JP6786151B2 - Hydrophobic group and polyalkylene glycol chain-containing copolymer and detergent composition - Google Patents

Description

The present invention relates to a copolymer containing a hydrophobic group and a polyalkylene glycol chain, and a detergent composition containing the polymer.

Conventionally, detergents used for clothing are blended with detergent builders (detergent aids) such as zeolite, carboxymethyl cellulose, and polyethylene glycol for the purpose of improving the cleaning effect of the detergent.

Further, in addition to the above-mentioned various detergent builders, in recent years, a polymer has been blended into the detergent composition as a detergent builder.

Patent Document 1 describes a copolymer having a vinyloxybutylene poly (ethylene glycol) structural unit as a polyether macromonomer structural unit in addition to the acid monomer structural unit. Furthermore, it has been disclosed that when this copolymer is used in a concrete mixture, it exhibits excellent adaptive properties.

The vinyloxybutylene poly (ethylene glycol) used as the monomer precursor product of these copolymers is obtained by ethoxylation of 4-hydroxybutyl vinyl ether. 4-Hydroxybutyl vinyl ether is synthesized by the Reppe reaction using acetylene as a raw material. Therefore, 4-hydroxybutyl vinyl ether has a problem that it is difficult to produce it at low cost. Further, when this copolymer is used as a detergent builder, there is a problem that the detergency against hydrophobic stains is low.

Special Table 2007-523235

As described above, although various copolymers have been reported in the past, none of them have sufficient dispersion performance for both hydrophilic stains and hydrophobic stains, and a detergent builder adapted to the above-mentioned current consumer needs. Development is required.
Therefore, the present invention exhibits high dispersion performance for both hydrophilic stains and hydrophobic stains when used in detergent applications, and is a copolymer and detergent having further improved anti-recontamination ability. It is an object of the present invention to provide a composition.

The present inventors have conducted diligent research to solve the above problems. As a result, the present inventors have obtained a hydrophobic group and a polyalkylene glycol chain by copolymerizing a monomer having a specific hydrophobic group and a polyalkylene glycol chain with a (meth) acrylic acid-based monomer. We have found that the ability of the copolymer to capture calcium is improved, the ability to disperse carbon black and the ability to disperse clay are improved, and the ability to prevent recontamination is improved, and the present invention has been completed.

That is, the present invention is a copolymer containing a hydrophobic group and a polyalkylene glycol chain, and the hydrophobic group and the polyalkylene glycol chain-containing copolymer is a monomer (A) containing a hydrophobic group and a polyalkylene glycol chain. Derived from the following general formula (1);

(In the above general formula (1), R ¹ , R ² and R ³ represent the same or different hydrogen atom or methyl group. R ⁴ is the same or different and has the same or different hydrogen atom or carbon number 1 to 30. Represents a chain hydrocarbon group. R is an integer from 0 to 2. s is an integer from 0 to 1. T is an integer from 0 to 2. W is the same or different carbon. Represents a trivalent aromatic group of number 6 to 30 or a trivalent group formed by removing three hydrogen atoms from a chain hydrocarbon having 1 to 30 carbon atoms. Z is the same or different, hydrogen atom or − SO ₃ NH represents ₄ groups. Y represents the same or different direct bond or oxygen atom. X represents the same or different oxyalkylene group having 2 to 20 carbon atoms. N represents 1 to 200. However, when R ⁴ is a hydrogen atom, Y is a direct bond. A trivalent group formed by removing three hydrogen atoms from a chain hydrocarbon having 1 to 30 carbon atoms. In the case of, R ⁴ is a structural unit (a) represented by a chain hydrocarbon group having 1 to 30 carbon atoms) and a structural unit derived from a carboxyl group-containing monomer (B). 1% by mass or more of the structural unit (a) with respect to 100% by mass of the total amount of structural units derived from all the monomers forming the above-mentioned hydrophobic group and polyalkylene glycol chain-containing copolymer including (b). , 99% by mass or less, and a hydrophobic group- and polyalkylene glycol chain-containing copolymer containing the structural unit (b) in a proportion of 1% by mass or more and 99% by mass or less.

The hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention is excellent in calcium trapping ability, carbon black dispersing ability and clay dispersing ability, and also has excellent recontamination prevention ability. Therefore, if the hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention is used as a detergent builder, recontamination of stains during washing can be prevented. Further, the copolymer of the present invention exhibits an excellent cleaning effect with less salt precipitation even when used in hard water having a high concentration of calcium ions and magnesium ions. Therefore, the hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention can be preferably used as a detergent additive.

Hereinafter, the present invention will be described in detail.

<1> The hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention is derived from the hydrophobic group and polyalkylene glycol chain-containing monomer (A) by the following general formula (1);

(In the above general formula (1), R ¹ , R ² and R ³ represent the same or different hydrogen atom or methyl group. R ⁴ is the same or different and has the same or different hydrogen atom or carbon number 1 to 30. Represents a chain hydrocarbon group. R is an integer from 0 to 2. s is an integer from 0 to 1. T is an integer from 0 to 2. W is the same or different carbon. Represents a trivalent aromatic group of number 6 to 30 or a trivalent group formed by removing three hydrogen atoms from a chain hydrocarbon having 1 to 30 carbon atoms. Z is the same or different, hydrogen atom or − SO ₃ NH represents ₄ groups. Y represents the same or different direct bond or oxygen atom. X represents the same or different oxyalkylene group having 2 to 20 carbon atoms. N represents 1 to 200. However, when R ⁴ is a hydrogen atom, Y is a direct bond. A trivalent group formed by removing three hydrogen atoms from a chain hydrocarbon having 1 to 30 carbon atoms. In the case of, R ⁴ is a structural unit (a) represented by a chain hydrocarbon group having 1 to 30 carbon atoms) and a structural unit derived from a carboxyl group-containing monomer (B). 1% by mass or more of the structural unit (a) with respect to 100% by mass of the total amount of structural units derived from all the monomers forming the above-mentioned hydrophobic group and polyalkylene glycol chain-containing copolymer including (b). , 99% by mass or less, and a hydrophobic group- and polyalkylene glycol chain-containing copolymer containing the structural unit (b) in a proportion of 1% by mass or more and 99% by mass or less.

<2> Further, the hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention can be used as a detergent composition.

When the expression "acid (salt)" is used herein, it means an acid and / or a salt salt. The "salt" is preferably an alkali metal salt such as a sodium salt or a potassium salt; an alkaline earth metal salt such as a calcium salt or a magnesium salt; an ammonium salt; a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt or the like. Organic amine salts; etc. The "salt" may be only one kind or a mixture of two or more kinds.
Of these, ammonium salt, sodium salt, and potassium salt are preferable as the "salt" because the obtained polymer has a high effect of improving the carbon black dispersible ability, recontamination prevention ability, clay dispersible ability, and calcium trapping ability. , Ammonium salt is more preferred.

In the present specification, the expression "(meth) acrylic" means "acrylic and / or methacrolein", and the expression "(meth) acrylate" means "acrylate and / or methacrylate". When the expression "(meth) allyl" is used, it means "allyl and / or methacrolein", and when the expression "(meth) acrolein" is used, "acrolein and / or methacrolein" is used. It means "rain".

≪A. Copolymer ≫
The hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention is derived from the structural unit (a) derived from the hydrophobic group and polyalkylene glycol chain-containing monomer (A) and the carboxyl group-containing monomer (B). Has a structural unit (b) to be formed.

The "monomer-derived structural unit" means a structural unit in which an unsaturated double bond involved in the polymerization reaction in the monomer becomes a single bond by the polymerization reaction, and specifically, the monomer. Is represented by "R ^a R ^b C = CR ^c R ^d ", which means a structural unit represented by "-R ^a R ^b C-CR ^c R ^d- " in the copolymer. For example, a structural unit derived from acrylic acid is represented by "-CH _2- CH (COOH)-".

In the copolymer of the present invention, the structural unit (a) is represented by a hydrophobic group represented by -R ⁴ or -W-Y-R ⁴ in the above general formula (1) and -O-Xn-Z. Since it has a structure in which the hydrophilic groups of the polyalkylene glycol chain are branched, the hydrophobic groups and the hydrophilic groups in the polymer can act simultaneously on various stains. As a result, the effects of each functional group can be effectively exhibited as compared with the conventionally known polymers having a substituent in which a hydrophobic group and a polyalkylene glycol chain are linear, so that hydrophilic stains and hydrophobic stains can be exhibited. Dispersion performance is improved. Further, in the above-mentioned conventional polymer, if the number of carbon atoms of the hydrophobic group in the monomer having a hydrophobic group and a polyalkylene glycol chain is large, aqueous polymerization becomes difficult, so that the number of carbon atoms of the hydrophobic group is limited to about 8. However, since the hydrophobic group and the polyalkylene glycol chain-containing monomer (A) of the present invention have branched hydrophobic groups and polyalkylene glycol chains, even when the hydrophobic group has a large number of carbon atoms, it is an aqueous solution. Polymerization becomes possible, and the copolymer of the present invention is superior in the dispersion performance of the hydrophobic substance.

In the general formula (1), R ¹ , R ² and R ³ represent the same or different hydrogen atoms or methyl groups. When W in the general formula (1) is a trivalent aromatic group having 6 to 30 carbon atoms, it is preferable that R ¹ and R ³ are hydrogen atoms and R ² is a methyl group. Further, when W is a trivalent group formed by removing three hydrogen atoms from a chain hydrocarbon having 1 to 30 carbon atoms, all of R ¹ , R ² and R ³ may be hydrogen atoms. preferable.

In the general formula (1), r is an integer of 0 to 2. s is an integer from 0 to 1. t is an integer from 0 to 2. When W is a trivalent aromatic group having 6 to 30 carbon atoms, r is preferably an integer of 0 to 1, s is preferably an integer of 0 to 1, and t. Is preferably an integer of 0 to 1. More preferably, r = s = t = 0.
Further, when W is a trivalent group formed by removing three hydrogen atoms from a chain hydrocarbon having 1 to 30 carbon atoms, r is preferably an integer of 0 to 1, and s is. It is preferably an integer of 0 to 1, and t is preferably an integer of 0 to 1. More preferably, r = s = t = 1.

In the general formula (1), W is the same or different, and is trivalent obtained by removing three hydrogen atoms from a trivalent aromatic group having 6 to 30 carbon atoms or a chain hydrocarbon having 1 to 30 carbon atoms. However, the trivalent aromatic group having 6 to 30 carbon atoms is not particularly limited as long as it has an aromatic ring. The number of carbon atoms of the trivalent aromatic group is preferably 6 to 14, and more preferably 6 to 10. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring and the like, and among these, a benzene ring is preferable.
The chain hydrocarbon having a trivalent group formed by removing three hydrogen atoms from the chain hydrocarbon is not particularly limited, and even if it is a chain saturated hydrocarbon, it is a chain unsaturated hydrocarbon. May be good. Further, the chain hydrocarbon may have a branch. The number of carbon atoms of the chain hydrocarbon is preferably 1 to 30, more preferably 1 to 5, and even more preferably 1 to 3. Examples of the chain hydrocarbon include alkanes, alkenes, alkynes and the like, and alkanes are preferable. When the trivalent group formed by removing three hydrogen atoms from the chain hydrocarbon has a branch, the carbon number of the trivalent group formed by removing three hydrogen atoms from the chain hydrocarbon is the main chain. And the total number of carbon atoms in the branched chain.

In the general formula (1), Y represents a direct bond or an oxygen atom, which is the same or different, but when R ⁴ is a hydrogen atom, Y is a direct bond.
Further, when W is a trivalent group formed by removing three hydrogen atoms from a chain hydrocarbon, Y is preferably an oxygen atom, and if Y is an oxygen atom, the polymer Since the water solubility is not impaired, clay dispersibility can be exhibited.

In the general formula (1), R ⁴ represents a hydrogen atom or a chain hydrocarbon group having 1 to 30 carbon atoms in the same or different manner, but W is a chain hydrocarbon having 1 to 30 carbon atoms to a hydrogen atom. when the a trivalent group that can be three except for, R ⁴ is a chain hydrocarbon group having 1 to 30 carbon atoms. Examples of R ^4, is preferably a chain hydrocarbon group having 1 to 30 carbon atoms. Examples of the chain hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group which may have a branch. As the chain hydrocarbon group, an alkenyl group or an alkyl group is preferable, and an alkyl group is more preferable. The number of carbon atoms of the chain hydrocarbon group is preferably 3 to 25, more preferably 5 to 20, and even more preferably 7 to 15.
When the number of carbon atoms is 3 or more, the carbon black dispersibility is further improved, and the ability to prevent recontamination against hydrophobic stains is further improved. When the number of carbon atoms is 25 or less, the hydrophobicity of the copolymer of the present invention does not become too high, and the water solubility of the copolymer of the present invention is in a preferable range. Therefore, clay dispersibility and recontamination prevention ability Is improved. When the chain hydrocarbon group has a branch, the carbon number of the chain hydrocarbon group means the total carbon number of the main chain and the branched chain.

In the general formula (1), X represents the same or different oxyalkylene group having 2 to 20 carbon atoms. It is preferably an oxyalkylene group having 2 to 10 carbon atoms, more preferably 2 to 5, still more preferably 2 to 3, and most preferably 2. When the carbon number of the oxyalkylene group of X in the general formula (1) is in the above preferable range, the copolymer of the present invention exhibits high hydrophilicity, so that the clay dispersibility is improved and is excellent. It is preferable because it can exert the ability to prevent recontamination.

In the general formula (1), n is an integer of 1 to 200. n represents a repeating unit of the oxyalkylene group. The value of n is preferably 2 to 100, more preferably 3 to 70, still more preferably 5 to 50, and most preferably 5 to 30.
When the value of n in the general formula (1) is 2 or more, the hydrophilicity of the copolymer of the present invention is further improved, so that the clay dispersibility is further improved. On the other hand, when the value of n in the general formula (1) is 100 or less, the hydrophobicity of the copolymer of the present invention falls within a more preferable range, the carbon black dispersibility is improved, and the copolymer is resistant to hydrophobic stains. Contamination prevention ability is further improved.

In the general formula (1), Z represents a hydrogen atom or _four -SO ₃ NH groups, which are the same or different.
If Z in the general formula (1) is a substituent selected from the above, the water solubility of the copolymer becomes sufficient, the clay dispersibility is improved, and excellent anti-recontamination ability is obtained. Can be demonstrated.

The structural unit (a) is the following general formula (2);

(In the above general formula (2), R ¹ , R ² and R ³ represent the same or different hydrogen atom or methyl group. R ⁵ represents a chain hydrocarbon group having 1 to 30 carbon atoms. Z is the same or different and represents a hydrogen atom or -SO ₃ NH ₄ groups. Y is the same or different and represents a direct bond or an oxygen atom. X is the same or different and represents 2 to 20 carbon atoms. Represents an oxyalkylene group. N is an integer of 1 to 200) or the following general formula (3);

(In the above general formula (3), R ¹ , R ² and R ³ represent the same or different hydrogen atom or methyl group. R ⁶ is the same or different and has the same or different hydrogen atom or carbon number 1 to 30. Represents a chain hydrocarbon group. Z represents a hydrogen atom or -SO ₃ NH ₄ groups. Z represents the same or different oxyalkylene group having 2 to 20 carbon atoms. N represents 1 to 200 carbon atoms. It is an integer. The -O-Xn-Z group is preferably bonded to -R ⁶ in the benzene ring at any of the ortho-position, meta-position or para-position). ..

Specific examples and preferable examples of X, Z and n in the general formulas (2) and (3) are the same as those in X, Z and n in the general formula (1).

In the general formula (2), R ¹ , R ² and R ³ are hydrogen atoms or methyl groups, but it is preferable that all of R ¹ , R ² and R ³ are hydrogen atoms.

R ⁵ in the general formula (2) is a chain hydrocarbon group having 1 to 30 carbon atoms, and examples of the chain hydrocarbon group include those similar to the chain hydrocarbon group in R ⁴ described above. Be done. As the chain hydrocarbon group, an alkenyl group or an alkyl group is preferable, and an alkyl group is more preferable. The number of carbon atoms of the chain hydrocarbon group is preferably 5 to 25, more preferably 7 to 20, and even more preferably 9 to 15. The number of carbon atoms of at R ⁵ on the general formula (2) is the number of carbon atoms is equal to 5 or more, further improved carbon black dispersibility, anti-soil redeposition ability is improved for the hydrophobic dirt. When the number of carbon atoms is 25 or less, the hydrophobicity of the copolymer of the present invention does not become too high, and the water solubility of the copolymer of the present invention is in a preferable range. Therefore, clay dispersibility and recontamination prevention ability Is improved.

In the general formula (3), R ¹ , R ² and R ³ are hydrogen atoms or methyl groups, but it is preferable that R ¹ and R ³ are hydrogen atoms and R ² is a methyl group.

R ⁶ in the general formula (3) is a hydrogen atom or a chain hydrocarbon group having 1 to 30 carbon atoms, and the chain hydrocarbon group is the same as the chain hydrocarbon group in R ⁴ described above. Things can be mentioned. As the chain hydrocarbon group, an alkenyl group or an alkyl group is preferable, and an alkyl group is more preferable. The number of carbon atoms of the chain hydrocarbon group is preferably 3 to 25, more preferably 5 to 20, and even more preferably 7 to 15. When the carbon number of R ^{6 in} the general formula (2) is 3 or more, the carbon black dispersibility is further improved, and the recontamination prevention ability against hydrophobic stains is further improved. When the number of carbon atoms is 20 or less, the hydrophobicity of the copolymer of the present invention does not become too high, and the water solubility of the copolymer of the present invention is in a preferable range. Therefore, clay dispersibility and recontamination prevention ability Is improved.

When the number of carbon atoms of R ⁵ in the general formula (2) and R ⁶ in the general formula (3) is as small as 1 to 3, for example, the number of repeating units n of the oxyalkylene group is reduced to make it hydrophobic. Since it is possible to adjust the degree of conversion and the degree of hydrophilicity, the carbon black dispersibility and the ability to prevent recontamination do not necessarily decrease when the number of carbon atoms is small.
On the contrary, when the number of carbon atoms of R ⁵ in the general formula (2) and R ⁶ in the general formula (3) is as large as 28 to 30, the number of repeating units n of the oxyalkylene group is increased to make it hydrophobic. Since it is possible to adjust the degree of conversion and the degree of hydrophilicity, the carbon black dispersibility and the ability to prevent recontamination do not necessarily decrease when the number of carbon atoms is large.

<Monomer containing hydrophobic group and polyalkylene glycol chain (A)>
As a hydrophobic group- and polyalkylene glycol chain-containing monomer (A) corresponding to the structural unit (a) represented by the general formulas (1) to (3) (hereinafter, also simply referred to as a monomer (A)). Can be represented by the following general formulas (4), respectively, and as a more preferable form, can be represented by the following general formulas (5) and (6).

(In the above general formula (4), R ¹ , R ² and R ³ represent the same or different hydrogen atom or methyl group. R ⁴ is the same or different and has the same or different hydrogen atom and carbon number 1 to 30. Represents a chain hydrocarbon group. R is an integer from 0 to 2. S is an integer from 0 to 1. T is an integer from 0 to 2. W is the same or different carbon. Represents a trivalent aromatic group of number 6 to 30 or a trivalent group formed by removing three hydrogen atoms from a chain hydrocarbon having 1 to 30 carbon atoms. Z is the same or different, hydrogen atom or − SO ₃ NH represents ₄ groups. Y represents the same or different direct bond or oxygen atom. X represents the same or different oxyalkylene group having 2 to 20 carbon atoms. N represents 1 to 200. However, when R ⁴ is a hydrogen atom, Y is a direct bond. A trivalent group formed by removing three hydrogen atoms from a chain hydrocarbon having 1 to 30 carbon atoms. If it is, ^{R 4} is a chain hydrocarbon group having 1 to 30 carbon atoms.)

(In the above general formula (5), R ¹ , R ² and R ³ represent the same or different hydrogen atom or methyl group. R ⁵ represents a chain hydrocarbon group having 1 to 30 carbon atoms. Z represents the same or different hydrogen atom, ₄ groups of -SO ₃ NH. Y represents the same or different, direct bond or oxygen atom. X represents the same or different, having 2 to 20 carbon atoms. Represents an oxyalkylene group. N is an integer from 1 to 200.)

(In the above general formula (6), R ¹ , R ² and R ³ represent the same or different hydrogen atom or methyl group. R ⁶ is the same or different and has the same or different hydrogen atom or carbon number 1 to 30. Represents a chain hydrocarbon group. Z represents a hydrogen atom or -SO ₃ NH ₄ groups. X represents the same or different oxyalkylene group having 2 to 20 carbon atoms. N represents 1 to 200 carbon atoms. It is an integer. The -O-Xn-Z group is attached to -R ^{6 on} the benzene ring at either the ortho-position, the meta-position or the para-position.)

^R 4 in the general formula (4), W, X, Y, Z and n are the same as ^R 4, W, X, Y, Z and n in the general formula (1).
In the general formula (4), R ¹ , R ² and R ³ represent a hydrogen atom or a methyl group. When W in the general formula (4) is a trivalent aromatic group having 6 to 30 carbon atoms, it is preferable that R ¹ and R ³ are hydrogen atoms and R ² is a methyl group. When R ¹ and R ³ are hydrogen atoms and R ² is a methyl group, the polymerizable property with the carboxyl group-containing monomer (B) is improved, which is preferable.
Further, when W is a trivalent group formed by removing three hydrogen atoms from a chain hydrocarbon having 1 to 30 carbon atoms, all of R ¹ , R ² and R ³ may be hydrogen atoms. preferable. It is preferable that all of R ¹ , R ² and R ³ are hydrogen atoms because the polymerizable property with the carboxyl group-containing monomer (B) is improved.

^R 5, X, Y, Z and n in the general formula (5) is the same as ^R 5, X, Y, Z and n in the general formula (2).
Although R ¹ , R ² and R ³ in the general formula (5) are hydrogen atoms or methyl groups, it is preferable that all of R ¹ , R ² and R ³ are hydrogen atoms. It is preferable that all of R ¹ , R ² and R ³ are hydrogen atoms because the polymerizable property with the carboxyl group-containing monomer (B) is improved.

Specific examples of the monomer (A) represented by the general formula (5) include ADEKA CORPORATION SR series (manufactured by ADEKA: ether sulfate type ammonium salt) and ADEKA rear soap ER series (manufactured by ADEKA: ether). (Sulfate type) Aqualon KH series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate) and the like can be mentioned.
Specifically, in the Adecaria soap SR series, SR-10 (EO 10 mol), SR-20 (EO 20 mol), SR-3025 (EO 30 mol, 25% aqueous solution) can be mentioned, and in the Adecaria soap ER series, ER-10 (EO 10 mol), ER-20 (EO 20 mol), ER-30 (EO 30 mol), ER-40 (EO 40 mol) are mentioned, and in the Aqualon KH series, Aqualon KH-05 (EO 5 mol), Aqualon KH -10 (10 mol of EO) can be mentioned.
More preferably, Adecaria Soap SR-10, SR-20, ER-20, KH-10.
When the monomer (A) represented by the general formula (5) is the above compound, the hydrophilicity and the hydrophobicity are balanced, so that the carbon black dispersibility is improved and the hydrophobic stain is dealt with. It is preferable because it can exhibit excellent anti-recontamination ability.

^R 6, X in the general formula (6), Z and n are, ^R 6, X, is the same as Z and n in the general formula (3).
In the general formula (6), R ¹ , R ² and R ³ are hydrogen atoms or methyl groups, but it is preferable that R ¹ and R ³ are hydrogen atoms and R ² is a methyl group. When R ¹ and R ³ are hydrogen atoms and R ² is a methyl group, the polymerizable property with the carboxyl group-containing monomer (B) is improved, which is preferable.
The monomer (A) represented by the general formula (6) preferably has an E-form (trans position) in which R ² and a phenyl group are located at the trans position. If the monomer (A) has such a structure, the polymerizable property with the carboxyl group-containing monomer (B) is improved, which is preferable.
The -O-Xn-Z group in the monomer (A) represented by the general formula (6) is located at either the ortho-position, the meta-position or the para-position with respect to -R ^{6 on} the benzene ring. It suffices if it is bound to, but it is preferable that it is bound to the para position. Further, it is preferable that the -O-Xn-Z group is bonded to the ortho position with respect to the carbon to which the polymerizable unsaturated group is bonded in the benzene ring of the general formula (6).

Specific examples of the monomer (A) represented by the general formula (6) include Aqualon HS / BC series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: ammonium polyoxyethylene nonylpropenylphenyl ether ammonium sulfate) and Aqualon RN series (first). Industrial Pharmaceutical Co., Ltd .: Polyoxyethylene nonylpropenylphenyl ether) and the like.
Specifically, in the Aqualon HS / BC series, HS-10 (EO 10 mol), BC-0515 (EO 5 mol), BC-10 (EO 10 mol), BC-20 (EO 20 mol) are mentioned, and the Aqualon RN series Then, RN-20 (EO 20 mol), RN-30 (EO 30 mol), RN-50 (EO 50 mol) can be mentioned.
More preferably, it is Aqualon BC-10, BC-20, RN-20, RN-30.
When the monomer (A) represented by the general formula (6) is the above compound, the hydrophilicity and the hydrophobicity are balanced, so that the carbon black dispersibility is improved and the hydrophobic stain is dealt with. It is preferable because it can exhibit excellent anti-recontamination ability.

<Carboxylic group-containing monomer (B)>
The carboxyl group-containing monomer (B) is not particularly limited as long as it is a monomer having a polymerizable unsaturated bond (carbon-carbon double bond) and a carboxyl group, and is, for example, acrylic. Unsaturated monocarboxylic acid-based monomers such as acids, methacrylic acids, crotonic acids, α-hydroxyacrylic acids, α-hydroxymethylacrylic acids and salts thereof; maleic acid, maleic anhydride, fumaric acid, itaconic acid, Unsaturated dicarboxylic acid-based monomers such as itaconic anhydride, 2-methyleneglutaric acid and salts thereof are exemplified.
The salt is a metal salt, an ammonium salt, an organic amine salt, and an alkali metal salt such as a sodium salt or a potassium salt is particularly preferable.
The salt of dicarboxylic acid anhydride refers to a salt in the form of hydrolyzed to dicarboxylic acid.

As the carboxyl group-containing monomer (B), one or more selected from the unsaturated monocarboxylic acid-based monomers and the unsaturated dicarboxylic acid-based monomers may be used.
The carboxyl group-containing monomer (B) is preferably acrylic acid (salt), maleic acid (salt), or maleic anhydride, and more preferably acrylic acid (salt) or maleic acid (salt).

<Other monomers (D)>
The hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention has a structural unit (d) derived from another monomer (D) in addition to the structural unit (a) and the structural unit (b). Is also good.

Examples of the other monomer (D) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Hydroxyl-containing alkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate and α-hydroxymethylethyl (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Alkyl (meth) acrylates which are esters of alkyl groups having 1 to 18 carbon atoms of (meth) acrylates such as cyclohexyl (meth) acrylate and lauryl (meth) acrylate; dimethylaminoethyl (meth) acrylate or its 4 Amino group-containing acrylates such as graded products; Amid group-containing monomers such as (meth) acrylamide, dimethylacrylamide and isopropylacrylamide; Vinyl esters such as vinyl acetate; Alkens such as ethylene and propylene; Fragrances such as styrene Group vinyl-based monomers; Maleimide derivatives such as maleimide, phenylmaleimide, cyclohexylmaleimide; nitrile group-containing vinyl-based monomers such as (meth) acrylonitrile; monomers having a sulfonic acid group such as isoprene sulfonic acid. Classes and salts thereof; monomers having a phosphonic acid group such as vinyl phosphonic acid and (meth) allyl phosphonic acid; aldehyde group-containing vinyl monomers such as (meth) achlorine; methyl vinyl ether, ethyl vinyl ether, Alkyl vinyl ethers such as butyl vinyl ether; 1 mol to 300 mol of alkylene oxide in unsaturated alcohols such as polyalkylene glycol (meth) acrylate, monoalkoxypolyalkylene glycol (meth) acrylate, vinyl alcohol, (meth) allyl alcohol, and isoprenol. Polyalkylene glycol chain-containing monomers having an added structure; 3- (meth) allyloxy-2-hydroxypropanesulfonic acid (salt), 3- (meth) allyloxy-1-hydroxypropanesulfonic acid Monomers having a sulfonic acid group such as (salt), 2-acrylamide-2-methylpropanesulfonic acid (salt), styrenesulfonic acid (salt), allylsulfonic acid (salt), vinyl sulfonic acid (salt); Has other functional groups such as vinyl chloride, vinylidene chloride, allyl alcohol, vinyl pyrrolidone, etc. Examples include monomers. These other monomers may be only one kind or two or more kinds.

The content ratio of the structural unit (a) in the hydrophobic group and polyalkylene glycol chain-containing copolymer of the present invention is the structural unit derived from all the monomers forming the hydrophobic group and the polyalkylene glycol chain-containing copolymer. It is 1% by mass to 99% by mass, preferably 10% by mass to 90% by mass, more preferably 15% by mass to 80% by mass, and further preferably 20% by mass with respect to 100% by mass of the total amount of. It is ~ 70% by mass, and particularly preferably 30% by mass to 70% by mass.
When the content ratio of the structural unit (a) in the copolymer of the present invention is less than 1% by mass, the carbon black dispersibility decreases, and the ability to prevent recontamination against hydrophobic stains does not reach the desired performance. May occur. If the content of the structural unit (a) in the hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention exceeds 99% by mass, the hydrophilicity is lowered and the recontamination prevention ability does not reach the desired performance. Problems may occur.

The content ratio of the structural unit (b) in the hydrophobic group and polyalkylene glycol chain-containing copolymer of the present invention is the structural unit derived from all the monomers forming the hydrophobic group and the polyalkylene glycol chain-containing copolymer. It is 1% by mass to 99% by mass, preferably 10% by mass to 90% by mass, more preferably 20% by mass to 85% by mass, and further preferably 30% by mass with respect to 100% by mass of the total amount of. It is about 80% by mass, and particularly preferably 30% by mass to 70% by mass.
When the content ratio of the structural unit (b) in the hydrophobic group and polyalkylene glycol chain-containing copolymer of the present invention is less than 1% by mass, the hydrophilicity is lowered and the recontamination prevention ability does not reach the desired performance. Problems may occur. When the content ratio of the structural unit (b) in the hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention exceeds 99% by mass, the carbon black dispersibility is lowered and recontamination prevention against hydrophobic stains is prevented. There may be a problem that the performance does not reach the desired performance.

The hydrophobic group and polyalkylene glycol chain-containing copolymer of the present invention preferably contains a structural unit derived from acrylic acid (salt) and / or maleic acid (salt) as the structural unit (b).
The total content of the structural units derived from acrylic acid (salt) and maleic acid (salt) in the copolymer is preferably 1 to 100% by mass with respect to 100% by mass of the structural unit (b). It is more preferably 50 to 100% by mass, and even more preferably 100% by mass.
The content ratio of the structural unit derived from acrylic acid (salt) in the copolymer is preferably 1 to 100% by mass with respect to 100% by mass of the structural unit (b). It is more preferably 20 to 100% by mass, and even more preferably 30 to 100% by mass.
The content ratio of the structural unit derived from maleic acid (salt) in the copolymer is preferably 0 to 40% by mass with respect to 100% by mass of the structural unit (b). It is more preferably 0 to 30% by mass, and further preferably 0 to 20% by mass.

The total content ratio of the structural unit (a) and the structural unit (b) to the structural unit derived from all the monomers in the hydrophobic group and polyalkylene glycol chain-containing copolymer of the present invention is 90% by mass to 100% by mass. %, preferably 95% by mass to 100% by mass, more preferably 98% by mass to 100% by mass, still more preferably 99% by mass to 100% by mass, and particularly preferably 100% by mass. .. If the total content ratio of the structural unit (a) and the structural unit (b) to the structural unit derived from all the monomers in the copolymer of the present invention is 90% by mass or more, the carbon black dispersibility or hydrophobicity The ability to prevent recontamination of dirt becomes more sufficient.

The content ratio of the structural unit (d) in the hydrophobic group and polyalkylene glycol chain-containing copolymer of the present invention is the structural unit derived from all the monomers forming the hydrophobic group and the polyalkylene glycol chain-containing copolymer. It is preferably 0% by mass to 10% by mass, more preferably 0% by mass to 5% by mass, and most preferably 0% by mass with respect to 100% by mass of the total amount of.

The weight average molecular weight Mw of the hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 150,000, and even more preferably 5. It is 000 to 130,000, particularly preferably 8,000 to 100,000, more preferably 10,000 to 90,000, even more preferably 12,000 to 80,000, and most preferably. It is preferably 15,000 to 70,000. When the weight average molecular weight Mw of the copolymer of the present invention is 1,000 or more, the calcium trapping ability is further improved, and the ability to prevent recontamination of hydrophobic stains is more sufficient. When the weight average molecular weight Mw of the hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention is 200,000 or less, the carbon black dispersibility becomes more sufficient.

The copolymer of the present invention can be produced by any suitable method. The copolymer of the present invention can preferably be produced by the production method of the present invention described below.

≪B. Copolymer production method ≫
The method for producing a hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention is a monomer component containing a hydrophobic group and a polyalkylene glycol chain-containing monomer (A) and a carboxyl group-containing monomer (B). Is a method for producing a copolymer by polymerizing.

The description of each of the hydrophobic group, the polyalkylene glycol chain-containing monomer (A), and the carboxyl group-containing monomer (B) is described in << A. The description in the section "Copolymers" is incorporated.

The monomer component may have other monomers (D) in addition to the hydrophobic group, the polyalkylene glycol chain-containing monomer (A), and the carboxyl group-containing monomer (B).

The description of the other monomer (D) is described in << A. The description in the section "Copolymers" is incorporated.

The content ratio of the hydrophobic group and the polyalkylene glycol chain-containing monomer (A) in all the monomer components is 1% by mass to 99% by mass, preferably 10 with respect to 100% by mass of all the monomers. It is from mass% to 90% by mass, more preferably 15% by mass to 80% by mass, further preferably 20% by mass to 70% by mass, and particularly preferably 30% by mass to 70% by mass.
When the content ratio of the hydrophobic group and the polyalkylene glycol chain-containing monomer (A) in all the monomer components is less than 1% by mass, the structural unit (a) in the hydrophobic group and the polyalkylene glycol chain-containing copolymer (a). Since the content of the copolymer is lowered, there is a possibility that it becomes difficult to obtain a copolymer containing a hydrophobic group and a polyalkylene glycol chain which is effective against hydrophobic stains. When the content ratio of the hydrophobic group and the polyalkylene glycol chain-containing monomer (A) in all the monomer components exceeds 99% by mass, the carboxyl group-containing monomer (B) is evenly introduced into the copolymer. This can lead to the problem of difficulty.

The content ratio of the carboxyl group-containing monomer (B) in all the monomer components is 1% by mass to 99% by mass, preferably 10% by mass to 90% by mass, based on 100% by mass of all the monomers. %, More preferably 20% by mass to 85% by mass, further preferably 30% by mass to 80% by mass, and particularly preferably 30% by mass to 70% by mass.
When the content ratio of the carboxyl group-containing monomer (B) in all the monomer components is less than 1% by mass, the weight average molecular weight Mw of the obtained polymer is lowered, and the recontamination prevention ability is sufficiently exhibited. May not reach a sufficient weight average molecular weight Mw. If the content ratio of the carboxyl group-containing monomer (B) in all the monomer components exceeds 99% by mass, there is a possibility that the ability to prevent recontamination against hydrophobic stains is lowered.
Further, when the content ratio of the monomer (B) is 10% by mass or more, the calcium trapping ability is further improved, and when the copolymer of the present invention is used for detergent use, the concentration of calcium ions and magnesium ions. Even in hard water with a high calcium content, there is little precipitation of salts, and an excellent cleaning effect is exhibited.

In the production method of the present invention, it is preferable to contain acrylic acid (salt) and / or maleic acid (salt) as the carboxyl group-containing monomer (B) in all the monomer components.
The total content ratio of acrylic acid (salt) and maleic acid (salt) in all the monomer components may be 1 to 100% by mass with respect to 100% by mass of the carboxyl group-containing monomer (B). preferable. It is more preferably 50 to 100% by mass, and even more preferably 100% by mass.
The content ratio of the acrylic acid (salt) is preferably 1 to 100% by mass with respect to 100% by mass of the carboxyl group-containing monomer (B). It is more preferably 20 to 100% by mass, and even more preferably 30 to 100% by mass.
The content ratio of the maleic acid (salt) is preferably 0 to 40% by mass with respect to 100% by mass of the carboxyl group-containing monomer (B). It is more preferably 0 to 30% by mass, and further preferably 0 to 20% by mass.

The total content ratio of the hydrophobic group and polyalkylene glycol chain-containing monomer (A) and the carboxyl group-containing monomer (B) in all the monomer components is 100% by mass of the total monomer. It is preferably 90% by mass to 100% by mass, more preferably 95% by mass to 100% by mass, further preferably 98% by mass to 100% by mass, and particularly preferably 99% by mass to 100% by mass. Yes, most preferably 100% by mass. When the total content ratio of the hydrophobic group and the polyalkylene glycol chain-containing monomer (A) and the carboxyl group-containing monomer (B) in all the monomer components is 90% by mass or more, the hydrophobic group and the hydrophobic group It is possible to more sufficiently synthesize a homogeneous copolymer by the polyalkylene glycol chain-containing monomer (A) and the carboxyl group-containing monomer (B), and more sufficiently a copolymer having a desired molecular weight. Can be obtained.

The content ratio of the other monomer (D) in all the monomer components is preferably 0% by mass to 10% by mass, more preferably 0% by mass, based on 100% by mass of all the monomers. It is ~ 5% by mass, and most preferably 0% by mass.

Any suitable polymerization method can be adopted as the polymerization method in the method for producing the hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention. Examples of such a polymerization method include a method of carrying out polymerization in an aqueous solvent in the presence of a radical polymerization initiator, in some cases using a chain transfer agent.

The solvent that can be used in the method for producing the hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention is preferably an aqueous solvent. Examples of the aqueous solvent include water, alcohol, glycol, glycerin, polyethylene glycol and the like, and water is preferable. In addition, in order to improve the solubility of the monomer in the solvent, any suitable organic solvent may be appropriately added as long as it does not adversely affect the polymerization. Examples of such an organic solvent include lower alcohols such as methanol, ethanol and isopropyl alcohol; lower ketones such as acetone, methyl ethyl ketone and diethyl ketone; ethers such as dimethyl ether, diethyl ether and dioxane; and amides such as dimethyl formaldehyde. Kind; etc. Only one kind of these solvents may be used, or two or more kinds may be used.

The amount of the solvent that can be used in the method for producing the hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention is preferably 80% by mass to 400% by mass, more preferably, based on the total amount of the monomer components. Is 150% by mass to 300% by mass, more preferably 200% by mass to 250% by mass. When the amount of the solvent used is 80% by mass or more with respect to the total amount of the monomer components, it is possible to sufficiently suppress the increase in viscosity during the polymerization and sufficiently suppress the formation of a gel. Can be done. When the amount of the solvent used is 400% by mass or less with respect to the total amount of the monomer components, a copolymer having a desired molecular weight can be obtained more sufficiently.

Examples of the radical polymerization initiator include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; 2,2'-azobis (2-amidinopropane) hydrochloride, and 4,4'-azobis-4-cyanovalerin. Acids, azobisisobutyronitrile, azo compounds such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl Organic peroxides such as peroxide and cumenehydroperoxide; hydrogen peroxide; and the like can be mentioned. The radical polymerization initiator is preferably persulfate such as ammonium persulfate, potassium persulfate, and sodium persulfate; hydrogen peroxide; The radical polymerization initiator is more preferably a persulfate such as ammonium persulfate, potassium persulfate, and sodium persulfate. The radical polymerization initiator may be only one kind or two or more kinds.

The amount of the radical polymerization initiator used is preferably 1 g to 10 g, and more preferably 2 g to 5 g, per 1 mol of the monomer component. When the amount of the radical polymerization initiator used is 1 g or more per mole of the monomer component, it is possible to sufficiently suppress a significant increase in the residual amount of the monomer component. When the amount of the radical polymerization initiator used is 10 g or less per mol of the monomer component, the effect of increasing the radical polymerization initiator appears effectively, which is economically advantageous, and the use of the radical polymerization initiator. Since the amount is not too large, it is possible to sufficiently suppress the decrease in the net content of the obtained copolymer and sufficiently suppress the decrease in physical properties such as the ability to prevent recontamination.

As the addition method and addition time of the radical polymerization initiator, any appropriate addition method and addition time can be adopted as long as the effects of the present invention are not impaired.

Examples of the chain transfer agent include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiophosphoric acid, octyl thioglycolate, octyl 3-mercaptopropionate, and 2-mercaptoethanesulfone. Phosphoric chain transfer agents such as acid, n-dodecyl mercaptan, octyl mercaptan, butyl thioglycolate; halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane; secondary alcohols such as isopropanol and glycerin; subphosphorus Phosphoric acid-based chain transfer agents such as acid and hypophosphoric acid; phosphite (sodium phosphite, potassium phosphite, etc.), hypophosphite (sodium hypophosphite, potassium hypophosphite, etc.) ) And other phosphate-based chain transfer agents; sulfite (salt); bisulfite (salt); phosphoric acid (salt); metaduosulfate (salt); pyrosulfite (salt); and the like. Here, the above-mentioned "salt" includes metal salts (alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt, transition metal salts such as iron salt), ammonium salts, and organic amines. Examples thereof include salts (primary to quaternary amine salts such as methylamine salt, n-butylamine salt, monoethanolamine salt, dimethylamine salt, diethanolamine salt, morpholine salt and trimethylamine salt). Only one type of chain transfer agent may be used, or two or more types may be used.

In the method for producing a copolymer containing a hydrophobic group and a polyalkylene glycol chain of the present invention, sodium bisulfite is preferably used as the chain transfer agent. As the sodium bisulfite, only one kind may be used, or two or more kinds may be used.

In the method for producing a copolymer containing a hydrophobic group and a polyalkylene glycol chain of the present invention, any suitable other component may be added into the polymerization reactor as long as the effect of the present invention is not impaired. Examples of such other components include pH adjusters, buffers, solvents and the like.

The total amount of the hydrophobic group and the polyalkylene glycol chain-containing monomer (A) may be added dropwise to the total amount used, a certain amount may be initially charged, and then the rest may be added dropwise, or the total amount may be initially charged. It doesn't matter.

The carboxyl group-containing monomer (B) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, particularly preferably the total amount, substantially, based on the total amount used. It is added into the polymerization reactor by continuously dropping it.

It is preferable that the carboxyl group-containing monomer (B) is not initially charged in the polymerization reactor in advance.

As the method for adding the other monomer (D), any appropriate addition method can be adopted as long as the effects of the present invention are not impaired.

The temperature at the time of the polymerization reaction is set from the start of the polymerization by the start of dropping the monomer component or the radical polymerization initiator to the end of the polymerization (or when the aging time of the obtained copolymer is further set after the completion of the polymerization. Until the end), it is preferably 70 ° C. or higher, more preferably 80 ° C. or higher.

When the temperature at the time of the polymerization reaction is 70 ° C. or higher, the decomposition efficiency of the radical polymerization initiator is good, and the residual amount of the monomer in the obtained copolymer can be sufficiently suppressed. Further, it is very preferable to carry out the polymerization at the boiling point because the temperature control becomes very easy, the reproducibility of the polymerization is good, and the quality of the obtained copolymer is very stable.

The concentration of the monomer component at the time of initial charging is preferably 35% by mass to 75% by mass, more preferably 40% by mass to 70% by mass, and further preferably 45% by mass to 60% by mass. When the concentration of the monomer component at the time of initial preparation is 35% by mass or more, the reactivity of the monomer component is good and the productivity is excellent. When the concentration of the monomer component at the time of initial preparation is 75% by mass or less, the water solubility of the monomer component is in a preferable range, and it is possible to prevent the polymerization reaction solution from becoming a slurry or a precipitate. Can be polymerized more uniformly.

The solid content concentration of the copolymer at the end of the polymerization is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 65% by mass, and further preferably 20% by mass to 60% by mass. .. In the method for producing a copolymer of the present invention, the concentration of additives such as a monomer component and a radical polymerization initiator is adjusted so that the solid content concentration of the copolymer at the end of polymerization is within such a range. Do. When the solid content concentration of the copolymer at the end of the polymerization is 10% by mass or more, it is possible to sufficiently suppress that the solid content concentration of the copolymer during the polymerization becomes very low, and the monomer. Since the polymerizability of the components is good, the residual amount of the monomer components in the obtained copolymer can be sufficiently suppressed, the productivity is improved, and it is economically excellent. When the solid content concentration of the copolymer at the end of polymerization is 70% by mass or less, the solid content concentration of the copolymer during polymerization becomes very high, and it is sufficient that the polymerization reaction solution has a very high viscosity. It can be suppressed and polymerized more uniformly, has an excellent handling surface, and can sufficiently suppress the obtained copolymer from becoming extremely high in molecular weight.

The pressure at the time of polymerization may be pressurized, normal pressure (atmospheric pressure), or reduced pressure, and may be appropriately set.

In the method for producing a copolymer containing a hydrophobic group and a polyalkylene glycol chain of the present invention, the polymerization equipment, particularly the polymerization reactor, is preferably processed so that metal ions do not dissolve. Specific examples of the material include SUS316, a metal subjected to a glass lining treatment, for example, stainless steel having a glass lining treatment.

In the method for producing a copolymer containing a hydrophobic group and a polyalkylene glycol chain of the present invention, a aging step may be performed at the end of the polymerization, if desired. Since the residual amount of the monomer component can be reduced by the aging step, it is preferable to provide the aging step. The aging time in the aging step can be set to any appropriate time.

The hydrophobic group and polyalkylene glycol chain-containing copolymer of the present invention can be used as a water treatment agent, a fiber treatment agent, a dispersant, a detergent builder (or a detergent composition), and the like. As a detergent builder, it can be added to detergents for various purposes such as clothing, tableware, housing, hair, body, toothpaste, and automobiles.

<Water treatment agent>
The acid group-containing graft polymer of the present invention can be used as a water treatment agent. If necessary, a polymerized phosphate, a phosphonate, an anticorrosive agent, a slime control agent, and a chelating agent may be used as the water treatment agent as other compounding agents.

The water treatment agent is useful for preventing scale in a cooling water circulation system, a boiler water circulation system, a seawater desalination device, a pulp cooking kettle, a black liquor concentrating kettle, and the like. Further, any suitable water-soluble polymer may be contained as long as it does not affect the performance and effect.

<Fiber treatment agent>
The acid group-containing graft polymer of the present invention can be used as a fiber treatment agent. The fiber treatment agent contains at least one selected from the group consisting of dyes, peroxides and surfactants, and the acid group-containing graft polymer of the present invention.

The content of the acid group-containing graft polymer of the present invention in the fiber treatment agent is preferably 1 to 100% by weight, more preferably 5 to 100% by weight, based on the entire fiber treatment agent. Further, any suitable water-soluble polymer may be contained as long as it does not affect the performance and effect.

An example of blending the fiber treatment agent, which is closer to the embodiment, is shown below. This fiber treatment agent can be used in the steps of refining, dyeing, bleaching and soaping in fiber treatment. Dyeing agents, peroxides and surfactants include those commonly used in fiber treatment agents.

The blending ratio of the acid group-containing graft polymer of the present invention and at least one selected from the group consisting of dyeing agents, peroxides and surfactants is, for example, the whiteness of fibers, color unevenness, and dyeing fastness. In order to improve the fiber treatment agent, at least one selected from the group consisting of a dyeing agent, a peroxide and a surfactant is used for 1 part by weight of the acid group-containing graft polymer of the present invention in terms of pure content of the fiber treatment agent. It is preferable to use the composition blended in a ratio of 0.1 to 100 parts by weight as the fiber treatment agent.

As the fiber to which the fiber treatment agent can be used, any suitable fiber can be adopted. Examples thereof include cellulosic fibers such as cotton and hemp, chemical fibers such as nylon and polyester, animal fibers such as wool and silk thread, semi-synthetic fibers such as rayon, and these woven fabrics and blended products.

When the fiber treatment agent is applied to the refining step, it is preferable to blend the acid group-containing graft polymer of the present invention with an alkaline agent and a surfactant. When applied to a bleaching step, it is preferable to blend the acid group-containing graft polymer of the present invention, a peroxide, and a silicic acid-based agent such as sodium silicate as a decomposition inhibitor of an alkaline bleaching agent.

<Inorganic pigment dispersant>
The acid group-containing graft polymer of the present invention can be used as an inorganic pigment dispersant. If necessary, condensed phosphoric acid and its salt, phosphonic acid and its salt, and polyvinyl alcohol may be used as other compounding agents for the inorganic pigment dispersant.

The content of the acid group-containing graft polymer of the present invention in the inorganic pigment dispersant is preferably 5 to 100% by weight with respect to the entire inorganic pigment dispersant. Further, any suitable water-soluble polymer may be contained as long as it does not affect the performance and effect.

The inorganic pigment dispersant can exhibit good performance as a dispersant for heavy or light calcium carbonate and clay inorganic pigments used for paper coating. For example, by adding a small amount of an inorganic pigment dispersant to an inorganic pigment and dispersing it in water, high-concentration calcium carbonate having low viscosity and high fluidity and good aging stability of their performance. A high-concentration inorganic pigment slurry such as a slurry can be produced.

When the inorganic pigment dispersant is used as a dispersant for an inorganic pigment, the amount of the inorganic pigment dispersant used is preferably 0.05 to 2.0 parts by weight with respect to 100 parts by weight of the inorganic pigment. When the amount of the inorganic pigment dispersant used is within the above range, a sufficient dispersion effect can be obtained, an effect commensurate with the amount added can be obtained, and it can be economically advantageous.

<Detergent composition>
The acid group-containing graft polymer of the present invention can also be added to the detergent composition.

When the acid group-containing graft polymer of the present invention is used in the detergent composition, the content of the acid group-containing graft polymer in the detergent composition is not particularly limited. However, from the viewpoint of exhibiting excellent builder performance, the content of the acid group-containing graft polymer is preferably 0.1 to 15% by mass, more preferably 0.1 to 15% by mass, based on the total amount of the detergent composition. It is 0.3 to 10% by mass, more preferably 0.5 to 5% by mass.

Detergent compositions used in detergent applications usually include surfactants and additives used in detergents. The specific form of these surfactants and additives is not particularly limited, and conventionally known findings in the detergent field can be appropriately referred to. Further, the detergent composition may be a powder detergent composition or a liquid detergent composition.

The surfactant is one or more selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. When two or more kinds are used in combination, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 60% by mass, based on the total amount of the surfactant. The above is more preferably 70% by mass or more, and particularly preferably 80% by mass or more.

Examples of anionic surfactants include alkylbenzene sulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, α-olefin sulfonates, α-sulfo fatty acids or ester salts, and alkane sulfonates. , Saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acylamino acid type surfactant, alkyl phosphate ester or its salt, alkenyl phosphate ester or The salt or the like is suitable. Alkyl groups such as methyl groups may be branched into the alkyl groups and alkenyl groups in these anionic surfactants.

Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycolides, and fatty acid glycerin mono. Esters, alkylamine oxides and the like are suitable. Alkyl groups such as methyl groups may be branched into the alkyl groups and alkenyl groups in these nonionic surfactants.

As the cationic surfactant, a quaternary ammonium salt or the like is suitable. Further, as the amphoteric surfactant, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant and the like are suitable. Alkyl groups such as methyl groups may be branched as the alkyl groups and alkenyl groups in these cationic surfactants and amphoteric surfactants.

The blending ratio of the surfactant is usually 10 to 60% by mass, preferably 15 to 50% by mass, more preferably 20 to 45% by mass, and particularly preferably 20 to 45% by mass, based on the total amount of the detergent composition. Is 25-40% by mass. If the blending ratio of the surfactant is too small, sufficient detergency may not be exhibited, and if the blending ratio of the surfactant is too large, the economic efficiency may be lowered.

Additives include alkali builders, chelate builders, anti-redeposition agents to prevent re-deposition of contaminants such as sodium carboxymethyl cellulose, stain inhibitors such as benzotriazole and ethylene-thiourea, soil release agents, and color transfer. Inhibitors, fabric softeners, alkaline substances for pH control, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents, bleaching aids, enzymes, dyes , Alkali and the like are suitable. Further, in the case of a powder detergent composition, it is preferable to add zeolite.

The detergent composition may contain other detergent builders in addition to the polymer composition of the present invention. Other detergent builders are not particularly limited, but are, for example, alkaline builders such as carbonates, bicarbonates, and silicates, tripolyphosphates, pyrophosphates, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, and citrate. Examples thereof include acetates, copolymer salts of (meth) acrylic acid, acrylic acid-maleic acid copolymers, chelatebuilders such as fumarate and zeolite, and carboxyl derivatives of polysaccharides such as carboxymethyl cellulose. Examples of the salt used in the builder include alkali metals such as sodium and potassium, ammonium, amines and the like.

The total blending ratio of the additive and the other detergent builder is usually preferably 0.1 to 50% by mass with respect to 100% by mass of the cleaning agent composition. It is more preferably 0.2 to 40% by mass, further preferably 0.3 to 35% by mass, particularly preferably 0.4 to 30% by mass, and most preferably 0.5 to 20% by mass or less. Is. If the blending ratio of the additive / other detergent builder is less than 0.1% by mass, sufficient detergent performance may not be exhibited, and if it exceeds 50% by mass, the economic efficiency may decrease.

In addition, the concept of the detergent composition includes specific uses such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance the function of one of its components. Detergents used only are also included.

When the detergent composition is a liquid detergent composition, the amount of water contained in the liquid detergent composition is usually preferably 0.1 to 75% by mass, more preferably 0.1 to 75% by mass, based on the total amount of the liquid detergent composition. Is 0.2 to 70% by mass, more preferably 0.5 to 65% by mass, even more preferably 0.7 to 60% by mass, and particularly preferably 1 to 55% by mass, most preferably. It is preferably 1.5 to 50% by mass.

When the detergent composition is a liquid detergent composition, the detergent composition preferably has a kaolin turbidity of 200 mg / L or less, more preferably 150 mg / L or less, still more preferably 120 mg / L or less. It is particularly preferably 100 mg / L or less, and most preferably 50 mg / L or less.

Further, the change (difference) in kaolin turbidity between the case where the acid group-containing graft polymer of the present invention is added to the liquid detergent composition as a detergent builder and the case where it is not added is preferably 500 mg / L or less. It is preferably 400 mg / L or less, more preferably 300 mg / L or less, particularly preferably 200 mg / L or less, and most preferably 100 mg / L or less. As the value of kaolin turbidity, the value measured by the following method shall be adopted.

<Measurement method of kaolin turbidity>
A sample (liquid detergent) that was uniformly stirred was placed in a 50 mm square cell with a thickness of 10 mm, air bubbles were removed, and then Tubidity (trade name, turbidity meter) manufactured by Nippon Denshoku Co., Ltd. was used at 25 ° C. Kaolin turbidity: mg / L) is measured.

Proteases, lipases, cellulase and the like are suitable as enzymes that can be blended in the cleaning composition. Of these, proteases, alkaline lipases and alkaline cellulase, which have high activity in alkaline cleaning solutions, are preferable.

The amount of the enzyme added is preferably 5% by mass or less with respect to 100% by mass of the cleaning agent composition. If it exceeds 5% by mass, the detergency will not be improved and the economy may be lowered.

The detergent composition of the present invention has an excellent cleaning effect with little salt precipitation even when used in an area of hard water (for example, 100 mg / L or more) having a high concentration of calcium ions and magnesium ions. This effect is particularly noticeable when the detergent composition contains an anionic surfactant such as LAS.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".

<Method for quantifying monomers, etc.>
Quantification of monomers and the like was performed using liquid chromatography under the following conditions, unless otherwise specified.
Measuring device: Tosoh Corporation Detector: RI
Column: CAPCELLLPAK C1 UG120 manufactured by Shiseido Co., Ltd.
Temperature: 40.0 ° C
Eluent: 10 mmol / L disodium hydrogen phosphate aqueous solution / acetonitrile = 45/55 wt%
Flow velocity: 1.0 ml / min

<Measurement method of weight average molecular weight>
Unless otherwise specified, the weight average molecular weight of the copolymer was measured by using gel permeation clamatography under the following conditions.
Equipment: HLC-8320GPC manufactured by Tosoh Corporation
Detector: RI
Column: Showa Denko Co., Ltd. Shodex Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B
Column temperature: 40 ° C
Flow velocity: 0.5 ml / min
Calibration curve: POLYACRYLIC ACID STANDARD manufactured by Sowa Kagaku Co., Ltd.
Eluent: 0.1 M aqueous sodium acetate solution / acetonitrile = 75/25 wt%

<Measuring method of solid content>
The copolymer (1.0 g of the copolymer plus 1.0 g of water) was left to stand for 1 hour in an oven heated to 130 ° C. for drying. The solid content (%) and the volatile component (%) were calculated from the weight change before and after drying.

<Measurement method of clay dispersibility>
(1) Pure water was added to 67.56 g of glycine, 52.6 g of sodium chloride, and 2.4 g of NaOH to make 600 g (this is used as a buffer).
(2) 0.082 g of calcium chloride dihydrate was added to 60 g of the buffer, and pure water was further added to make 1000 g (this is used as a buffer).
(3) After putting 0.3 g of JIS11 type clay in a test tube (manufactured by IWAKI GLASS: diameter 18 mm, height 180 mm), a 0.1% by weight aqueous solution (solid content weight equivalent) of the copolymer to be measured was added to 3 g. , 27 g of buffer was added and sealed.
(4) The test tube was shaken to disperse the clay. Then, the test tube was allowed to stand in a dark place for 20 hours. After 20 hours, 5 cc of the supernatant of the dispersion was taken, and the absorbance was measured with a UV spectroscope (Shimadzu Corporation, UV-1200; 1 cm cell, wavelength 380 nm).

<Measurement method of carbon black dispersibility>
(1) A glycine buffer solution was prepared by adding ion-exchanged water to 67.6 g of glycine, 52.6 g of sodium chloride, and 60 ml of a 1 mol / L NaOH aqueous solution to make 600 g.
(2) Pure water was added to 0.082 g of calcium chloride dihydrate and 60.0 g of the glycine buffer prepared in (1) to make 1000 g, and a dispersion was prepared.
(3) An aqueous solution of a polymer composition having a solid content of 0.1% was prepared.
(4) Add 0.1 g of carbon black (obtained from the Laundry Science Association), 28.5 g of the dispersion liquid of (2), and 1.5 g of the polymer aqueous solution of (3) to a general test tube having a capacity of about 30 cc. did. At this time, the calcium concentration of the test solution was 50 ppm in terms of calcium carbonate.
(5) After sealing the test tube with a rubber stopper, it was shaken up and down 60 times. The test tube was allowed to stand in a place not exposed to direct sunlight for 20 hours, and then the dispersion was visually observed.
(6) After 20 hours, 5 cc of the supernatant of the dispersion was taken, and the absorbance was measured with a UV spectroscope (Shimadzu Corporation, UV-1200; 1 cm cell, wavelength 380 nm).

<Measurement method of calcium ion trapping ability>
(1) Using calcium chloride dihydrate as a calcium ion standard solution for calibration lines, 50 g of 0.01 mol / L, 0.001 mol / L, and 0.0001 mol / L aqueous solutions were prepared, and 4 Prepare the pH in the range of 7 to 8 with an 8% NaOH aqueous solution, add 1 mL of a 4 mol / L potassium chloride aqueous solution (hereinafter abbreviated as 4M-KCl aqueous solution), and further stir well using a magnetic stirrer. A sample solution for calibration lines was prepared. In addition, a required amount (50 g per sample) of an aqueous solution of 0.001 mol / L was prepared using calcium chloride dihydrate as a test calcium ion standard solution.
(2) 10 mg of the test sample (polymer) was weighed in a 100 cc beaker in terms of solid content, 50 g of the above-mentioned test calcium ion standard solution was added, and the mixture was sufficiently stirred using a magnetic stirrer. Further, similarly to the sample for the calibration curve, the pH was adjusted to a range of 7 to 8 with a 4.8% NaOH aqueous solution, and 1 mL of a 4M-KCl aqueous solution was added to prepare a test sample solution.
(3) The prepared sample solution for the calibration curve and the sample solution for the test were measured by a calcium ion electrode using a titrator COMITE-550 manufactured by Hiranuma Sangyo Co., Ltd.
(4) The amount of calcium ions captured by the sample (polymer) was calculated from the calibration curve and the measured value of the sample solution for the test, and the value was calculated and the captured amount per 1 g of the polymer solid content was mg in terms of calcium carbonate. Expressed as a number, this value was taken as the calcium ion trapping ability value.

<Evaluation of recontamination prevention ability>
(1) A cotton cloth obtained from Test fabric was cut into 5 cm × 5 cm pieces to prepare a white cloth. The whiteness of this white cloth was measured in advance by the reflectance using a colorimetric color difference meter SE6000 manufactured by Nippon Denshoku Kogyo Co., Ltd.
(2) Pure water was added to 7.5 g of calcium chloride dihydrate to make 17 kg, and hard water was prepared.
(3) Pure water was added to 4.0 g of polyoxyethylene (8) lauryl ether to make 100.0 g, and an aqueous surfactant solution was prepared. The pH was adjusted to 8.5 with sodium hydroxide.
(4) The turgot meter was set at 25 ° C., 1 L of hard water, 5 g of a surfactant aqueous solution, 1 g of a polymer aqueous solution having a solid content of 5%, and 1 g of carbon black were placed in a pot and stirred at 100 rpm for 1 minute. Then, 5 white cloths were put in and stirred at 100 rpm for 10 minutes.
(5) The water of the white cloth was drained by hand, 1 L of hard water at 25 ° C. was put into a pot, and the mixture was stirred at 100 rpm for 2 minutes.
(6) A cloth was applied to a white cloth and dried while smoothing wrinkles with an iron, and then the whiteness of the white cloth was measured again by the reflectance with the above colorimetric color difference meter.
(7) From the above measurement results, the recontamination prevention ability was determined by the following formula.
(8) Recontamination prevention ability (%) = [(whiteness after washing) / (whiteness of raw white cloth)] × 100.

<Example 1>
70 g of pure water was placed in a glass separable flask having a capacity of 300 mL equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 85 ° C. under stirring.
Next, under stirring, 90 g of an 80 mass% acrylic acid aqueous solution (hereinafter referred to as 80% AA), 72 g of Adecaria Soap SR-10 (hereinafter referred to as SR-10), and 15 mass% persulfite were placed in the polymerization reaction system. 29 g of a sodium aqueous solution (hereinafter referred to as 15% NaPS), 12.4 g of a 35 mass% sodium hydrogen sulfite aqueous solution (hereinafter referred to as 35% SBS), and 10 g of pure water were added dropwise from separate dropping nozzles. The dropping time was 180 minutes for 80% AA, 120 minutes for SR-10, 190 minutes for 15% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization.
In this way, a copolymer (1) having a solid content concentration of 54.1% by mass and a weight average molecular weight of 61,000 was obtained. The residual acrylic acid was 3,400 ppm.

<Example 2>
In Example 1, except that 80% AA was changed to 126.0 g, SR-10 was changed to 43.2 g, 15% NaPS was changed to 38.7 g, 35% SBS was changed to 16.6 g, and pure water was changed to 5.0 g. In the same manner as in Example 1, a copolymer (2) having a solid content concentration of 52.8% by mass and a weight average molecular weight of 35,000 was obtained. The residual acrylic acid was 0 ppm.

<Example 3>
70 g of pure water and 12 g of maleic acid were placed in a glass separable flask having a capacity of 300 mL equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 85 ° C. under stirring.
Next, under stirring, 0.006 g of molle salt was added into the polymerization reaction system, followed by 90.0 g of 80% AA, 36.0 g of SR-10, 38.2 g of 15% NaPS, and 13 of 35% SBS. .1 g and 7.0 g of pure water were dropped from separate dropping nozzles. The dropping time was 180 minutes for 80% AA, 120 minutes for SR-10, 190 minutes for 15% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization.
In this way, a copolymer (3) having a solid content concentration of 49.4% by mass and a weight average molecular weight of 30,000 was obtained. The residual acrylic acid was 0 ppm and the residual maleic acid was 5,000 ppm.

<Example 4>
70 g of pure water was placed in a glass separable flask having a capacity of 300 mL equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 85 ° C. under stirring.
Next, under stirring, 0.006 g of molle salt was added into the polymerization reaction system, and then 90.0 g of 80% AA and 72.0 g of Adecaria Soap SR-20 (hereinafter referred to as SR-20) were added. 35.2 g of% NaPS, 9.1 g of 35% SBS, and 10.0 g of pure water were added dropwise from separate dropping nozzles. The dropping time was 180 minutes for 80% AA, 90 minutes for SR-20, 190 minutes for 15% NaPS, 170 minutes for 35% SBS, and 170 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization.
In this way, a copolymer (4) having a solid content concentration of 53.3% by mass and a weight average molecular weight of 80,000 was obtained. The residual acrylic acid was 0 ppm.

<Example 5>
70 g of pure water and 12.6 g of maleic acid were placed in a glass separable flask having a capacity of 300 mL equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 85 ° C. under stirring.
Next, under stirring, 0.006 g of molle salt was added into the polymerization reaction system, and then 63.0 g of 80% AA, 63.0 g of SR-20, 28.6 g of 15% NaPS, and 9 of 35% SBS. 8.8 g and 10.0 g of pure water were added dropwise from separate dropping nozzles. The dropping time was 180 minutes for 80% AA, 90 minutes for SR-20, 190 minutes for 15% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization.
In this way, a copolymer (5) having a solid content concentration of 49.2% by mass and a weight average molecular weight of 64,000 was obtained. The residual acrylic acid was 0 ppm and the residual maleic acid was 18,000 ppm.

<Example 6>
In a glass separable flask with a capacity of 300 mL equipped with a thermometer, a reflux condenser, and a stirrer, 90.0 g of ADEKA REASORP SR-3025 (25% aqueous solution) (hereinafter referred to as SR-3025) is charged and stirred. The temperature was raised to 85 ° C.
Then, under stirring, 0.006 g of molle salt was added into the polymerization reaction system, and then 72.0 g of 80% AA, 63.6 g of SR-3025, 20.6 g of 20% NaPS, and 7 of 35% SBS. .1 g and 10.0 g of pure water were dropped from separate dropping nozzles. The dropping time was 180 minutes for 80% AA, 120 minutes for SR-3025, 190 minutes for 15% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization.
In this way, a copolymer (6) having a solid content concentration of 39.0% by mass and a weight average molecular weight of 70,000 was obtained. The residual acrylic acid was 3,400 ppm.

<Example 7>
70 g of pure water was placed in a glass separable flask having a capacity of 300 mL equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 85 ° C. under stirring.
Next, under stirring, 0.006 g of molle salt was added into the polymerization reaction system, and then 108.0 g of 80% AA and ADEKA REASORP ER-20 (75% aqueous solution) (hereinafter referred to as ER-20) were added. 49.4 g, 32.8 g of 15% NaPS, 14.1 g of 35% SBS, and 5.0 g of pure water were added dropwise from separate dropping nozzles. The dropping time was 180 minutes for 80% AA, 120 minutes for ER-20, 190 minutes for 15% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization.
In this way, a copolymer (7) having a solid content concentration of 47.6% by mass and a weight average molecular weight of 35,000 was obtained. The residual acrylic acid was 0 ppm.

<Example 8>
70 g of pure water was placed in a glass separable flask having a capacity of 300 mL equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 85 ° C. under stirring.
Then, under stirring, 90.0 g of 80% AA, 72.0 g of Aqualon BC-20 (hereinafter referred to as BC-20), 28.2 g of 15% NaPS, and 18 of 35% SBS were added to the polymerization reaction system. .1 g and 6.0 g of pure water were dropped from separate dropping nozzles. The dropping time was 180 minutes for 80% AA, 90 minutes for BC-20, 190 minutes for 15% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization.
In this way, a copolymer (8) having a solid content concentration of 56.2% by mass and a weight average molecular weight of 25,000 was obtained. The residual acrylic acid was 0 ppm.

<Example 9>
70 g of pure water was placed in a glass separable flask having a capacity of 300 mL equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 85 ° C. under stirring.
Then, under stirring, 0.006 g of molle salt was added into the polymerization reaction system, then 90.0 g of 80% AA, 72.0 g of Aqualon BC-10 (hereinafter referred to as BC-10), and 15% NaPS. 29.1 g, 6.2 g of 35% SBS, and 15.0 g of pure water were added dropwise from separate dropping nozzles. The dropping time was 180 minutes for 80% AA, 120 minutes for BC-10, 190 minutes for 15% NaPS, 170 minutes for 35% SBS, and 170 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization.
In this way, a copolymer (9) having a solid content concentration of 53.4% by mass and a weight average molecular weight of 130,000 was obtained. The residual acrylic acid was 0 ppm.

<Example 10>
Initially charge 70 g of pure water, 16.5 g of SR-10, and 0.009 g of molle salt in a glass separable flask with a capacity of 500 mL equipped with a thermometer, a reflux condenser, and a stirrer, and bring the temperature to 85 ° C. under stirring. The temperature was raised until it became.
Then, under stirring, in the polymerization reaction system, 63 g of an 80 mass% acrylic acid aqueous solution (hereinafter referred to as 80% AA), 60.4 g of SR-10, and a 15 mass% sodium persulfite aqueous solution (hereinafter referred to as 15% NaPS) were added. 37 g (referred to as), 11.3 g of a 35 mass% sodium hydrogen sulfite aqueous solution (hereinafter referred to as 35% SBS), and 10 g of pure water were added dropwise from separate dropping nozzles. The dropping time was 180 minutes for 80% AA, 90 minutes for SR-10, 190 minutes for 15% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization. Subsequently, while cooling, 9.8 g of monoethanolamine (hereinafter referred to as MEA) was added for neutralization.
In this way, a copolymer (1) having a solid content concentration of 46.3% by mass and a weight average molecular weight of 49,000 was obtained. The residual acrylic acid was 0 ppm.

<Example 11>
Initially charge 80 g of pure water, 20 g of SR-10, and 0.012 g of moor salt in a glass separable flask with a capacity of 500 mL equipped with a thermometer, a reflux condenser, and a stirrer, and under stirring until the temperature reaches 85 ° C. The temperature was raised.
Then, under stirring, 72 g of 80% AA, 66.4 g of SR-10, 54.3 g of 15% NaPS, 15.5 g of 35% SBS, and 15 g of pure water were separately added dropwise to the polymerization reaction system. Dropped from the nozzle. The dropping time was 240 minutes for 80% AA, 120 minutes for SR-10, 270 minutes for 15% NaPS, 240 minutes for 35% SBS, and 240 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization. Subsequently, while cooling, 9.8 g of MEA was added for neutralization.
In this way, a copolymer (2) having a solid content concentration of 36.9% by mass and a weight average molecular weight of 30,000 was obtained. The residual acrylic acid was 0 ppm.

<Example 12>
In a glass separable flask with a capacity of 500 mL equipped with a thermometer, a reflux condenser, and a stirrer, 70 g of pure water, 23 g of maleic acid, 16.6 g of 48% caustic soda, and 0.006 g of molle salt were initially charged, and the mixture was stirred. The temperature was raised to 85 ° C.
Then, under stirring, 72 g of 80% AA, 34.6 g of SR-10, 41.6 g of 15% NaPS, 14.9 g of 35% SBS, and 10 g of pure water were separately added dropwise to the polymerization reaction system. Dropped from the nozzle. The dropping time was 180 minutes for 80% AA, 120 minutes for SR-10, 190 minutes for 15% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization. Subsequently, while cooling, 14.6 g of MEA was added to neutralize the mixture.
In this way, a copolymer (3) having a solid content concentration of 45.62% by mass and a weight average molecular weight of 17,000 was obtained. The residual acrylic acid was 0 ppm and the residual maleic acid was 1,000 ppm.

<Example 13>
70 g of pure water and 0.006 g of Mohr salt were initially charged in a glass separable flask having a capacity of 500 mL equipped with a thermometer, a reflux condenser and a stirrer, and the temperature was raised to 85 ° C. under stirring.
Then, under stirring, 63 g of 80% AA, 75.6 g of SR-10, 26.4 g of 15% NaPS, 6.8 g of 35% SBS, and 20 g of pure water were separately added dropwise to the polymerization reaction system. Dropped from the nozzle. The dropping time was 180 minutes for 80% AA, 120 minutes for SR-10, 190 minutes for 15% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization. Subsequently, while cooling, 8.6 g of MEA was added to neutralize the mixture.
In this way, a copolymer (4) having a solid content concentration of 50.8% by mass and a weight average molecular weight of 80,000 was obtained. The residual acrylic acid was 300 ppm.

<Example 14>
Initially charge 80 g of pure water, 20.0 g of SR-20, and 0.006 g of moor salt in a glass separable flask with a capacity of 500 mL equipped with a thermometer, a reflux condenser, and a stirrer, and bring the temperature to 85 ° C. under stirring. The temperature was raised until it became.
Then, under stirring, 63 g of 80% AA, 55.6 g of SR-20, 45.6 g of 15% NaPS, 13.0 g of 35% SBS, and 10 g of pure water were separately added dropwise to the polymerization reaction system. Dropped from the nozzle. The dropping time was 240 minutes for 80% AA, 120 minutes for SR-20, 270 minutes for 15% NaPS, 240 minutes for 35% SBS, and 240 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization. Subsequently, while cooling, 8.6 g of MEA was added to neutralize the mixture.
In this way, a copolymer (5) having a solid content concentration of 43.2% by mass and a weight average molecular weight of 43,000 was obtained. The residual acrylic acid was 650 ppm.

<Example 15>
120 g of pure water, 14.4 g of maleic acid, 30.0 g of SR-20, and 0.009 g of moor salt were initially charged in a glass separable flask having a capacity of 500 mL equipped with a thermometer, a reflux condenser, and a stirrer. The temperature was raised to 85 ° C. with stirring.
Then, under stirring, 54 g of 80% AA, 56.4 g of SR-20, 40.1 g of 15% NaPS, 15.3 g of 35% SBS, and 13 g of pure water were separately added dropwise to the polymerization reaction system. Dropped from the nozzle. The dropping time was 240 minutes for 80% AA, 120 minutes for SR-20, 270 minutes for 15% NaPS, 240 minutes for 35% SBS, and 240 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization. Subsequently, while cooling, 7.3 g of MEA was added for neutralization.
In this way, a copolymer (6) having a solid content concentration of 40.8% by mass and a weight average molecular weight of 25,000 was obtained. The residual acrylic acid was 200 ppm and the residual maleic acid was 7,000 ppm.

<Example 16>
70 g of pure water and 0.006 g of Mohr salt were initially charged in a glass separable flask having a capacity of 500 mL equipped with a thermometer, a reflux condenser and a stirrer, and the temperature was raised to 85 ° C. under stirring.
Then, under stirring, 108 g of 80% AA, 37.0 g of SR-20, 32.8 g of 15% NaPS, 14.0 g of 35% SBS, and 5 g of pure water were separately added dropwise to the polymerization reaction system. Dropped from the nozzle. The dropping time was 180 minutes for 80% AA, 120 minutes for SR-20, 190 minutes for 15% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization. Subsequently, while cooling, 14.7 g of MEA was added for neutralization.
In this way, a copolymer (7) having a solid content concentration of 52.3% by mass and a weight average molecular weight of 34,000 was obtained. The residual acrylic acid was 0 ppm.

<Example 17>
Initially charge 70 g of pure water, 12.0 g of maleic acid, and 0.006 g of moor salt in a glass separable flask with a capacity of 500 mL equipped with a thermometer, a reflux condenser, and a stirrer, and stir to reach 85 ° C. The temperature was raised.
Then, under stirring, 90 g of 80% AA, 36 g of SR-20, 37.7 g of 15% NaPS, 11.8 g of 35% SBS, and 7 g of pure water were added to the polymerization reaction system from separate dropping nozzles. Dropped. The dropping time was 180 minutes for 80% AA, 120 minutes for SR-20, 190 minutes for 15% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization. Subsequently, while cooling, 14.7 g of MEA was added for neutralization.
In this way, a copolymer (8) having a solid content concentration of 48.8% by mass and a weight average molecular weight of 41,000 was obtained. The residual acrylic acid was 0 ppm and the residual maleic acid was 1,000 ppm.

<Example 18>
In a glass separable flask with a capacity of 500 mL equipped with a thermometer, a reflux condenser, and a stirrer, 70 g of pure water, 23 g of maleic acid, 16.6 g of 48% caustic soda, and 0.006 g of moor salt were initially charged, and the mixture was stirred. The temperature was raised to 85 ° C.
Then, under stirring, 72 g of 80% AA, 34.6 g of SR-20, 41.0 g of 15% NaPS, 14.7 g of 35% SBS, and 10 g of pure water were separately added dropwise to the polymerization reaction system. Dropped from the nozzle. The dropping time was 180 minutes for 80% AA, 120 minutes for SR-20, 190 minutes for 15% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization. Subsequently, while cooling, 14.6 g of MEA was added to neutralize the mixture.
In this way, a copolymer (9) having a solid content concentration of 47.1% by mass and a weight average molecular weight of 25,000 was obtained. The residual acrylic acid was 0 ppm and the residual maleic acid was 1,300 ppm.

<Example 19>
30 g of pure water, 9.6 g of maleic acid, 30 g of 25% SR-3025, and 0.005 g of moor salt were initially charged in a glass separable flask having a capacity of 500 mL equipped with a thermometer, a reflux condenser, and a stirrer. The temperature was raised to 85 ° C. with stirring.
Then, under stirring, 72 g of 80% AA, 85.2 g of SR-3025, 21.8 g of 15% NaPS, 9.3 g of 35% SBS, and 9 g of pure water were separately added dropwise to the polymerization reaction system. Dropped from the nozzle. The dropping time was 180 minutes for 80% AA, 120 minutes for SR-3025, 190 minutes for 15% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization. Subsequently, while cooling, 9.8 g of MEA was added for neutralization.
In this way, a copolymer (10) having a solid content concentration of 40.3% by mass and a weight average molecular weight of 49,000 was obtained. The residual acrylic acid was 540 ppm and the residual maleic acid was 6,400 ppm.

<Example 20>
Initially charge 65 g of pure water, 10.8 g of maleic acid, and 0.006 g of moor salt in a glass separable flask with a capacity of 500 mL equipped with a thermometer, a reflux condenser, and a stirrer, and under stirring until the temperature reaches 85 ° C. The temperature was raised.
Next, under stirring, 81 g of 80% AA, 43.2 g of ER-20 (75% aqueous solution), 34.0 g of 15% NaPS, 11.7 g of 35% SBS, and 10 g of pure water were added to the polymerization reaction system. , Each was dropped from a separate dropping nozzle. The dropping time was 180 minutes for 80% AA, 120 minutes for ER-20, 190 minutes for 15% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization. Subsequently, while cooling, 11.0 g of MEA was added for neutralization.
In this way, a copolymer (11) having a solid content concentration of 43.2% by mass and a weight average molecular weight of 55,000 was obtained. The residual acrylic acid was 0 ppm and the residual maleic acid was 3,300 ppm.

<Comparative example 1>
In a glass separable flask with a capacity of 1500 mL equipped with a thermometer, a reflux condenser, and a stirrer, 42 g of pure water and an adduct of lauryl glycidyl ether to an adduct of 50 mol of ethylene oxide to isoprenol (hereinafter referred to as IPN50-LGE). ) 168.0 g was charged, and the temperature was raised to 90 ° C. with stirring.
Then, under stirring, 0.011 g of molle salt was added into the polymerization reaction system, then 90.0 g of 80% AA, 46.9 g of 15% NaPS, 13.7 g of 35% SBS, and 54.0 g of pure water. , 4.2 g of 48% caustic soda was added dropwise from separate dropping nozzles. The dropping time was 180 minutes for 80% AA and 48% caustic soda, 210 minutes for 15% NaPS, 175 minutes for 35% SBS, and 180 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 90 ° C. for another 60 minutes and aged to complete the polymerization. After cooling to 60 ° C. or lower, 51.0 g of pure water and 70.8 g of 48% caustic soda were added for post-treatment.
In this way, the comparative polymer composition (1) having a solid content concentration of 51.4% by mass and a weight average molecular weight of 31,000 was obtained. The residual acrylic acid was 0 ppm.

<Comparative example 2>
200 g of pure water was charged into a reaction vessel made of SUS316 having a capacity of 2500 mL equipped with a thermometer, a reflux condenser and a stirrer, and the temperature was raised to 90 ° C. under stirring.
Next, under stirring, 0.026 g of molle salt was added into the polymerization reaction system, and then 351.0 g of 80% AA and 200% aqueous solution of an adduct of 25 mol of ethylene oxide of isoprenol (hereinafter referred to as IPN25) were added. .66 g, 26.7 g of denacol 121 adduct (hereinafter referred to as IPN10-EHGE) to 10 mol of isoprenol ethylene oxide adduct, 82.28 g of 15% NaPS, 34.1 g of 35% SBS, pure water 82 9.9 g and 15.5 g of 48% caustic soda were added dropwise from separate dropping nozzles. The respective dropping times were 80 minutes for 80% AA and 48% caustic soda, 120 minutes for 20 mol of isoprenol ethylene oxide adduct, 120 minutes for denacol 121 adduct to 10 mol of isoprenol ethylene oxide adduct, and 190 minutes for 15% NaPS. , 35% SBS and pure water for 180 minutes. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 90 ° C. for another 30 minutes and aged to complete the polymerization. After cooling to 60 ° C. or lower, 35.0 g of pure water and 276.1 g of 48% caustic soda were added for post-treatment.
In this way, a comparative polymer composition (2) having a solid content concentration of 41.9% by mass and a weight average molecular weight of 28,000 was obtained. The residual acrylic acid was 400 ppm.

<Comparative example 3>
150 g of pure water was charged into a reaction kettle made of SUS316 having a capacity of 2500 mL equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 85 ° C. under stirring.
Next, under stirring, 0.023 g of molle salt was added into the polymerization reaction system, followed by 252.0 g of 80% AA and a 60% aqueous solution of 50 mol of isoprenol ethylene oxide adduct (hereinafter referred to as 60% IPN50). 286.2 g, 15% NaPS 44.1 g, 35% SBS 21.4 g, pure water 10.0 g, and 48% caustic soda 11.7 g were added dropwise from separate dropping nozzles. The dropping time was 180 minutes for 80% AA and 48% caustic soda, 120 minutes for 50 molar adduct of ethylene oxide of isoprenol, 210 minutes for 15% NaPS, 35% SBS, and 200 minutes for pure water. In addition, regarding the dropping start time, dropping was started at the same time, the dropping rate was kept constant, and dropping was continued.
After completion of the dropping, the reaction solution was kept at 85 ° C. for a further 30 minutes and aged to complete the polymerization.
In this way, a comparative polymer composition (3) having a solid content concentration of 41.9% by mass and a weight average molecular weight of 45,000 was obtained. The residual acrylic acid was 400 ppm.

<Comparative example 4>
In a glass separable flask with a capacity of 500 ml equipped with a thermometer, a SUS 4-blade stirrer, and a reflux condenser, Newcol 2305 (manufactured by Nippon Emulsifier Co., Ltd .; 5 mol adduct of ethylene oxide of C12C13 synthetic alcohol, hereinafter, NC2305) (Referred to as) 150.9 g was charged, the temperature was raised to 128 ° C. while blowing nitrogen, and the temperature was maintained for 30 minutes. Next, 7.04 g of di-t-butyl peroxide (hereinafter referred to as PBD) was added for 220 minutes, and 100.6 g of 100% acrylic acid (hereinafter referred to as 100% AA) was added for 210 minutes 20 minutes after the start of dropping PBD. Dropped separately and continuously over. After completion of 100% AA dropping, the mixture was stirred at 128 ° C. for 60 minutes (aging) and diluted with water after completion of aging to obtain the comparative polymer composition (4) of the present invention. The weight average molecular weight of the polymer contained in the polymer composition (4) was 30,000, and the solid content was 73.1%.
The acrylic acid content of the polymer composition (4) was 0 ppm with respect to 100% by mass of the polymer composition (solid content equivalent).

Calcium trapping ability, carbon black dispersing ability, clay dispersing ability and recontamination prevention ability were measured for the copolymers of Examples 1 to 20 and Comparative Examples 1 to 4, and the results are shown in Table 1.

ＰＯＡ種：ポリアルキレングリコール鎖含有単量体
注＊：比較例２は、ＭＡの代わりにＩＰＮ１０−ＥＨＧＥ（ＩＰＮ１０へのデナコール１２１付加物）を６質量％用いた。

POA type: Polyalkylene glycol chain-containing monomer Note *: In Comparative Example 2, IPN10-EHGE (Denacol 121 adduct to IPN10) was used in an amount of 6% by mass instead of MA.

From Table 1, it is clear that the hydrophobic group- and polyalkylene glycol chain-containing copolymer of the present invention exhibits excellent carbon black dispersibility. By showing excellent carbon black dispersibility, it shows excellent anti-recontamination ability against hydrophobic stains.
Further, since the copolymer of the present invention has a high calcium trapping ability, it has an effect of preventing calcium scale even in water having high hardness. In addition, since the clay has a high dispersibility, it can be expected to improve the ability to prevent recontamination against hydrophilic stains such as mud stains.

In addition to being used in detergent builders and detergent compositions, the hydrophobic group- and polyalkylene glycol chain-containing copolymers of the present invention can be used as other compounding agents, for example, polymerized phosphates and phosphonates, if necessary. , Anticorrosive agent, slime control agent, chelating agent can be used as a water treatment agent as a composition. Such a water treatment agent is useful for preventing scale in, for example, a cooling water circulation system, a boiler water circulation system, a seawater desalination apparatus, a pulp cooking kettle, a black liquor concentrating kettle, and the like.

Claims (5)

A copolymer containing a hydrophobic group and a polyalkylene glycol chain.
Hydrophobic group and polyalkylene glycol chain containing copolymers are water soluble and
The following general formula (1) derived from the hydrophobic group and the polyalkylene glycol chain-containing monomer (A);

(In the general formula ^{(1), R 1, R} 2 and ^{R 3} are the same or different, .R ⁴ represents a hydrogen atom or a methyl group are the same or different, like chains of carbon number 1 to 30 carbon Representing a hydrogen group, r is an integer of 0 to 2. s is an integer of 0 to 1. t is an integer of 0 to 2. W is the same or different and has 6 to 6 carbon atoms. Represents a trivalent aromatic group of 30 or a trivalent group formed by removing three hydrogen atoms from a chain hydrocarbon having 1 to 30 carbon atoms. Z is the same or different, hydrogen atom or -SO ₃ NH. Represents ₄ groups. Y represents the same or different direct bond or oxygen atom. X represents the same or different oxyalkylene group having 2 to 20 carbon atoms. N is an integer of 1 to 200. However , when W is a trivalent group formed by removing three hydrogen atoms from a chain hydrocarbon having 1 or 2 carbon atoms, R ⁴ is a chain hydrocarbon group having 3 to 30 carbon atoms. The structural unit (a) represented by) and
Containing a structural unit (b) derived from a carboxyl group-containing monomer (B),
The structural unit (a) is 10% by mass or more, 99% by mass or less, and 10% by mass or less, based on 100% by mass of the total amount of the structural units derived from all the monomers forming the hydrophobic group and the polyalkylene glycol chain-containing copolymer.
The structural unit (b) is contained in a proportion of 1% by mass or more and 90% by mass or less.
The total content ratio of the structural unit (a) and the structural unit (b) is 90 to 100% by mass.
The carboxyl group-containing monomer (B) includes acrylic acid, methacrylic acid, crotonic acid, α-hydroxyacrylic acid, α-hydroxymethylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride. , 2-Methyleneglutaric acid and a copolymer containing a hydrophobic group and a polyalkylene glycol chain, which is at least one selected from the group consisting of salts thereof. The hydrophobic group and poly according to claim 1, wherein the content ratio of the structural unit (a) is 10 to 60% by mass, and the content ratio of the structural unit (b) is 40 to 90% by mass. An alkylene glycol chain-containing copolymer. The structural unit (a) is the following general formula (2);

(In the above general formula (2), R ¹ , R ² and R ³ represent the same or different hydrogen atom or methyl group. R ⁵ represents a chain hydrocarbon group having 1 to 30 carbon atoms. Z is the same or different and represents a hydrogen atom or -SO ₃ NH ₄ groups. Y is the same or different and represents a direct bond or an oxygen atom. X is the same or different and represents 2 to 20 carbon atoms. Represents an oxyalkylene group. N is an integer of 1 to 200) or the following general formula (3);

(In the general formula ^{(3), R 1, R} 2 and ^{R 3} are the same or different, .R ⁶ represents a hydrogen atom or a methyl group are the same or different, like chains of carbon number 1 to 30 carbon Represents a hydrogen group. Z represents a hydrogen atom or -SO ₃ NH ₄ groups. X represents the same or different oxyalkylene group having 2 to 20 carbon atoms. N is an integer of 1 to 200. The -O-Xn-Z group is attached to -R ⁶ in the benzene ring at any of the ortho-position, meta-position or para-position). 2. The hydrophobic group- and polyalkylene glycol chain-containing copolymer according to 2. The hydrophobic group and the polyalkylene glycol chain-containing copolymer may have a structural unit (d) derived from another monomer (D) in addition to the structural unit (a) and the structural unit (b). , amount of the structural units (d) is either the total amount 100 mass% of structural units derived from the total monomer, of claim 1 to 3, characterized in that the 0 wt% to 10 wt% A copolymer containing a hydrophobic group and a polyalkylene glycol chain according to the above. A detergent composition containing the hydrophobic group according to any one of claims 1 to 4 and a polyalkylene glycol chain-containing copolymer.