oil fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine sodium, sodium laurylaminopropionate, sodium laurylaminodipropionate, triethanolamine laurylaminopropionate, coconut oil alkylbetaine, Lauryl dimethylaminoacetate betaine, stearyl dimethylamino acetate betaine, stearyl dimethyl betaine sodium, coconut oil fatty acid amide propyl betaine (cocamidopropyl betaine), palm oil fatty acid amide propyl betaine, laurate amide propyl acetate betaine, ricinoleate amide propyl betaine, Examples thereof include stearyldihydroxyethylbetaine, lauroyl sarcosine sodium, and lauryl hydroxysulfobetaine.

As these amphoteric surfactants (c2), only one kind may be used, or two or more kinds may be used.

The content of the surfactant (C) in the cosmetic composition of the present invention is not particularly limited, and a suitable amount can be blended according to the intended use, but particularly when it is used as a hair cleansing agent. , It is preferable to mix so that the content in the composition is 5.0 to 30% by mass, particularly 10 to 20% by mass. When the content of the surfactant (C) is not less than the above lower limit, sufficient detergency can be obtained, and when it is not more than the above upper limit, the feeling of use when washing hair and scalp is excellent.

<Cationic polymer (D)>
The cosmetic composition of the present invention contains the cationic polymer (D).
The cationic polymer (D) has a cationic group, and the upper limit of the amount thereof is usually 10.0 meq / g, preferably 5.0 meq / g, and the lower limit is usually 0.1 meq / g. It is preferably 0.4 meq / g. If the amount of cationic groups is 10.0 meq / g or less, it is possible to suppress a decrease in compoundability such as the formation of aggregates when blended in shampoo, and if it is 0.1 meq / g or more, it can be suppressed. , When used as a hair cleansing agent, it tends to have good adsorptivity to hair.

As the cationic copolymer (D), one that is blended as a conditioning imparting material in the cleaning cosmetics can be used. As the cationic copolymer (D), when the shampoo is diluted with water, a water-insoluble precipitate (complex) is formed by the cationic copolymer (D) and the surfactant (C). Such cationic polymers are preferable, and for example, cationized guar, polyquaternium-10, polyquaternium-73, (propyltrimonium chloride acrylamide / dimethylacrylamide) copolymer, (ethylmethacrylate trimonium chloride / hydroxyethylacrylamide) copolymer and the like are used. Can be done.

The weight average molecular weight of the cationic copolymer (D) is preferably 5000 to 5000000, particularly preferably 1000 to 2000000. When the weight average molecular weight is at least the above lower limit, irritation to the skin or the like is reduced, and when it is at least the above upper limit, it is preferable from the viewpoint of usability.

Commercially available products can be used as the cationic copolymer (D). Examples of the cationized guar include Jaguar C13S and C13C manufactured by Sansho Co., Ltd., and Polyquaternium-10 is manufactured by Dow Chemical Co., Ltd. Examples include JR400. Examples of the polyquaternium-73 include DIASLEEEK C-802 and TOMICIDE C-871 manufactured by Mitsubishi Chemical Corporation, and examples of the (propyltrimonium chloride acrylamide / dimethylacrylamide) copolymer include DIASLEEEK C-822 manufactured by Mitsubishi Chemical Corporation. Can be mentioned.

Only one kind of these cationic copolymers (D) may be used, or two or more kinds thereof may be used.

The content of the cationic copolymer (D) in the cosmetic composition of the present invention is not particularly limited, and a suitable amount can be blended depending on the intended use, but particularly when it is used as a hair cleaning agent. The content of the cationic copolymer (D) in the composition is preferably 0.05 to 2% by mass, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more. Is. When the content of the cationic copolymer (D) is 0.05% by mass or more, the above-mentioned complex can be generated and a good conditioning effect can be exhibited. On the other hand, if it is 2% by mass or less, it is possible to prevent this complex from being excessively generated to cause discomfort to the skin and deterioration of the feel such as stiff hair.

<Water-soluble anti-dandruff agent (E)>
The cosmetic composition of the present invention contains a water-soluble antidandruff agent (E).
The water-soluble antidandruff agent (E) has an antibacterial activity effect and exhibits an antidandruff effect when blended in a cosmetic composition. By using a hair cleanser or the like containing a water-soluble anti-dandruff agent (E), the water-soluble anti-dandruff agent (E) is left on the hair to exert its effect, but the more it can be left, the more. A high anti-dandruff effect can be obtained. The cosmetic composition of the present invention comprises a water-soluble antidandruff agent (E) blended with the above-mentioned acid (B) or acid (B) and a vinyl copolymer (A) to prepare a cosmetic composition. After use, excellent persistence of the water-soluble antidandruff agent (E) on hair, skin and the like can be realized.

The water-soluble antidandruff agent (E) means an agent that dissolves in an aqueous solvent such as alcohol, water, or an aqueous surfactant solution in an amount of 0.5% by mass or more.

Examples of the water-soluble antidandruff agent (E) include piroctone olamine, ciclopirox olamine, cleanbazole, salicylic acid, miconazole salt, ketoconazole salt and the like. As the water-soluble antidandruff agent as a cosmetic composition, piroctone olamine and cleanbazole are preferable, and piroctone olamine is most preferable from the viewpoint of antidandruff power.

The cosmetic composition of the present invention may contain only one of these water-soluble antidandruff agents (E), or may contain two or more of them.

The content of the water-soluble antidandruff agent (E) in the cosmetic composition of the present invention is not particularly limited, and an appropriate amount can be blended according to the intended use, but particularly when it is used as a hair cleansing agent. Is preferably blended so that the content in the composition is 0.01 to 10% by mass, particularly 0.1 to 2.0% by mass. If the content of the water-soluble anti-dandruff agent (E) is at least the above lower limit, the anti-dandruff effect of the water-soluble anti-dandruff agent (E) can be effectively obtained, and if it is at least the above upper limit, it is uniform in the cosmetic composition. And has low irritation to the skin.

<Arbitrary ingredient>
In addition to the above-mentioned ingredients, an ingredient that can be usually blended in a cosmetic can be optionally added to the cosmetic composition of the present invention as long as its effect is not impaired. Other ingredients contained in the cosmetic composition are not particularly limited, and can be blended within a range that does not impair the object and effect of the present invention. Examples of such components include the following, and usually, in the following solvents and dispersion media, an acid (B), an anionic surfactant (c1) as a surfactant (C), and an amphoteric surfactant ( In addition to c2), the cationic copolymer (D) and the aqueous anti-surfactant (E), preferably the vinyl-based copolymer (A), the following components are appropriately blended to prepare the cosmetic composition of the present invention. Can be manufactured.

(Water-soluble polymer)
Examples of the water-soluble polymer include methyl cellulose and hydroxymethyl cellulose. Examples of the anionic polymer include acrylic acid derivatives (polyacrylic acid and salts thereof, acrylic acid / acrylamide / ethyl acrylate copolymers and salts thereof, etc.), methacrylic acid derivatives, crotonic acid derivatives and the like. Examples of the nonionic polymer include acrylic acid derivatives (hydroxyethyl acrylate / methoxyethyl acrylate copolymers, polyacrylamide, etc.), vinylpyrrolidone derivatives (polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, etc.) and the like. .. Examples of the amphoteric polymer include dimethyldiallylammonium chloride derivatives (acrylamide / acrylic acid / dimethyldialylammonium chloride copolymer, acrylic acid / dimethyldialylammonium chloride copolymer, etc.) and the like. Only one kind of these may be used, or two or more kinds may be used. It is preferable that these water-soluble polymers are contained in the cosmetic composition in an amount of 0.1 to 1% by mass.

(Hydrophilic nonionic surfactant)
Examples of the hydrophilic nonionic surfactant include polyoxyethylene (hereinafter, may be abbreviated as POE) sorbitan fatty acid esters (for example, POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan monooleate). , POE sorbitan tetraoleate, etc.); POE sorbit fatty acid esters (eg, POE sorbit monolaurate, POE sorbit monooleate, POE sorbit pentaoleate, POE sorbit monostearate, etc.); POE glycerin fatty acid esters (eg, , POE glycerin monostearate, POE glycerin monoisostearate, POE monooleate such as POE glycerin triisostearate); POE fatty acid esters (eg, POE distearate, POE monodiolate, ethylene glycol distearate, etc.); POE alkyl ethers Classes (eg, POE lauryl ether, POE oleyl ether, POE stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE cholestanol ether, etc.); Pluronic types (eg, Pluronic, etc.); POE / polyoxy Propropylene (hereinafter sometimes abbreviated as POP) alkyl ethers (for example, POE / POP cetyl ether, POE / POP-2-decyltetradecyl ether, POE / POP monobutyl ether, POE / POP hydrogenated lanolin, POE / POP glycerin ether, etc.); Tetra POE / Tetra POP ethylenediamine condensates (eg, Tetronic, etc.); POE castor oil cured castor oil derivative (eg, POE castor oil, POE cured castor oil, POE cured castor oil monoisostearate) , POE hardened castor oil triisostearate, POE hardened castor oil monopyroglutamic acid monoisostearic acid diester, POE cured castor oil maleic acid, etc.; POE honeybee / lanolin derivative (eg, POE sorbit honeybee, etc.); Palm oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, cocamidomethylmonoethanolamine, etc.); POE propylene glycol fatty acid ester; POE alkylamine; POE fatty acid amide; sucrose fatty acid ester; alkylethoxydimethylamine oxide; Trioleyl phosphate etc. Can be mentioned.

(Lipophilic nonionic surfactant)
Examples of the lipophilic nonionic surfactant include sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, etc. Polysorbate, penta-2-ethylhexylate diglycerol sorbitan, tetra-2-ethylhexylate diglycerol sorbitan, etc.; glycerin polyglycerin fatty acids (for example, monocotton oil fatty acid glycerin, monoerucate glycerin, sesquioleate glycerin, monosteare Glycerin acid, α, α'-glycerin pyroglutamate oleate, glycerin monostearate, malic acid, etc.); propylene glycol fatty acid esters (for example, propylene glycol monostearate, etc.); cured castor oil derivative; glycerin alkyl ether, etc. Be done.

(Oil)
As the oil content, chain polysiloxane (dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.), cyclic polysiloxane (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.), three-dimensional Silicone resin, silicone rubber, various modified silicones (alkyl-modified silicone, phenyl-modified silicone, amino-modified silicone, polyether-modified silicone, fluorine-modified silicone, etc.) forming a network structure, linear alcohol (lauryl alcohol, cetyl alcohol, etc.) Stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, etc.), branched chain alcohol (monostearyl glycerin ether (bacyl alcohol), 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl (Alcohol, octyldodecanol, etc.), olive oil, jojoba oil, liquid paraffin, fatty acid alkyl ester oil, etc. can be mentioned. The oil content is preferably contained in the cosmetic composition in an amount of 0.1 to 3% by mass.

(Antibacterial active substance other than the water-soluble antidandruff agent (E) having an antidandruff effect)
Examples of antibacterial active substances other than the water-soluble anti-fluffing agent (E) having an anti-fluffing effect include zinc pyrithione, selenium sulfide, particulate sulfur, coal tar, sulfur, whitfield ointment, castellani coating agent, and the like. Aluminum chloride, gentiana violet, undecylene acid and its metal salts, potassium permanganate, sodium thiosulfate, propylene glycol, bitter orange oil, urea preparation, glyceofrubin, 8-hydroxyquinolin siroquinol, thiobendazole, thiocarbamate, halopro Gin, polyene, hydroxypyridone, morpholin, benzylamine, allylamine (eg, terbinafine), tea tree oil, clove leaf oil, coriander, palmarossa, velverin, thyme red, cinnamon oil, synamic aldehyde, citronellic acid, hinokitol ), Ichthiol pail, Sensiva SC-50, Elestab HP-100, azelaic acid, lyticase, iodopropynylbutylcarbamate (IPBC), isothiazalinone and azoles such as octylisothiazalinone, and These combinations can be mentioned.

(Other ingredients)
Other components other than the above include natural extracts of animals and plants and their derivatives, inorganic salts such as sodium chloride, amino acids (glutamic acid or its salts, arginine or its salts, glycine, etc.), solubilizers (ethanol, isopropanol, butanol, etc.) ), Polyhydric alcohols (ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butylene glycol, glycerin, diglycerin, isoprene glycol, etc.), sugars (sorbitol, martitol, xylitol, glucose, etc.) , Fructose, mannitol, inositol, etc.), polymers such as hyaluronic acid, antioxidants, UV absorbers, bactericides, preservatives, chelating agents, fragrances, coloring agents, higher fatty acids, thickeners, metal sequestering agents ( (Edetoate, etc.), pH adjuster, foaming enhancer, pearlizing agent, etc. can be appropriately blended as long as the effects of the present invention are not impaired.

(Solvent or dispersion medium)
The cosmetic composition of the present invention dissolves each of the above-mentioned components in a solvent or disperses them in a dispersion medium, and is particularly preferably used as a hair cosmetic composition, particularly a hair cleansing agent.

Examples of the solvent or dispersion medium used in the cosmetic composition of the present invention include lower alcohols such as ethanol, isopropanol and butanol mentioned as solubilizers for the other components, and water. One type or two or more types of these solvents and dispersion media can be used in combination. Of these, the cosmetic composition of the present invention preferably contains water.

When the cosmetic composition is used as a hair cleanser in a preferred mode of use such as in a bathroom or the like, that is, in the case of an in-bath system application, the content of water in the cosmetic composition. Is preferably 55 to 99.6% by mass. In this case, it is possible to prevent the viscosity from becoming too high and improve the handleability and the usability at the time of application. On the other hand, when the cosmetic composition is used as a hair cleanser outside the bathroom such as an out bath treatment, that is, in a usage form in which rinsing is not preferable, the content of water in the cosmetic composition Is preferably 0.1 to 99% by mass.

Specific embodiments of the present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples as long as the gist of the present invention is not exceeded.

[Example 1-15, Comparative Example 1-6]
A hair cleansing agent containing piroctone olamine was prepared according to the following procedure, and an evaluation test of the amount of piroctone olamine adsorbed on the scalp was conducted by the following method.
The reason why the amount of the water-soluble antidandruff agent (E) adsorbed on the scalp is particularly important in the present invention is as follows.
The water-soluble antidandruff agent (E) exerts its effect by killing bacteria on the scalp. Therefore, it is preferable to adsorb a large amount of antidandruff agent on the scalp or a portion close to the scalp. The method for evaluating the amount of the water-soluble antidandruff agent (E) adsorbed on the scalp was carried out using artificial skin instead of the scalp, as described later.

<Preparation of base shampoo>
In a container, 79.4 parts by mass of a 31 mass% aqueous solution of cocamidopropyl betaine (“AN3130W” manufactured by Nikko Chemicals Co., Ltd.) as an amphoteric surfactant (c2) and a 10 mass% aqueous solution of sodium chloride as a thickener 18. 8 parts by mass, 5.0 parts by mass of cocamidomethylmonoethanolamine as a surfactant ("Aminone C-11S" manufactured by Kao Co., Ltd.), 5.0 parts by mass of a 10% by mass aqueous solution of sodium benzoate as an antiseptic. , 5.0 parts by mass of dipropylene glycol of polyhydric alcohols and 28.2 parts by mass of water were added and stirred, and sufficiently mixed.
Then, 203.6 parts by mass of a 27% by mass aqueous solution of polyoxyethylene (2) sodium lauryl ether sulfate (Hana Seisakusho Emar E-27C) as an anionic surfactant (c1) was further added to the container. , Well mixed to prepare base shampoo.
This base shampoo contains 15.7% by mass of polyoxyethylene (2) sodium lauryl ether sulfate, which is a surfactant (C), 8.6% by mass of cocamidopropyl betaine, and 1. of cocamidomethylmonoethanolamine. It contains 43% by mass.

<Preparation of hair cleanser for evaluation>
Using the above base shampoo, each component was blended with the compositions shown in Tables 1 to 3 to prepare a hair cleanser for evaluation. Each of the evaluation hair cleansers contains 18% by mass of the surfactant (C).

Details of each compounding ingredient in Tables 1 to 3 are as follows.

Vinyl-based copolymer (A-1): (methacryloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer "Yukaformer 301" manufactured by Mitsubishi Chemical Corporation
Vinyl-based copolymer (A-2): (methacryloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer "Yukaformer 104D" manufactured by Mitsubishi Chemical Corporation
Vinyl-based copolymer (A-3): (methacryloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer "Yukaformer 120D" manufactured by Mitsubishi Chemical Corporation
Vinyl-based copolymer (A-4): (Acrylate / Lauryl acrylate / Stearyl acrylate / Ethylamine methacrylate) Copolymer: "Diaformer Z-632" manufactured by Mitsubishi Chemical Co., Ltd.
Vinyl-based copolymer (A-5): (methacryloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer "Yukaformer WPS" manufactured by Mitsubishi Chemical Co., Ltd.
Vinyl-based copolymer (A-6): (methacryloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer "Yukaformer SM" manufactured by Mitsubishi Chemical Co., Ltd.

Cationic copolymer (D-1): Polyquaternium-73 "TOMICIDE C-871" manufactured by Mitsubishi Chemical Corporation
Cationic Copolymer (D-2): (Propyltrimonium Chloride Acrylamide / Dimethylacrylamide) Copolymer "DIASLEEEK C-822" manufactured by Mitsubishi Chemical Corporation
Cationic copolymer (D-3): "Jaguar C13C" manufactured by cationized Guar Sansho Co., Ltd.
Cationic copolymer (D-4): Polyquaternium-10 Dow Chemical Co., Ltd. "JR400"

The vinyl copolymer (A) and the cationic copolymer (D) used for preparing the hair cleansing agent were blended using the following concentrations (mass%).
A-1: Yukaformer 301 30% ethanol solution A-2: Yukaformer 104D 30% ethanol solution A-3: Yukaformer 120 30% ethanol solution A-4: Diaformer Z-632 30% ethanol solution A-5: Yukaformer WPS 30% ethanol solution A-6: Yukaformer SM 30% ethanol solution D-1: TOMICIDE C-871 20% aqueous solution D-2: DIASLEEEK C-822 20% aqueous solution D-3: Jaguar C13C 3% aqueous solution D-4: JR400 5% aqueous solution

<Evaluation of piroctone olamine adsorption amount>
The amount of piroctone olamine adsorbed by the water-soluble antidandruff agent (E) was evaluated using artificial skin. As the artificial skin, "VITRO-SKIN" (4 cm x 4 cm) manufactured by IMS was used.

(Piroctone olamine adsorption test)
A 4 cm × 4 cm artificial skin was placed in a chamber containing 350 g of a 15 mass% glycerin aqueous solution and immersed for 16 to 24 hours to moisten it.
Wet artificial skin was placed in a petri dish with a diameter of 6 cm, 0.2 g of a hair cleaning agent and 0.8 mL of distilled water were added, and the surface was rubbed by hand for 30 seconds. The treated artificial skin was transferred to another petri dish having a diameter of 6 cm, 4 mL of distilled water was added, and the surface was rubbed and washed by hand for 30 seconds. This cleaning operation was repeated once more. Then, the water adhering to the artificial skin was removed, and piroctone olamine adsorbed on the surface was extracted with 8 mL of methanol to obtain an extract. Extraction was performed at 20 to 25 ° C. for 1 hour or longer. The extract was analyzed by HPLC (high performance chromatography) under the following conditions, and the amount of piroctone olamine adsorbed on the artificial skin and remained was quantified.

(Quantification of piroctone olamine by HPLC)
Quantification was performed by the absolute calibration curve method using piroctone olamine using the following high performance chromatography device.
The amount of piroctone olamine adsorbed was expressed as the amount of piroctone olamine adsorbed per artificial skin (4 cm × 4 cm) (μg / plate).
Equipment: Shimadzu SLC-10A / LC-10AT / DGU-14A / SPD-10A / CTO-10AC
Column: GL Sciencesstein C18 3μ × 4.6 × 150mm
Developing solvent: MeOH / aqueous solution 1 = 80/20 (volume ratio)
Aqueous solution 1: 0.1% trifluoroacetic acid / 0.025% EDTA-4Na aqueous solution Flow rate: 0.7 mL / min
Detection wavelength: 300 nm
Column temperature: 40 ° C
Injection volume: 20 μL

<Evaluation result>
The amount of piroctone olamine adsorbed in each example is shown in Tables 1 to 3. In addition, the ratio of the piroctone olamine adsorption amount of each example to the piroctone olamine adsorption amount of Comparative Example 1 was calculated and shown in Tables 1 to 3 as the adsorption promotion rate.
In addition, the adsorption promotion rate of each example is shown as a graph in FIGS.

<Discussion>
Comparative Example 1 contains an acid (B), a surfactant (C), and a water-soluble antidandruff agent (E) (piroctone olamine), and Comparative Examples 2 to 6 are further cationic copolymers (Piroctone olamine). Although it contains D), since the acid (B) / water-soluble antidandruff agent (E) molar ratio is lower than the specified value of the present invention, the adsorption amount of piroctone olamine is low in all cases, and Comparative Example 1 ( The adsorption amount was equal to or less than the reference value).

Examples 1 to 5 contain an acid (B), a surfactant (C), a cationic copolymer (D), and a water-soluble antidandruff agent (E) (piroctone olamine). When the amount of acid (B) to be blended is more than a predetermined value with respect to the water-soluble antidandruff agent (E), the amount of piroctone olamine adsorbed can be dramatically improved. confirmed.
From Examples 1 and 2, it was confirmed that the cationic copolymer (D) is effective in both polyquaternium-73 and cationized guar.
In addition, citric acid is the most effective acid (B), but the adsorption promoting effect of piroctone olamine was also confirmed in Examples 4 and 5 using lactic acid and malic acid.

Examples 6 to 14 further contain a vinyl-based copolymer (A), and when Example 6 and Comparative Example 6 are compared, the vinyl-based copolymer (A) and the acid (B) coexist. , It was confirmed that the adsorption amount of piroctone olamine was improved.
Further, comparing Example 1 and Example 6, the coexistence of the vinyl-based copolymer (A) provides a sufficient effect of promoting the adsorption of piroctone olamine even if the amount of the acid (B) blended is reduced. You can see that you can.

Claims (9)

A cosmetic composition containing an acid (B), a surfactant (C), a cationic copolymer (D), and a water-soluble antidandruff agent (E). Further, a structural unit derived from a vinyl-based monomer having a hydrophilic group represented by the following (Formula 1) and a structural unit derived from a vinyl-based monomer having a hydrophobic group represented by the following (Formula 2). The cosmetic composition according to claim 1, which contains a vinyl-based copolymer (A) having and.
CH ₂ = C (R ¹ ) -COO- (CH ₂ ) _m- N ⁺ R ² R ³ R ⁴ (Equation 1)
(In (Equation 1), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents CH ₂ COO ⁻ or O. ^- group .m is an integer from 1 to 4).
CH ₂ = C (R ⁵ ) -COOR ⁶ (Equation 2)
(In (Formula 2), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a linear, branched or cyclic alkyl group or aromatic group having 1 to 40 carbon atoms.) The vinyl-based copolymer (A) is a (methacryloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer, a (ethyl betaine methacrylate / acrylate) copolymer, (acrylate / lauryl acrylate / stearyl acrylate / ethyl amine oxide oxide). The cosmetic composition according to claim 2, which is one or more selected from the group consisting of a copolymer and a copolymer (stearyl acrylate / ethylamine methacrylate) copolymer. The cosmetic composition according to any one of claims 1 to 3, wherein the acid (B) is an organic acid and is contained in a molar ratio of 1.8 or more with respect to the water-soluble antidandruff agent (E). The cationic copolymer (D) is obtained from the cationized guar, polyquaternium-10, polyquaternium-73, (propyltrimonium chloride acrylamide / dimethylacrylamide) copolymer, and (ethyltrimonium methacrylate chloride / hydroxyethylacrylamide) copolymer. The cosmetic composition according to any one of claims 1 to 4, which is one kind or two or more kinds selected from the group. The cosmetic composition according to any one of claims 2 to 5, which contains 0.01% by mass or more of the vinyl-based copolymer (A). The cosmetic composition according to any one of claims 1 to 6, which contains one or both of an anionic surfactant and an amphoteric surfactant as the surfactant (C). The cosmetic composition according to any one of claims 1 to 7, wherein the water-soluble antidandruff agent (E) is piroctone olamine. A hair cleansing agent comprising the cosmetic composition according to any one of claims 1 to 8.

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