JP6921580B2 - Water-soluble polymer - Google Patents

Description

The present invention relates to water-soluble polymers. More specifically, the present invention relates to a water-soluble polymer useful as a raw material for detergent additives and the like.

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.
In recent years, as consumers have become more environmentally conscious, washing such as using the remaining hot water from the bath for washing has become established for the purpose of saving water. As a result, there is a problem that the dirt component contained in the remaining hot water of the bath adheres to the fibers during washing, and the hard water component is concentrated due to the reheating of the bath. The ability to suppress the reattachment of dirt components to fibers during washing (called "recontamination prevention ability") is becoming more stringent than before. Research and development have been made on polymers that meet such demands. For example, in Patent Document 1, a water-soluble polymer that requires an amino group-containing monomer unit, and the water-soluble polymer is described. A water-soluble polymer having a molecular weight distribution of 12 or less is disclosed. Patent Documents 2 to 4 also disclose copolymers having an amino group.

Japanese Patent Application Laid-Open No. 2008-523162 Japanese Unexamined Patent Publication No. 2012-56911 Japanese Unexamined Patent Publication No. 2012-57091 International Publication No. 2012/033183

As described above, various polymers have been disclosed and their ability to prevent recontamination has been reported, but their effects have not been sufficient. In particular, there is a problem that the effect of preventing recontamination against composite stains in which mud and the like and sebum are combined in a complex manner is not sufficient, and it is necessary to improve the ability to prevent recontamination against composite stains.

The present invention has been made in view of the above situation, and an object of the present invention is to provide a water-soluble polymer having an excellent ability to prevent recontamination against complex stains of mud and the like and sebum and the like.

As a result of various studies on a polymer that solves the above problems, the present inventor found that a copolymer of two kinds of amino group-containing monomers having a specific structure and an unsaturated carboxylic acid-based monomer was found to be mud or the like. It was found that it has an excellent ability to prevent re-staining against complex stains with skin oils and the like. Specifically, an amino group having two or more functional groups exhibiting an adsorptive ability to a metal or the like is adsorbed on the metal contained in the composite stain, and an amino group having a hydrophobic group is adsorbed on the hydrophobic portion in the composite stain. However, it has been found that the complex stain can be dispersed and recontamination can be prevented by the synergistic effect of these amino groups and the carboxyl group derived from the unsaturated carboxylic acid-based monomer, and the above-mentioned problems can be solved brilliantly. We came up with the idea of being able to do this, and arrived at the present invention.

That is, the present invention has the following equation (1);

(In the formula (1), R ¹ , R ² , and R ³ represent the same or different hydrogen atom or methyl group. P1, r1 represent the same or different numbers 0 to 5. Q1 , 0 or 1. X represents an amino group having two or more functional groups exhibiting an adsorptive ability for at least one of a metal, a metal compound and a metal ion). The structural unit (a) derived from the body (A) and the following formula (2);

(In the formula (2), R ¹ , R ² , and R ³ represent the same or different hydrogen atom or methyl group. P2 and r2 represent the same or different numbers 0 to 5. Q2 is the same or different. , 0 or 1. Y represents a secondary or tertiary amino group having a hydrophobic group, a neutralized product of these acids, or a quaternary ammonium base having a hydrophobic group). It is a water-soluble polymer having a structural unit (b) derived from the amino group-containing monomer (B) represented by and a structural unit (c) derived from the unsaturated carboxylic acid-based monomer (C).
The present invention will be described in detail below.
A combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

<Water-soluble polymer>
The water-soluble polymer of the present invention has a structural unit (a) derived from the amino group-containing monomer (A) represented by the above formula (1) and an amino group-containing monomer represented by the above formula (2). It has a structural unit (b) derived from (B) and a structural unit (c) derived from an unsaturated carboxylic acid-based monomer (C), and as long as it has these structures, it has other structures. May be.

In the water-soluble polymer, the ratio of the structural unit (a) derived from the amino group-containing monomer (A) is preferably 1 to 98% by mass with respect to 100% by mass of the total structural units. It is more preferably 3 to 70% by mass, even more preferably 5 to 60% by mass, further preferably 7 to 50% by mass, particularly preferably 9 to 40% by mass, and most preferably 10 to 10% by mass. It is 30% by mass.

In the water-soluble polymer, the ratio of the structural unit (b) derived from the amino group-containing monomer (B) is preferably 1 to 98% by mass with respect to 100% by mass of the total structural unit. It is more preferably 2 to 70% by mass, further preferably 3 to 60% by mass, further preferably 4 to 50% by mass, particularly preferably 4.5 to 40% by mass, and most preferably. It is 5 to 30% by mass.

In the water-soluble polymer, the ratio of the structural unit (a) is preferably 1.1 to 9000% by mass with respect to 100% by mass of the structural unit (b). It is more preferably 5 to 5000% by mass, further preferably 10 to 3000% by mass, and particularly preferably 15 to 1000% by mass.

In the water-soluble polymer, the ratio of the structural unit (c) derived from the unsaturated carboxylic acid-based monomer (C) is preferably 5 to 98% by mass with respect to 100% by mass of the total structural unit. It is more preferably 15 to 97% by mass, further preferably 30 to 96% by mass, and particularly preferably 50 to 95% by mass.

The water-soluble polymer of the present invention may have a structural unit (e) derived from other monomers (E) other than the above-mentioned monomers (A), (B) and (C).
In the water-soluble polymer, the ratio of the structural unit (e) is preferably 0 to 97% by mass with respect to 100% by mass of all the structural units. It is more preferably 0 to 70% by mass, further preferably 0 to 50% by mass, particularly preferably 0 to 30% by mass, and most preferably 0 to 10% by mass.

The water-soluble polymer preferably has a weight average molecular weight of 5000 to 20000. It is more preferably 7,000 to 14,000, further preferably 9000 to 70000, and particularly preferably 11,000 to 50,000.
The weight average molecular weight of the water-soluble polymer can be measured by the method described in Examples.

<Amino group-containing monomer (A)>
The amino group-containing monomer (A) (hereinafter, also referred to as monomer (A)) is a compound represented by the above formula (1).
X in the above formula (1) represents an amino group having two or more functional groups exhibiting an adsorptive ability for at least one of a metal, a metal compound and a metal ion (hereinafter, also referred to as a metal or the like).
By having X, the water-soluble polymer of the present invention can be adsorbed on at least one of a metal, a metal compound, and a metal ion contained in a composite stain.
The functional group exhibiting the adsorptive ability is not particularly limited as long as it can be adsorbed on at least one metal or the like, but the functional group preferably has an electron donating group having a lone electron pair. As a result, a coordination bond can be formed with an atom such as a metal.
When two or more functional groups of X have an electron-donating group having a lone electron pair and they coordinate to an atom such as the same metal, the metal becomes stronger due to the chelating effect. It is more preferable because it will be adsorbed to the like.

The functional group of X is preferably at least one selected from the group consisting of a carboxyl group, a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphoric acid group, a phosphite group and a silane group.
The above-mentioned carboxyl group is a functional group having a carbonyl group, but is not classified as a carbonyl group.
The functional group of X is preferably a carboxyl group, a hydroxyl group, or an amino group, more preferably a carboxyl group or a hydroxyl group, and further preferably a carboxyl group.

The above X may have two or more functional groups exhibiting an adsorptive ability to at least one of a metal or the like. For example, the nitrogen atom of an amino group has an adsorptive ability to at least one of a metal or the like. Even if it is a secondary or tertiary amino group to which one organic group having two or more functional groups showing the above is bonded, there are two organic groups having at least one functional group exhibiting an adsorptive ability to a metal or the like. It may be a tertiary amino group to be bonded. Further, X may be a neutralized product of a secondary or tertiary amino group with an acid, or may be a quaternary ammonium base.

The organic group having at least one functional group exhibiting an adsorptive ability with respect to the metal or the like is not particularly limited, but the following formulas (3) to (5);

(In formula (3), Q ¹ represents a divalent hydrocarbon group. In formula (4), Q ² represents a trivalent hydrocarbon group. In formula (5), Q ³ represents a tetravalent hydrocarbon. Represents a hydrogen group. In formulas (3) to (5), W ^{1 to} W ⁶ represent functional groups that are the same or different and exhibit an adsorptive ability to a metal or the like). Is preferable.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group and the like. The hydrocarbon group may be linear, may have a branched chain or a ring structure, and has a carbon atom substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. May be good.
The number of carbon atoms of the hydrocarbon group is preferably 1 to 20, more preferably 1 to 18, still more preferably 1 to 12, particularly preferably 1 to 8, and most preferably 1 to 4.
When the carbon atom of the hydrocarbon group is substituted with a heteroatom, the number of carbon atoms of the hydrocarbon group shall be calculated without including the number of substituted heteroatoms.

As the organic group having at least one functional group exhibiting an adsorptive ability to the metal or the like, preferably, a hydroxy having 1 to 5 carbon atoms such as a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group and a hydroxyisopropyl group. Alkyl group: A carboxyalkyl group having 1 to 5 carbon atoms such as a carboxymethyl group, a 1-carboxyxethyl group, a 2-carboxyethyl group and a carboxyisopropyl group. It is more preferably a carboxyalkyl group having 1 to 4 carbon atoms, and even more preferably a carboxymethyl group.

The above X is the following equation (6);

(In the formula (6), R ⁴ and R ⁵ represent organic groups having at least one functional group exhibiting an adsorptive ability for at least one of a metal, a metal compound and a metal ion, which are the same or different.) It is preferably a group represented by. For example, if the ^{functional groups having the adsorptive ability of R 4} and R ⁵ are coordinated to the same metal atom, a more stable chelate is formed, which is preferable.

The method for producing the monomer (A) is not particularly limited, and for example, an unsaturated monomer having an epoxy group such as vinyl glycidyl ether, (meth) allyl glycidyl ether, and isoprenyl glycidyl ether and an amine compound are used. Reaction; It can be produced by reacting an unsaturated alcohol such as vinyl alcohol, (meth) allyl alcohol, isoprenol or the like with an amine compound having a reactive functional group other than an amino group.
The amine compound to be reacted with the unsaturated monomer having an epoxy group may or may not have a reactive functional group other than the amino group. In these reactions, the epoxy group may react with the amino group, or the epoxy group may react with another reactive functional group.
In the reaction of the unsaturated alcohol with an amine compound having a reactive functional group other than the amino group, a single amount is obtained by reacting the hydroxyl group of the unsaturated alcohol with another reactive functional group of the amine compound. The body (A) can be obtained.
The reactive functional group other than the amino group is not particularly limited, and examples thereof include a carboxyl group and a hydroxyl group.
The preferred method for producing the monomer (A) is a method of reacting an unsaturated monomer having an epoxy group with an amine compound.

The amine compound is not particularly limited as long as it is a compound having two or more functional groups exhibiting an adsorptive ability to at least one of metals and the like and capable of reacting with an epoxy group, and is not particularly limited, but for example, glutamate and aspartic acid. Primary amine compounds such as acids, 3- (3,4-dihydroxyphenyl) -L-alanine, 3-hydroxytyramine, histidine, triaminotriethylamine, trishydroxymethylaminomethane, dopamine;
Secondary amine compounds such as diethanolamine, diisopropanolamine, iminodiacetic acid, DL-adrenaline, diethylenetriamine, triethylenetetramine;
Triethanolamine, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexacetic acid, tetraethylenepentamineheptaacetic acid, glycol etherdiaminetetraacetic acid, o, o'-bis (2-aminophenyl) ethylene glycol-N, N, N', N'-tetraacetic acid, o, o-bis (2-aminoethyl) ethylene glycol-N, N, N', N'-tetraacetic acid, glycine, N, N-bis (2-hydroxyethyl) glycine , Trans-1,2-Cyclohexanediamine-N, N, N', N'-tetraacetic acid, 1,3-diamino-2-hydroxypropane-N, N, N', N'-tetraacetic acid, diethylenetriamine-N , N, N', N'', N''-pentaacetic acid, 1,6-hexamethylenediamine-N, N, N', N'-tetraacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, 1, , 2-Diaminopropane-N, N, N', N'-tetraacetic acid, triethylenetetramine-N, N, N', N'', N''', N'''-hexaacetic acid, bicin, ethylenediamine Examples thereof include tertiary amine compounds such as −N, N, N', N'-tetrakis (methylenephosphonic acid) and nitrilotris (methylenephosphonic acid), or salts thereof. Here, the salt includes inorganic acid salts such as hydrochloric acid and sulfuric acid; organic acid salts such as acetic acid, citric acid, tartrate acid, toluenesulfonic acid, lactic acid, succinic acid and glycolic acid, and preferably hydrochloride and acetate. be.
As the amine compound, diethanolamine, diisopropanolamine, and iminodiacetic acid are preferable. More preferably, it is iminodiacetic acid.

In the production of the above-mentioned monomer (A), even if the unsaturated monomer having an epoxy group, the unsaturated alcohol or the like is reacted with the amine compound and then neutralized with an acid, a quaternizing agent is added. May be good.
The acid is not particularly limited, and examples thereof include the above-mentioned inorganic acid and organic acid.
The quaternizing agent is not particularly limited, but is an alkyl halide such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide; dimethyl sulfate, diethyl sulfate, di-n-propyl sulfate and the like. Examples thereof include general alkylating agents such as alkyl sulfate.

When an unsaturated monomer having an epoxy group is used in the production of the monomer (A), the unsaturated monomer having an epoxy group and the amine compound are used in bulk or as a solvent, particularly a polar solvent such as water. It is preferable to react at a reaction temperature of 50 to 80 ° C. in the presence of. For example, the reaction may be carried out in the presence of a reaction catalyst such as acid or alkali. The reaction is preferably carried out in a closed reaction vessel or under pressurized conditions.

<Amino group-containing monomer (B)>
The amino group-containing monomer (B) (hereinafter, also referred to as monomer (B)) is a compound represented by the above formula (2), and is a secondary or tertiary amino group having a hydrophobic group. Alternatively, it has a neutralized product of these acids or a quaternary ammonium base having a hydrophobic group. As a result, it can interact with and adsorb the hydrophobic portion of the composite stain. Further, since the water-soluble polymer of the present invention has a structural unit (b) derived from the amino group-containing monomer (B), it has an ability to prevent recontamination against complex stains and also has compatibility with liquid detergents. It will be excellent.

The hydrophobic group is not particularly limited, but is preferably a hydrophobic organic group having 1 to 20 carbon atoms.
The hydrophobic organic group is not particularly limited, and examples thereof include a hydrocarbon group.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group and the like. The hydrocarbon group is preferably an alkyl group, an alkenyl group or an aryl group, more preferably an alkyl group or an alkenyl group, and even more preferably an alkyl group.
The number of carbon atoms of the hydrophobic organic group is preferably 2 to 18, more preferably 3 to 12, still more preferably 4 to 8, and particularly preferably 4 to 6. When the number of carbon atoms is 4 or more, the hydrophobicity can be more sufficiently exhibited, and when the number of carbon atoms is 6 or less, the polymerizable property can be more sufficiently improved.
The hydrophobic organic group may contain a hetero atom as long as it is hydrophobic. For example, in the hydrocarbon group, a carbon atom is replaced by an oxygen atom, a sulfur atom, a nitrogen atom or the like. Also, the hydrogen atom may be substituted with halogen or the like.
When the carbon atom of the hydrocarbon group is substituted with a heteroatom, the number of carbon atoms of the hydrocarbon group shall be calculated without including the number of substituted heteroatoms.

The hydrophobic group is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or a t-butyl group.

Y in the formula (2) is the following formulas (7) to (9);

(In formulas (7) and (8), R ⁶ and R ⁷ are hydrocarbon groups having 1 to 20 carbon atoms, which are the same or different and may have a hydrogen atom or a part of a carbon atom substituted with a hetero atom. in represents. equation (9), R ⁸ ~R ¹⁰ are the same or different and each represents a hydrocarbon group partially carbon atoms which may be substituted with a hetero atom having 1 to 20 carbon atoms .R ⁶ And R ⁷ or two of R ^{8 to} R ¹⁰ may be combined to form a ring structure ^{. Z −} represents an anion). Is preferable. If Y has a structure represented by any of the above formulas (7) to (9), the monomer (B) has two or more hydrophobic groups per molecule, and the hydrophobicity is further improved. Therefore, it is superior in the ability to prevent recontamination against complex stains.

The hydrocarbon group may have a chain structure or a ring structure, and in the case of a chain structure, it may be linear or have a branch.
Further, two of R ⁶ and R ⁷ or R ^{8 to} R ¹⁰ may be bonded to form a ring structure, and the ring structure is preferably a 5- to 10-membered ring, more preferably 5. ~ 6 member ring.
Preferred examples of the hydrocarbon groups of R ^{6 to} R ^{10 are as described above.}

The anion Z ⁻ is not particularly limited, and examples thereof include halide ions such as chlorine ion, bromine ion, and iodide ion; alkyl sulfate ion such as methyl sulfate ion; and organic acid ion such as acetate ion. ..

The method for producing the monomer (B) is not particularly limited, but for example, it can be obtained by reacting an unsaturated monomer having an epoxy group; an unsaturated alcohol or the like with an amine compound having a hydrophobic group. Can be done. The reaction between the unsaturated monomer having an epoxy group; the unsaturated alcohol or the like and the amine compound having a hydrophobic group is not particularly limited, and examples thereof include the same reaction form as in the production of the monomer (A).
The unsaturated monomer and unsaturated alcohol having an epoxy group are as described in the production of the monomer (A).

Examples of the amine compound having a hydrophobic group include monoalkylamines having 1 to 20 carbon atoms such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine and t-butylamine; dimethylamine, methylethylamine and diethylamine. , Din-propylamine, diisopropylamine, din-butylamine, dit-butylamine, methylisopropylamine, ethylisopropylamine and other dialkylamines having 2 to 40 carbon atoms; oxazines such as morpholine; monomethylaminoethanol, dimethyl Hydroxyl group-containing amine compounds having 3 to 40 carbon atoms such as aminoethanol and diethylaminoethanol; carboxyl group-containing amines having 3 to 40 carbon atoms such as methylaminoacetic acid, dimethylaminoacetic acid, ethylaminoacetic acid and diethylaminoacetic acid; trimethylamine salts and triethylamine salts. Examples thereof include trialkylamine salts having 3 to 40 carbon atoms. Here, the salt includes an inorganic acid salt such as a hydrochloride and an organic acid salt such as acetic acid, and is preferably a hydrochloride.
The amine compound having a hydrophobic group is preferably dialkylamine having 2 to 40 carbon atoms, and more preferably dimethylamine, diethylamine, din-propylamine, diisopropylamine, din-butylamine, or dit-butylamine. Is.

In the production of the above-mentioned monomer (B), even if an unsaturated monomer having an epoxy group, an unsaturated alcohol or the like is reacted with an amine compound having a hydrophobic group and then neutralized with an acid, it is quaternary. An agent may be added.
The acid and quaternizing agent are as described in the production of the monomer (A).
Also. The preferred production method when an unsaturated monomer having an epoxy group is used in the production of the monomer (B) is as described in the production of the monomer (A).
A preferred method for producing the monomer (B) is a method in which an unsaturated monomer having an epoxy group and an amine compound having a hydrophobic group are reacted.

<Unsaturated carboxylic acid-based monomer (C)>
The unsaturated carboxylic acid-based monomer (C) (hereinafter, also referred to as the monomer (C)) is preferably an unsaturated monocarboxylic acid-based monomer, an unsaturated dicarboxylic acid-based monomer, or the like. The unsaturated monocarboxylic acid-based monomer may be a monomer having one unsaturated group and one group capable of forming a carboanion in the molecule, and may be, for example, (meth) acrylic acid or crotonic acid. , Tyglyconic acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, itaconic acid and the like; these monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts are preferable. The unsaturated dicarboxylic acid-based monomer may be a monomer having one unsaturated group and two groups capable of forming a carboanion in the molecule, and may be maleic acid, citraconic acid, mesaconic acid, etc. Citraconic acid, fumaric acid and the like, their monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts and the like, anhydrides thereof, or half esters thereof are preferable.
As the unsaturated carboxylic acid-based monomer, (meth) acrylic acid, maleic acid and salts thereof are preferable.

As long as the monomer (E) other than the monomer (A), (B), (C) can be copolymerized with the monomer (A), (B), (C). , But not particularly limited, for example, 2-acrylamide-2-methylpropanesulfonic acid, (meth) allylsulfonic acid, vinylsulfonic acid, 2-hydroxy-3-allyloxy-1-propanesulfonic acid, 2-hydroxy-3-3. Monomer having a sulfonic acid group such as butene sulfonic acid; Monomer having a phosphonic acid group such as vinylphosphonic acid and (meth) allylphosphonic acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, α-hydroxymethylethyl (meth) acrylate and other hydroxyl group-containing alkyl (meth) acrylates; Alkyl obtained by esterification of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate with an alcohol having 1 to 18 carbon atoms. (Meta) acrylates; Amino group-containing acrylates such as dimethylaminoethyl (meth) acrylates or quaternized products thereof; Amid group-containing monomers such as (meth) acrylamide, dimethylacrylamide and isopropylacrylamide; Vinyls such as vinyl acetate Esters; Alkens such as ethylene and propylene; Aromatic vinyl monomers such as styrene and styrene sulfonic acid; Maleimide derivatives such as maleimide, phenylmaleimide and cyclohexylmaleimide; Monomers; aldehyde group-containing vinyl-based monomers such as (meth) acrylate; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; vinyl chloride, vinylidene chloride, allyl alcohol: other such as vinyl pyrrolidone. Examples thereof include functional group-containing monomers.

<Manufacturing method of water-soluble polymer>
The method for producing the water-soluble polymer of the present invention is not particularly limited, but it can be produced by polymerizing a monomer component, and specific examples and preferable examples of the monomer component, and each monomer. The preferred proportions are as described above.
In the above method for producing a water-soluble polymer, a monomer component containing an amino group-containing monomer (A), an amino group-containing monomer (B), and an unsaturated carboxylic acid-based monomer (C) is polymerized. It is preferable to include a step (hereinafter, also referred to as “polymerization step”).

The method for initiating the polymerization of the monomer component in the above polymerization step is not particularly limited, but for example, a method for adding a polymerization initiator, a method for irradiating UV, a method for applying heat, and a method in the presence of a light initiator. Examples thereof include a method of irradiating light.
It is preferable to use a polymerization initiator in the above polymerization step.
Examples of the polymerization initiator include hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-. Azobis (isobutyronitrile), 2,2'-azobis (2-methylpropion amidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropion amidine] hydrate , 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2' Azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride and other azo compounds; benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydroperoxide and the like Organic peroxides; oxidation-reduction initiators that generate radicals by combining an oxidizing agent and a reducing agent, such as ascorbic acid and hydrogen peroxide, and persulfate and metal salt, are suitable. Among these polymerization initiators, hydrogen peroxide, persulfates, and azo compounds are preferable, and persulfates are most preferable, because the residual monomer tends to decrease. These polymerization initiators may be used alone or in the form of a mixture of two or more.
The amount of the polymerization initiator used is preferably 0.1 g or more, 15 g or less, and more preferably 1 g to 12 g, based on 1 mol of the total monomer used.

In the above polymerization step, a chain transfer agent may be used if necessary. Specific examples of the chain transfer agent include thiol-based chain transfer agents such as mercaptoethanol and mercaptopropionic acid; halides such as carbon tetrachloride and methylene chloride; secondary alcohols such as isopropyl alcohol and glycerin; hypophosphorous acid. Hypophosphorous acid (salt) such as acid and sodium hypophosphate (including hydrates thereof); Phosphorous acid (salt) such as phosphorous acid and sodium bisulfite; Sulfite (salt) such as sodium sulfite ); Dithionite (salt) such as sodium hydrogen sulfite; Phosphorous acid (salt) such as sodium dithionite; Pyrosulfite (salt) such as potassium pyrosulfite, hydrogen peroxide and the like. The chain transfer agent is preferably hypophosphorous acid (salt), heavy sulfite (salt), and hydrogen peroxide. The chain transfer agent may be used alone or in the form of a mixture of two or more.
The amount of the chain transfer agent used is preferably 0 g or more and 20 g or less, and more preferably 0 g or more and 15 g or less, with respect to 1 mol of the monomer (all monomers) used.
As another additive that can be used in the polymerization step, an appropriate amount of an appropriate additive can be added as long as it does not affect the action and effect of the present invention. Such additives include, for example, heavy metal concentration adjusting agent, an organic peroxide, such as H 2 _O 2 _/ metal salts.

In the above polymerization step, a decomposition catalyst of the polymerization initiator or a reducing compound (also referred to as a reaction accelerator) may be used (added to the polymerization system). Examples of the compound that acts as a decomposition catalyst of the polymerization initiator or a reducing compound include heavy metal ions (or heavy metal salts), and one or more of them can be used.
In the present specification, the heavy metal ion means a metal having ^{a specific gravity of 4 g / cm 3 or more.}

Specific examples of the heavy metal ions include those similar to those described in International Publication No. 2010/0244448. Among them, iron is more preferable.

The ionic value of the heavy metal ion is not particularly limited. For example, when iron is used as the heavy metal, the iron ion in the initiator may be Fe ²⁺ or Fe ³⁺ , and these may be used. It may be combined.

When using iron as the heavy metal ions, Mohr's salt _{(Fe (NH 4) 2 (} SO 4) 2 · 6H 2 O), ferrous sulfate heptahydrate, ferrous chloride, ferric chloride It is preferable to use a heavy metal salt or the like.

The content of the heavy metal ions is preferably 0.1 to 5 ppm with respect to the total mass of the polymerization reaction solution at the time of completion of the polymerization reaction (after neutralization when the neutralization step is performed after the polymerization reaction). When it is 0.1 ppm or more, the effect of heavy metal ions can be more sufficiently exhibited, and when it is 5 ppm or less, the obtained polymer can be made more excellent in color tone, and the water-soluble content of the present invention can be obtained. It does not adversely affect the expression of heavy metal chelating ability of the sex polymer.

When a solvent is used in the above polymerization step, an aqueous solvent is preferable as the solvent. Examples of the aqueous solvent include water, methyl alcohol, ethyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, alcohols such as diethylene glycol, glycol, glycerin, polyethylene glycol and the like, and water is preferable. ..
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 and the like. Only one kind of these solvents may be used, or two or more kinds may be used.
The amount of the solvent used is preferably 40 to 300% by mass with respect to 100% by mass of the monomer.

In the above polymerization step, the polymerization temperature is not particularly limited, but is preferably 20 ° C. to 110 ° C., more preferably 50 to 105 ° C., and even more preferably 60 to 100 ° C.
The reaction time should be appropriately set according to the reaction temperature, the type (property) of the monomer component, the polymerization initiator, the solvent, etc., the combination, the amount used, etc. so that the above-mentioned polymerization reaction is completed. Just do it.

The method for producing the water-soluble polymer preferably includes a step of aging the water-soluble polymer after the polymerization reaction. By performing the aging step, the amount of residual monomer can be reduced. The temperature in the aging step is not particularly limited, but is preferably 60 to 100 ° C. The aging time in the aging step is not particularly limited, but is preferably 10 minutes to 5 hours. More preferably, it is 30 minutes to 3 hours.

Even if a salt of the unsaturated carboxylic acid-based monomer (C) is used as a part of the raw material of the monomer in order to keep the neutralization rate of the polymer in a suitable range, a neutralizing agent is used during and after the polymerization. As a result, an alkali metal hydroxide or the like such as sodium hydroxide may be added.

<Metal, etc. adsorbed by water-soluble polymer>
The metal adsorbed by the water-soluble polymer of the present invention is not particularly limited, and examples thereof include metals of heavy metal elements having a specific gravity of 4 or more, metal ions, and metal compounds containing these. As a heavy metal element having a specific gravity of 4 or more, a transition metal element of groups 3 to 11 of the periodic table such as iron, cobalt, nickel, lead and copper, a group 12 element of the periodic table such as zinc and the like are preferable. Can be mentioned.

<Detergent builder / detergent composition>
The present invention is also a detergent builder or detergent composition containing the water-soluble polymer of the present invention.
The content of the water-soluble polymer in the detergent composition is not particularly limited, but from the viewpoint of exhibiting excellent builder performance, the content of the water-soluble polymer is relative to the total amount of the detergent composition. It is preferably 0.1 to 15% by mass, more preferably 0.3 to 10% by mass, and even 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 tenside, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant and the like are suitable. Alkyl groups such as methyl groups may be branched in the alkyl groups and alkenyl groups of 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 water-soluble polymer of the present invention. Other detergent builders are not particularly limited, but are, for example, alkaline builders such as carbonates, hydrogen carbonates, and silicates, tripolyphosphates, pyrophosphates, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, and citrate. Examples thereof include acid salts, copolymer salts of (meth) acrylic acid, acrylic acid-maleic acid copolymers, chelate builders such as fumarate and zeolite, and carboxyl derivatives of polysaccharides such as carboxymethyl cellulose. Examples of the anti-salt used in the above builder include alkali metals such as sodium and potassium, ammonium, amines and the like.

The total blending ratio of the above additive and other detergent builders 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. be. 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.

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 that are only used 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.

Proteases, lipases, cellulase and the like are suitable as the enzymes that can be blended in the detergent 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 detergent composition. If it exceeds 5% by mass, the detergency will not be improved and the economic efficiency may be lowered.

The detergent composition has an excellent cleaning effect with little salt precipitation even when used in a region 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.

Since the water-soluble polymer of the present invention has the above-mentioned structure and is excellent in the ability to prevent recontamination against complex stains of mud and the like and sebum and the like, it can be suitably used as a raw material such as a detergent additive.

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, "%" shall mean "mass%".

[Analysis method]
<Measuring method of weight average molecular weight of copolymer>
The weight average molecular weight of the copolymer was measured under the following conditions.
Equipment: Tosoh high-speed GPC equipment (HLC-8320GPC)
Detector: RI detector Column: Showa Denko SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B
Column temperature: 40 ° C
Flow velocity: 0.5 ml / min
Calibration curve: Polyethylene glycol standard eluent manufactured by GL Science Co., Ltd .: 0.1N Sodium acetate / acetonitrile = 3/1 (mass ratio)

<Measuring method of solid content>
The polymer composition of the present invention (1.0 g of the polymer of the present invention plus 1.0 g of pure water) was left to stand for 1 hour in an oven heated to 130 ° C. for drying. The solid content (%) was calculated from the weight change before and after drying.
Solid content (%) = (weight of composition after drying) / (weight of composition before drying) x 100

[Manufacturing method of monomer]
<Monomer (1)>
(Synthesis of 2,2'-(3-allyloxy-2-hydroxypropyl azandiyl) sodium diacetate)
230.0 g of iminodiacetic acid and 291.2 g of pure water were placed in a 2 L glass four-necked flask equipped with a thermometer, agitator, a nitrogen inflow pipe and a cooling trap at the nitrogen outlet, and the room temperature was introduced while nitrogen was introduced. Was stirred with. To this, 288.0 g of a 48% by weight aqueous sodium hydroxide solution (hereinafter referred to as 48% NaOH) was added for neutralization. After raising the temperature to 60 ° C. with stirring, 197.2 g of allyl glycidyl ether (hereinafter referred to as AGE) was added over 1 hour. Then, by reacting for 5 hours, 42.4% of 2,2'-(3-aryloxy-2-hydroxypropyl azandiyl) diacetate was 2,2'-(3-aryloxy-2-hydroxypropyl azandiyl). ) Sodium diacetate-containing composition (hereinafter referred to as monomer (1)) was obtained.

<Monomer (2)>
(Synthesis of 1-allyloxy-3-dibutylaminopropan-2-ol)
380.7 g of dibutylamine and 319.9 g of pure water were charged into a 2 L glass four-necked flask equipped with a thermometer, a stirrer, a nitrogen inflow pipe and a cooling trap at the nitrogen outlet, and stirred while introducing nitrogen. , The temperature was raised to 60 ° C. Next, 353.7 g of AGE was added over 1 hour and then reacted for 5 hours. This solution is transferred to a separatory funnel, washed with pure water and saturated brine, and then dried over sodium sulfate to form a 100% 1-allyloxy-3-dibutylaminopropan-2-ol-containing composition. Hereinafter, a monomer (2) was obtained.

<Monomer (3)>
(Synthesis of 1-Aryloxy-3-morpholinopropan-2-ol)
177.7 g of morpholine and 101.5 g of pure water were charged into a 1 L glass four-necked flask equipped with a thermometer, a stirrer, a nitrogen inflow pipe and a cooling trap at the nitrogen outlet, and stirred while introducing nitrogen. The temperature was raised to 60 ° C. Next, 228.3 g of AGE was added over 1 hour, and then the reaction was carried out for 5 hours to obtain an 80.0% 1-allyloxy-3-morpholinopropan-2-ol-containing composition (hereinafter, monomer). (Called (3)) was obtained.

<Monomer (4)>
(Synthesis of 3-allyloxy-2-hydroxy-N, N, N-trimethylpropan-1-aminium hydrochloride)
191.1 g of trimethylamine hydrochloride and 104.9 g of pure water are charged in a 1 L glass four-necked flask equipped with a thermometer, a stirrer, a nitrogen inflow pipe and a cooling trap at the nitrogen outlet, and stirred while introducing nitrogen. Then, the temperature was raised to 50 ° C. Next, 228.3 g of AGE was added over 2 hours, and then the reaction was carried out for 2 hours to obtain 66.5% of 3-allyloxy-2-hydroxy-N, N, N-trimethylpropan-1-aminium. A composition containing 3-allyloxy-2-hydroxy-N, N, N-trimethylpropan-1-aminium hydrochloride (hereinafter referred to as monomer (4)) was obtained.

<Monomer (5)>
(Synthesis of 2,2'-(3-allyloxy-2-hydroxypropyl azandiyl) bis (ethane-1-ol))
214.5 g of diethanolamine and 110.7 g of pure water were charged into a 1 L glass four-necked flask equipped with a thermometer, a stirrer, a nitrogen inflow pipe and a cooling trap at the nitrogen outlet, and stirred while introducing nitrogen. The temperature was raised to 60 ° C. Next, 228.3 g of AGE was added over 1 hour, and then the reaction was carried out for 5 hours to obtain 80.0% of 2,2'-(3-aryloxy-2-hydroxypropyl azandiyl) bis (ethane-). A composition containing 1-ol) (hereinafter referred to as monomer (4)) was obtained.

[Method for producing copolymer]
<Example 1>
110.5 g of pure water was charged into 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 (initial preparation).
Then, under stirring, 108.1 g of an 80 mass% acrylic acid aqueous solution (hereinafter referred to as 80% AA), 37.1 g of the monomer (1), and the monomer (2) 18 were placed in a polymerization reaction system at a constant state of 85 ° C. 5.5 g, 15 mass% sodium persulfite aqueous solution (hereinafter referred to as 15% NaPS) 21.4 g, 35 mass% sodium bisulfite aqueous solution (hereinafter referred to as 35% SBS) 5.7 g, and pure water 15.0 g are separately separated. Dropped from the dropping nozzle of. For each dropping time and dropping sequence, 80% AA had a constant rate of 180 minutes from the start of the reaction, monomer (1) had a constant rate of 120 minutes from the start of the reaction, and monomer (2) had a constant rate of 120 minutes from the start of the reaction. The rate was constant in minutes, 15% NaPS was constant in 210 minutes from the start of the reaction, 35% SBS was constant in 180 minutes from the start of the reaction, and pure water was constant in 180 minutes from the start of the reaction. Regarding the dropping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, 35% SBS, and pure water were used at the same time. The reaction was started at the timing of starting dropping of 80% AA, monomer (1), monomer (2), 15% NaPS, 35% SBS, and pure water. After the completion of all the droppings, the reaction solution was kept at 85 ° C. for an additional 30 minutes and aged to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and then 55.8 g of 48% NaOH was added for neutralization.
In this way, a copolymer (1) having a weight average molecular weight (hereinafter referred to as Mw) of 43000 and a solid content of 40.1% was obtained.

<Example 2>
In a 2.5 L kettle made of SUS316 equipped with a thermometer, a reflux condenser, and a stirrer, 265.2 g of pure water and 0.023 g of moor salt (mass of iron (II) with respect to the total charge (here, total charge). Refers to the weight of all the input including the neutralization step after the completion of the polymerization. The same applies to the following.) 3 ppm) was charged, and the temperature was raised to 85 ° C. under stirring (initial preparation).
Then, under stirring, 80% AA 315.3 g, monomer (1) 84.9 g, monomer (2) 72.1 g, 15% NaPS 105.1 g, 35% in a polymerization reaction system in a constant state at 85 ° C. 16.9 g of SBS was dropped from each of the separate dropping nozzles. For each dropping time and dropping sequence, 80% AA had a constant rate of 180 minutes from the start of the reaction, monomer (1) had a constant rate of 120 minutes from the start of the reaction, and monomer (2) had a constant rate of 120 minutes from the start of the reaction. A constant rate was set for minutes, 15% NaPS was set to a constant rate for 210 minutes from the start of the reaction, and 35% SBS was set to a constant rate for 180 minutes from the start of the reaction. Further, regarding the dropping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Further, the reaction start was defined as the timing of starting dropping of 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS. After the completion of all the droppings, the reaction solution was kept at 85 ° C. for an additional 30 minutes and aged to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and then neutralized by adding 165.3 g of 48% NaOH, and then 51.5 g of pure water was added.
In this way, a copolymer (2) having Mw150,000 and a solid content of 41.3% was obtained.

<Example 3>
In a 2.5 L kettle made of SUS316 equipped with a thermometer, a reflux condenser, and a stirrer, 201.4 g of pure water and 0.018 g of moor salt (3 ppm when converted to the mass of iron (II) with respect to the total amount charged) are charged. The temperature was raised to 85 ° C. under stirring (initial preparation).
Then, under stirring, 80% AA 243.2 g, monomer (1) 65.5 g, monomer (2) 55.6 g, 15% NaPS 81.1 g, 35% in a polymerization reaction system in a constant state at 85 ° C. 26.1 g of SBS was dropped from separate dropping nozzles. For each dropping time and dropping sequence, 80% AA had a constant rate of 180 minutes from the start of the reaction, monomer (1) had a constant rate of 120 minutes from the start of the reaction, and monomer (2) had a constant rate of 120 minutes from the start of the reaction. A constant rate was set for minutes, 15% NaPS was set to a constant rate for 210 minutes from the start of the reaction, and 35% SBS was set to a constant rate for 180 minutes from the start of the reaction. Further, regarding the dropping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Further, the reaction start was defined as the timing of starting dropping of 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS. After the completion of all the droppings, the reaction solution was kept at 85 ° C. for an additional 30 minutes and aged to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and then 127.5 g of 48% NaOH was added for neutralization, and then 41.2 g of pure water was added.
In this way, a copolymer (3) having Mw43000 and a solid content of 41.4% was obtained.

<Example 4>
In a 2.5 L kettle made of SUS316 equipped with a thermometer, a reflux condenser, and a stirrer, 129.4 g of pure water and 0.013 g of moor salt (3 ppm when converted to the mass of iron (II) with respect to the total amount charged) were charged. The temperature was raised to 85 ° C. under stirring (initial preparation).
Then, under stirring, 80% AA 180.2 g, monomer (1) 97.0 g, monomer (2) 20.6 g, 15% NaPS 60.0 g, 35% in a polymerization reaction system in a constant state at 85 ° C. 22.5 g of SBS was dropped from each of the separate dropping nozzles. For each dropping time and dropping sequence, 80% AA had a constant rate of 180 minutes from the start of the reaction, monomer (1) had a constant rate of 120 minutes from the start of the reaction, and monomer (2) had a constant rate of 120 minutes from the start of the reaction. A constant rate was set for minutes, 15% NaPS was set to a constant rate for 210 minutes from the start of the reaction, and 35% SBS was set to a constant rate for 180 minutes from the start of the reaction. Further, regarding the dropping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Further, the reaction start was defined as the timing of starting dropping of 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS. After the completion of all the droppings, the reaction solution was kept at 85 ° C. for an additional 30 minutes and aged to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and then 88.9 g of 48% NaOH was added for neutralization, and then 33.5 g of pure water was added.
In this way, a copolymer (4) having Mw36000 and a solid content of 42.7% was obtained.

<Example 5>
In a 2.5 L kettle made of SUS316 equipped with a thermometer, a reflux condenser, and a stirrer, 166.4 g of pure water and 0.016 g of moor salt (3 ppm when converted to the mass of iron (II) with respect to the total amount charged) were charged. The temperature was raised to 85 ° C. under stirring (initial preparation).
Then, under stirring, 270.0 g of 80% AA, 28.3 g of monomer (1), 12.0 g of monomer (2), 82.5 g of 15% NaPS, 35% in a polymerization reaction system in a constant state at 85 ° C. 17.7 g of SBS was dropped from each of the separate dropping nozzles. For each dropping time and dropping sequence, 80% AA had a constant rate of 180 minutes from the start of the reaction, monomer (1) had a constant rate of 120 minutes from the start of the reaction, and monomer (2) had a constant rate of 120 minutes from the start of the reaction. A constant rate was set for minutes, 15% NaPS was set to a constant rate for 210 minutes from the start of the reaction, and 35% SBS was set to a constant rate for 180 minutes from the start of the reaction. Further, regarding the dropping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Further, the reaction start was defined as the timing of starting dropping of 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS. After the completion of all the droppings, the reaction solution was kept at 85 ° C. for an additional 30 minutes and aged to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and then neutralized by adding 146.6 g of 48% NaOH, and then 22.3 g of pure water was added.
In this way, a copolymer (5) having Mw80000 and a solid content of 44.8% was obtained.

<Example 6>
In a 2.5 L kettle made of SUS316 equipped with a thermometer, a reflux condenser, and a stirrer, 122.3 g of pure water and 0.014 g of moor salt (3 ppm when converted to the mass of iron (II) with respect to the total amount charged) were charged. The temperature was raised to 85 ° C. under stirring (initial preparation).
Then, under stirring, 80% AA 180.2 g, monomer (1) 97.0 g, monomer (2) 20.6 g, 15% NaPS 60.0 g, 35% in a polymerization reaction system in a constant state at 85 ° C. 51.5 g of SBS was dropped from each of the separate dropping nozzles. For each dropping time and dropping sequence, 80% AA had a constant rate of 180 minutes from the start of the reaction, monomer (1) had a constant rate of 120 minutes from the start of the reaction, and monomer (2) had a constant rate of 120 minutes from the start of the reaction. A constant rate was set for minutes, 15% NaPS was set to a constant rate for 210 minutes from the start of the reaction, and 35% SBS was set to a constant rate for 180 minutes from the start of the reaction. Further, regarding the dropping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Further, the reaction start was defined as the timing of starting dropping of 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS. After the completion of all the droppings, the reaction solution was kept at 85 ° C. for an additional 30 minutes and aged to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and then 88.9 g of 48% NaOH was added for neutralization, and then 36.4 g of pure water was added.
In this way, a copolymer (6) having Mw15000 and a solid content of 42.2% was obtained.

<Example 7>
In a 2.5 L kettle made of SUS316 equipped with a thermometer, a reflux condenser, and a stirrer, 134.0 g of pure water and 0.015 g of moor salt (3 ppm when converted to the mass of iron (II) with respect to the total amount charged) were charged. The temperature was raised to 85 ° C. under stirring (initial preparation).
Then, under stirring, 80% AA 180.2 g, monomer (1) 104.5 g, monomer (2) 33.3 g, 15% NaPS 61.8 g, 35% in a polymerization reaction system in a constant state at 85 ° C. 66.2 g of SBS was dropped from separate dropping nozzles. For each dropping time and dropping sequence, 80% AA had a constant rate of 180 minutes from the start of the reaction, monomer (1) had a constant rate of 120 minutes from the start of the reaction, and monomer (2) had a constant rate of 120 minutes from the start of the reaction. A constant rate was set for minutes, 15% NaPS was set to a constant rate for 210 minutes from the start of the reaction, and 35% SBS was set to a constant rate for 180 minutes from the start of the reaction. Further, regarding the dropping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Further, the reaction start was defined as the timing of starting dropping of 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS. After the completion of all the droppings, the reaction solution was kept at 85 ° C. for an additional 30 minutes and aged to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and then 88.0 g of 48% NaOH was added for neutralization, and then 42.8 g of pure water was added.
In this way, a copolymer (7) having Mw13000 and a solid content of 41.8% was obtained.

<Example 8>
In a 2.5 L kettle made of SUS316 equipped with a thermometer, a reflux condenser, and a stirrer, 156.2 g of pure water and 0.015 g of moor salt (3 ppm when converted to the mass of iron (II) with respect to the total amount charged) were charged. The temperature was raised to 85 ° C. under stirring (initial preparation).
Then, under stirring, 80% AA 198.2 g, monomer (1) 53.3 g, monomer (2) 45.3 g, 15% NaPS 66.1 g, 35% in a polymerization reaction system in a constant state at 85 ° C. 56.6 g of SBS was dropped from separate dropping nozzles. For each dropping time and dropping sequence, 80% AA had a constant rate of 180 minutes from the start of the reaction, monomer (1) had a constant rate of 120 minutes from the start of the reaction, and monomer (2) had a constant rate of 120 minutes from the start of the reaction. A constant rate was set for minutes, 15% NaPS was set to a constant rate for 210 minutes from the start of the reaction, and 35% SBS was set to a constant rate for 180 minutes from the start of the reaction. Further, regarding the dropping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Further, the reaction start was defined as the timing of starting dropping of 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS. After the completion of all the droppings, the reaction solution was kept at 85 ° C. for an additional 30 minutes and aged to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and then 103.9 g of 48% NaOH was added for neutralization, and then 37.0 g of pure water was added.
In this way, a copolymer (8) having Mw14000 and a solid content of 41.2% was obtained.

<Example 9>
In a 2.5 L kettle made of SUS316 equipped with a thermometer, a reflux condenser, and a stirrer, 133.9 g of pure water and 0.015 g of moor salt (3 ppm when converted to the mass of iron (II) with respect to the total amount charged) were charged. The temperature was raised to 85 ° C. under stirring (initial preparation).
Then, under stirring, 80% AA 225.2 g, monomer (1) 79.6 g, monomer (2) 11.3 g, 15% NaPS 71.5 g, 35% in a polymerization reaction system in a constant state at 85 ° C. 61.3 g of SBS was dropped from each of the separate dropping nozzles. For each dropping time and dropping sequence, 80% AA had a constant rate of 180 minutes from the start of the reaction, monomer (1) had a constant rate of 120 minutes from the start of the reaction, and monomer (2) had a constant rate of 120 minutes from the start of the reaction. A constant rate was set for minutes, 15% NaPS was set to a constant rate for 210 minutes from the start of the reaction, and 35% SBS was set to a constant rate for 180 minutes from the start of the reaction. Further, regarding the dropping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Further, the reaction start was defined as the timing of starting dropping of 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS. After the completion of all the droppings, the reaction solution was kept at 85 ° C. for an additional 30 minutes and aged to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and then neutralized by adding 115.9 g of 48% NaOH, and then 33.6 g of pure water was added.
In this way, a copolymer (9) having Mw18000 and a solid content of 42.3% was obtained.

<Example 10>
146.1 g of pure water and 0.017 g of moor salt (3 ppm when converted to the mass of iron (II) relative to the total amount charged) are charged in a 2.5 L kettle made of SUS316 equipped with a thermometer, a reflux condenser, and a stirrer. The temperature was raised to 85 ° C. under stirring (initial preparation).
Then, under stirring, 80% AA 225.2 g, monomer (1) 121.2 g, monomer (3) 32.2 g, 15% NaPS 75.6 g, 35% in a polymerization reaction system in a constant state at 85 ° C. 64.8 g of SBS was dropped from each of the separate dropping nozzles. For each dropping time and dropping sequence, 80% AA had a constant rate of 180 minutes from the start of the reaction, monomer (1) had a constant rate of 120 minutes from the start of the reaction, and monomer (3) had a constant rate of 120 minutes from the start of the reaction. A constant rate was set for minutes, 15% NaPS was set to a constant rate for 210 minutes from the start of the reaction, and 35% SBS was set to a constant rate for 180 minutes from the start of the reaction. Further, regarding the dropping start time, 80% AA, monomer (1), monomer (3), 15% NaPS, and 35% SBS were set at the same time. Further, the reaction start was defined as the timing of starting dropping of 80% AA, monomer (1), monomer (3), 15% NaPS, and 35% SBS. After the completion of all the droppings, the reaction solution was kept at 85 ° C. for an additional 30 minutes and aged to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and then 111.1 g of 48% NaOH was added for neutralization, and then 45.4 g of pure water was added.
In this way, a copolymer (10) having Mw15000 and a solid content of 42.7% was obtained.

<Example 11>
In a 2.5 L kettle made of SUS316 equipped with a thermometer, a reflux condenser, and a stirrer, 78.1 g of pure water and 0.009 g of moor salt (3 ppm when converted to the mass of iron (II) with respect to the total amount charged) were charged. The temperature was raised to 85 ° C. under stirring (initial preparation).
Then, under stirring, 80% AA 117.1 g, monomer (1) 63.0 g, monomer (4) 20.1 g, 15% NaPS 39.6 g, 35% in a polymerization reaction system in a constant state at 85 ° C. 33.9 g of SBS was dropped from each of the separate dropping nozzles. For each dropping time and dropping sequence, 80% AA had a constant rate of 180 minutes from the start of the reaction, monomer (1) had a constant rate of 120 minutes from the start of the reaction, and monomer (4) had a constant rate of 120 minutes from the start of the reaction. A constant rate was set for minutes, 15% NaPS was set to a constant rate for 210 minutes from the start of the reaction, and 35% SBS was set to a constant rate for 180 minutes from the start of the reaction. Further, regarding the dropping start time, 80% AA, monomer (1), monomer (4), 15% NaPS, and 35% SBS were set at the same time. Further, the reaction start was defined as the timing of starting dropping of 80% AA, monomer (1), monomer (4), 15% NaPS, and 35% SBS. After the completion of all the droppings, the reaction solution was kept at 85 ° C. for an additional 30 minutes and aged to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and then 57.8 g of 48% NaOH was added for neutralization, and then 24.7 g of pure water was added.
In this way, a copolymer (11) having Mw12000 and a solid content of 42.7% was obtained.

<Example 12>
In a 2.5 L kettle made of SUS316 equipped with a thermometer, a reflux condenser, and a stirrer, 141.5 g of pure water and 0.012 g of moor salt (3 ppm when converted to the mass of iron (II) with respect to the total amount charged) were charged. The temperature was raised to 85 ° C. under stirring (initial preparation).
Then, under stirring, 80% AA 153.1 g, monomer (5) 43.8 g, monomer (2) 17.5 g, 15% NaPS 51.5 g, 35% in a polymerization reaction system in a constant state at 85 ° C. 44.1 g of SBS was dropped from each of the separate dropping nozzles. For each dropping time and dropping sequence, 80% AA had a constant rate of 180 minutes from the start of the reaction, monomer (5) had a constant rate of 120 minutes from the start of the reaction, and monomer (2) had a constant rate of 120 minutes from the start of the reaction. A constant rate was set for minutes, 15% NaPS was set to a constant rate for 210 minutes from the start of the reaction, and 35% SBS was set to a constant rate for 180 minutes from the start of the reaction. Further, regarding the dropping start time, 80% AA, monomer (5), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Further, the reaction start was defined as the timing of starting dropping of 80% AA, monomer (5), monomer (2), 15% NaPS, and 35% SBS. After the completion of all the droppings, the reaction solution was kept at 85 ° C. for an additional 30 minutes and aged to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and then 74.4 g of 48% NaOH was added for neutralization, and then 23.7 g of pure water was added.
In this way, a copolymer (12) having Mw7500 and a solid content of 40.9% was obtained.

<Comparative example 1>
110.5 g of pure water was charged into 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 (initial preparation).
Then, under stirring, 80% AA 108.1 g, monomer (1) 43.2 g, 15% NaPS 20.4 g, 35% SBS 9.1 g, pure water 15.0 g in a polymerization reaction system in a constant state at 85 ° C. Was dropped from separate dropping nozzles. For each dropping time and dropping sequence, 80% AA was constant at 180 minutes from the start of the reaction, monomer (1) was constant at 180 minutes from the start of the reaction, and 15% NaPS was constant at 210 minutes from the start of the reaction. The rate, 35% SBS, was set to a constant rate 180 minutes from the start of the reaction, and pure water was set to a constant rate 180 minutes from the start of the reaction. Regarding the dropping start time, 80% AA, monomer (1), 15% NaPS, 35% SBS, and pure water were used at the same time. The reaction was started at the timing of starting dropping of 80% AA, monomer (1), 15% NaPS, 35% SBS, and pure water. After the completion of all the droppings, the reaction solution was kept at 85 ° C. for an additional 30 minutes and aged to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and then 55.1 g of 48% NaOH was added for neutralization.
In this way, a copolymer (13) having Mw23000 and a solid content of 38.3% was obtained.

<Comparative example 2>
In a glass separable flask with a capacity of 500 mL equipped with a thermometer, a reflux condenser, and a stirrer, 75.6 g of pure water and 0.007 g of molle salt (mass of iron (II) relative to the total charge (here, total charge). The amount refers to the weight of all the input including the neutralization step after the completion of the polymerization.) 3 ppm) was charged, and the temperature was raised to 85 ° C. under stirring (initial preparation).
Then, under stirring, 80% AA 108.1 g, monomer (2) 21.6 g, 15% NaPS 0.6 g, 35% SBS 4.8 g, pure water 20.0 g in a polymerization reaction system in a constant state at 85 ° C. Was dropped from separate dropping nozzles. For each dropping time and dropping sequence, 80% AA was constant at 180 minutes from the start of the reaction, monomer (2) was constant at 180 minutes from the start of the reaction, and 15% NaPS was constant at 210 minutes from the start of the reaction. The rate, 35% SBS, was set to a constant rate 180 minutes from the start of the reaction, and pure water was set to a constant rate 180 minutes from the start of the reaction. Regarding the dropping start time, 80% AA, monomer (2), 15% NaPS, 35% SBS, and pure water were used at the same time. The reaction was started at the timing of starting dropping of 80% AA, monomer (2), 15% NaPS, 35% SBS, and pure water. After the completion of all the droppings, the reaction solution was kept at 85 ° C. for an additional 30 minutes and aged to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool, and then 60.0 g of 48% NaOH was added for neutralization.
In this way, a copolymer (14) having Mw48000 and a solid content of 42.5% was obtained.

[Evaluation method]
<Carbon black-iron dispersibility evaluation>
(1) 9.68 g of iron (III) chloride hexahydrate was placed in a 200 mL beaker, and pure water was added to make 200 g, and a 1% iron (III) aqueous solution was prepared. Using this 1% iron (III) aqueous solution, 100 g of a 0.01% iron (III) aqueous solution was prepared.
(2) 0.73 g of calcium chloride dihydrate was put in a 500 mL beaker, and pure water was added to make 500 g, and hard water was prepared.
(3) 10 g of a 0.1% solid content aqueous solution of each evaluation sample was prepared in a 20 mL screw tube.
(4) 7.51 g of glycine, 1.18 g of ethanol, and 7.00 g of 48% NaOH were put in a 1 L beaker, and pure water was added to make 1000 g, and a glycine buffer solution having a pH of 10.5 was prepared.
(5) Next, a 30 mL test tube having an inner diameter of 16 mm was prepared for the number of evaluation samples, and 0.03 g of carbon black, 1.50 g of the 0.01% iron (III) aqueous solution of (1), and the hard water of (2) were prepared for each. 50 g, 1.50 g of the sample aqueous solution of (3), and 25.5 g of the glycine buffer solution of (4) were added and capped with septum. In this way, a suspended aqueous solution containing 1000 ppm of carbon black, 5 ppm of iron (III), and 50 ppm of sample solid content was prepared in each test tube.
(6) After slowly reversing each test tube 60 times, the cap was removed and the test tube was allowed to stand in a horizontal and stable place for 18 hours. After 18 hours, 5 mL of the supernatant was collected using a whole pipette.
(7) The absorbance of the supernatant at 380 nm was measured using an ultraviolet-visible spectrophotometer UV-1800 manufactured by Shimadzu Corporation. This absorbance was used as the dispersibility. The larger the absorbance value, the higher the dispersibility.

<Carbon black-iron recontamination prevention ability evaluation>
(1) A polyester cloth (PW19) obtained from Testfabrics was cut into a size of 5 cm × 5 cm to prepare a white cloth. The whiteness of this white cloth was measured in advance by the reflectance using a color measurement color difference system SE2000 type manufactured by Nippon Denshoku Kogyo Co., Ltd.
(2) Pure water was added to 1.47 g of calcium chloride dihydrate to make 20 kg, and hard water was prepared.
(3) 10 g of a 1% solid content aqueous solution of each evaluation sample was prepared in a 20 mL screw tube.
(4) 100 g of 4% sodium laurylbenzene sulfonate was prepared and used as an aqueous surfactant solution.
(5) 9.68 g of iron (III) chloride hexahydrate was placed in a 200 mL beaker, and pure water was added to make 200 g, and a 1% iron (III) aqueous solution was prepared. Using this 1% iron (III) aqueous solution, 100 g of a 0.1% iron (III) aqueous solution was prepared.
(6) Set the turgot meter to 25 ° C., 1 L of hard water of (2), 5.0 g of the sample aqueous solution of (3), 5.0 g of the surfactant aqueous solution of (4), 0.25 g of carbon black, and ( 5.0 g of a 0.1% iron (III) aqueous solution of 5) was placed in a pot, and the mixture was stirred at 100 rpm for 1 minute. Then, 5 pieces of white cloth were put in and stirred at 100 rpm for 10 minutes. (As a reference, the one to which pure water was added instead of the sample aqueous solution of (3) was also evaluated.)
(7) The water of the white cloth was drained by hand, 1 L of the hard water of (2) was put into a pot, and the mixture was stirred at 100 rpm for 2 minutes.
(8) A white cloth was applied to the cloth, dried with an iron while smoothing out wrinkles, and then the whiteness of the white cloth was measured again by the reflectance with the above color difference meter.
(9) From the above measurement results, the recontamination prevention rate (recontamination prevention ability) was calculated by the following formula.
Recontamination prevention rate (%) = (whiteness after cleaning) / (whiteness before cleaning) x 100
The larger the value of the recontamination prevention rate, the better the recontamination prevention ability.

<Carbon black-clay dispersibility evaluation>
(1) 2.94 g of calcium chloride dihydrate was placed in a 500 mL beaker, and pure water was added to make 500 g, and hard water was prepared.
(2) 10 g of a 0.1% solid content aqueous solution of each evaluation sample was prepared in a 20 mL screw tube.
(3) 7.51 g of glycine, 1.18 g of ethanol, and 7.00 g of 48% NaOH were put in a 1 L beaker, and pure water was added to make 1000 g, and a glycine buffer solution having a pH of 10.5 was prepared.
(4) Next, a 30 mL test tube having an inner diameter of 16 mm was prepared for the number of evaluation samples, and each of them had 0.03 g of carbon black, 0.30 g of JIS 11 type clay, 1.50 g of hard water of (1), and an aqueous sample solution of (2). 50 g and 27.0 g of the glycine buffer solution of (3) were added and capped with septum. In this way, a suspended aqueous solution containing 1000 ppm of carbon black, 10000 ppm of clay, and 50 ppm of sample solid content was prepared in each test tube.
(5) After slowly reversing each test tube 60 times, the cap was removed and the test tube was allowed to stand in a horizontal and stable place for 18 hours. After 18 hours, 5 mL of the supernatant was collected using a whole pipette.
(6) The absorbance of the supernatant at 380 nm was measured using an ultraviolet-visible spectrophotometer UV-1800 manufactured by Shimadzu Corporation. This absorbance was used as the dispersibility. The larger the absorbance value, the higher the dispersibility.

Table 1 shows the monomer composition and Mw of the copolymers obtained in Examples 1 to 12 and Comparative Examples 1 and 2.
The copolymers obtained in Examples 1, 3, 4, 6-9, 11, 12 and Comparative Examples 1 and 2 were evaluated for their carbon black-iron recontamination prevention ability. Moreover, the carbon black-iron dispersibility was evaluated for the copolymers obtained in Examples 4 and 12 and Comparative Examples 1 and 2. The results are shown in Table 2.

Claims (5)

The following formula (1);

(In the formula (1), R ¹ , R ² , and R ³ represent the same or different hydrogen atom or methyl group. P1, r1 represent the same or different numbers 0 to 5. Q1 is 0 or 1 .X is a metal, and Table 2 or more with an amino group a functional group showing adsorption capacity for at least one metal compound and a metal ion, the functional group is a carboxyl group, a carbonyl It is at least one selected from the group consisting of a group, a hydroxyl group, an amino group, a thiol group, a phosphoric acid group, a phosphite group and a silane group, and a reaction product of these with an acid or an alkali. ) The structural unit (a) derived from the group-containing monomer (A) and the following formula (2);

(In the formula (2), R ¹ , R ² , and R ³ represent the same or different hydrogen atom or methyl group. P2 and r2 represent the same or different numbers 0 to 5. Q2 is the same or different. , 0 or 1. Y represents a secondary or tertiary amino group having a hydrophobic group, a neutralized product of these acids, or a quaternary ammonium base having a hydrophobic group). Water-soluble, characterized by having a structural unit (b) derived from the amino group-containing monomer (B) represented by and a structural unit (c) derived from the unsaturated carboxylic acid-based monomer (C). Polymer. X in the above formula (1) is the following formula (6);

(In the formula ^{(6), R 4, R} 5 are the same or different, metallic and Table having at least one organic group A functional group which exhibits an adsorption ability with respect to at least one metal compound and a metal ion, The functional group is at least one selected from the group consisting of a carboxyl group, a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphoric acid group, a phosphite group and a silane group, and a reaction product of these with an acid or an alkali. water-soluble polymer according to claim 1, characterized in that a group represented by a.) a. The functional group of X in the formula (1) or (6) is composed of a carboxyl group, a carbonyl group, a hydroxyl group, an amino group, a thiol group , a phosphite group and a silane group , and a reaction product of these with an acid or an alkali. The water-soluble polymer according to claim 1 or 2, wherein the water-soluble polymer is at least one selected from the group. Y in the above formula (2) is the following formulas (7) to (9);

(In formulas (7) and (8), R ⁶ and R ⁷ are hydrocarbon groups having 1 to 20 carbon atoms, which are the same or different and may have a hydrogen atom or a part of a carbon atom substituted with a hetero atom. in represents. equation (9), R ⁸ ~R ¹⁰ are the same or different and each represents a hydrocarbon group partially carbon atoms which may be substituted with a hetero atom having 1 to 20 carbon atoms .R ⁶ And R ⁷ or two of R ^{8 to} R ¹⁰ may be combined to form a ring structure ^{. Z −} represents an anion). The water-soluble polymer according to any one of claims 1 to 3. The water-soluble polymer is characterized in that the ratio of the structural unit (c) derived from the unsaturated carboxylic acid-based monomer (C) is 5 to 98% by mass with respect to 100% by mass of the total structural unit. The water-soluble polymer according to any one of claims 1 to 4.