JP2015074637A - Copolymer for detergent compositions and detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copolymer for detergent compositions excellent in finger combing and sliding properties when washing and rinsing, and feels such as softness after drying.SOLUTION: The invention provides a copolymer for detergent compositions consisting of the copolymer having a unit from the formula (1), (2), and other ethylenic unsaturated monomer. [Ris H or methyl; Rto Rare an alkyl group and the like; Xis Halogen anion or monoalkyl sulfate ester anion; n is an integer of 1-10; Y is NH or O] [Ris H or methyl; Mis H, an alkyl metallic cation, or onium cations]

Description

  The present invention relates to a copolymer for a detergent composition and a detergent composition.

Conventionally, various anionic surfactants and amphoteric surfactants are blended in hair and body cleaners, but these are excellent in foaming, but after washing and after washing and after washing. There is a problem that hair is tangled or skin is often tangled.
Therefore, it is known to add cationic polymers such as cationized cellulose, cationized guar gum, acrylamide and dimethyldiallylammonium chloride copolymer for the purpose of improving the feeling when washing and rinsing and after washing. (Patent Document 1). When they are diluted with water at the time of washing or rinsing, they form a complex with the anionic surfactant contained in the detergent and precipitate, reducing the friction of the hair surface and skin surface, improving the feel can do.

  However, all of these can improve the feel during washing, but after adhering to the surface of the hair and skin, they remain sticky, become hard after drying, and the feeling after drying becomes worse. is there. In addition, when a conditioner is used after the detergent containing the cationic polymer is used as a shampoo, there is a problem that the performance of the conditioner cannot be sufficiently exhibited because these cationic polymers cover the hair surface.

  Patent Document 2 proposes a detergent composition that is excellent in fingering property at the time of rinsing, smoothness after drying, smoothness and the like by blending a specific acrylic acid-based cationic polymer. However, when blended with a cleaning agent, there is often a problem that precipitates are formed over time, and the feeling of rinsing is not sufficient.

Japanese Examined Patent Publication No. 45-20318 JP 2007-63543 A

  An object of the present invention is to provide a copolymer for a detergent composition that is excellent in fingering property and slipperiness during washing and rinsing, and excellent in touch such as softness after drying.

［式中、Ｒ¹は水素原子又はメチル基を表し、Ｒ²及びＲ³はそれぞれ独立して炭素数１〜２４のアルキル基を表し、Ｒ⁴は水素原子、炭素数１〜２４のアルキル基又は炭素数７〜２４のアラルキル基を表し、Ｘ^-はハロゲンアニオン又はアルキルの炭素数が１〜８のモノアルキル硫酸エステルアニオンを表し、ｎは１〜１０の整数を表し、ＹはＮＨまたはＯを表す。］

［式中、Ｒ⁵は水素原子又はメチル基を表し、Ｍ⁺はプロトン、アルキル金属カチオン又はオニウムカチオンを表す。］ The present invention is derived from the structural unit (a) represented by the following general formula (1), the structural unit (b) represented by the following general formula (2), and other ethylenically unsaturated monomers (C). It is a copolymer for cleaning composition which consists of a copolymer (D) which has a structural unit (c).

[Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents an alkyl group having 1 to 24 carbon atoms, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 24 carbon atoms. Alternatively, it represents an aralkyl group having 7 to 24 carbon atoms, X ⁻ represents a halogen anion or an alkyl monoalkyl sulfate anion having 1 to 8 carbon atoms, n represents an integer of 1 to 10, and Y represents NH or O Represents. ]

[Wherein R ⁵ represents a hydrogen atom or a methyl group, and M ⁺ represents a proton, an alkyl metal cation or an onium cation. ]

  When the hair and skin are washed with the detergent composition containing the copolymer for the detergent composition of the present invention, it is excellent in fingering and slipperiness during washing and rinsing, and is soft and non-sticky after drying. Can be given.

  The copolymer for cleaning compositions of the present invention is characterized by comprising a copolymer (D) having the structural units (a), (b) and (c).

R ¹ in the general formula (1) is a hydrogen atom or a methyl group.
R ² and R ³ in the general formula (1) each independently represent an alkyl group having 1 to 24 carbon atoms, and R ⁴ is a hydrogen atom, an alkyl group having 1 to 24 carbon atoms or an aralkyl group.
The alkyl group having 1 to 24 carbon atoms may be a linear or branched alkyl group and may contain an unsaturated bond. Examples of the alkyl group having 1 to 24 carbon atoms include methyl group, ethyl group, propyl group, 2-propenyl group, butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, and decyl group. , Dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, octadecenyl group, eicosyl group, and tetracosyl group.
Examples of the aralkyl group having 7 to 24 carbon atoms include a benzyl group and a phenethyl group.
R ² and R ³ are preferably a methyl group and an ethyl group from the viewpoint of feel after drying.
R ⁴ is preferably a hydrogen atom, a methyl group, an ethyl group, or a benzyl group from the viewpoint of feel after drying.

X ⁻ in the general formula (1) is a halogen anion or an alkyl monoalkyl sulfate anion having 1 to 8 carbon atoms.
Examples of the halogen anion include a fluorine anion (F ⁻ ), a chlorine anion (Cl ⁻ ), a bromine anion (Br ⁻ ), and an iodine anion (I ⁻ ).
Among these, from the viewpoint of feeling during rinsing, a chlorine anion and a bromine anion are preferable, and a chlorine anion is more preferable.
Examples of the monoalkyl sulfate anion having 1 to 8 carbon atoms of alkyl include monomethyl sulfate anion, monoethyl sulfate anion, monopropyl sulfate anion, monobutyl sulfate anion, monopentyl sulfate anion, monohexyl sulfate anion, monoheptyl Examples include sulfate ester anions and monooctyl sulfate anions.
Among these, from the viewpoint of the feel at the time of rinsing, a monomethyl sulfate anion (CH ₃ SO ₄ ⁻ ) and a monoethyl sulfate anion (CH ₃ CH ₂ SO ₄ ⁻ ) are preferable.

N in the general formula (1) is the number of methylene groups, and is an integer of 1 to 10.
n is preferably an integer of 2 or 3 from the viewpoint of feel after drying.

  Y in the general formula (1) is NH or O.

In the copolymer for a detergent composition of the present invention, the structural unit (a) is a structural unit obtained by polymerization of the monomer (A) represented by the following general formula (3), It may be a structural unit obtained by polymerizing a group-containing (meth) acrylate and then cationizing an amino group.
From the viewpoint of the reaction efficiency of the cationization reaction, a structural unit obtained by polymerizing the monomer (A) represented by the following general formula (3) is preferable.
The polymerization method may be any of radical polymerization, cationic polymerization and anionic polymerization.

In General Formula (3), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents an alkyl group having 1 to 24 carbon atoms, and R ⁴ represents a hydrogen atom or 1 to 24 carbon atoms. Or an alkyl group of 7 to 24 carbon atoms, X ⁻ represents a halogen anion or an alkyl monoalkyl sulfate anion having 1 to 8 carbon atoms, m represents an integer of 1 to 10, and Y represents NH or O is represented.

In the general formula (3), R ¹ is the same group as R ¹ in the general formula (1), and preferred ones are also the same.
R ² and R ³ are the same groups as R ² and R ³ in the general formula (1), and preferred ones are also the same.
R ⁴ is the same group as R ⁴ in the general formula (1), and preferred ones are also the same.
n is the same number as n in the said General formula (1), and its preferable thing is also the same.
X ⁻ is the same group as X ⁻ in the general formula (1), and preferred ones are also the same.

Monomer (A) is composed of the following amino group-containing (meth) acrylate and inorganic acid (hydrochloric acid, hydrobromic acid, hydroiodic acid, etc.) or quaternizing agent (methyl chloride, ethyl chloride, dimethyl sulfate, diethyl) A monomer in which an amino group is cationized by mixing and reacting with sulfuric acid, benzyl chloride, hexadecyl chloride, octadecyl chloride, and the like.
As amino group-containing (meth) acrylates, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate and N, N-dioctyl Aminoethyl (meth) acrylate etc. are mentioned.
As the monomer (A), N, N, N-trimethyl-N- (2-acryloyloxyethyl) ammonium chloride, N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium chloride, N , N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium methyl sulfate, N-benzyl-N, N-dimethyl-N- (2-methacryloyloxyethyl) ammonium chloride, N, N-dimethyl-N- Ethyl-N- (2-methacryloyloxyethyl) ammonium chloride, N, N-dimethyl-N-ethyl-N- (2-methacryloyloxyethyl) ammonium ethyl sulfate and N, N-dimethyl-N-ethyl-N- ( 2-Methacryloyloxypropyl) ammonium chloride And the like.
The monomer (A) is preferably N, N, N-trimethyl-N- (2-acryloyloxyethyl) ammonium chloride, N, N, N-trimethyl-N- () from the viewpoint of feel after drying. 2-Methacryloyloxyethyl) ammonium chloride, N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium methyl sulfate and N-benzyl-N, N-dimethyl-N- (2-methacryloyloxyethyl) ammonium It is chloride.
As a monomer (A), 1 type may be used and 2 or more types may be used together.

R ⁵ in the general formula (2) is a hydrogen atom or a methyl group.

M ⁺ in the general formula (2) is a proton, an alkyl metal cation or an onium cation.
Examples of the alkali metal constituting the alkali metal cation include sodium, potassium, and lithium.

  Examples of the onium cation include an ammonium ion, an organic amine cation, a quaternary ammonium cation, a basic amino acid cation, a tertiary sulfonium cation, and a quaternary phosphonium cation.

  Examples of the organic amine constituting the organic amine cation include primary, secondary and tertiary aliphatic amines (amines having an alkyl group having 1 to 20 carbon atoms and / or a hydroxyalkyl group having 2 to 4 carbon atoms: for example, diethylamine, Triethylamine, monoethanolamine, triethanolamine and monopropanolamine), alicyclic amines (cyclohexylamine and dicyclohexylamine etc.), aromatic amines (aniline and toluidine etc.), aromatic heterocyclic amines (pyridine and quinoline etc.), Heterocyclic amines (morpholine, N-methylmorpholine, piperazine, etc.), and those in which the hydrogen atom at the N-position of the heterocyclic amine is substituted with a hydroxyalkyl group having 2 to 4 carbon atoms (N-hydroxyethylmorpholine, etc.), etc. Can be mentioned.

The quaternary ammonium constituting the quaternary ammonium cation includes aliphatic quaternary ammonium and alicyclic quaternary ammonium, such as tetra (cyclo) alkylammonium [alkyl group having 1 to 12 carbon atoms (methyl, ethyl, Propylbutyl, hexyl, octyl, and dodecyl groups) and / or cycloalkyl groups (such as cyclohexyl groups); the four (cyclo) alkyl groups may be the same or different. ] Etc. are mentioned.
The (cyclo) alkyl group represents an alkyl group and / or a cycloalkyl group, and the same expression is used hereinafter.

  Examples of basic amino acids constituting the basic amino acid cation include lysine and arginine.

  The tertiary sulfonium constituting the tertiary sulfonium cation includes an aliphatic tertiary sulfonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms {trimethylsulfonium, triethylsulfonium, ethyldimethylsulfonium, diethylmethylsulfonium, etc. }, Aromatic tertiary sulfoniums having 6 to 30 or more carbon atoms {phenyldimethylsulfonium, phenylethylmethylsulfonium, phenylmethylbenzylsulfonium and the like} and alicyclic tertiary sulfoniums having 3 to 30 or more carbon atoms {methylthio Ranium, phenylthiolanium, etc.}.

  The quaternary phosphonium constituting the quaternary phosphonium cation includes an aliphatic quaternary phosphonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms {tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium. Methyltriethylphosphonium, methyltripropylphosphonium, methyltributylphosphonium, dimethyldiethylphosphonium, dimethyldipropylphosphonium, dimethyldibutylphosphonium, trimethylethylphosphonium, trimethylpropylphosphonium, trimethylbutylphosphonium, etc.}, having 6 to 30 or more carbon atoms Aromatic quaternary phosphonium {triphenylmethylphosphonium, diphenyldimethylphosphonium and triphenyl And benzyl phosphonium}, and the number 3 to 30 or more alicyclic quaternary phosphonium such as carbon.

M ⁺ can be arbitrarily selected from protons, alkyl metal cations or onium cations, but from the viewpoint of feel after drying, protons and alkyl metal cations are preferred, and protons and sodium cations are more preferred.

The structural unit (b) is a structural unit obtained by polymerizing the monomer (B) represented by the following general formula (4) from the viewpoint of easy preparation of the copolymer (D). preferable.

In the general formula (4), R ⁵ represents a hydrogen atom or a methyl group, and M ⁺ represents a proton, an alkyl metal cation or an onium cation.
In the general formula (4), M ⁺ is the same group as M ⁺ in the general formula (2), and preferred ones are also the same.

Examples of the monomer (B) include acrylic acid, methacrylic acid, sodium acrylate, sodium methacrylate, triethanolamine acrylate, and triethanolamine methacrylate.
Of the monomers (B), acrylic acid, methacrylic acid, sodium acrylate and sodium methacrylate are preferred from the viewpoint of feel during rinsing, and acrylic acid and methacrylic acid are more preferred.
As a monomer (B), 1 type may be used and 2 or more types may be used together.

  The molar fraction of the monomer (A), the monomer (B) and the other ethylenically unsaturated monomer (C) in the monomer constituting the copolymer (D) is (A), Based on the total number of moles of (B) and (C), from the viewpoint of feel during rinsing, (A) is 2 to 50 mol%, (B) is 1 to 40 mol%, and (C) is 10 to 97. It is preferable that it is mol%, More preferably, (A) is 5-40 mol%, (B) is 2-30 mol%, (C) is 30-93 mol%.

The other ethylenically unsaturated monomer (C) is an ethylenically unsaturated monomer other than (A) and (B).
As (C), the monomer (C1) represented by the general formula (5), (meth) acrylamide, dialkyl (C1-8) (meth) acrylamide, amino group-containing (meth) acrylate, vinylpyrrolidone, dialkyl (C1-3) Amidopropyl (meth) acrylamide, acrylonitrile and styrene are included.
The copolymer for a cleaning composition of the present invention comprises (C) as an essential constituent monomer, but from the viewpoint of feeling during rinsing, (C) is preferably represented by the general formula (5). The monomer (C1) is an essential constituent monomer.

In General Formula (5), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, or an aralkyl group having 7 to 24 carbon atoms, m represents the average addition mole number of an alkyleneoxy group, is an integer of 0 to 30, AO represents an alkyleneoxy group having 2 to 4 carbon atoms, and Y represents NH or O.

In R ⁷ , the alkyl group having 1 to 24 carbon atoms may be a linear or branched alkyl group and may contain an unsaturated bond.
Examples of the alkyl group having 1 to 24 carbon atoms include methyl group, ethyl group, propyl group, 2-propenyl group, butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, and decyl group. , Dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, octadecenyl group, eicosyl group, and tetracosyl group.
Examples of the aryl group having 6 to 24 carbon atoms include phenyl group, hydroxyphenyl group, carboxylphenyl group, methylphenyl group, ethylphenyl group, naphthyl group, and anthracenyl group.
Examples of the aralkyl group having 7 to 24 carbon atoms include a benzyl group and a phenethyl group.
R ⁷ is preferably an alkyl group having 1 to 12 carbon atoms from the viewpoint of foaming of the cleaning composition.

m is preferably an integer of 0 to 30, and more preferably 0 to 10, from the viewpoint of easy handing during rinsing.
Examples of AO include an ethyleneoxy group (—CH ₂ CH ₂ O—), a propyleneoxy group (—CH ₂ C (CH ₃ ) O— or —CH ₂ CH ₂ CH ₂ O—) and a butyleneoxy group. .
AO is preferably an ethyleneoxy group or a propyleneoxy group from the viewpoint of blending stability.

  The proportion of (C1) in the monomer (C) constituting the copolymer for the detergent composition is such that other ethylenically unsaturated monomers constituting the copolymer (from the viewpoint of feel during rinsing ( 0.5-60 mol% is preferable based on the total number of moles of C), and more preferably 1-40 mol%.

  The weight average molecular weight of the copolymer (D) is preferably 10,000 to 5,000,000, more preferably 50,000 to 2,000,000, from the viewpoint of feel during rinsing.

The weight average molecular weight (hereinafter abbreviated as Mw) in the present invention is measured by gel permeation chromatography (hereinafter abbreviated as GPC). The measurement shall comply with the following measurement conditions.
<GPC measurement conditions>
GPC model: HLC-8120GPC, column made by Tosoh Corporation: TSKgel 2 GMHXL + TSKgel
Multipore HXL-M, solvent manufactured by Tosoh Corporation: Tetrahydrofuran (THF)
Detection device: Refractive index detector reference material: Standard polystyrene (TSK standard POLYSYRENE), manufactured by Tosoh Corporation

The copolymer (D) is a known solution polymerization (for example, as described in JP-A-55-133413) using a radical polymerization initiator (d) and, if necessary, a chain transfer agent for radical polymerization (e). Adiabatic polymerization, thin film polymerization, spray polymerization, etc.) and known reverse phase suspension polymerization (for example, those described in JP-B-54-30710, JP-A-56-26909, JP-A-1-5808) Various polymerization methods including [photopolymerization (for example, described in JP-B-6-804), precipitation polymerization (for example, described in JP-A-61-123610), reverse-phase emulsion polymerization (for example, JP-A-5858). -The one described in No. 1973398) etc.].
Among the polymerization methods, solution polymerization, reverse phase suspension polymerization, photopolymerization and reverse phase emulsion polymerization are preferable from an industrial viewpoint, and solution polymerization is more preferable.

  Examples of the radical polymerization initiator (d) include azo compounds [water-soluble [azobisamidinopropane (salt), azobiscyanovaleric acid (salt), etc.] and oil-soluble [azobisdimethylvaleronitrile, azobisiso]. Butyronitrile, azobiscyclohexanecarbonitrile, etc.]; peroxides [water-soluble [peracetic acid, t-butyl peroxide, hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, etc.] and oil-soluble [Benzoyl peroxide, cumene hydroxy peroxide, etc.].

Examples of the salt in the azo compound include inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.) salts, alkali metal (lithium, sodium, potassium, etc.) salts, ammonium salts, and the like.
The above peroxide may be used as a redox initiator in combination with a reducing agent. Examples of the reducing agent include bisulfites (sodium bisulfite, potassium bisulfite, ammonium bisulfite, etc.), reducing metal salts [iron sulfate (II ), Etc.], amine complexes of transition metal salts [pentamethylenehexamine complexes of cobalt (III) chloride, diethylenetriamine complexes of copper (II) chloride, etc.], organic reducing agents [ascorbic acid, tertiary amine [dimethylaminobenzoic acid ( Salt), dimethylaminoethanol and the like].
Further, the azo compound, peroxide and redox initiator may be used alone or in combination of two or more.

Of the radical polymerization initiator (d), an azo compound is preferred from the viewpoint of reducing the water-insoluble content of the copolymer (D) to be obtained.
The amount of (d) used is preferably 0.01 to 3.0 based on the total weight of the monomers constituting (D) from the viewpoint of making the molecular weight of the copolymer (D) appropriate. % By weight, more preferably 0.1 to 2.0% by weight.

The chain transfer agent for radical polymerization (e) is not particularly limited. For example, a compound having one or two or more hydroxyl groups in the molecule [molecular weight of 32 or more and number average molecular weight (hereinafter abbreviated as Mn) of 50,000 or less. For example, methanol, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, polyethylene glycol (molecular weight of 100 or more and Mn 50,000 or less) and polyethylene polypropylene glycol (molecular weight of 100 or more and Mn 50,000 or less) etc.], ammonia , Compounds having one or more amino groups in the molecule [for example, amines (including those having 1 to 30 carbon atoms, such as methylamine, dimethylamine, triethylamine and propanolamine)], 1 in the molecule described below One or more thios And the like, and (hypo) phosphorous acid compounds [phosphorous acid, hypophosphorous acid, and salts thereof [alkali metal (Na, K, etc.) salts, etc.], and derivatives thereof], etc.] .
Among these, from the viewpoint of controlling the molecular weight of the copolymer (D), a compound having one or more thiol groups in the molecule is preferable.

Compounds having one or more thiol groups in the molecule include the following (1), (2), mixtures thereof and salts thereof [alkali metal (for example, lithium, sodium and potassium etc.) salts, alkalis Earth metal (such as magnesium and calcium) salts, ammonium salts, amine (C1-20) salts and inorganic acids (such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid salts).
(1) Monovalent thiol Aliphatic thiol [including those having 1 to 20 carbon atoms, alkyl thiol (for example, methanethiol, ethanethiol, propanethiol, n-octanethiol, n-dodecanethiol, hexadecanethiol, n-octadecane) Thiol, etc.), thiolic acid (mercaptoacetic acid, 3-mercaptopropionic acid, thiomaleic acid, etc.), 2-mercaptoethanol, 1-thioglycerol, thioglycolic acid monoethanolamine, cysteine, 2-mercaptoethylamine, etc.], alicyclic Thiols (including those having 5 to 20 carbon atoms such as cyclopentanethiol and cyclohexanethiol) and aromatic (aliphatic) thiols (including those having 6 to 12 carbon atoms such as benzenethiol, benzyl mercaptan and thiosalicylic acid) Etc.).

(2) Polyvalent thiol Dithiol [aliphatic (2 to 40 carbon atoms) dithiol (for example, ethanedithiol, diethylenedithiol, triethylenedithiol, propanedithiol, 1,3- or 1,4-butanedithiol, 1,6-hexane Dithiol, neopentanedithiol, etc.), alicyclic (carbon number 5-20) dithiol (eg cyclopentanedithiol, cyclohexanedithiol etc.) and aromatic (aliphatic) aliphatic (6-16 carbons) dithiol (eg benzenedithiol, biphenyldithiol) Etc.), trithiol (having 3 to 20 carbon atoms, such as thioglycerin) and the like.

  The amount of the radical transfer chain transfer agent (e) used is preferably 0.01 based on the total weight of monomers constituting (D) from the viewpoint of making the molecular weight of the copolymer (D) appropriate. It is -3.0 weight%, More preferably, it is 0.1-2.0 weight%.

Among the methods for producing the copolymer (D), examples of the solution polymerization method include the following methods.
The solvent (f) and, if necessary, the chain transfer agent for radical polymerization (e) are charged into a polymerization tank, and while heating, a predetermined polymerization temperature (from the viewpoint of making the weight average molecular weight of the copolymer (D) moderate, 40 ~ 100 ° C is preferable, and more preferably 50-80 ° C), and then the inside of the tank is sufficiently substituted with an inert gas (for example, nitrogen).
On the other hand, a monomer solution to which the monomers (A), (B), (C), the radical polymerization initiator (e), and the solvent (f) were added was prepared and sufficiently substituted with an inert gas. It puts in a polymerization tank and polymerizes while suspending.
As a method for charging the monomer solution, either batch charging or dropping may be used. In this case, the monomer solution may be a uniform solution of (A), (B), (C), (d) and (f), or a separate solution, which is mixed immediately before dropping. Alternatively, they may be dropped simultaneously at the same time. Examples of the method of replacing the monomer solution with an inert gas include a method of bubbling and supplying an inert gas to the monomer solution, a method of blending an inert gas with a static mixer or the like in a dropping line, and the like. From the viewpoint of properties, a method of blending an inert gas with a static mixer is preferred.

Examples of the solvent (f) include water and hydrophilic organic solvents (such as alcohols having 1 to 4 carbon atoms, glycol solvents, and ketone solvents), and may be a mixed solvent of water and a hydrophilic organic solvent.
Examples of the alcohol having 1 to 4 carbon atoms include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and t-butyl alcohol.
Glycol solvents include glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, etc.), monoalkyl ethers of glycols (ethylene glycol) Monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether and dipropylene glycol monomethyl ether) and dialkyl ethers of these glycols (ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol). Call isopropyl ether, etc.).
Examples of ketone solvents include acetone and methyl ethyl ketone.

  The copolymer for a cleaning composition of the present invention can be used in a cleaning composition as a conditioning agent, a thickening agent, an antistatic agent and a film forming agent.

The cleaning composition of the present invention contains a copolymer for cleaning composition and water.
In the present invention, the copolymer for the detergent composition is the above-mentioned copolymer (D).
The content of the copolymer (D) in the cleaning composition of the present invention is 0.01 to 2 weights on the basis of the weight of the cleaning composition from the viewpoint of cleaning properties and rinsing properties of the cleaning composition. % Is preferable, and 0.1 to 1% by weight is more preferable.

In the cleaning composition of the present invention, the content of water is preferably 35 to 95% by weight, more preferably 50 to 90% by weight, from the viewpoint of handling properties of the cleaning composition.
Moreover, although pH of a cleaning composition is not specifically limited, From a viewpoint of the safety | security with respect to a human body, neutral-weakly acidic (for example, pH 4-9) is preferable.

  The cleaning composition of the present invention further comprises an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, a cationic surfactant, a humectant, a conditioning agent, a chelating agent, a builder, and a carbon number of 1 to 6 at least one selected from the group consisting of lower alcohols, thickeners, pearling agents, fragrances, coloring agents, preservatives, medicinal agents, anti-inflammatory agents, bactericides, ultraviolet absorbers and antioxidants. An additive (E) other than D) may be contained.

  Examples of the anionic surfactant include hydrocarbon sulfonates having 8 to 24 carbon atoms [sodium dodecylbenzenesulfonate, sodium α-olefin sulfonate, etc.], hydrocarbon phosphate esters having 8 to 24 carbon atoms [ Sodium lauryl phosphate, (poly) oxyethylene (average addition mole number = 1-100) sodium lauryl ether phosphate, etc.], fatty acid salt [sodium laurate, triethanolamine laurate, etc.], carbon number 10-18 Condensates of acids with aminocarboxylic acids such as acyl sarcosine salts [oleyl sarcosine sodium, lauryl sarcosine sodium, palmityl sarcosine sodium, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine and “new” Surfactant "Hiroshi Horiguchi (Published by Sankyo Publishing Co., Ltd. in 1975); acyl glutamate [sodium oleyl glutamate, sodium lauryl glutamate, sodium palmityl glutamate, coconut oil fatty acid glutamate triethanolamine, coconut oil fatty acid sodium glutamate, etc. ] And acylalanine salts [such as sodium lauroylmethyl-β-alanine], condensates of carboxylic acids having 10 to 18 carbon atoms and aminosulfonic acid type amino acids: for example, acylmethyl taurine salts [such as coconut oil fatty acid methyl taurine sodium], Condensates of carboxylic acids having 10 to 18 carbon atoms and isethionic acid: for example acyl isethionate [coconut oil fatty acid sodium isethionate and the like], hydrocarbon ether carboxylic acids having 8 to 24 carbon atoms or salts thereof [( I) Oxyethylene (average added mole number = 2 to 20) sodium lauryl ether acetate, etc.], C8-24 hydrocarbon sulfate salt [sodium lauryl sulfate, (poly) oxyethylene (average added mole number = 2) -20) Sodium lauryl ether sulfate, (poly) oxyethylene (average added mole number = 2-20) lauryl sulfate triethanolamine, (poly) oxyethylene (average added mole number = 2-20) coconut oil fatty acid monoethanolamide Sodium sulfate], hydrocarbon phosphate ester having 8 to 24 carbon atoms [sodium lauryl phosphate, (poly) oxyethylene (average addition mole number = 2 to 20) sodium lauryl ether phosphate, etc.] sulfosuccinate: for example Alkyl (C6-C18) sulfosuccinic acid ester salt [di-2-ethylhexyl Rusulfosuccinic acid ester mono-salt, mono-2-ethylhexyl sulfosuccinic acid ester di-salt, etc.] and (poly) oxyethylene (average number of added moles = 1-50) alkyl (carbon number 8-24) sulfosuccinic acid ester salt [ Di-polyoxyethylene (average added mole number = 2 to 20) lauryl sulfosuccinic acid ester mono-salt, mono-polyoxyethylene (average added mole number = 2 to 20) lauryl sulfosuccinic acid ester di-salt, and the like. .

  Amphoteric surfactants include betaine-type amphoteric surfactants [coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, laurylhydroxy Sulfobetaine, lauroylamidoethylhydroxyethylcarboxymethylbetaine hydroxypropyl sodium phosphate, etc.], amino acid type amphoteric surfactant [sodium β-laurylaminopropionate, etc.] and the like.

  Nonionic surfactants include monoaliphatic alcohols (8 to 24 carbon atoms), alkylene oxide (2 to 8 carbon atoms) adducts (average number of added moles = 1 to 100) {polyoxyethylene (average added moles) Number = 1 to 100) dodecylene glycol, etc., polyvalent (divalent to 10-valent or higher) aliphatic alcohol (carbon number 8 to 24) alkylene oxide (carbon number 2 to 8) adduct (average addition) Mol number = 1-100), (poly) oxyalkylene (carbon number 2-8, average addition mole number = 1-100) higher fatty acid (carbon number 8-24) ester [polyethylene glycol monostearate (average addition mole number) = 20), polyethylene glycol distearate (average number of added moles = 30), etc.], polyvalent (divalent to 10-valent or higher) alcohol fatty acid (carbon number 8 to 24) [Glycerol monostearate, ethylene glycol monostearate, sorbitan monolaurate, etc.], (poly) oxyalkylene (2 to 8 carbon atoms, degree of polymerization = 1 to 100) polyvalent (divalent to 10-valent or more) Alcohol higher fatty acid (carbon number 8-24) ester [polyoxyethylene monolaurate (average number of added moles = 10) sorbitan, polyoxyethylene (average number of added moles = 50) dioleic acid methylglucoside, etc.], fatty acid alkanolamide [coconut Oil fatty acid monoethanolamide, 1: 1 type coconut oil fatty acid diethanolamide, 1: 1 type lauric acid diethanolamide, etc.], (poly) oxyalkylene (2-8 carbon atoms, average number of added moles = 1-100) alkyl ( C1-C22) phenyl ether, (poly) oxyalkylene ( Prime number 2 to 8, average number of added moles = 1 to 100) alkyl (carbon number 8 to 24) amino ether and alkyl (carbon number 8 to 24) dialkyl (carbon number 1 to 6) amine oxide [lauryl dimethylamine oxide and the like] Etc.

  Cationic surfactants include quaternary ammonium salt type [stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, ethyl lanolin sulfate fatty acid aminopropylethyl dimethyl ammonium, etc.], amine salt type [diethylamino stearate] Ethylamide lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.].

  Further, anionic surfactants, amphoteric surfactants, cationic surfactants and nonionic surfactants described in US Pat. No. 4,331,447 are also included.

  As humectants, glycerin, sodium pyrrolidone carboxylate, etc .; as conditioning agents, when (D) is used as a conditioning agent, those other than (D) are included, and cationized cellulose having a weight average molecular weight in the range of 5 to 5 million , Cationized guar gum, silicones, polyethylene glycol, sodium polyacrylate, (cationized) hydroxyethyl cellulose, protein derivatives, ceramides, pseudoceramides, 18-methyleicosane, etc., linear or branched carbon number 16-40 fatty acids, hydroxy acids, panthenol, etc .; as a chelating agent, sodium ethylenediaminetetraacetate, sodium 1-hydroxyethane-1, 1-diphosphonate, etc .; as a builder, polycarboxylate (acrylate homopolymer And maleate homopolymers), polyvalent carboxylates (such as citric acid and malic acid), and alkali builders (such as caustic soda, soda ash, ammonia, triethanolamine, sodium tripolyphosphate and sodium silicate); carbon number 1-6 lower alcohols such as ethanol, propylene glycol, dipropylene glycol, etc .; thickeners such as cellulose derivatives, polyvinyl alcohol and sodium polyacrylate; pearlizing agents such as glycol distearate; As a preparation, an antiseptic, a medicinal agent, an anti-inflammatory agent, a bactericidal agent, an ultraviolet absorber, and an antioxidant, “Perfumery” described in p. 150 to 176 published by the Japan Hair Science Association, 1976 , P145-148 colorants, p185-196 preservatives And fungicides, anti-inflammatory agent according to P172, ultraviolet absorbent described in P177～183, and antioxidants according to P199～p203.

  In the cleaning composition of the present invention, the total content of additives (E) other than (D) is determined from the viewpoint of basic performance as a cleaning agent such as handling properties and foaming power of the cleaning composition. Based on the weight of the composition, it is preferably 3 to 40% by weight, more preferably 5 to 30% by weight.

  In the cleaning composition of the present invention, the total surfactant content is preferably 3 to 35% by weight based on the weight of the cleaning composition from the viewpoint of foaming power and handling properties of the cleaning composition, More preferably, it is 5 to 30% by weight. When it is 3% by weight or more, the foaming power becomes sufficient, and when it is 35% by weight or less, the viscosity of the cleaning composition becomes appropriate, and the handling property is good.

The amount of additives other than surfactants varies depending on the use of the detergent, but moisturizers, conditioning agents, chelating agents, builders, lower alcohols having 1 to 6 carbon atoms, thickeners, pearlizing agents The addition amount of each of the medicinal agent and the anti-inflammatory agent is preferably 0 to 20% by weight based on the weight of components other than water in the cleaning composition from the viewpoint of foaming power and feel during rinsing. More preferably, it is 0.1 to 15% by weight.
From the viewpoint of safety, the amount of each of the fragrance, colorant, preservative, bactericidal agent, ultraviolet absorber and antioxidant is 0 to 5 based on the weight of components other than water in the cleaning composition. % By weight is preferred, more preferably 0.01 to 3% by weight.
Further, the total addition amount of these additives is preferably 0 to 25% by weight based on the weight of components other than water in the cleaning composition from the viewpoints of foaming power, feel during rinsing and safety. More preferably, it is 0.01 to 18% by weight.

  The cleaning composition of the present invention is suitably used for, for example, a hair cleaning agent (hair shampoo, etc.) and a skin cleaning agent (body shampoo, facial cleansing cream, etc.). Used as a cleaning agent.

  The cleaning composition of the present invention can be produced by blending (D) and water, and if necessary, (E). The order of blending is not particularly limited, but from the viewpoint of mixing time, (D) is preferably dissolved in water in advance to prepare an aqueous solution of 1 to 5% by weight of (D), separately (E) and the remaining water. Is mixed, and the aqueous solution (D) is mixed there.

The typical example of the composition of the hair shampoo which consists of the cleaning composition of this invention is given below.
Polyoxyethylene (average added mole number = 2.0) Sodium lauryl ether sulfate: 2 to 6%
Polyoxyethylene (average number of moles added = 3.0) sodium lauryl ether acetate: 5 to 13%
Coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine: 1-5%
Palm oil fatty acid monoethanolamide: 1-5%
Moisturizer (such as glycerin): 0-5%
Copolymer (D): 0.1 to 0.7%
Conditioning agents other than (D) (cationized cellulose, etc.): 0 to 0.5%
Pearling agent (ethylene glycol distearate, etc.): 0 to 2%
Metal sequestering agent (such as EDTA): appropriate amount pH adjuster (such as citric acid, triethanolamine): appropriate amount UV absorber: appropriate amount preservative: appropriate amount purified water: remaining amount (100% in total)

Typical examples of the composition of the body shampoo comprising the cleaning composition of the present invention are listed below.
Polyoxyethylene (average number of moles added = 2.0) sodium lauryl ether sulfate: 1 to 5%
Sodium alkyl hydroxy ether carboxylate: 1-3%
Potassium laurate: 5-10%
Potassium myristate: 5-10%
Coconut oil alkyldimethylaminoacetic acid betaine: 3-8%
Alkylene oxide adduct of 1,2-dodecanediol: 1 to 5%
Copolymer (D): 0.1 to 0.7%
Moisturizer (such as glycerin): 0-5%
Pearling agent (ethylene glycol distearate, etc.): 0 to 3%
pH adjuster (citric acid, triethanolamine, etc.): appropriate amount preservative: appropriate amount purified water: remaining amount (total 100%)

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

<Production Example 1>
Monomer (A-1): 50.0% IPA solution of N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium methyl sulfate Stirrer, heating / cooling device, thermometer, dropping funnel and nitrogen Into a reaction vessel equipped with an introduction tube, 500 parts of IPA (isopropyl alcohol) and 278 parts of dimethylaminoethyl methacrylate (Light Ester DM, manufactured by Kyoeisha Chemical Co., Ltd.) are charged, and the gas phase part of the reaction vessel is replaced with nitrogen. After that, 222 parts of dimethyl sulfate prepared in a dropping funnel was added dropwise at 10 ° C. in a sealed manner over 2 hours. After completion of the dropwise addition, the mixture was reacted at the same temperature for 4 hours to obtain 1000 parts of a 50.0% IPA solution of N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium methyl sulfate.

<Production Example 2>
Monomer (A-2): 50.0% IPA solution of N, N-dimethyl-N-ethyl-N- (2-methacryloyloxyethyl) ammonium ethyl sulfate In Production Example 1, “278 parts of dimethylaminoethyl methacrylate” N, N-dimethyl-N-ethyl-N in the same manner except that “dimethylaminoethyl methacrylate 253 parts” was used instead of “dimethylsulfuric acid” and “247 parts of diethylsulfuric acid” was used instead of “222 parts of dimethylsulfuric acid”. -1000 parts of 50.0% IPA solutions of-(2-methacryloyloxyethyl) ammonium ethyl sulfate were obtained.

<Production Example 3>
A reaction vessel was charged with 52 parts of a 78% aqueous solution of N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium chloride, 9 parts of an 80% aqueous solution of acrylic acid, and 98 parts of an acrylamide 50% aqueous solution. 35 parts of ion-exchanged water was added so that the total concentration of monomers in the system was 50%, and the mixture was stirred until a uniform solution was obtained. Next, the temperature of the contents is adjusted to 40 ° C. in a constant temperature bath at 40 ° C., and after sufficiently replacing the reaction system with nitrogen (gas phase oxygen concentration of 10 ppm or less), 2,2′-azobis- (amidinopropane) ) 2 parts of a 0.2% aqueous solution of dihydrochloride and 2 parts of a 0.2% aqueous solution of sodium hypophosphite were added with stirring. The temperature of the contents was adjusted to 40 to 50 ° C., and the reaction and aging were performed for 10 hours. In addition, since the content became high viscosity during polymerization and stirring became difficult, stirring was stopped on the way. After completion of the polymerization, the contents are taken out, chopped, dried in a circulating dryer at 50 ° C. for 10 hours, and further pulverized with a mixer to obtain 100 parts of a particulate water-soluble copolymer (D-1). (Yield 97%, solid content 93%, weight average molecular weight 500,000).

<Production Example 4>
In Production Example 3, 67 parts instead of 52 parts 78% aqueous solution of N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium chloride, 11 parts instead of 9 parts 80% aqueous solution of acrylic acid. Particulate water-soluble copolymer (D) in the same manner as in Production Example 3, except that the same 66 parts were used instead of 98 parts of acrylamide 50% aqueous solution and 45 parts were used instead of 35 parts of ion-exchanged water. -2) 100 parts were obtained (yield 97%, solid content 92%, weight average molecular weight 800,000).

<Production Example 5>
In Production Example 3, N, N, N-trimethyl-N- (2-acryloyloxyethyl) was used instead of 52 parts of a 78% aqueous solution of N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium chloride. In the same manner as in Production Example 3, except that 49 parts of an 80% aqueous solution of ammonium chloride, 100 parts of the same were used instead of 98 parts of the 50% aqueous solution of acrylamide, and 35 parts of the same were used instead of 35 parts of ion-exchanged water. 100 parts of a water-soluble copolymer (D-3) were obtained (yield 97%, solid content 93%, weight average molecular weight 1,000,000).

<Production Example 6>
After charging 117 parts of the monomer (A-1), 9 parts of an 80% aqueous solution of acrylic acid, 34 parts of dimethylacrylamide, and 6 parts of 2-ethylhexyl acrylate into the reaction vessel, the total concentration of the monomers in the reaction system is 50%. Then, 46 parts of IPA was added and stirred until a homogeneous solution was obtained. Next, the temperature of the contents is adjusted to 40 ° C. in a constant temperature bath at 40 ° C., and after sufficiently replacing the reaction system with nitrogen (gas phase oxygen concentration of 10 ppm or less), 2,2′-azobis- (amidinopropane) ) 2 parts of a 0.2% aqueous solution of dihydrochloride and 2 parts of a 0.2% IPA solution of 1-thioglycerol were added with stirring. The temperature of the contents was adjusted to 40 to 50 ° C., and the reaction and aging were performed for 10 hours. In addition, since the content became high viscosity during polymerization and stirring became difficult, stirring was stopped on the way. After completion of the polymerization, the contents are taken out, shredded, dried under reduced pressure in a desiccator at room temperature, dried in a circulating dryer at 50 ° C. for 5 hours, and further pulverized with a mixer to form a particulate water-soluble copolymer. (D-4) 100 parts were obtained (yield 93%, solid content 99%, weight average molecular weight 500,000).

<Production Example 7>
In Production Example 6, 121 parts of monomer (A-2) instead of 117 parts of monomer (A-1), 29 parts of the same instead of 34 parts of dimethylacrylamide, n instead of 6 parts of 2-ethylhexyl acrylate -100 parts of a particulate water-soluble copolymer (D-5) was obtained in the same manner as in Production Example 6 except that 9 parts of butyl methacrylate and 43 parts of IPA were used instead of 43 parts (yield 94). %, Solid content 99%, weight average molecular weight 400,000).

<Comparative Production Example 1>
In Production Example 3, 93 parts of a particulate water-soluble copolymer (D′-1) was obtained in the same manner as in Production Example 3 except that 9 parts of an 80% aqueous solution of acrylic acid were not used (yield 97 %, Solid content 92%, weight average molecular weight 700,000).

<Comparative Production Example 2>
In Production Example 6, 93 parts of a particulate water-soluble copolymer (D′-2) was obtained in the same manner as in Production Example 6 except that 9 parts of an 80% aqueous solution of acrylic acid were not used (yield 97 %, Solid content 92%, weight average molecular weight 500,000).

<Examples 1 to 10 and Comparative Examples 1 to 5>
Each component was mix | blended with the compounding quantity described in Table 1, and the cleaning composition was produced.

<Use test>
Panelists of 10 men and women each fully wet their hair with 40 ° C hot water, then shampooed with 5 g of each of the cleaning compositions of Examples 1 to 10 and Comparative Examples 1 to 5, and the hot water is 40 ° C. Then, 5 g of a standard conditioner prepared according to the following formulation was applied to the hair by hand, rinsed and dried with a drier. Foam quality at the time of washing (feel of foam, fineness of foam), feeling of use at the time of washing (handing to hair), feeling of rinsing (handing to hair, hand and scalp) The items of moistness, familiarity of the conditioner, and finish after drying (conditioning effect) were evaluated.
The sensory evaluation results when the panelists actually used were expressed by points, and the total score was evaluated.
(Scoring criteria)
Very good: 5 points good: 4 points normal: 3 points bad: 2 points very bad: 1 point (standard conditioner prescription)
Polydimethylsiloxane 2.0 parts Cetyl alcohol 2.5 parts Stearyl alcohol 2.5 parts Behenyltrimethylammonium chloride 1.5 parts Glycerin 4.0 parts Water 87.5 parts

In Table 1, each component used the following.
Anionic surfactant (1): Polyoxyethylene (average added mole number = 2) Sodium lauryl ether sulfate Anionic surfactant (2): Polyoxyethylene (average added mole number = 3) Sodium lauryl ether acetate amphoteric interface Activator (1): Palm oil fatty acid amidopropyldimethylaminoacetic acid betaine amphoteric surfactant (2): 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine nonionic surfactant (1): Coconut oil fatty acid monoethanolamide nonionic surfactant (2): polyoxyethylene (average number of added moles = 1) dodecylene glycol Conventional conditioning agent: cationized hydroxyethyl cellulose, manufactured by Lion Corporation, “Leoguard GP”

  As is clear from Table 1, the detergent compositions (Examples 1 to 10) containing the copolymer of the present invention had a total score of 70 points or more in all performance evaluation items, Fineness), feeling of use at the time of washing and rinsing (feeling of touching the hair, moist feeling on the skin), conditioner and rinse are used well after shampooing, and the conditioner and rinse are familiar and effective conditioning effect It can be seen that On the other hand, although the cleaning composition of Comparative Examples 1-5 has a thing of 70 or more in some performance evaluation items, it turns out that all the performance evaluation items cannot fully be satisfied.

  The detergent composition blended with the copolymer of the present invention is excellent in foam quality (fineness of foam), feeling in use at the time of washing and rinsing (feeling of fingering to the hair, moist feeling on the skin), conditioner and rinse. It is a detergent composition that improves the familiarity and conditioning effect, and is suitable as a detergent for hair. It may also be used as household cleaners (clothing detergents, tableware detergents, etc.) and industrial cleaners (metals, precision parts, etc.).

Claims (10)

Structural units (a) represented by the following general formula (1), structural units (b) represented by the following general formula (2), and structural units derived from other ethylenically unsaturated monomers (C) (c And a copolymer for a cleaning composition comprising a copolymer (D).

[Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents an alkyl group having 1 to 24 carbon atoms, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 24 carbon atoms. Alternatively, it represents an aralkyl group having 7 to 24 carbon atoms, X ⁻ represents a halogen anion or an alkyl monoalkyl sulfate anion having 1 to 8 carbon atoms, n represents an integer of 1 to 10, and Y represents NH or O. Represents. ]

[Wherein R ⁵ represents a hydrogen atom or a methyl group, and M ⁺ represents a proton, an alkyl metal cation or an onium cation. ] The monomer (A) in which the copolymer (D) is represented by the following general formula (3), the monomer (B) represented by the following general formula (4), and other ethylenically unsaturated monomers The copolymer for a cleaning composition according to claim 1, which is a copolymer obtained by copolymerizing (C).

[Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents an alkyl group having 1 to 24 carbon atoms, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 24 carbon atoms. Alternatively, it represents an aralkyl group having 7 to 24 carbon atoms, X ⁻ represents a halogen anion or an alkyl monoalkyl sulfate anion having 1 to 8 carbon atoms, n represents an integer of 1 to 10, and Y represents NH or O. Represents. ]

[Wherein R ⁵ represents a hydrogen atom or a methyl group, and M ⁺ represents a proton, an alkyl metal cation or an onium cation. ] The molar fraction of the monomer (A), the monomer (B) and the other ethylenically unsaturated monomer (C) in the monomer constituting the copolymer (D) is (A), 3. Based on the total number of moles of (B) and (C), (A) is 2 to 50 mole%, (B) is 1 to 40 mole%, and (C) is 10 to 97 mole%. The copolymer for cleaning composition of description. The detergent composition according to any one of claims 1 to 3, wherein the monomer (C1) represented by the general formula (5) is an essential monomer as the other ethylenically unsaturated monomer (C). Copolymer for materials.

[Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, or an aralkyl group having 7 to 24 carbon atoms, and m is 0 Represents an integer of ˜30, AO represents an alkyleneoxy group having 2 to 4 carbon atoms, and Y represents NH or O. ] The proportion of the monomer (C1) is 0.5 to 60 mol% based on the total number of moles of other ethylenically unsaturated monomers (C) constituting the copolymer. Copolymer for cleaning composition. The copolymer for cleaning composition according to any one of claims 1 to 5, wherein the copolymer (D) has a weight average molecular weight of 10,000 to 5,000,000. It is a conditioning agent, The copolymer for cleaning compositions in any one of Claims 1-6. A detergent composition comprising the copolymer for a detergent composition according to any one of claims 1 to 7 and water. The cleaning composition according to claim 8, wherein the content of the cleaning composition copolymer is 0.01 to 2% by weight based on the weight of the cleaning composition. Further, anionic surfactants, amphoteric surfactants, nonionic surfactants, cationic surfactants, moisturizers, conditioning agents, chelating agents, builders, lower alcohols having 1 to 6 carbon atoms, thickeners, An additive (E) other than at least one (D) selected from the group consisting of a pearling agent, a fragrance, a colorant, an antiseptic, a medicinal agent, an anti-inflammatory agent, a bactericidal agent, an ultraviolet absorber and an antioxidant; The cleaning composition according to claim 8 or 9, comprising a total of 3 to 40% by weight based on the weight of the cleaning composition.