JP2008031449A - Cationic group-containing copolymer and cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new copolymer improving foam quality in cleansing the hair using the cleanser therefrom and hair strokability with fingers in rinsing the hair and imparting moist touch feeling and conditioning effect to the hair and the skin after use. <P>SOLUTION: The copolymer is provided, which is obtained by copolymerization between a specific cationic group-containing monomer, a diallylamine-based monomer and a (meth)acrylamide-based monomer. By using this copolymer, a cosmetic significantly improved in moist touch feeling and conditioning effect is obtained. When this copolymer is used in a hair/skin cleanser, it has been found that the cleanser is good in foamability. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a cationic group-containing copolymer and a cosmetic, particularly a hair and skin cleanser.

  Generally, in cosmetics, the touch during use and after use is emphasized. For example, in the case of hair and skin cleansers, in addition to the detergency that is the original function, the foam quality generated during washing and the feel of the hair and skin after washing are regarded as important. As for the foam quality, creamy foam quality with particularly fine bubbles tends to be preferred. On the other hand, with regard to the feel of hair and skin, a detergent containing a surfactant having a high detergency may degrease hair and skin more than necessary, and it is desired to give a moist and preferable feel. Yes. There is also a desire for a conditioning effect that prevents hair damage during shampooing.

Therefore, it is widely practiced to improve the foam quality and feel of use by blending various polymers in the detergent base. For example, Patent Documents 1, 2, and 3 disclose cleaning materials in which an anionic monomer, a cationic monomer, and an amphoteric copolymer composed of a nonionic monomer are blended. . Further, Patent Document 4 discloses a cleaning material in which a cationic polymer composed only of a cationic monomer and a cationic copolymer composed of a cationic monomer and a nonionic monomer are blended. Yes.
Special table 2002-532532 gazette Japanese Examined Patent Publication No. 7-88289 JP-A-7-166191 Japanese Patent Laid-Open No. 3-93711

  Although the cleaning materials described in the above-mentioned patent documents improve the texture of dry hair after shampooing, the conditioning effect is insufficient. Therefore, the problem to be solved by the present invention is to improve the foam quality at the time of washing and the fingering of the hair at the time of rinsing, and to provide a moist feeling and conditioning effect to the hair and skin after use. It is to provide a polymer.

  In view of the above circumstances, as a result of extensive research, by using a copolymer obtained by polymerizing a specific cationic group-containing monomer, a diallylamine monomer, and a (meth) acrylamide monomer, The present inventors have found that a cosmetic material with significantly improved moist feeling and conditioning effect can be obtained. Moreover, when it used for hair and skin washing | cleaning material, it discovered that foaming became favorable and came to complete this invention.

（式中、Ｒ_１は水素原子又はメチル基を示し、Ｒ_２及びＲ_３はそれぞれ独立して炭素数１〜４のアルキル基又はアルケニル基を表し、Ｒ_４は水素原子又は炭素数１〜４のアルキル基又はアルケニル基を表し、Ｙは酸素原子又は−ＮＨ−又は−Ｏ−ＣＨ_２ＣＨ（ＯＨ）−基を表し、Ｚは炭素数１〜４の直鎖状又は分岐状のアルキレン基を表し、Ｘは酸の共役塩基、ハロゲン原子、炭素数１〜４のアルキルサルフェート基を示す）で表されるカチオン性基含有ビニル単量体である。）

（式中、Ｒ_５およびＲ_６はそれぞれ独立して水素またはメチル基を表し、Ｒ_７およびＲ_８はそれぞれ独立して水素または炭素数１〜６のアルキル基あるいはアルコキシ基を表し、Ｘ⁻は前記の意味を表す。）

（式中、Ｒ_１は前記の意味を表し、Ｒ_９及びＲ_１０はそれぞれ独立して水素原子又は炭素数１〜４の直鎖状もしくは分岐状のアルキル基又はアルケニル基を表す。） That is, the first subject of the present invention is (A) a cationic group-containing monomer represented by the following general formula (I), and (B) a diallylamine monomer represented by the following general formula (II). And a copolymer having (C) (meth) acrylamide monomer represented by the following general formula (III) as an essential constituent monomer.

(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ each independently represents an alkyl group or an alkenyl group having 1 to 4 carbon atoms, and R ₄ represents a hydrogen atom or 1 to 4 carbon atoms. Y represents an oxygen atom or —NH— or —O—CH ₂ CH (OH) — group, and Z represents a linear or branched alkylene group having 1 to 4 carbon atoms. X represents a conjugate group of an acid, a halogen atom, or an alkyl sulfate group having 1 to 4 carbon atoms). )

(Wherein R ₅ and R ₆ each independently represent hydrogen or a methyl group, R ₇ and R ₈ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group, and X ⁻ Represents the above meaning.)

(In the formula, R ₁ represents the above meaning, and R ₉ and R ₁₀ each independently represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms.)

  In the copolymer, the molar ratio of structural units derived from (A) a cationic group-containing monomer, (B) a diallylamine monomer, and (C) a (meth) acrylamide monomer is ((A) + It is preferable that (B)) / (C) = 2/99 to 99/2 and (A) / (B) = 2/98 to 98/2. In the copolymer, the weight average molecular weight is preferably 10,000 to 10,000,000.

  The second subject of the present invention is (A) a cationic group-containing monomer represented by the following general formula (I), and (B) a diallylamine-based monomer represented by the following general formula (II): A cosmetic containing a copolymer having (C) (meth) acrylamide monomer represented by the following general formula (III) as an essential constituent monomer.

It is preferable that the cosmetic further contains an anionic surfactant or a fatty acid soap.
The cosmetic is preferably hair and skin cleanser.

  The copolymer of the present invention comprises a specific cationic group-containing monomer, a diallylamine monomer, and a (meth) acrylamide monomer as essential constituent monomers, so that hair and skin after use It becomes useful as a conditioning base material which can give a moist feeling and a conditioning effect.

（式中、Ｒ_１は水素原子又はメチル基を示し、Ｒ_２及びＲ_３はそれぞれ独立して炭素数１〜４のアルキル基又はアルケニル基を表し、Ｒ_４は水素原子又は炭素数１〜４のアルキル基又はアルケニル基を表し、Ｙは酸素原子、−ＮＨ−又は−Ｏ−ＣＨ_２ＣＨ（ＯＨ）−基を表し、Ｚは炭素数１〜４の直鎖状又は分岐状のアルキレン基を表し、Ｘは酸の共役塩基、ハロゲン原子、炭素数１〜４のアルキルサルフェート基で表されるカチオン性基含有ビニル単量体である。） Hereinafter, embodiments of the present invention will be described in detail.
Cationic group-containing copolymer The cationic group-containing copolymer according to the present invention includes a cationic group-containing monomer represented by the following general formula (I) and a diallylamine represented by the following general formula (II). And a (meth) acrylamide monomer represented by the following general formula (III) as essential constituent monomers.

(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ each independently represents an alkyl group or an alkenyl group having 1 to 4 carbon atoms, and R ₄ represents a hydrogen atom or 1 to 4 carbon atoms. Y represents an oxygen atom, —NH— or —O—CH ₂ CH (OH) — group, and Z represents a linear or branched alkylene group having 1 to 4 carbon atoms. X is a cationic group-containing vinyl monomer represented by a conjugate base of an acid, a halogen atom, or an alkyl sulfate group having 1 to 4 carbon atoms.)

（式中、Ｒ_５およびＲ_６はそれぞれ独立して水素またはメチル基を表し、Ｒ_７およびＲ_８はそれぞれ独立して水素または炭素数１〜６のアルキル基あるいはアルコキシ基を表し、Ｘ⁻は前記の意味を表す。）

(Wherein R ₅ and R ₆ each independently represent hydrogen or a methyl group, R ₇ and R ₈ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group, and X ⁻ Represents the above meaning.)

（式中、Ｒ_１は前記の意味を表し、Ｒ_９及びＲ_１０はそれぞれ独立して水素原子又は炭素数１〜４の直鎖状もしくは分岐状のアルキル基又はアルコキシ基を表す。）

(Wherein R ₁ represents the above meaning, and R ₉ and R ₁₀ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alkoxy group.)

The cationic group-containing monomer represented by the general formula (I) includes dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, and diisopropylaminoethyl (meth) acrylate. , Dibutylaminoethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) Acrylamide, diisopropylaminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butylamido (Meth) acrylic acid ester or (meth) acrylamide having a dialkylamino group such as propyl (meth) acrylamide, styrene having a dialkylamino group such as dimethylaminostyrene, dimethylaminomethylstyrene, 4-vinylpyridine, 2- List quaternized monomers having amino groups such as vinyl pyridines such as vinyl pyridine, N-vinyl heterocyclic compounds such as N-vinyl imidazole, vinyl ethers such as aminoethyl vinyl ether and dimethylaminoethyl vinyl ether. X ⁻ is a monovalent inorganic or organic anion and may be any one as long as it can form a salt of quaternary ammonium. For example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid , Maleic acid, fumaric acid, citric acid, tartaric acid, adipine Acid neutralized products with inorganic or organic acids such as sulfamic acid, toluenesulfonic acid, lactic acid, pyrrolidone-2-carboxylic acid and succinic acid, or halogenation such as methyl chloride, ethyl chloride, methyl bromide and methyl iodide Examples thereof include quaternary ammonium salts quaternized with a general quaternizing agent such as alkyl, dimethyl sulfate, diethyl sulfate, and di-n-propyl sulfate.

Among these, quaternary ammonium salts obtained by quaternizing alkylaminoalkyl (meth) acrylate or alkylaminoalkyl (meth) acrylamide with the quaternizing agent are preferable. The present invention is not limited to such examples, and one or more of these cationic group-containing monomers can be arbitrarily used.

The diallylamine monomer of the component (B) used in the present invention is an alkyl diallyl ammonium salt represented by the general formula (II). In the general formula (II), R ₇ and R ₈ which are substituents of the quaternary ammonium nitrogen are the same or different and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group. The alkyl group or alkoxy group having 1 to 4 carbon atoms may be linear or branched, and the hydroxyl group may be partially substituted. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a 2-hydroxyethyl group, and a 2-hydroxypropyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a tert-butoxy group.
Further, in the general formula (II), X ⁻ is a monovalent inorganic or organic anion and may be any one as long as it can form a quaternary ammonium salt. , Nitric acid, acetic acid, formic acid, maleic acid, fumaric acid, citric acid, tartaric acid, adipic acid, sulfamic acid, toluenesulfonic acid, lactic acid, pyrrolidone-2-carboxylic acid, acid neutralized products such as succinic acid, or methyl chloride, Examples thereof include alkyl halides such as ethyl chloride, methyl bromide and methyl iodide, and quaternary ammonium salts quaternized with a general quaternizing agent such as dimethyl sulfate, diethyl sulfate and di-n-propyl sulfate. R ₇ and R ₈ may be the same or different.

Among these, diallyl-type quaternary ammonium salts such as dimethyldiallylammonium chloride, diethyldiallylammonium chloride, and dipropyldiallylammonium chloride are preferable. The present invention is not limited to such examples, and one or more of these cationic group-containing monomers can be arbitrarily used.

As the (meth) acrylamide monomer of the component (C) used in the present invention, in the general formula (III), R ₉ and R ₁₀ which are nitrogen substituents are the same or different and are hydrogen atoms or The straight chain or branched chain having 1 to 4 carbon atoms may be used. (Meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide , Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide and the like.

Of these, (meth) acrylamide is preferred. The present invention is not limited to such examples, and one or more of these (meth) acrylamide monomers can be arbitrarily used.

In order to obtain the cationic group-containing copolymer of the present invention, preferred (A) cationic group-containing monomer, (B) diallylamine monomer and (C) (meth) acrylamide monomer-derived composition The molar ratio of units is ((A) + (B)) / (C) = 2/98 to 98/2, and the molar ratio of structural units derived from (A) and (B) is (A) / ( B) = 2/98 to 98/2, more preferably ((A) + (B)) / (C) = 7/93 to 93/7, (A) / (B) = 9/91 to 91/9, more preferably ((A) + (B)) / (C) = 15/85 to 60/40, (A) / (B) = 20/80 to 80/20. When the constitutional unit derived from the cationic group-containing monomer is excessive, the moist feeling and the conditioning effect are not sufficiently exhibited when blended in a cosmetic.

（式中、Ｒ_１は水素原子又はメチル基を示し、Ｒ_２及びＲ_３はそれぞれ独立して炭素数１〜４のアルキル基又はアルケニル基を示し、Ｒ_４は水素原子又は炭素数１〜４のアルキル基を示し、Ｙは酸素原子、−ＮＨ−又は−Ｏ−ＣＨ_２ＣＨ（ＯＨ）−基を表し、Ｚは炭素数１〜４の直鎖状又は分岐状のアルキレン基を表し、Ｘ⁻は酸の共役塩基、ハロゲン原子、炭素数１〜４のアルキルサルフェート基で表されるカチオン性基含有ビニル単量体である。） Cosmetics The cosmetic of the present invention comprises a cationic group-containing monomer represented by the following general formula (I), a diallylamine monomer represented by the following general formula (II), and the following general formula (III) And a cationic copolymer having an essential component as a (meth) acrylamide monomer represented by the formula:

(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ each independently represents an alkyl group or an alkenyl group having 1 to 4 carbon atoms, and R ₄ represents a hydrogen atom or 1 to 4 carbon atoms. Y represents an oxygen atom, —NH— or —O—CH ₂ CH (OH) — group, Z represents a linear or branched alkylene group having 1 to 4 carbon atoms, X ^- is a conjugate base, a halogen atom, a cationic group-containing vinyl monomer represented by alkyl sulfates group having 1 to 4 carbon atoms acid).

The cationic group-containing monomer represented by the general formula (I) is a quaternary ammonium salt obtained by quaternizing alkylaminoalkyl (meth) acrylate or alkylaminoalkyl (meth) acrylamide.
In the general formula (I), R ₂ and R ₃ which are nitrogen substituents are an alkyl group having 1 to 4 carbon atoms or an alkoxy group, a cycloalkyl group having 3 to 6 carbon atoms, and a phenyl group. In the general formula (I), R ₄ which is a nitrogen substituent is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkenyl group.

The alkyl group or alkoxy group having 1 to 4 carbon atoms may be linear or branched, and the hydroxyl group may be partially substituted. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a 2-methylethyl group, a 2-methylpropyl group, a 2-hydroxyethyl group, and a 2-hydroxypropyl group. . Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a tert-butoxy group. Moreover, as a C3-C6 cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group etc. are mentioned. R ₂ and R ₃ and R ₄ may be the same or different.
Examples of the cationic group-containing monomer used in the present invention include a quaternary ammonium salt modified product of N, N-dimethylaminoethyl (meth) acrylate, and a quaternary N, N-dimethylaminopropyl (meth) acrylamide. Examples thereof include ammonium salt-modified products, and preferred are quaternary ammonium salt-modified products of N, N-dimethylaminopropyl (meth) acrylamide.
In the general formula (I), X ^- conjugate base of the acid, a halogen atom, an alkyl sulfate group having 1 to 4 carbon atoms, but may as long as it can form a quaternary ammonium salt, for example, Examples include chloride ion, fluoride ion, iodide ion, sulfate ion, and benzenesulfonate ion.

（式中、Ｒ_５およびＲ_６はそれぞれ独立して水素またはメチル基を表し、Ｒ_７およびＲ_８はそれぞれ独立して水素または炭素数１〜６のアルキル基あるいはアルコキシ基を表し、Ｘ⁻は前記の意味を表す。） Examples of diallylamine monomers represented by the general formula (II) include N, N-dialkyldiallylammonium salts and N, N-dialkoxydiallylammonium salts.

(Wherein R ₅ and R ₆ each independently represent hydrogen or a methyl group, R ₇ and R ₈ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group, and X ⁻ Represents the above meaning.)

In the general formula (II), R ₇ and R ₈ which are substituents of the quaternary ammonium nitrogen are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group. The alkyl group or alkoxy group having 1 to 4 carbon atoms may be linear or branched, and the hydroxyl group may be partially substituted.
Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a 2-hydroxyethyl group, and a 2-hydroxypropyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a tert-butoxy group.
In the general formula (II), X ^- conjugate base of the acid, a halogen atom, an alkyl sulfate group having 1 to 4 carbon atoms, but may as long as it can form a quaternary ammonium salt, for example, Although chloride ion, fluoride ion, iodide ion, sulfate ion, benzenesulfonate ion, etc. are mentioned, N, N-dimethyldiallylammonium chloride or N, N-diethyldiallylammonium chloride is preferable.

（式中、Ｒ_１は前記の意味を表し、Ｒ_９及びＲ_１０はそれぞれ独立して水素原子又は炭素数１〜４の直鎖状もしくは分岐状のアルキル基又はアルコキシ基を表す。） Examples of the (meth) acrylamide monomer represented by the general formula (III) include (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N, N-diethyl. (Meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide and the like can be mentioned.

(Wherein R ₁ represents the above meaning, and R ₉ and R ₁₀ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alkoxy group.)

In the general formula (III), R ₉ and R ₁₀ may be either a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group that is linear or branched.
Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a tert-butyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a tert-butoxy group.

 In the cosmetic according to the present invention, the amount of the cationic group-containing copolymer can be adjusted as appropriate, but is 0.01 to 10% by weight, more preferably 0.1%, based on the total amount of the cosmetic. ~ 5% by weight. When the amount of the copolymer is too small, the moist feeling may not be sufficiently improved. On the other hand, when the amount is too large, a sticky feeling may occur.

The method for producing the cationic group-containing copolymer of the present invention is not particularly limited, but it is usually preferable to use a method such as an aqueous solution polymerization method, a suspension polymerization method, an emulsion polymerization method or a precipitation polymerization method. Although there is no restriction | limiting in particular as an apparatus, The kneader which has a lid | cover can also be used, when becoming high viscosity. As an aqueous solution polymerization method, a soluble monomer component is added to water or a hydrophilic organic solvent or a mixed solvent thereof, and dissolved oxygen in the system is removed by substitution with an inert gas such as nitrogen or carbon dioxide. And a method in which a polymerization initiator is added and reacted. The polymerization initiation temperature is usually about 20 to 90 ° C., preferably normal temperature or 40 to 80 ° C., and the reaction time is about 1 to 10 hours. The concentration of the monomer mixed solution used here is preferably 10 to 50% by weight.

Representative examples of the hydrophilic organic solvent include lower alcohols such as methanol, ethanol and 2-propanol, cyclic ethers such as tetrahydrofuran and dioxane, acetone, acetonitrile, dimethyl sulfoxide and the like. Among these, ethanol, 2-propanol is preferred.

In addition, as the polymerization initiator, a peroxide that dissolves uniformly in water, an organic or inorganic peracid or a salt thereof, an azobis-based compound alone or a redox-based compound in combination with a reducing agent is used. Specific examples include, for example, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride Salt, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, persulfate and triethylamine, triethanolamine And combinations with tertiary amines such as dimethylaniline. Among these, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazoline- 2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, sodium persulfate, potassium persulfate or ammonium persulfate alone, or these A combination of a persulfate and a tertiary amine such as triethylamine, triethanolamine or dimethylaniline is particularly preferred.

The amount of the polymerization initiator used is in the range of 0.01 to 5 mol%, preferably 0.01 to 3 mol%, particularly preferably 0.01 to 1 mol%, based on the monomer component. Incidentally, when the amount of the polymerization initiator used is too large, the polymerization degree of the polymer chain of the main chain does not increase, and the expected performance cannot be exhibited. On the other hand, when the amount is too small, the reaction rate of the polymerization reaction does not increase and the amount of residual monomer increases.

The weight average molecular weight of the copolymer of the present invention is preferably from 10,000 to 10,000,000, more preferably from 100,000 to 5,000,000, more preferably from 500,000 to 4,000,000, and more preferably 1,000,000. It is most preferable if it is 3 million or less. When the weight average molecular weight is too small, the properties as a polymer are hardly exhibited, and a moist feeling cannot be sufficiently obtained when blended in a cosmetic. Moreover, even if it is too large, the moist feeling tends to be reduced. In the polymer of the present invention, the order in which the monomers are added is not particularly specified, and the monomers may be added in blocks or randomly. Usually, the monomers are randomly added. A polymer added to is obtained.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to an Example. Examples 1 to 4 show specific production methods of the cationic group-containing copolymer of the present invention, and Comparative Example 1 shows various copolymers used as controls. The weight average molecular weight was measured by gel permeation chromatography (hereinafter abbreviated as GPC). The measurement conditions for GPC are shown below.
GPC measuring condition column: OHpak SB-806MHQ × 2 (manufactured by Showa Denko KK)
Column temperature: 40 ° C
Detector: RI
Solvent: 0.25M acetic acid / 0.05M sodium nitrate aqueous solution (pH = 3.5)
Flow rate: 1.0 ml / min Sample concentration: 0.5%
Injection volume: 50 μl
Standard: Pullulan (Shodex STANDARD P-82, Showa Denko KK)

(Example 1)
Methacryloyloxyethyltrimethylammonium chloride (MOETAC) 25.3 g (122 mmol), diallyldimethylammonium chloride (DADMAC) 19.7 g (122 mmol), acrylamide (AAm) 44.6 g (627 mmol), ion-exchanged water 646.7 g It was put into a 1 L glass flask, mixed and dissolved, and purged with nitrogen. The mixture was gradually heated to 50 ° C. with stirring in a nitrogen atmosphere. To this polymerization composition, 0.18 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added to initiate polymerization. The polymerization was completed at 45 to 55 ° C. for 6 hours to complete the polymerization, and a cationic copolymer aqueous solution having a weight average molecular weight of about 1.6 million was obtained. The viscosity of the obtained 10% by mass aqueous polymer solution was 9,100 mPa · s with a BM rotational viscometer (25 ° C., rotor No. 4, 30 rpm). Further, the viscosity of the 0.5% by mass aqueous solution of the polymer was 25 mPa · s by a BM type rotational viscometer (25 ° C., rotor No. 2, 30 rpm).

(Example 2)
14.5 g (70 mmol) of MOETAC, 11.3 g (70 mmol) of DADMAC, 49.2 g (692 mmol) of AAm, and 418.9 g of ion-exchanged water were placed in a glass flask having an internal volume of 1 L, mixed and dissolved, and purged with nitrogen. The mixture was gradually heated to 80 ° C. with stirring under a nitrogen atmosphere. 0.19 g of sodium persulfate was added to this polymerization system composition to initiate polymerization. The mixture was maintained at 75 to 85 ° C. for 6 hours to complete the polymerization, and an aqueous cationic copolymer solution having a weight average molecular weight of about 640,000 was obtained. The viscosity of the 10% by weight aqueous polymer solution obtained was 600 mPa · s using a BM type rotational viscometer (25 ° C., rotor No. 4, 30 rpm). The viscosity of the 0.5% by mass aqueous solution of the polymer was 21 mPa · s with a BM type rotational viscometer (25 ° C., rotor No. 2, 30 rpm).

(Example 3)
MOETAC 10.5 g (51 mmol), DADMAC 24.5 g (152 mmol), AAm 37.0 g (521 mol), and ion-exchanged water 514.7 g were put into a glass flask having an internal volume of 1 L, mixed and dissolved, and purged with nitrogen. The mixture was gradually heated to 50 ° C. with stirring in a nitrogen atmosphere. To this polymerization composition, 0.14 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added to initiate polymerization. The mixture was maintained at 45 to 55 ° C. for 6 hours to complete the polymerization, and a cationic copolymer aqueous solution having a weight average molecular weight of about 1,500,000 was obtained. The viscosity of the 10% by weight aqueous polymer solution obtained was 1,500 mPa · s using a BM type rotational viscometer (25 ° C., rotor No. 4, 30 rpm). Further, the viscosity of the 0.5% by mass aqueous solution of the polymer was 23 mPa · s by a BM type rotational viscometer (25 ° C., rotor No. 2, 30 rpm).

Example 4
19.3 g (93 mmol) of MOETAC, 15.0 g (212 mmol) of DADMAC, 65.6 g (923 mmol) of AAm, and 391.8 g of ion-exchanged water were placed in a glass flask having an internal volume of 1 L, mixed and dissolved, and purged with nitrogen. The mixture was gradually heated to 60 ° C. with stirring in a nitrogen atmosphere. To this polymerization composition, 100 g of a 0.5 wt% sodium persulfate aqueous solution and 100 g of a 0.5 wt% sodium bisulfite aqueous solution were added dropwise over 3 hours to initiate polymerization. The mixture was maintained at 55 to 65 ° C. for 3 hours to complete the polymerization, and a cationic copolymer aqueous solution having a weight average molecular weight of about 180,000 was obtained. The viscosity of the 10% by weight aqueous polymer solution obtained was 55 mPa · s with a BM rotational viscometer (25 ° C., rotor No. 2, 30 rpm). Further, the viscosity of the 0.5% by mass aqueous solution of the polymer was 10 mPa · s by a BM type rotational viscometer (25 ° C., rotor No. 2, 30 rpm).

(Example 5)
Methacrylamidopropyltrimethylammonium chloride (MAPTAC) 30.8 g (140 mmol), DADMAC 22.6 g (140 mmol), AAm 51.2 g (720 mmol), and ion-exchanged water 657.7 g were put into a glass flask having an internal volume of 1 L and mixed and dissolved. And replaced with nitrogen. The mixture was gradually heated to 50 ° C. with stirring in a nitrogen atmosphere. To this polymerization composition, 0.21 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added to initiate polymerization. The polymerization was terminated at 45 to 55 ° C. for 6 hours to complete the polymerization, and a cationic copolymer aqueous solution having a weight average molecular weight of about 2.8 million was obtained. The viscosity of the obtained 10% by mass aqueous polymer solution was 11,200 mPa · s with a BM type rotational viscometer (25 ° C., rotor No. 4, 30 rpm). Moreover, the viscosity of 0.5 mass% polymer aqueous solution was 30 mPa * s by BM type | mold rotational viscometer (25 degreeC, rotor No. 2,30 rpm).

(Example 6)
15.4 g (70 mmol) of MAPTAC, 33.9 g (210 mmol) of DADMAC, 51.2 g (720 mmol) of AAm, and 729.0 g of ion-exchanged water were placed in a glass flask having an internal volume of 1 L, mixed and dissolved, and purged with nitrogen. The mixture was gradually heated to 50 ° C. with stirring in a nitrogen atmosphere. To this polymerization composition, 0.20 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added to initiate polymerization. The polymerization was terminated at 45 to 55 ° C. for 6 hours to complete the polymerization, and a cationic copolymer aqueous solution having a weight average molecular weight of about 2.2 million was obtained. The viscosity of the obtained 10% by mass aqueous polymer solution was 2,600 mPa · s with a BM type rotational viscometer (25 ° C., rotor No. 4, 30 rpm). Further, the viscosity of the 0.5% by mass aqueous solution of the polymer was 25 mPa · s by a BM type rotational viscometer (25 ° C., rotor No. 2, 30 rpm).

(Example 7)
30.8 g (140 mmol) of MAPTAC, 34.9 g (140 mmol) of DADMAC, 51.2 g (720 mmol) of AAm, and 592.6 g of ion-exchanged water were placed in a glass flask having an internal volume of 1 L, mixed and dissolved, and purged with nitrogen. The mixture was gradually heated to 70 ° C. with stirring in a nitrogen atmosphere. To this polymerization composition, 0.23 g of sodium persulfate was added to initiate polymerization. The mixture was maintained at 75 to 85 ° C. for 6 hours to complete the polymerization, and an aqueous cationic copolymer solution having a weight average molecular weight of about 1 million was obtained. The viscosity of the 10% by mass aqueous polymer solution obtained was 320 mPa · s with a BM rotational viscometer (25 ° C., rotor No. 4, 30 rpm). The viscosity of the 0.5% by mass aqueous solution of the polymer was 21 mPa · s with a BM type rotational viscometer (25 ° C., rotor No. 2, 30 rpm).

(Example 8)
15.4 g (70 mmol) of MAPTAC, 33.9 g (210 mmol) of DADMAC, 51.2 g (720 mmol) of AAm, and 570.0 g of ion-exchanged water were placed in a glass flask having an internal volume of 1 L, mixed and dissolved, and purged with nitrogen. The mixture was gradually heated to 70 ° C. with stirring in a nitrogen atmosphere. To this polymerization composition, 0.25 g of sodium persulfate was added to initiate polymerization. The mixture was maintained at 75 to 85 ° C. for 6 hours to complete the polymerization, and a cationic copolymer aqueous solution having a weight average molecular weight of about 1,200,000 was obtained. The viscosity of the obtained 10% by mass aqueous polymer solution was 500 mPa · s with a BM rotational viscometer (25 ° C., rotor No. 4, 30 rpm). Moreover, the viscosity of 0.5 mass% polymer aqueous solution was 20 mPa * s by BM type | mold rotational viscometer (25 degreeC, rotor No. 2,30 rpm).

(Comparative Example 1)
As a general cationic copolymer, polyquaternium-7 (copolymer of DADMAC and AAm) having a weight average molecular weight of about 2.45 million was used. The viscosity of the obtained 10% by mass aqueous polymer solution was 6,000 mPa · s with a BM type rotational viscometer (25 ° C., rotor No. 4, 30 rpm). Further, the viscosity of the 0.5% by mass aqueous solution of the polymer was 25 mPa · s by a BM type rotational viscometer (25 ° C., rotor No. 2, 30 rpm).

 An actual use test was carried out on skin cleansing agents blended with various copolymers. When each of the cleaning materials was adjusted according to the following formulation and diluted 20 times with ion-exchanged water, the foam quality of the resulting cleaning materials was compared sensorily and evaluated according to the following criteria. The foam viscosity measurement results are shown in Table 1. In addition, the compounding quantity of surfactant to mix | blend and a copolymer is a pure part conversion value.

Evaluation criteria used in the present invention will be shown.
(1) Foam quality With respect to the foam quality of each skin cleanser, an actual use test was carried out by 10 panelists based on the following evaluation criteria, and the average score was calculated.
5 points: Creamy.
4 points: Slightly creamy.
3 points: normal 2 points: not a little creamy
1 point: Not creamy.

(2) Feel when rinsing 5 points: Slip feeling 4 points: Slight slip feeling 3 points: Normal 2 points: Slight squeaking feeling 1 point: Squeaking feeling

(3) Feels of dry skin after rinsing 5 points: Slip feeling 4 points: Slight slip feeling 3 points: Normal 2 points: Slight feeling 1 point: Tight feeling

In the skin cleansing materials of Test Example (9) and Test Example (10), the foam quality at the time of washing, and the feeling at the time of rinsing and after rinsing were inferior. On the other hand, in the skin cleansing agents of Test Examples (1) to (8) in which the cationic group-containing copolymer of the present invention consisting of Examples 1 to 8 was blended, the foam quality at the time of washing, It was confirmed that the feeling after rinsing was excellent.

 An actual use test was carried out on a hair cleansing agent blended with various copolymers. For each, a hair cleanser was prepared according to the following formulation, and the evaluation at the time of rinsing with hair was sensory compared and evaluated according to the following criteria. The evaluation results are shown in Table 2. In addition, the compounding quantity of surfactant to mix | blend and a copolymer is a pure part conversion value.

(2) Conditioning effect at the time of rinsing and after rinsing For the fingering of the hair after rinsing and after rinsing with each hair washing agent, an actual use test was carried out by 10 panelists based on the following evaluation criteria, and the average score Was calculated.
5 points: Good fingering.
4 points: Slightly good according to the finger.
3 points: Normal 2 points: Somewhat bad fingering 1 point: Bad fingering

The hair cleansing material of Test Example (20) in which no copolymer was blended resulted in poor fingering during rinsing.
On the other hand, in the hair washing material of Test Example (19) in which the copolymer of Comparative Example 1 was blended, although the fingering during rinsing was improved to some extent, it was not a satisfactory result.
On the other hand, with regard to the hair cleaning materials of Test Examples (11) to (18) in which the cationic group-containing copolymer of the present invention consisting of Examples 1 to 8 was blended, the fingering of the hair during rinsing was excellent. It was confirmed that

From the above, quaternary ammonium salt monomer obtained by quaternizing alkylaminoalkyl (meth) acrylate or alkylaminoalkyl (meth) acrylamide, and cationic monomer and (meth) acrylamide obtained by quaternizing diallylamine series. It has been clarified that the use of a copolymer containing a monomer as a constituent monomer improves the foam quality specifically.
The above-mentioned effects are obtained by using a quaternary ammonium salt monomer quaternized with alkylaminoalkyl (meth) acrylate or alkylaminoalkyl (meth) acrylamide, a cationic monomer quaternized with diallylamine, and a (meth) acrylamide system. This is an effect exhibited by using a monomer as a constituent monomer, and is an effect that cannot be obtained when one of these constituent monomers is missing.
Cosmetics with different dosage forms, such as a hair treatment composition and a skin cosmetic composition, which are obtained by the cosmetic composition of the present invention, utilizing the foam quality, conditioning effect, and further improvement of dosage form stability. The material composition was prepared by conventional methods and further confirmed in each case. Other examples of the present invention will be given below, but the present invention is not limited thereto.

（製法）
精製水を７０°Cに加熱し、他成分を加え均一に溶解した後、冷却した。
上記シャンプーは、洗浄時の泡質とともに、すすぎ時の指通りにもきわめて優れているものであった。 Example 9
shampoo

(Manufacturing method)
Purified water was heated to 70 ° C., and other components were added and dissolved uniformly, followed by cooling.
The shampoo was extremely excellent in the quality of the foam during washing and the fingering during rinsing.

（製法）
常法に基づき、液体状ボディ用洗浄剤(ボディソープ)を製造した。
上記ボディーシャンプーは、洗浄時の泡質とともに、洗浄後のしっとり感にも極めて優れているものであった。 (Example 10)
Body shampoo

(Manufacturing method)
A liquid body cleaning agent (body soap) was produced based on a conventional method.
The body shampoo was extremely excellent in the moist feeling after washing as well as the foam quality during washing.

（製法）
常法に基づき、洗顔料を製造する。
上記洗顔料は、洗浄時の泡質及び洗浄後のしっとり感にも極めて優れているものであった。
(Example 11)
Facial wash

(Manufacturing method)
A face wash is manufactured based on a conventional method.
The above-mentioned face wash was extremely excellent in foam quality during washing and moist feeling after washing.

Claims (8)

(A) The following general formula (I)

(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ each independently represents an alkyl group or an alkenyl group having 1 to 4 carbon atoms, and R ₄ represents a hydrogen atom or 1 to 4 carbon atoms. Y represents an oxygen atom or —NH— or —O—CH ₂ CH (OH) — group, and Z represents a linear or branched alkylene group having 1 to 4 carbon atoms. X represents a conjugate base of an acid, a halogen atom, or an alkyl sulfate group having 1 to 4 carbon atoms), and (B) the following general formula (II) )

(Wherein R ₅ and R ₆ each independently represent hydrogen or a methyl group, R ₇ and R ₈ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group, and X ⁻ At least one diallylamine-based monomer represented by the above-mentioned meaning), and (C) the following general formula (III)

(Wherein R ₁ represents the above meaning, and R ₉ and R ₁₀ each independently represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms). A cationic group-containing copolymer obtained by polymerizing at least one (meth) acrylamide monomer as an essential constituent monomer. The molar ratio of the structural units derived from (A), (B) and (C) is ((A) + (B)) / (C) = 2/98 to 98/2, and (A) and (B The cationic group-containing copolymer according to claim 1, wherein the molar ratio of the structural units derived from () is (A) / (B) = 2/98 to 98/2.   The cationic group-containing copolymer according to claim 1, wherein the weight average molecular weight is 10,000 to 10,000,000.   The cationic group-containing vinyl monomer represented by the general formula (I) is a (meth) acryloyloxyalkylenealkylammonium quaternized product and / or a (meth) acrylamidoalkylammonium quaternized product, Item 4. The cationic group-containing copolymer according to any one of Items 1 to 3.   Cosmetics containing the cationic group containing copolymer of any one of Claims 1-4.   The cosmetic according to claim 5, further comprising an anionic surfactant.   The cosmetic according to claim 5 or 6, which is a hair and skin cleanser. Furthermore, fatty acid soap is included, Cosmetics of any one of Claims 5-7 characterized by the above-mentioned.