JP2017002133A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition used for skin care such as shampoo and body shampoo, containing an anion surfactant excellent washability and foaming property as a main component, good in not only foaming during washing but also foam quality and excellent in fresh feeling during rinsing and touch feeling (softness, moist feeling) after washing.SOLUTION: There is provided a detergent composition containing a cationic group-containing copolymer constituted by a specific cationic monomer and a specific nonionic monomer (for example methacrylamide propyltrimethylammonium chloride/diaryldimethylammonium chloride/acrylamide=24:29:47 (mol%) copolymer) and a non-ionic polymer.SELECTED DRAWING: None

Description

  The present invention relates to a cleaning composition, and more particularly to a cleaning composition having good foaming and foam quality during cleaning, and a refreshing feeling during rinsing, smoothness after cleaning, and a moist feeling.

  Conventionally, cleaning compositions such as shampoos and body shampoos have been formulated with various cleaning components mainly composed of an anionic surfactant having excellent cleaning properties and foaming properties. When the foam quality is fine and not creamy, or after washing, the skin and hair may be degreased more than necessary, which may worsen.

  Therefore, the blending of various polymers has been studied for the purpose of improving the foam quality at the time of washing and the feel after washing. For example, Patent Document 1 describes the washing performance and conditioning effect obtained by blending an amphoteric polymer and a cationic polymer. An excellent composition, Patent Document 2, a composition excellent in foaming property, foam modification, and feel during rinsing, in which a monosaccharide derivative or oligosaccharide derivative and an amphoteric polymer are blended; Compositions with ampholytic monomers, anionic monomers, and amphoteric polymers composed of cationic monomers have been proposed that have excellent conditioning effects. In these proposals, foaming during use, foam modification and feel, after use The touch was not satisfactory.

  Furthermore, Patent Documents 4 and 5 propose a composition excellent in imparting a conditioning effect in which a polymer composed of a specific cationic monomer and a specific nonionic monomer is blended. The composition ratio between the cationic monomer and the specific nonionic monomer was insufficient in foam modification and smoothness and moist feeling after washing.

Special table 2002-532532 gazette JP-A-7-166191 JP-A-5-246828 US Pat. No. 5,338,541 JP 2008-31449 A

  The present invention relates to a cleaning composition, and more particularly, to provide a cleaning composition that has good foaming and foam quality during cleaning, a refreshing feeling during rinsing, a smoothness after cleaning, and a moist feeling. is there.

（式中、Ｒ_１は水素原子又はメチル基を表し、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のアルキル基若しくはアルケニル基を表し、Ｘ⁻は酸の共役塩基、ハロゲン原子、又は炭素数１〜４のアルキルサルフェート基を表し、ｎは１〜５の整数を表す。）
単量体（ｂ）

（式中、Ｒ_５及びＲ_６はそれぞれ独立して水素原子又はメチル基を表し、Ｒ_７及びＲ_８はそれぞれ独立して水素原子又は炭素数１〜４のアルキル基若しくはアルコキシ基を表し、Ｘ⁻は酸の共役塩基、ハロゲン原子又は炭素数１〜４のアルキルサルフェート基を表す。）
単量体（ｃ）

（式中、Ｒ_９は水素原子又はメチル基を表し、Ｒ_１０及びＲ_１１はそれぞれ独立して水素原子又は炭素数１〜４のアルキル基若しくはアルケニル基を表す。） As a result of intensive studies to solve the above problems, the present inventors have found that the cation having a structural unit derived from the monomers (a) to (c) represented by the following general formulas (1) to (3) Copolymer having a proportion of each constituent monomer of 40 to 80% by weight of monomer (a), 10 to 35% by weight of monomer (b), 10 to 10% of monomer (c) It was found that a detergent composition satisfying the above requirements can be obtained by blending 40% by weight of (A) a cationic group-containing copolymer and (B) a nonionic polymer. Completed.
Monomer (a)

(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. of an alkyl or alkenyl group, X ^- is the conjugate acid-base, a halogen atom, or an alkyl sulfate group having 1 to 4 carbon atoms, n represents an integer of 1 to 5).
Monomer (b)

(Wherein R ₅ and R ₆ each independently represent a hydrogen atom or a methyl group, R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and ^- represents a conjugate base, a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms acid).
Monomer (c)

(Wherein R ₉ represents a hydrogen atom or a methyl group, and R ₁₀ and R ₁₁ each independently represent a hydrogen atom, an alkyl group or an alkenyl group having 1 to 4 carbon atoms)

  That is, according to the present invention, by blending a cationic group-containing copolymer composed of a specific cationic monomer and a specific nonionic monomer, and a nonionic polymer, It is possible to provide a detergent composition having good foaming and foam quality, and excellent refreshing feeling during rinsing, smoothness after washing, and moist feeling.

Below, the cleaning composition of this invention is explained in full detail.
The cationic group-containing copolymer of the component (A) used in the present invention is a structural unit derived from the monomers (a) to (c) represented by the following general formulas (1) to (3) (A) 40 to 80% by weight, (2) 10 to 35% by weight, and (3) 10 to 40% by weight of each constituent monomer (A) It is a cationic group-containing copolymer.

（式中、Ｒ_１は水素原子又はメチル基を表し、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のアルキル基若しくはアルケニル基を表し、Ｘ⁻は酸の共役塩基、ハロゲン原子、又は炭素数１〜４のアルキルサルフェート基を表し、ｎは１〜５の整数を表す。）

(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. of an alkyl or alkenyl group, X ^- is the conjugate acid-base, a halogen atom, or an alkyl sulfate group having 1 to 4 carbon atoms, n represents an integer of 1 to 5).

（式中、Ｒ_５及びＲ_６はそれぞれ独立して水素原子又はメチル基を表し、Ｒ_７及びＲ_８はそれぞれ独立して水素原子、又は炭素数１〜４のアルキル基若しくはアルコキシ基を表し、Ｘ⁻は酸の共役塩基、ハロゲン原子、又は炭素数１〜４のアルキルサルフェート基を表す。）

(Wherein, R ₅ and R ₆ each independently represent a hydrogen atom or a methyl group, R ₇ and R ₈ each independently represent a hydrogen atom, or an alkyl group or alkoxy group having 1 to 4 carbon atoms, X ^- represents a conjugate base, a halogen atom, or an alkyl sulfate group having 1 to 4 carbon atoms acid).

（式中、Ｒ_９は水素原子又はメチル基を表し、Ｒ_１０及びＲ_１１はそれぞれ独立して水素原子又は炭素数１〜４のアルキル基若しくはアルケニル基を表す。）

(Wherein R ₉ represents a hydrogen atom or a methyl group, and R ₁₀ and R ₁₁ each independently represent a hydrogen atom, an alkyl group or an alkenyl group having 1 to 4 carbon atoms)

The cationic group-containing monomer represented by the general formula (1) is dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dipropylaminoethyl (meth) acrylamide, diisopropylaminoethyl (meth) acrylamide. , Dibutylaminoethyl (meth) acrylamide, diisobutylaminoethyl (meth) acrylamide, di-t-butylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) ) Acrylamide, diisopropylaminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, Quaternized products of the monomers mentioned with dialkylamino groups such as acrylamide -t- butyl aminopropyl (meth), X ^- is an inorganic or organic anion, long as it can form a salt of quaternary ammonium Any quaternary quaternary compounds such as alkyl halides such as methyl chloride, ethyl chloride, methyl bromide and methyl iodide, dimethyl sulfate, diethyl sulfate and di-n-propyl sulfate may be used. And a quaternary ammonium salt quaternized with an agent.

  Of these, quaternized dimethylaminopropyl (meth) acrylamide is particularly preferably used. In this invention, 1 or more types chosen from these cationic group containing monomers can be used arbitrarily.

The cationic group-containing monomer represented by the general formula (2) is an alkyl diallylammonium salt. In the general formula (2), R ₇ and R ₈ which are substituents of the quaternary ammonium nitrogen are the same. Or they may be different, and are a hydrogen atom, a C1-C4 alkyl group, 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 t-butoxy group. Further, in the general formula (2), X ⁻ is an inorganic or organic anion and may be any one as long as it can form a quaternary ammonium salt. For example, methyl chloride, ethyl chloride, odor Quaternary ammonium salts quaternized with a general quaternizing agent such as alkyl halides such as methyl iodide and methyl iodide, dimethyl sulfate, diethyl sulfate and di-n-propyl sulfate.

  Of these, dimethyldiallylammonium chloride is particularly preferably used. In this invention, 1 or more types chosen from these cationic group containing monomers can be used arbitrarily.

The nonionic monomer represented by the general formula (3) is a (meth) acrylamide monomer. In the general formula (3), R ₁₀ and R ₁₁ which are nitrogen substituents are the same. Or any one as long as it is a hydrogen atom, an alkyl group or an alkenyl group having 1 to 4 carbon atoms, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meta ) Acrylamide, N, N-diethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, etc. Can be mentioned.

  Among these, (meth) acrylamide monomers are preferable, and (meth) acrylamide and N, N-dimethyl (meth) acrylamide are particularly preferably used. In the present invention, one or more selected from these (meth) acrylamide monomers can be arbitrarily used.

  Monomer constituting the cationic group-containing copolymer (a) cationic group-containing monomer, (b) diallylamine monomer, (c) (meth) acrylamide monomer a) 40-80 wt%, (b) 10-35 wt%, (c) 10-40 wt% are preferred, (a) 40-70 wt%, (b) 15-35 wt%, (c) 15 -35 wt% is more preferable, and (1) 40-60 wt%, (b) 15-35 wt%, and (c) 20-30 wt% are particularly preferable. Even if the composition ratio of the cationic group-containing monomer (a) cationic group-containing monomer and (b) diallylamine-based monomer is too small, it becomes difficult to form a complex with the surfactant component, and squeezes upon rinsing. Such a feeling is insufficient, and if it is too much, it is not preferable because it feels bad after being washed.

  The compounding amount of the component (A) in the cleaning composition is 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight. If the blending amount is less than 0.01% by weight, it is difficult to form a complex with a surfactant, and a sufficient conditioning effect cannot be obtained.

  Furthermore, the weight average molecular weight of (A) component is 100,000-5 million, Preferably it is 300,000-3,500,000, More preferably, it is 500,000-2,500,000. If the weight average molecular weight is too small, the properties as a polymer are hardly exhibited. If the weight average molecular weight is too large, the conditioning effect and the foam modifying effect are not improved.

  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, 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. Then, the method of adding a polymerization initiator and making it react is mentioned. 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. As a specific example, 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.

  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.

  Specific examples of the nonionic polymer of component (B) used in the present invention include hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, polyethylene glycol, highly polymerized polyethylene glycol, and polyvinyl alcohol. A seed | species or 2 or more types can be used arbitrarily.

  (B) As for the compounding quantity in the cleaning composition of a component, 0.001-2 weight% is preferable, More preferably, it is 0.01-1 mass%, More preferably, it is 0.05-0.5 mass%. . By setting the component (B) within the above range, it is preferable from the viewpoint of realizing foaming, foam quality, no slickness during washing, and a moist feeling after towel drying.

  Furthermore, (C) anionic surfactant can be mix | blended with the cleaning composition of this invention. Specifically, higher fatty acid salts such as sodium laurate and sodium palmitate, alkyl sulfates such as potassium lauryl sulfate, alkyl sulfonates, polyoxyethylene alkyl sulfates, alkyl benzene sulfonates, N-acyl sarcosine salts, N-acyl amino acid salt, α-olefin sulfonate, alkyl ether acetate, polyoxyethylene alkyl ether acetate, sodium such as N-acyl-N-alkyl taurine salt such as N-acyl-N-methyl taurate, Although potassium, ammonium, triethanolamine, diethanolamine, etc. are mentioned, it is not specifically limited.

  (C) As for the compounding quantity in the cleaning composition of a component, 5 to 40 weight% is preferable, More preferably, it is 10 to 30 weight%. By setting the component (C) within the above range, a complex of an anionic surfactant and a copolymer is formed in the detergent composition, and this complex is precipitated during washing and rinsing, thereby improving the usability. However, if the blending amount of the component (C) is too small, the function as the cleaning composition cannot be obtained, and if it is too much, the effect is not improved and it is not preferable.

  A cationic polymer other than (A) can be blended in the cleaning composition of the present invention. Specifically, cation-modified cellulose ether derivatives, cation-modified natural polysaccharide derivatives, polydimethyldiallylammonium halides, copolymers of dimethyldiallylammonium halide and acrylamide, dimethyldiallylammonium chloride derivatives (both acrylamide / acrylic acid / dimethyldiallylammonium chloride) Polymer, acrylic acid / dimethyldiallylammonium chloride copolymer, etc.). Among these, O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose chloride, O- [2- chloride] Hydroxy-3- (trimethylammonio) propyl] guar gum, dimethyldiallylammonium chloride / acrylamide copolymer, and acrylamide / acrylic acid / dimethyldiallyl chloride Moniumu copolymer are particularly preferably used.

  The detergent composition of the present invention includes surfactants, medicinal agents, anti-inflammatory agents, bactericides, preservatives, ultraviolet absorbers, antioxidants that are usually used in the detergent composition within a range that does not impair the effects of the invention. Agents, organic and inorganic powders, viscosity modifiers, pigments, solid oils, semi-solid oils, pearling agents, thickeners, and the like can be blended as needed within a range that does not impair the effects of the invention. Specifically, it may be one that is usually used in a detergent composition and the like, and is appropriately selected depending on the purpose of use and required functions. Examples of amphoteric surfactants include lauric acid amidopropyl betaine, coconut oil fatty acid amidopropyl Amide betaines such as betaine, amide sulfobetaines such as laurylamide alkylenedimethylaminosulfobetaine, betaines such as lauryl (dimethyl) betaine, stearyl (dimethyl) betaine, stearyl dihydroxyethyl betaine, lauryl sulfobetaine, lauryl hydroxysulfobetaine Such as sulfobetaine type, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium Salt, imidazolinium type amphoteric active agents such as coconut oil alkyl N-carboxyethyl N-hydroxyethyl imidazolinium betaine and the like, and nonionic surfactants include sorbitan monostearate, sorbitan sesquioleate, etc. Sorbitan fatty acid esters, diethylene glycol laurate, propylene glycol laurate, ethylene glycol monooleate, ethylene glycol distearate, etc., hardened castor oil derivatives, glycerin alkyl ether, POE sorbitan monooleate, monostearic acid POE sorbitan fatty acid esters such as polyoxyethylene sorbitan, POE sorbite fatty acid esters such as POE-sorbit monolaurate, POE-glycerin POE glycerin fatty acid esters such as noisostearate, POE glycerin fatty acid esters such as polyethylene glycol monooleate and POE distearate, POE alkyl ethers such as POE-octyldodecyl ether, and POE alkyl phenyl ethers such as POE nonylphenyl ether , POE / POP alkyl ethers, Pluronic types, POE castor oil, POE hydrogenated castor oil derivatives, sugar esters, sugar ethers, sugar amides and other sugars, alkyl glycosides, etc., as semipolar surfactants Lauramine oxide (lauryl dimethylamine oxide) can be used, and these amphoteric surfactants, nonionic surfactants, and semipolar surfactants can be used as they are, and the blending amount is usually 0-10. Heavy % Is preferred.

  Examples of anionic polymers include acrylic acid derivatives (polyacrylic acid and salts thereof, acrylic acid / acrylamide / ethyl acrylate copolymers and salts thereof), methacrylic acid derivatives, crotonic acid derivatives, and the like as nonionic polymers. Examples include acrylic acid derivatives (hydroxyethyl acrylate / methoxyethyl acrylate copolymer, polyacrylamide, etc.), vinyl pyrrolidone derivatives (polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymer, etc.), etc. 0.1 to 1% by weight is preferred.

  Examples of the oil include higher alcohol, silicone oil, olive oil, jojoba oil, liquid paraffin, and fatty acid alkyl ester oil. Among these, the addition of silicone oil and / or higher alcohol is particularly effective for the purpose of the present invention because the smoothness after drying is improved. Nonvolatile polydimethylsiloxanes are preferably used as the silicone oil. The higher alcohol usually refers to an alcohol having 8 or more carbon atoms, but an alcohol having 8 to 22 carbon atoms is preferably used, and cetyl alcohol (cetanol) or stearyl alcohol is more preferably used. The amount of oil is preferably 0.1 to 3% by weight.

  Examples of the pearlizing agent include fatty acid ethylene glycol such as ethylene glycol distearate, and examples of the suspending agent include polystyrene emulsion, and the blending amount is preferably 0.1 to 2% by weight. Examples of the thickener include propylene glycol laurate, butylene glycol laurate, alkylene glycol laurate such as diethylene glycol laurate, and fatty acid ethanolamides such as lauric acid monoethanolamide and coconut oil fatty acid diethanolamide. .1 to 5% by weight is preferred.

  Other ingredients include natural extracts of animals and plants and derivatives thereof, organic acids such as citric acid and lactic acid, inorganic salts such as sodium chloride, amino acids (glutamic acid or salts thereof, arginine or salts thereof, 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, Maltitol, xylitol, glucose, fructose, mannitol, inositol, etc.), polymers such as hyaluronic acid, antioxidants, UV absorbers, bactericides, preservatives, chelating agents, fragrances, colorants, higher fatty acids, increased Agents, sequestering agents (edetic acid salts, etc.), pH adjusting agent, may be appropriately blended foam boosters such as within a range not to impair the effects of the present invention.

  The cleaning composition of the present invention means any cleaning composition used for skin and hair, for example, so-called cleaning agents such as shampoos and body shampoos, rinses, conditioners, treatments, hair packs, hair sprays, It includes a wide range of so-called hair treatment agents such as hair foams and styling agents, and there are no restrictions on the usage, but it exhibits excellent effects as a cleaning agent for shampoos and body shampoos. In addition, the usage forms include those that are applied to the skin, hair, etc., and then thoroughly rinsed after rinsing, and those that are not washed away.

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to an Example.

(Manufacture of copolymer)
In a reactor equipped with a thermometer, a nitrogen gas inlet tube and a stirrer, 40 parts by mass of methacrylamidopropyltrimethylammonium chloride (MAPTAC), 35 parts by mass of diallyldimethylammonium chloride (DADMAC) (54 parts by mass as a 65% by mass aqueous solution) Then, 25 parts by mass of acrylamide (AAm) (50 parts by mass as a 50% by mass aqueous solution) and 700 parts by mass of ion-exchanged water were placed in a glass flask having an internal volume of 1 L, 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, 0.20 parts by mass of 2,2′-azobis (2-amidinopropane) dihydrochloride was added to initiate polymerization. After reacting at 45 to 55 ° C. for 15 hours, the mixture was cooled to obtain a copolymer 1.

  The ratio of each monomer of the obtained polymer was MAPTAC / DADMAC / AAm = 24/29/47 (mole percentage), and the weight average molecular weight was 2.2 million. The weight average molecular weight was measured as follows. Gel permeation chromatography (column: OHpakSB-806MHQ × 2 (manufactured by Showa Denko KK), column temperature: 40 ° C., detector: RI, solvent: 0.25 M acetic acid / 0.05 M sodium nitrate aqueous solution (pH = 3. 5), flow rate: 1.0 ml / min, sample concentration: 0.5%, injection volume: 50 μl), weight average molecular weight was determined using pullulan (Shodex STANDARDP-82, Showa Denko KK) as a standard substance. .

  Copolymers 2 to 5 were produced in the same manner as the copolymer 1 except that the monomer composition shown in Table 1 was used. Table 1 shows the weight parts / mole percentage and the weight average molecular weight of the structural units corresponding to the respective monomers in the obtained copolymer. All numerical values in Table 1 are masses as solid contents.

MAPTAC: methacrylamidopropyltrimethylammonium chloride DADMAC: diallyldimethylammonium chloride AAm: acrylamide DMAA: N, N-dimethylacrylamide

  Moreover, the skin cleaning composition shown in Examples 1-4 and Comparative Examples 1-8 was prepared by a conventional method, the effect was measured by the following test method 1, and the results are shown in Table 2. All the contents indicate the weight percentage of the active ingredient.

  The test methods used in this example are as follows.

Test method 1 (foaming, foam quality (creaminess), refreshing feeling during rinsing, smoothness after washing, moist feeling)
After wetting both hands with water, take 1 ml of skin cleanser composition and rub both hands for 10 seconds, then foam (fast foaming), foam quality (creamy), and then attach to your fingers with running water Rinse the foam and washing liquid, and after refreshing the towel, dry the towel and feel the smoothness and moistness after washing from the feel of the hand skin. .
◎: If there are more than 9 people who answered good
○: When there are 6-8 people who answered good
△: 3 to 5 people answered good
×: When two or less people answered that it was good

  Next, hair cleaning compositions shown in Examples 5 to 7 and Comparative Examples 9 to 10 were prepared by a conventional method, and the effect was measured by the following test method 2. The results are shown in Table 3. The content is% by weight.

Test method 2 (feeling during washing and feel after washing)
Using a damaged hair bundle (20 g x 20 cm) that was bleached for 30 minutes on healthy black hair, apply 1.0 g of a hair cleaner, foam for 30 seconds, then rinse, dry with a towel and then dry with a dryer. The feeling of use (foaming, foam quality, slipperiness) and the feeling after washing (smoothness, moist feeling) were sensorially compared by 10 professional panelists and evaluated according to the following criteria.

◎: If there are more than 9 people who answered good
○: When there are 6-8 people who answered good
△: 3 to 5 people answered good
×: When two or less people answered that it was good

  As is clear from Examples 1 to 7 and Comparative Examples 1 to 10, the cleaning composition of the present invention imparts foaming at the time of washing, foam quality, a refreshing feeling at the time of rinsing, smoothness after washing, and a moist feeling. Excellent performance.

  As described above, the present invention provides a cationic group-containing copolymer composed of a specific cationic monomer and a specific nonionic monomer and a nonionic polymer at the time of washing. It is possible to provide a detergent composition having good foaming and foam quality, and excellent refreshing feeling during rinsing, smoothness after washing, and moist feeling.

Claims (5)

A cationic group-containing copolymer having structural units derived from monomers (a) to (c) represented by the following general formulas (1) to (3), wherein the proportion of each structural unit is simply The structural unit derived from the monomer (a) is 40 to 80% by weight, the structural unit derived from the monomer (b) is 10 to 35% by weight, and the structural unit derived from the monomer (c) is 10 to 40% by weight. (A) a cationic group-containing copolymer;
(B) A cleaning composition comprising a nonionic polymer.
Monomer (a)

(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. of an alkyl or alkenyl group, X ^- represents a conjugate base, a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms acids, n represents an integer of 1 to 5).
Monomer (b)

(Wherein R ₅ and R ₆ each independently represent a hydrogen atom or a methyl group, R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and ^- represents a conjugate base, a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms acid).
Monomer (c)

(Wherein R ₉ represents the above meaning, and R ₁₀ and R ₁₁ each independently represent a hydrogen atom, an alkyl group or an alkenyl group having 1 to 4 carbon atoms) The cleaning composition according to claim 1, comprising 0.01 to 10% by weight of the (A) cationic group-containing copolymer. The detergent composition according to claim 1 or 2, wherein the (A) cationic group-containing copolymer has a weight average molecular weight of 100,000 to 5,000,000. The said (B) nonionic polymer is 1 type (s) or 2 or more types chosen from hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, polyethyleneglycol, and highly polymerized polyethyleneglycol. The cleaning composition according to Item 1. The detergent composition according to any one of claims 1 to 4, further comprising (C) an anionic surfactant.