JP2018168312A - Water-soluble polymer - Google Patents

Abstract

To provide a water-soluble polymer having an enhanced ability to prevent re-contamination by composite stains of e.g. mud and sebum.SOLUTION: A water-soluble polymer has a structural unit (a) derived from an amino group-containing monomer (A) represented by a predetermined structure, a structural unit (b) derived from an amino group-containing monomer (B) represented by a predetermined structure, and a structural unit (c) derived from an unsaturated carboxylic acid monomer (C).SELECTED DRAWING: None

Description

The present invention relates to a water-soluble polymer. 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 in apparel have been blended with detergent builders (detergent assistants) such as zeolite, carboxymethylcellulose, and polyethylene glycol for the purpose of improving the cleaning effect of the detergent. In addition to the above various detergent builders, in recent years, polymers have been blended into detergent compositions as detergent builders.
In recent years, as consumers have become more aware of the environment, washing, such as using the remaining hot water from a bath for washing, has become established for the purpose of saving water. As a result, it becomes a problem that the dirt component contained in the remaining hot water of the bath adheres to the fibers during washing, or the hard water component is concentrated due to the chasing of the bath, so even under higher hardness, The ability to suppress the reattachment of dirt components to the fiber during washing (referred to as “recontamination prevention ability”) has been demanded more severely than before. Research and development of a polymer that meets such a demand has been made. For example, Patent Document 1 discloses a water-soluble polymer having an amino group-containing monomer unit as an essential component. A water-soluble polymer having a molecular weight distribution of 12 or less is disclosed. Patent Documents 2 to 4 also disclose copolymers having amino groups.

Special table 2008-523162 JP 2012-56911 A JP 2012-57091 A International Publication No. 2012/033183

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

This invention is made | formed in view of the said present condition, and it aims at providing the water-soluble polymer excellent in the recontamination prevention ability with respect to the composite dirt of mud etc. and sebum.

The inventor has made various studies on the polymer that solves the above-mentioned problems. As a result, the copolymer of two amino group-containing monomers having a specific structure and an unsaturated carboxylic acid monomer is mud and the like. It has been found that it has excellent anti-staining ability against complex dirt with sebum and the like. Specifically, an amino group having two or more functional groups that can adsorb metal or the like is adsorbed on a metal contained in the composite soil, and an amino group having a hydrophobic group is adsorbed on a hydrophobic portion in the composite soil. And found that it is possible to disperse the composite dirt by the synergistic effect of these amino groups and the carboxyl group derived from the unsaturated carboxylic acid monomer to prevent re-contamination, and solve the above problems brilliantly. Thus, the present invention has been achieved.

That is, the present invention provides the following formula (1);

(In formula (1), R ¹ , R ² and R ³ are the same or different and represent a hydrogen atom or a methyl group. P1 and r1 are the same or different and represent a number of 0 to 5. q1 is , 0 or 1. X represents an amino group having two or more functional groups exhibiting adsorption 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 Formula (2), R ¹ , R ² and R ³ are the same or different and represent a hydrogen atom or a methyl group. P2 and r2 are the same or different and represent a number of 0 to 5. q2 is 0 or 1. Y represents a secondary or tertiary amino group having a hydrophobic group, a neutralized product thereof with these acids, or a quaternary ammonium base having a hydrophobic group.) A water-soluble polymer having a structural unit (b) derived from an amino group-containing monomer (B) and a structural unit (c) derived from an unsaturated carboxylic acid monomer (C).
The present invention is described in detail below.
A combination of two or more 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 comprises 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 monomer (C), and has other structures as long as it has these structures. It may be.

In the water-soluble polymer, the proportion 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 all structural units. More preferably, it is 3-70 mass%, More preferably, it is 5-60 mass%, More preferably, it is 7-50 mass%, Especially preferably, it is 9-40 mass%, Most preferably, it is 10- mass%. 30% by mass.

In the water-soluble polymer, the proportion 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 all structural units. More preferably, it is 2-70 mass%, More preferably, it is 3-60 mass%, More preferably, it is 4-50 mass%, Especially preferably, it is 4.5-40 mass%, Most preferably It is 5-30 mass%.

In the water-soluble polymer, the proportion of the structural unit (a) is preferably 1.1 to 9000 mass% with respect to 100 mass% of the structural unit (b). More preferably, it is 5-5000 mass%, More preferably, it is 10-3000 mass%, Most preferably, it is 15-1000 mass%.

In the water-soluble polymer, the proportion of the structural unit (c) derived from the unsaturated carboxylic acid monomer (C) is preferably 5 to 98% by mass with respect to 100% by mass of all the structural units. More preferably, it is 15-97 mass%, More preferably, it is 30-96 mass%, Most preferably, it is 50-95 mass%.

The water-soluble polymer of the present invention may have a structural unit (e) derived from the monomer (E) other than the monomers (A), (B), and (C).
In the water-soluble polymer, the proportion of the structural unit (e) is preferably 0 to 97% by mass with respect to 100% by mass of all the structural units. More preferably, it is 0-70 mass%, More preferably, it is 0-50 mass%, Especially preferably, it is 0-30 mass%, Most preferably, it is 0-10 mass%.

The water-soluble polymer preferably has a weight average molecular weight of 5,000 to 200,000. More preferably, it is 7000-140000, More preferably, it is 9000-70000, Most preferably, it is 11000-50000.
The weight average molecular weight of the water-soluble polymer can be measured by the method described in the 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 adsorbability for at least one of a metal, a metal compound, and a metal ion (hereinafter also referred to as a metal).
Since the water-soluble polymer of the present invention has X, it can be adsorbed to at least one of a metal, a metal compound, and a metal ion contained in the composite soil.
The functional group exhibiting the adsorptive ability is not particularly limited as long as it can be adsorbed to at least one metal or the like, but the functional group preferably has an electron donating group having a lone electron pair. Thereby, a coordinate bond can be formed with atoms, such as a metal.
When two or more functional groups possessed by X have an electron donating group having a lone pair of electrons, and these coordinate to an atom such as the same metal, the metal is stronger due to the chelate effect. It is more preferable because it adsorbs to the

The functional group possessed by 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 phosphorous acid group, and a silane group.
The carboxyl group is a functional group having a carbonyl group, but is not classified as a carbonyl group.
The functional group possessed by X is preferably a carboxyl group, a hydroxyl group or an amino group, more preferably a carboxyl group or a hydroxyl group, and still more preferably a carboxyl group.

Said X should just have two or more functional groups which show adsorption ability with respect to at least one, such as a metal, for example, the nitrogen atom of an amino group adsorbs at least one with respect to a metal etc. Even if it is a secondary or tertiary amino group to which one organic group having 2 or more functional groups is bonded, there are 2 organic groups having at least one functional group exhibiting an adsorbing ability for metals and the like. It may be a tertiary amino group bonded to one another. X may be a neutralized product of a secondary or tertiary amino group with an acid or a quaternary ammonium base.

The organic group having at least one functional group exhibiting adsorption ability for 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 group. Represents a hydrogen group, and in formulas (3) to (5), W ^{1 to} W ⁶ are the same or different and each represents a functional group exhibiting an adsorbing ability to a metal or the like. Is preferred.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and an aryl group. The hydrocarbon group may be a straight chain, a branched chain or a ring structure, and a carbon atom is substituted by a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Also good.
As carbon number of the said hydrocarbon group, 1-20 are preferable, More preferably, it is 1-18, More preferably, it is 1-12, Most preferably, it is 1-8, Most preferably, it is 1-4.
When the carbon atom of the said hydrocarbon group is substituted by the hetero atom, the carbon number of a hydrocarbon group shall be calculated without including the number of the substituted hetero atom.

Preferably, the organic group having at least one functional group exhibiting adsorbability to the metal or the like is a hydroxy group having 1 to 5 carbon atoms such as hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, hydroxyisopropyl group An alkyl group; a carboxyalkyl group having 1 to 5 carbon atoms such as a carboxymethyl group, a 1-carboxyxyethyl group, a 2-carboxyethyl group, and a carboxyisopropyl group. More preferably, it is a C1-C4 carboxyalkyl group, More preferably, it is a carboxymethyl group.

X is the following formula (6);

(In Formula (6), R ⁴ and R ⁵ are the same or different and each represents an organic group having at least one functional group exhibiting an adsorptivity to at least one of a metal, a metal compound, and a metal ion.) It is preferable that it is group represented by these. For example, it is preferable that a functional group exhibiting adsorption ability possessed by R ⁴ and R ⁵ is coordinated to the same metal atom, thereby forming a more stable chelate.

The method for producing the monomer (A) is not particularly limited. For example, an unsaturated monomer having an epoxy group such as vinyl glycidyl ether, (meth) allyl glycidyl ether, isoprenyl glycidyl ether, and an amine compound are used. It can be produced by reacting an unsaturated alcohol such as vinyl alcohol, (meth) allyl alcohol, or isoprenol 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 an amino group. In these reactions, an epoxy group and an amino group may react or an epoxy group and another reactive functional group may react.
In the reaction of the unsaturated alcohol with an amine compound having a reactive functional group other than an amino group, the hydroxyl group of the unsaturated alcohol is reacted with the other reactive functional group of the amine compound to obtain a single amount. A 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 method for producing the monomer (A) is preferably a method in which an unsaturated monomer having an epoxy group is reacted with an amine compound.

The amine compound is not particularly limited as long as it is a compound that has two or more functional groups that can adsorb at least one of metals and can react with an epoxy group. For example, glutamic acid, asparagine, and the like. Primary amine compounds such as acid, 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, triethylenetetraminehexaacetic 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′-teto Laacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, 1,2-diaminopropane-N, N, N ′, N′-tetraacetic acid, triethylenetetramine-N, N, N ′, N ″, N Tertiary amine compounds such as''', N '''-hexaacetic acid, bicine, ethylenediamine-N, N, N', N'-tetrakis (methylenephosphonic acid), nitrilotris (methylenephosphonic acid) or the like Salt. Examples of the salt herein include inorganic acid salts such as hydrochloric acid and sulfuric acid; and organic acid salts such as acetic acid, citric acid, tartaric acid, toluenesulfonic acid, lactic acid, succinic acid, and glycolic acid. Preferred are hydrochlorides and acetates. is there.
As the amine compound, diethanolamine, diisopropanolamine, and iminodiacetic acid are preferable. More preferred is iminodiacetic acid.

In the production of the monomer (A), a quaternizing agent is added even if neutralization with an acid is performed after the reaction of an unsaturated monomer having an epoxy group, an unsaturated alcohol or the like with an amine compound. Also good.
Although it does not restrict | limit especially as said acid, The above-mentioned inorganic acid and organic acid are mentioned.
The quaternizing agent is not particularly limited, but alkyl halides such as methyl chloride, ethyl chloride, methyl bromide and methyl iodide; dimethyl sulfate, diethyl sulfate, di-n-propyl sulfate and the like. Common alkylating agents such as alkyl sulfuric acid may be mentioned.

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 an amine compound are used in bulk, or a polar solvent such as a solvent, particularly water. It is preferable to make it react at reaction temperature 50-80 degreeC in presence of this. For example, the reaction may be performed in the presence of a reaction catalyst such as acid or alkali. The reaction is preferably carried out in a sealed reaction vessel or in a pressurized condition.

<Amino group-containing monomer (B)>
The amino group-containing monomer (B) (hereinafter also referred to as the monomer (B)) is a compound represented by the above formula (2), and is a secondary or tertiary amino group having a hydrophobic group, Or it has the quaternary ammonium base which has the neutralized material by these acids, or a hydrophobic group. Thereby, it can interact and adsorb the hydrophobic part in the composite soil. In addition, the water-soluble polymer of the present invention has a structural unit (b) derived from the amino group-containing monomer (B), so that it is compatible with liquid detergents in addition to the ability to prevent re-contamination against composite dirt. It will be excellent.

Although it does not restrict | limit especially as said hydrophobic group, It is preferable that it is a C1-C20 hydrophobic organic group.
Although it does not restrict | limit especially as said hydrophobic organic group, For example, a hydrocarbon group etc. are mentioned.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and an aryl group. As said hydrocarbon group, an alkyl group, an alkenyl group, and an aryl group are preferable, More preferably, they are an alkyl group and an alkenyl group, More preferably, it is an alkyl group.
Moreover, as carbon number of the said hydrophobic organic group, 2-18 are preferable, More preferably, it is 3-12, More preferably, it is 4-8, Most preferably, it is 4-6. If the number of carbon atoms is 4 or more, the hydrophobicity can be more fully exhibited, and if it is 6 or less, the polymerizability can be sufficiently improved.
The hydrophobic organic group may contain a hetero atom as long as it is hydrophobic. For example, the hydrophobic organic group is a hydrocarbon group in which a carbon atom is substituted by an oxygen atom, a sulfur atom, a nitrogen atom, or the like. Alternatively, a hydrogen atom may be substituted with halogen or the like.
When the carbon atom of the said hydrocarbon group is substituted by the hetero atom, the carbon number of a hydrocarbon group shall be calculated without including the number of the substituted hetero atom.

The hydrophobic group is preferably an alkyl group having 1 to 8 carbon atoms, 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) represents the following formulas (7) to (9);

(In Formula (7) and (8), R < ⁶ >, R <^7> is the same or different and a C1-C20 hydrocarbon group in which a hydrogen atom or a part of carbon atom may be substituted by the hetero atom. In formula (9), R ^{8 to} R ¹⁰ are the same or different and each represents a hydrocarbon group having 1 to 20 carbon atoms in which a part of carbon atoms may be substituted with a hetero atom, R ⁶ And R ⁷ or two of R ^{8 to} R ¹⁰ may be bonded to each other to form a ring structure. Z ⁻ represents an anion. Is preferred. If Y is a structure represented by any one 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 will be more excellent in the ability to prevent re-contamination against complex dirt.

The hydrocarbon group may have a chain structure or a ring structure. In the case of a chain structure, the hydrocarbon group may be linear or branched.
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 A 6-membered ring.
Preferable 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 iodine ion; alkyl sulfate ions such as methyl sulfate ion; organic acid ions such as acetate ion and the like. .

The method for producing the monomer (B) is not particularly limited, and can be obtained, for example, by reacting an unsaturated monomer having an epoxy group; an unsaturated alcohol or the like with an amine compound having a hydrophobic group. Can do. Reaction of unsaturated monomer having epoxy group; unsaturated alcohol or the like and amine compound having hydrophobic group is not particularly limited, and examples thereof include the same reaction form as in the production of monomer (A).
The unsaturated monomer and unsaturated alcohol having the 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. Dialkylamines having 2 to 40 carbon atoms such as di-n-propylamine, diisopropylamine, di-n-butylamine, di-t-butylamine, methylisopropylamine and ethylisopropylamine; oxazines such as morpholine; monomethylaminoethanol, dimethyl C3-C40 hydroxyl group-containing amine compounds such as aminoethanol and diethylaminoethanol; C3-C40 carboxyls such as methylaminoacetic acid, dimethylaminoacetic acid, ethylaminoacetic acid, diethylaminoacetic acid Containing amines; trimethylamine salt, trialkyl amine salts of 3 to 40 carbon atoms such as triethylamine salts. Here, examples of the salt include inorganic acid salts such as hydrochloride and organic acid salts such as acetic acid, preferably hydrochloride.
The amine compound having a hydrophobic group is preferably a dialkylamine having 2 to 40 carbon atoms, more preferably dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-t-butylamine. It is.

In the production of the monomer (B), even if neutralization with an acid is carried out after the reaction of an unsaturated monomer having an epoxy group, an unsaturated alcohol, etc. with an amine compound having a hydrophobic group, it is quaternary. An agent may be added.
The acid and quaternizing agent are as described in the production of the monomer (A).
Also. A preferable production method in the case of using an unsaturated monomer having an epoxy group in the production of the monomer (B) is as described in the production of the monomer (A).
A preferable method for producing the monomer (B) is a method of reacting an unsaturated monomer having an epoxy group with an amine compound having a hydrophobic group.

<Unsaturated carboxylic acid monomer (C)>
The unsaturated carboxylic acid monomer (C) (hereinafter also referred to as monomer (C)) is preferably an unsaturated monocarboxylic acid monomer or unsaturated dicarboxylic acid monomer, The unsaturated monocarboxylic acid monomer may be any monomer having one unsaturated group and one group capable of forming a carbanion in the molecule. For example, (meth) acrylic acid, crotonic acid , Tiglic 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 preferred. The unsaturated dicarboxylic acid monomer may be any monomer having one unsaturated group and two groups capable of forming a carbanion in the molecule. Maleic acid, itaconic acid, mesaconic acid, Citraconic acid, fumaric acid, etc., their monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts, etc., their anhydrides or half esters are preferred.
As the unsaturated carboxylic acid 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) Although not particularly limited, for example, 2-acrylamido-2-methylpropanesulfonic acid, (meth) allylsulfonic acid, vinylsulfonic acid, 2-hydroxy-3-allyloxy-1-propanesulfonic acid, 2-hydroxy-3- Monomers having a sulfonic acid group such as butenesulfonic acid; monomers having a phosphonic acid group such as vinylphosphonic acid and (meth) allylphosphonic acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta ) Acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, α-hydride Hydroxyl-containing alkyl (meth) acrylates such as xymethylethyl (meth) acrylate; (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate Alkyl (meth) acrylates obtained by esterification of acrylic acid and alcohols having 1 to 18 carbon atoms; amino group-containing acrylates such as dimethylaminoethyl (meth) acrylate or quaternized products thereof; (meth) acrylamide, dimethylacrylamide Amide group-containing monomers such as isopropyl acrylamide; vinyl esters such as vinyl acetate; alkenes such as ethylene and propylene; aromatic vinyl monomers such as styrene and styrene sulfonic acid; maleimide, phenylmaleimide, Cyclohexyl male Maleimide derivatives such as imide; Nitrile group-containing vinyl monomers such as (meth) acrylonitrile; Aldehyde group-containing vinyl monomers such as (meth) acrolein; Alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether And other functional group-containing monomers such as vinyl chloride, vinylidene chloride, and allyl alcohol: vinyl pyrrolidone.

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

The method for initiating the polymerization of the monomer component in the polymerization step is not particularly limited. For example, a method of adding a polymerization initiator, a method of irradiating UV, a method of applying heat, and in the presence of a photoinitiator. Examples include a method of irradiating light.
In the polymerization step, it is preferable to use a polymerization initiator.
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-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2 ′ -Azo compounds such as azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride; benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydro Preferred are organic peroxides such as peroxides; redox initiators that generate radicals by combining an oxidizing agent and a reducing agent, such as ascorbic acid and hydrogen peroxide, and a persulfate and metal salt. Of these polymerization initiators, since residual monomers tend to decrease, hydrogen peroxide, persulfate, and azo compounds are preferable, and persulfate is most preferable. These polymerization initiators may be used alone or in the form of a mixture of two or more.
As the usage-amount of the said polymerization initiator, it is 0.1g or more and 15g or less with respect to 1 mol of usage-amounts of all the monomers, More preferably, it is 1g-12g.

In the polymerization step, a chain transfer agent may be used as necessary. Specific examples of chain transfer agents include thiol 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 Acid, hypophosphorous acid (salt) such as sodium hypophosphite (including these hydrates); phosphorous acid (salt) such as phosphorous acid and sodium phosphite; sulfurous acid (salt) such as sodium sulfite ); Bisulfite (salt) such as sodium bisulfite; dithionic acid (salt) such as sodium dithionite; pyrosulfurous acid (salt) such as potassium pyrosulfite, hydrogen peroxide, and the like. The chain transfer agent is preferably hypophosphorous acid (salt), bisulfite (salt), or 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, more preferably 0 g or more and 15 g or less, with respect to 1 mol of the monomer (total monomer) used.
As other additives that can be used in the polymerization step, an appropriate amount of an appropriate additive can be added as long as the effects of the present invention are not affected. Examples of such additives include heavy metal concentration adjusting agents, organic peroxides, H ₂ O ₂ / metal salts, and the like.

In the polymerization step, a polymerization initiator decomposition catalyst 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 for 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 this 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 described in International Publication No. 2010/024448. Among these, 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+. It may be combined.

When iron is used as the heavy metal ion, the mole salt (Fe (NH ₄ ) ₂ (SO ₄ ) ₂ · 6H ₂ O), ferrous sulfate · 7 hydrate, ferrous chloride, ferric chloride, etc. 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 completion of the polymerization reaction (after neutralization when a neutralization step is performed after the polymerization reaction). If it is 0.1 ppm or more, the effect of heavy metal ions can be fully expressed, and if it is 5 ppm or less, the resulting polymer can be made more excellent in color tone, Does not adversely affect the expression of the heavy metal chelating ability of the functional polymer.

In the polymerization step, when a solvent is used, an aqueous solvent is preferable as the solvent. Examples of the aqueous solvent include water, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, and diethylene glycol, glycol, glycerin, polyethylene glycol, and the like, preferably water. .
In order to improve the solubility of the monomer in the solvent, any appropriate organic solvent may be added as appropriate within a range that does not adversely affect the polymerization. Examples of such organic solvents 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; amides such as dimethylformaldehyde And the like. These solvents may use only 1 type and may use 2 or more types.
As a usage-amount of a solvent, 40-300 mass% is preferable with respect to 100 mass% of monomers.

In the polymerization step, the polymerization temperature is not particularly limited, but is preferably 20 ° C to 110 ° C, more preferably 50 to 105 ° C, and further preferably 60 to 100 ° C.
In addition, the reaction time is appropriately set according to the reaction temperature, the type (property) and combination of the monomer component, the polymerization initiator, and the solvent, the amount used, etc. so that the polymerization reaction is completed. That's fine.

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.

In order to bring the neutralization rate of the polymer into a suitable range, even if a salt of the unsaturated carboxylic acid monomer (C) is used as part of the raw material of the monomer, the neutralizing agent is used during and after the polymerization. As an alkali metal hydroxide such as sodium hydroxide may be added.

<Metals that water-soluble polymers adsorb>
Although the metal etc. which the water-soluble polymer of this invention adsorb | suck are not restrict | limited in particular, For example, the metal of heavy metal element whose specific gravity is 4 or more, a metal ion, and a metal compound containing these are mentioned. Preferably, the heavy metal element having a specific gravity of 4 or more is preferably a Group 12 element of the periodic table, such as a transition metal element of Group 3 to 11 of the periodic table such as iron, cobalt, nickel, lead, or copper, or zinc. Is mentioned.

<Detergent builder / detergent composition>
The present invention is also a detergent builder or detergent composition comprising 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 that excellent builder performance can be exhibited, the content of the water-soluble polymer is based on the total amount of the detergent composition. Preferably it is 0.1-15 mass%, More preferably, it is 0.3-10 mass%, More preferably, it is 0.5-5 mass%.

Detergent compositions used in detergent applications usually include surfactants and additives used in detergents. Specific forms of these surfactants and additives are not particularly limited, and conventionally known knowledge can be appropriately referred to in the detergent field. 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 an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant. 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 with respect to the total amount of the surfactant. Or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.

Examples of anionic surfactants include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonate. , Saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, alkenyl phosphate ester or Its salts are preferred. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group 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 glycoxides, fatty acid glycerin mono Esters, alkylamine oxides and the like are preferred. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these nonionic surfactants.

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

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 based on the total amount of the detergent composition. Is 25-40 mass%. If the surfactant content is too small, sufficient detergency may not be achieved, and if the surfactant content is too high, the economy may be reduced.

Additives include anti-redeposition agent to prevent redeposition of contaminants such as alkali builder, chelate builder, sodium carboxymethyl cellulose, stain inhibitor such as benzotriazole and ethylene-thiourea, soil release agent, color transfer Inhibitors, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents, bleaching aids, enzymes, dyes A solvent or the like is preferable. In the case of a powder detergent composition, it is preferable to blend zeolite.

The detergent composition may contain other detergent builders in addition to the water-soluble polymer of the present invention. Examples of other detergent builders include, but are not limited to, alkali builders such as carbonates, hydrogen carbonates, and silicates, tripolyphosphates, pyrophosphates, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, Examples thereof include acid salts, (meth) acrylic acid copolymer salts, acrylic acid-maleic acid copolymers, chelate builders such as fumarate and zeolite, and carboxyl derivatives of polysaccharides such as carboxymethylcellulose. Examples of the counter salt used in the builder include alkali metals such as sodium and potassium, ammonium and amine.

The total blending ratio of the additive and other detergent builder is usually preferably 0.1 to 50% by mass with respect to 100% by mass of the cleaning composition. More preferably, it is 0.2-40 mass%, More preferably, it is 0.3-35 mass%, Especially preferably, it is 0.4-30 mass%, Most preferably, it is 0.5-20 mass% is there. If the additive / other detergent builder content is less than 0.1% by mass, sufficient detergent performance may not be achieved, and if it exceeds 50% by mass, the economy may be reduced.

In addition, the concept of the above-mentioned detergent composition includes specific detergents such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance one of the 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 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, still more preferably 0.7 to 60% by mass, particularly preferably 1 to 55% by mass, Preferably it is 1.5-50 mass%.

Proteases, lipases, cellulases, and the like are suitable as enzymes that can be incorporated into the cleaning composition. Of these, proteases, alkaline lipases, and alkaline cellulases that are highly active in an alkaline cleaning solution are preferred.

The amount of the enzyme added is preferably 5% by mass or less with respect to 100% by mass of the cleaning composition. If it exceeds 5% by mass, improvement in detergency cannot be seen, and the economy may be reduced.

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

The water-soluble polymer of the present invention has the above-described configuration and is excellent in the ability to prevent recontamination against complex dirt such as mud and sebum, and therefore can be suitably used for raw materials such as detergent additives.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Note that “%” means “mass%” unless otherwise specified.

[Analysis method]
<Method for measuring 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: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B manufactured by Showa Denko KK
Column temperature: 40 ° C
Flow rate: 0.5 ml / min
Calibration curve: manufactured by GL Science Co., Ltd. Polyethylene glycol standard eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio)

<Measurement method of solid content>
In an oven heated to 130 ° C., 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 dry for 1 hour. 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) × 100

[Monomer Production Method]
<Monomer (1)>
(Synthesis of 2,2 ′-(3-allyloxy-2-hydroxypropylazanediyl) sodium diacetate)
A 2 L glass four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet pipe and a cooling trap at the nitrogen outlet was charged with 230.0 g of iminodiacetic acid and 291.2 g of pure water at room temperature while introducing nitrogen. Stir with. This was neutralized by adding 288.0 g of a 48 wt% aqueous sodium hydroxide solution (hereinafter referred to as 48% NaOH). After heating to 60 ° C. with stirring, 197.2 g of allyl glycidyl ether (hereinafter referred to as AGE) was added over 1 hour. Thereafter, by reacting for 5 hours, 42.4% of 2,2 ′-(3-allyloxy-2-hydroxypropylazanediyl) was obtained as 2,2 ′-(3-allyloxy-2-hydroxypropylazanediyl) diacetic acid. ) A sodium diacetate-containing composition (hereinafter referred to as monomer (1)) was obtained.

<Monomer (2)>
(Synthesis of 1-allyloxy-3-dibutylaminopropan-2-ol)
A 2-liter glass four-neck flask equipped with a thermometer, stirrer, nitrogen inlet pipe and cooling trap at the nitrogen outlet was charged with 380.7 g of dibutylamine and 319.9 g of pure water, 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 allowed to react for 5 hours. The solution was transferred to a separatory funnel, washed with pure water and saturated saline, and then dried using sodium sulfate, whereby a 100% 1-allyloxy-3-dibutylaminopropan-2-ol-containing composition ( Hereinafter, monomer (2)) was obtained.

<Monomer (3)>
(Synthesis of 1-allyloxy-3-morpholinopropan-2-ol)
A 1 L glass four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet pipe and a cooling trap at the nitrogen outlet was charged with 177.7 g of morpholine and 101.5 g of pure water, 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 reacted for 5 hours, whereby a composition containing 80.0% of 1-allyloxy-3-morpholinopropan-2-ol (hereinafter, monomer) (Referred to as (3)).

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

<Monomer (5)>
(Synthesis of 2,2 ′-(3-allyloxy-2-hydroxypropylazanediyl) bis (ethane-1-ol))
A 1 L glass four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a cooling trap at the nitrogen outlet was charged with 214.5 g of diethanolamine and 110.7 g of pure water, 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 allowed to react for 5 hours, whereby 80.0% 2,2 ′-(3-allyloxy-2-hydroxypropylazanediyl) bis (ethane- A 1-ol) -containing composition (hereinafter referred to as monomer (4)) was obtained.

[Method for producing copolymer]
<Example 1>
In a 500 mL glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, 110.5 g of pure water was charged, and the temperature was raised to 85 ° C. with stirring (initial charging).
Next, 108.1 g of an 80% by weight aqueous acrylic acid solution (hereinafter referred to as 80% AA), 37.1 g of monomer (1), monomer (2) 18 in a polymerization reaction system at a constant temperature of 85 ° C. with stirring. .5g, 15% by weight sodium persulfate aqueous solution (hereinafter referred to as 15% NaPS) 21.4g, 35% by weight sodium bisulfite aqueous solution (hereinafter referred to as 35% SBS) 5.7g and pure water 15.0g It dripped from the dripping nozzle. For each dropping time and dropping sequence, 80% AA is a constant rate in 180 minutes from the start of the reaction, monomer (1) is a constant rate in 120 minutes from the start of the reaction, and monomer (2) is 120 minutes from the start of the reaction. The constant speed was 15 minutes, 15% NaPS was constant at 210 minutes from the start of the reaction, 35% SBS was constant at 180 minutes from the start of the reaction, and pure water was constant at 180 minutes from the start of the reaction. Moreover, regarding the dripping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, 35% SBS, and pure water were simultaneously used. Moreover, the timing of the dripping start timing of 80% AA, monomer (1), monomer (2), 15% NaPS, 35% SBS, and pure water was set as the reaction start. After completion of all the dropwise additions, the reaction solution was kept at 85 ° C. for 30 minutes to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 55.8 g of 48% NaOH.
Thus, a copolymer (1) having a weight average molecular weight (hereinafter referred to as Mw) of 43,000 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 Mole salt (the total amount of iron (II) with respect to the total amount charged (here, total amount charged) Means the total weight of the charged product including the neutralization step after the completion of the polymerization. The same applies to the following.) 3 ppm) was added, and the temperature was raised to 85 ° C. with stirring (initial charging).
Next, under stirring, in a polymerization reaction system at a constant temperature of 85 ° C., 315.3 g of 80% AA, 84.9 g of monomer (1), 72.1 g of monomer (2), 105.1 g of 15% NaPS, 35% 16.9 g of SBS was dropped from separate dropping nozzles. For each dropping time and dropping sequence, 80% AA is a constant rate in 180 minutes from the start of the reaction, monomer (1) is a constant rate in 120 minutes from the start of the reaction, and monomer (2) is 120 minutes from the start of the reaction. The rate was constant for 15 minutes, 15% NaPS was constant for 210 minutes from the start of the reaction, and 35% SBS was constant for 180 minutes from the start of the reaction. Moreover, regarding the dripping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Moreover, the timing of the start of dropping 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS was set as the reaction start. After completion of all the dropwise additions, the reaction solution was kept at 85 ° C. for 30 minutes to complete the polymerization. After the 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.
Thus, a copolymer (2) having a Mw of 150,000 and a solid content of 41.3% was obtained.

<Example 3>
A 2.5L kettle made of SUS316 equipped with a thermometer, reflux condenser, and stirrer is charged with 201.4 g of pure water and 0.018 g of Mole salt (3 ppm in terms of the mass of iron (II) with respect to the total charged amount). The temperature was raised to 85 ° C. with stirring (initial charge).
Next, 243.2 g of 80% AA, 65.5 g of monomer (1), 55.6 g of monomer (2), 81.1 g of 15% NaPS, 35% in a polymerization reaction system at a constant temperature of 85 ° C. with stirring. 26.1 g of SBS was dropped from a separate dropping nozzle. For each dropping time and dropping sequence, 80% AA is a constant rate in 180 minutes from the start of the reaction, monomer (1) is a constant rate in 120 minutes from the start of the reaction, and monomer (2) is 120 minutes from the start of the reaction. The rate was constant for 15 minutes, 15% NaPS was constant for 210 minutes from the start of the reaction, and 35% SBS was constant for 180 minutes from the start of the reaction. Moreover, regarding the dripping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Moreover, the timing of the start of dropping 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS was set as the reaction start. After completion of all the dropwise additions, the reaction solution was kept at 85 ° C. for 30 minutes to complete the polymerization. After the completion of the polymerization, the reaction solution was allowed to cool, neutralized by adding 127.5 g of 48% NaOH, and then 41.2 g of pure water was added.
Thus, a copolymer (3) having Mw 43000 and a solid content of 41.4% was obtained.

<Example 4>
A 2.5L kettle made of SUS316 equipped with a thermometer, reflux condenser, and stirrer was charged with 129.4 g of pure water and 0.013 g of Mole salt (3 ppm in terms of the mass of iron (II) with respect to the total charged amount). The temperature was raised to 85 ° C. with stirring (initial charge).
Next, 180.2 g of 80% AA, 97.0 g of monomer (1), 20.6 g of monomer (2), 60.0 g of 15% NaPS, 35% in a polymerization reaction system at a constant temperature of 85 ° C. with stirring. 22.5 g of SBS was dropped from a separate dropping nozzle. For each dropping time and dropping sequence, 80% AA is a constant rate in 180 minutes from the start of the reaction, monomer (1) is a constant rate in 120 minutes from the start of the reaction, and monomer (2) is 120 minutes from the start of the reaction. The rate was constant for 15 minutes, 15% NaPS was constant for 210 minutes from the start of the reaction, and 35% SBS was constant for 180 minutes from the start of the reaction. Moreover, regarding the dripping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Moreover, the timing of the start of dropping 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS was set as the reaction start. After completion of all the dropwise additions, the reaction solution was kept at 85 ° C. for 30 minutes to complete the polymerization. After the completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 88.9 g of 48% NaOH, and then 33.5 g of pure water was added.
Thus, a copolymer (4) having Mw 36000 and a solid content of 42.7% was obtained.

<Example 5>
A 2.5L kettle made of SUS316 equipped with a thermometer, reflux condenser, and stirrer is charged with 166.4 g of pure water and 0.016 g of Mole salt (3 ppm in terms of the mass of iron (II) with respect to the total charged amount). The temperature was raised to 85 ° C. with stirring (initial charge).
Next, under stirring, in a polymerization reaction system at a constant temperature of 85 ° C., 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% 17.7 g of SBS was dropped from separate dropping nozzles. For each dropping time and dropping sequence, 80% AA is a constant rate in 180 minutes from the start of the reaction, monomer (1) is a constant rate in 120 minutes from the start of the reaction, and monomer (2) is 120 minutes from the start of the reaction. The rate was constant for 15 minutes, 15% NaPS was constant for 210 minutes from the start of the reaction, and 35% SBS was constant for 180 minutes from the start of the reaction. Moreover, regarding the dripping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Moreover, the timing of the start of dropping 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS was set as the reaction start. After completion of all the dropwise additions, the reaction solution was kept at 85 ° C. for 30 minutes to complete the polymerization. After the 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.
Thus, a copolymer (5) having an Mw of 80000 and a solid content of 44.8% was obtained.

<Example 6>
A 2.5L kettle made of SUS316 equipped with a thermometer, a reflux condenser, and a stirrer is charged with 122.3 g of pure water and 0.014 g of Mole salt (3 ppm in terms of the mass of iron (II) with respect to the total charged amount). The temperature was raised to 85 ° C. with stirring (initial charge).
Next, 180.2 g of 80% AA, 97.0 g of monomer (1), 20.6 g of monomer (2), 60.0 g of 15% NaPS, 35% in a polymerization reaction system at a constant temperature of 85 ° C. with stirring. 51.5 g of SBS was dropped from separate dropping nozzles. For each dropping time and dropping sequence, 80% AA is a constant rate in 180 minutes from the start of the reaction, monomer (1) is a constant rate in 120 minutes from the start of the reaction, and monomer (2) is 120 minutes from the start of the reaction. The rate was constant for 15 minutes, 15% NaPS was constant for 210 minutes from the start of the reaction, and 35% SBS was constant for 180 minutes from the start of the reaction. Moreover, regarding the dripping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Moreover, the timing of the start of dropping 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS was set as the reaction start. After completion of all the dropwise additions, the reaction solution was kept at 85 ° C. for 30 minutes to complete the polymerization. After the completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 88.9 g of 48% NaOH, and then 36.4 g of pure water was added.
Thus, a copolymer (6) having a Mw of 15000 and a solid content of 42.2% was obtained.

<Example 7>
A 2.5L kettle made of SUS316 equipped with a thermometer, reflux condenser, and stirrer was charged with 134.0 g of pure water and 0.015 g of Mole salt (3 ppm in terms of the mass of iron (II) with respect to the total charged amount). The temperature was raised to 85 ° C. with stirring (initial charge).
Next, 180.2 g of 80% AA, 104.5 g of monomer (1), 33.3 g of monomer (2), 61.8 g of 15% NaPS, 35% in a polymerization reaction system at a constant temperature of 85 ° C. with stirring. 66.2 g of SBS was dropped from a separate dropping nozzle. For each dropping time and dropping sequence, 80% AA is a constant rate in 180 minutes from the start of the reaction, monomer (1) is a constant rate in 120 minutes from the start of the reaction, and monomer (2) is 120 minutes from the start of the reaction. The rate was constant for 15 minutes, 15% NaPS was constant for 210 minutes from the start of the reaction, and 35% SBS was constant for 180 minutes from the start of the reaction. Moreover, regarding the dripping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Moreover, the timing of the start of dropping 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS was set as the reaction start. After completion of all the dropwise additions, the reaction solution was kept at 85 ° C. for 30 minutes to complete the polymerization. After the completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 88.0 g of 48% NaOH, and then 42.8 g of pure water was added.
Thus, a copolymer (7) having Mw 13000 and a solid content of 41.8% was obtained.

<Example 8>
A 2.5L kettle made of SUS316 equipped with a thermometer, reflux condenser, and stirrer was charged with 156.2 g of pure water and 0.015 g of Mole salt (3 ppm in terms of the mass of iron (II) with respect to the total charged amount). The temperature was raised to 85 ° C. with stirring (initial charge).
Then, under stirring, in a polymerization reaction system at a constant temperature of 85 ° C., 198.2 g of 80% AA, 53.3 g of monomer (1), 45.3 g of monomer (2), 66.1 g of 15% NaPS, 35% 56.6 g of SBS was added dropwise from a separate dropping nozzle. For each dropping time and dropping sequence, 80% AA is a constant rate in 180 minutes from the start of the reaction, monomer (1) is a constant rate in 120 minutes from the start of the reaction, and monomer (2) is 120 minutes from the start of the reaction. The rate was constant for 15 minutes, 15% NaPS was constant for 210 minutes from the start of the reaction, and 35% SBS was constant for 180 minutes from the start of the reaction. Moreover, regarding the dripping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Moreover, the timing of the start of dropping 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS was set as the reaction start. After completion of all the dropwise additions, the reaction solution was kept at 85 ° C. for 30 minutes to complete the polymerization. After the completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 103.9 g of 48% NaOH, and then 37.0 g of pure water was added.
Thus, a copolymer (8) having an Mw of 14,000 and a solid content of 41.2% was obtained.

<Example 9>
A 2.5L kettle made of SUS316 equipped with a thermometer, reflux condenser, and stirrer was charged with 133.9 g of pure water and 0.015 g of Mole salt (3 ppm in terms of the mass of iron (II) with respect to the total charged amount). The temperature was raised to 85 ° C. with stirring (initial charge).
Next, under stirring, in a polymerization reaction system at a constant state of 85 ° C., 225.2 g of 80% AA, 79.6 g of monomer (1), 11.3 g of monomer (2), 71.5 g of 15% NaPS, 35% 61.3 g of SBS was dropped from a separate dropping nozzle. For each dropping time and dropping sequence, 80% AA is a constant rate in 180 minutes from the start of the reaction, monomer (1) is a constant rate in 120 minutes from the start of the reaction, and monomer (2) is 120 minutes from the start of the reaction. The rate was constant for 15 minutes, 15% NaPS was constant for 210 minutes from the start of the reaction, and 35% SBS was constant for 180 minutes from the start of the reaction. Moreover, regarding the dripping start time, 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Moreover, the timing of the start of dropping 80% AA, monomer (1), monomer (2), 15% NaPS, and 35% SBS was set as the reaction start. After completion of all the dropwise additions, the reaction solution was kept at 85 ° C. for 30 minutes to complete the polymerization. After the 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.
Thus, a copolymer (9) having Mw 18000 and a solid content of 42.3% was obtained.

<Example 10>
A SUS316 2.5L kettle equipped with a thermometer, reflux condenser, and stirrer is charged with 146.1 g of pure water and 0.017 g of molle salt (3 ppm in terms of the mass of iron (II) with respect to the total charged amount). The temperature was raised to 85 ° C. with stirring (initial charge).
Next, under stirring, in a polymerization reaction system at a constant state of 85 ° C., 225.2 g of 80% AA, 121.2 g of monomer (1), 32.2 g of monomer (3), 75.6 g of 15% NaPS, 35% SBS 64.8g was dripped from each separate dripping nozzle. For each dropping time and dropping sequence, 80% AA has a constant rate in 180 minutes from the start of the reaction, monomer (1) has a constant rate in 120 minutes from the start of the reaction, and monomer (3) has a constant rate of 120 from the start of the reaction. The rate was constant for 15 minutes, 15% NaPS was constant for 210 minutes from the start of the reaction, and 35% SBS was constant for 180 minutes from the start of the reaction. Moreover, regarding the dripping start time, 80% AA, monomer (1), monomer (3), 15% NaPS, and 35% SBS were set at the same time. Moreover, the timing of the start of dropping of 80% AA, monomer (1), monomer (3), 15% NaPS, and 35% SBS was set as the reaction start. After completion of all the dropwise additions, the reaction solution was kept at 85 ° C. for 30 minutes to complete the polymerization. After the completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 111.1 g of 48% NaOH, and then 45.4 g of pure water was added.
Thus, a copolymer (10) having a Mw of 15000 and a solid content of 42.7% was obtained.

<Example 11>
A 2.5L kettle made of SUS316 equipped with a thermometer, reflux condenser, and stirrer was charged with 78.1 g of pure water and 0.009 g of Mole salt (3 ppm in terms of the mass of iron (II) with respect to the total charged amount). The temperature was raised to 85 ° C. with stirring (initial charge).
Next, 117.1 g of 80% AA, 63.0 g of monomer (1), 20.1 g of monomer (4), 39.6 g of 15% NaPS, 35% in a polymerization reaction system at a constant state of 85 ° C. with stirring. 33.9 g of SBS was dropped from a separate dropping nozzle. For each dropping time and dropping sequence, 80% AA is a constant rate in 180 minutes from the start of the reaction, monomer (1) is a constant rate in 120 minutes from the start of the reaction, and monomer (4) is 120 minutes from the start of the reaction. The rate was constant for 15 minutes, 15% NaPS was constant for 210 minutes from the start of the reaction, and 35% SBS was constant for 180 minutes from the start of the reaction. Moreover, regarding the dripping start time, 80% AA, monomer (1), monomer (4), 15% NaPS, and 35% SBS were set at the same time. Moreover, the timing of the start of dropping 80% AA, monomer (1), monomer (4), 15% NaPS, and 35% SBS was set as the reaction start. After completion of all the dropwise additions, the reaction solution was kept at 85 ° C. for 30 minutes to complete the polymerization. After the completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 57.8 g of 48% NaOH, and then 24.7 g of pure water was added.
Thus, a copolymer (11) having an Mw of 12000 and a solid content of 42.7% was obtained.

<Example 12>
A 2.5L kettle made of SUS316 equipped with a thermometer, reflux condenser, and stirrer was charged with 141.5 g of pure water and 0.012 g of Mole salt (3 ppm in terms of the mass of iron (II) with respect to the total charged amount). The temperature was raised to 85 ° C. with stirring (initial charge).
Next, 153.1 g of 80% AA, 43.8 g of monomer (5), 17.5 g of monomer (2), 51.5 g of 15% NaPS, 35% in a polymerization reaction system at a constant temperature of 85 ° C. with stirring. 44.1 g of SBS was dropped from separate dropping nozzles. For each dropping time and dropping sequence, 80% AA is a constant rate in 180 minutes from the start of the reaction, monomer (5) is a constant rate in 120 minutes from the start of the reaction, and monomer (2) is 120 minutes from the start of the reaction. The rate was constant for 15 minutes, 15% NaPS was constant for 210 minutes from the start of the reaction, and 35% SBS was constant for 180 minutes from the start of the reaction. Moreover, regarding the dripping start time, 80% AA, monomer (5), monomer (2), 15% NaPS, and 35% SBS were set at the same time. Moreover, the timing of the start of dropping of 80% AA, monomer (5), monomer (2), 15% NaPS, and 35% SBS was set as the reaction start. After completion of all the dropwise additions, the reaction solution was kept at 85 ° C. for 30 minutes to complete the polymerization. After the completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 74.4 g of 48% NaOH, and then 23.7 g of pure water was added.
Thus, a copolymer (12) having Mw 7500 and a solid content of 40.9% was obtained.

<Comparative Example 1>
In a 500 mL glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, 110.5 g of pure water was charged, and the temperature was raised to 85 ° C. with stirring (initial charging).
Next, 108.1 g of 80% AA, 43.2 g of monomer (1), 20.4 g of 15% NaPS, 9.1 g of 35% SBS, 15.0 g of pure water in a polymerization reaction system at a constant temperature of 85 ° C. with stirring. Were dropped from separate dropping nozzles. For each dropping time and dropping sequence, 80% AA is constant at 180 minutes from the start of the reaction, monomer (1) is constant at 180 minutes from the start of the reaction, and 15% NaPS is constant at 210 minutes from the start of the reaction. The rate, 35% SBS was constant at 180 minutes from the start of the reaction, and pure water was constant at 180 minutes from the start of the reaction. Moreover, regarding the dripping start time, 80% AA, monomer (1), 15% NaPS, 35% SBS, and pure water were simultaneously used. Moreover, the timing of the start of dropping of 80% AA, monomer (1), 15% NaPS, 35% SBS, and pure water was set as the reaction start. After completion of all the dropwise additions, the reaction solution was kept at 85 ° C. for 30 minutes to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 55.1 g of 48% NaOH.
Thus, a copolymer (13) having Mw of 23,000 and a solid content of 38.3% was obtained.

<Comparative example 2>
In a 500 mL glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, 75.6 g of pure water and 0.007 g of molle salt (the amount of iron (II) relative to the total charged amount (where total charged The amount refers to the weight of all inputs including the neutralization step after completion of the polymerization.)), And the temperature was raised to 85 ° C. with stirring (initial charge).
Next, 108.1 g of 80% AA, 21.6 g of monomer (2), 0.6 g of 15% NaPS, 4.8 g of 35% SBS, and 20.0 g of pure water in a polymerization reaction system at a constant temperature of 85 ° C. with stirring. Were dropped from separate dropping nozzles. For each dropping time and dropping sequence, 80% AA is constant at 180 minutes from the start of the reaction, monomer (2) is constant at 180 minutes from the start of the reaction, and 15% NaPS is constant at 210 minutes from the start of the reaction. The rate, 35% SBS was constant at 180 minutes from the start of the reaction, and pure water was constant at 180 minutes from the start of the reaction. Moreover, regarding the dripping start time, 80% AA, monomer (2), 15% NaPS, 35% SBS, and pure water were simultaneously used. Moreover, the timing of the start of dropping of 80% AA, monomer (2), 15% NaPS, 35% SBS, and pure water was set as the reaction start. After completion of all the dropwise additions, the reaction solution was kept at 85 ° C. for 30 minutes to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 60.0 g of 48% NaOH.
Thus, a copolymer (14) having Mw 48000 and a solid content of 42.5% was obtained.

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

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

<Evaluation of carbon black-clay dispersibility>
(1) 2.94 g of calcium chloride dihydrate was put into a 500 mL beaker and 500 g was added with pure water to prepare hard water.
(2) 10 g of a solid content 0.1% 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 added to a 1 L beaker, and pure water was added to 1000 g to prepare a glycine buffer solution having a pH of 10.5.
(4) Next, 30 mL test tubes with an inner diameter of 16 mm were prepared for the number of evaluation samples, and 0.03 g of carbon black, 0.30 g of JIS11 class clay, 1.50 g of hard water of (1), and an aqueous sample solution of (2) 1. 50 g and 27.0 g of the glycine buffer solution of (3) were added and capped with a septum. In this way, a suspension aqueous solution containing 1000 ppm of carbon black, 10000 ppm of clay, and 50 ppm of sample solid content in each test tube was prepared.
(5) Each test tube was slowly reversed 60 times, and then the cap was removed and the test tube was allowed to stand for 18 hours in a horizontal and stable place. 5 mL of the supernatant after 18 hours was collected using a whole pipette.
(6) The absorbance at 380 nm of this supernatant was measured using an ultraviolet-visible spectrophotometer UV-1800 manufactured by Shimadzu Corporation. This absorbance was defined as dispersibility. A larger absorbance value means higher 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 carbon black-iron recontamination prevention ability. Further, the carbon black-iron dispersibility of the copolymers obtained in Examples 4 and 12 and Comparative Examples 1 and 2 was evaluated. The results are shown in Table 2.

Claims (5)

Following formula (1);

(In formula (1), R ¹ , R ² and R ³ are the same or different and represent a hydrogen atom or a methyl group. P1 and r1 are the same or different and represent a number of 0 to 5. q1 is , 0 or 1. X represents an amino group having two or more functional groups exhibiting adsorption 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 Formula (2), R ¹ , R ² and R ³ are the same or different and represent a hydrogen atom or a methyl group. P2 and r2 are the same or different and represent a number of 0 to 5. q2 is 0 or 1. Y represents a secondary or tertiary amino group having a hydrophobic group, a neutralized product thereof with these acids, or a quaternary ammonium base having a hydrophobic group.) And a structural unit (b) derived from an amino group-containing monomer (B) and a structural unit (c) derived from an unsaturated carboxylic acid monomer (C). Polymer. X in the formula (1) represents the following formula (6);

(In Formula (6), R ⁴ and R ⁵ are the same or different and each represents an organic group having at least one functional group exhibiting an adsorptivity to at least one of a metal, a metal compound, and a metal ion.) The water-soluble polymer according to claim 1, wherein the water-soluble polymer is a group represented by the formula: The functional group possessed by X in the formula (1) or (6) is at least 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 phosphorous acid group, and a silane group. The water-soluble polymer according to claim 1, wherein the number is one. Y in the formula (2) represents the following formulas (7) to (9);

(In Formula (7) and (8), R < ⁶ >, R <^7> is the same or different and a C1-C20 hydrocarbon group in which a hydrogen atom or a part of carbon atom may be substituted by the hetero atom. In formula (9), R ^{8 to} R ¹⁰ are the same or different and each represents a hydrocarbon group having 1 to 20 carbon atoms in which a part of carbon atoms may be substituted with a hetero atom, R ⁶ And R ⁷ or two of R ^{8 to} R ¹⁰ may be bonded to each other 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 proportion of the structural unit (c) derived from the unsaturated carboxylic acid monomer (C) is 5 to 98% by mass with respect to 100% by mass of all structural units. The water-soluble polymer in any one of Claims 1-4.