JP6002198B2 - NOVEL POLYMER AND PROCESS FOR PRODUCING THE SAME - Google Patents

Description

The present invention relates to a novel polymer and a method for producing the same.

Conventionally, detergents used in apparel have been 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.

In recent years, in addition to the above-mentioned various detergent builders, sodium polyacrylate and the like are blended in detergent compositions as detergent builders (for example, Patent Document 1).
Further, it is disclosed that a copolymer of acrylic acid and 2-hydroxyethyl (meth) acrylate exhibits good clay dispersibility and can be suitably used for various uses such as detergent builders (for example, Patent Document 2). .

JP 2000-80369 A JP 2008-534694 A

As described above, development of various types of detergent builders has been attempted.
Here, in recent years, the use of liquid detergents has increased due to the widespread use of drum-type washing machines, etc., so various detergent builders are compatible with sufficient surfactants so that they can be incorporated into liquid detergents. It is required to have Furthermore, as a recent market trend, liquid detergents tend to prefer highly concentrated types (low water composition ratio), and consumers prefer the liquid detergents with high transparency and no turbidity. It is in. Therefore, the demand for compatibility with other liquid detergent components typified by surfactants and the like required for polymers has become very strict as compared with the prior art.

In addition, with regard to builder performance, it has become established that consumers are trying to save water by using the remaining hot water in the bath for washing due to the recent increase in consumers' awareness of environmental problems. In order to cope with the problem of having to wash under conditions of high hardness due to the concentration of calcium components and conditions with a lot of soil components by using the remaining hot water, the soil components can be reattached to the fibers being washed. There is a demand for an agent that has a further improved ability to prevent so-called recontamination, and an agent that further improves the dispersibility of hydrophobic soils.
The sodium polyacrylate used in Patent Document 1 has a relatively good ability to prevent re-contamination of hydrophilic soil, but from the aspect of compatibility with liquid detergents and the ability to prevent re-contamination of hydrophobic soil. Its performance is not enough.
Moreover, the copolymer of acrylic acid and 2-hydroxyethyl (meth) acrylate used in Patent Document 2 has room for improving the ability to prevent recontamination of hydrophobic soils.
Thus, although various polymers have been reported in the past, there is a demand for the development of a detergent builder that is further adapted to the current consumer needs described above.
Accordingly, the present invention provides a polymer having both improved compatibility with a surfactant that has been improved more than before when used in detergent applications, and an effect of improving the ability to prevent recontamination of hydrophobic soil, and its production It aims to provide a method.

As a result of intensive studies on various polymers and copolymers in order to achieve the above object, the present inventors have found that a structural unit derived from hydroxypropyl (meth) acrylate and a structural unit derived from a carboxyl group-containing monomer It has been found that a copolymer in which a structural unit derived from a sulfonic acid group-containing monomer is introduced at a specific ratio (copolymer of the present invention) has an excellent anti-recontamination ability. It has also been found that the copolymer of the present invention has good compatibility with a surfactant and resistance to hard water. Based on the above findings, the present invention has been completed.
That is, the present invention relates to a structural unit (a) derived from 1% by mass to 89% by mass of hydroxypropyl (meth) acrylate (A), 10% by mass to 98% by mass of a carboxyl group-containing monomer ( A copolymer having the structural unit (b) derived from B) and the structural unit (c) derived from 1% by mass or more and 89% by mass or less of the sulfonic acid group-containing monomer (C) as essential structural units. is there.

In another aspect of the present invention, a method for producing a copolymer is provided. That is, in the method for producing a copolymer of the present invention, 1% by mass or more and 89% by mass or less of hydroxypropyl (meth) acrylate (A) (monomer (A) 10% by mass to 98% by mass of the carboxyl group-containing monomer (B) (also referred to as monomer (B)), and 1% by mass to 89% by mass of sulfonic acid group A method for producing a copolymer, which comprises copolymerizing monomer (C) (also referred to as monomer (C)) as an essential component.

Since the copolymer of the present invention exhibits an excellent ability to prevent recontamination, the copolymer of the present invention can be suitably used for a detergent composition. Moreover, since it has the compatibility with the outstanding surfactant, it can mix | blend preferably also in a liquid detergent composition.

Hereinafter, the present invention will be described in detail.

[Copolymer of the present invention]
<Hydroxypropyl (meth) acrylate>
The copolymer of the present invention essentially has a specific proportion of the structural unit (a) derived from hydroxypropyl (meth) acrylate (A) (also referred to as monomer (A)).
The hydroxypropyl (meth) acrylate is a general term that combines hydroxypropyl acrylate and hydroxypropyl methacrylate, and the hydroxypropyl (meth) acrylate (A) is either hydroxypropyl acrylate or hydroxypropyl methacrylate. It may also contain both hydroxypropyl acrylate and hydroxypropyl methacrylate. Among them, the copolymer of the present invention is derived from hydroxypropyl methacrylate because the copolymer of the present invention can exhibit stable and excellent anti-fouling ability even under alkaline conditions. It is preferable to have a structural unit.
When the hydroxypropyl (meth) acrylate (A) contains both hydroxypropyl acrylate and hydroxypropyl methacrylate, the copolymer of the present invention is a total of structural units derived from hydroxypropyl acrylate and hydroxypropyl methacrylate. In a specific proportion as the structural unit (a) derived from hydroxypropyl (meth) acrylate (A).

The structural unit (a) is in a form in which the polymerizable carbon-carbon unsaturated double bond is a single bond in the monomer (A), that is, hydroxypropyl (meth) acrylate (A). Specifically, the structural unit (a) can be represented by the following general formulas (a1) to (a3).

In the general formulas (a1) to (a3), R ₀ represents a hydrogen atom or a methyl group.
Among these, since the hydrolysis resistance of the copolymer of the present invention is particularly good, it is particularly preferable that the structural unit (a) has the general formula (a1) and / or (a2). .

The copolymer of the present invention has a structural unit (a) derived from hydroxypropyl (meth) acrylate (A) (monomer A) of 1% by mass or more with respect to 100% by mass of the structure derived from all monomers, It is essential to have a ratio of 89% by mass or less. In the present invention, the total monomer means monomer (A), monomer (B), monomer (E) described later (that is, hydroxypropyl (meth) acrylate (A), carboxyl group-containing monomer). Other than the monomer (B) and the sulfonic acid group-containing monomer (C). When the proportion of the structural unit (a) is within the above range, excellent effects of preventing re-contamination of the copolymer and compatibility with the surfactant can be obtained. The ratio of the structural unit (a) to 100% by mass of the structure derived from all monomers (total mass of 100% by mass of the structural units (a), (b), (c), (e)) is preferably 3% by mass. It is more than 88 mass%, More preferably, it is 7 mass% or more and 87 mass% or less, Most preferably, it is 16 mass% or more and 86 mass% or less. When the copolymer of the present invention has the structural unit (a) derived from the monomer (A) within the above range, the recontamination preventing ability and the compatibility with the surfactant are further improved.

Since the structural unit (a) has a high affinity with the surfactant, it is considered that the compatibility with the surfactant is improved by having the structural unit in the above range. Moreover, since the structural unit (a) has a moderate affinity for hydrophobic dirt, it is considered that the re-contamination preventing ability is improved by having the structural unit in the above range.

Although the structural unit (a) has an ester group, since the periphery of the ester group is in a hydrophobic atmosphere, the copolymer of the present invention is stable and excellent because of strong hydrolysis resistance and high stability. The ability to prevent recontamination and compatibility with a surfactant can be exhibited. Further, even if the ester group of the structural unit (a) is hydrolyzed, the produced propylene glycol is safer than ethylene glycol and the like, so the copolymer of the present invention is safe for cosmetic use and the like. Can be preferably used even in a field where the demand is severely required. Furthermore, since monomer (A) is water-soluble, it can be polymerized in aqueous solution and can be designed with extremely low mixing of organic solvents and the like, and mixing of organic solvents and the like is strictly controlled. Application to applications is also possible.

<Carboxyl group-containing monomer (B)>
The copolymer of the present invention is required to have the structural unit (b) derived from the carboxyl group-containing monomer (B) at a specific ratio.
The carboxyl group-containing monomer (B) of the present invention (also referred to as monomer (B)) is a single monomer containing 1) an unsaturated double bond and 2) a carboxyl group and / or a salt thereof as essential components. Is the body. Specifically, unsaturated monocarboxylic acid monomers and salts thereof such as acrylic acid, methacrylic acid, crotonic acid, α-hydroxyacrylic acid, α-hydroxymethylacrylic acid and derivatives thereof; itaconic acid, fumaric acid Examples thereof include unsaturated dicarboxylic acid monomers such as acid, maleic acid and 2-methylene glutaric acid, and salts thereof.
The unsaturated monocarboxylic acid monomer may be any monomer having one polymerizable carbon-carbon unsaturated group and one carboxyl group in the molecule, but acrylic acid and methacrylic acid. And their metal salts, ammonium salts, and organic amine salts are preferred.
The unsaturated dicarboxylic acid monomer may be any monomer having one polymerizable carbon-carbon unsaturated group and two carboxyl groups in the molecule. Maleic acid, itaconic acid, citraconic acid , Fumaric acid and the like, metal salts thereof, ammonium salts, organic amine salts and the like, or anhydrides thereof are suitable.
The carboxyl group-containing monomer (B) is also a half ester of the unsaturated dicarboxylic acid monomer and an alcohol having 1 to 22 carbon atoms, the unsaturated dicarboxylic acid and an amine having 1 to 22 carbon atoms. A half amide of the above unsaturated dicarboxylic acid monomer and a C 2-4 glycol, a half amide of maleamic acid and a C 2-4 glycol, or the like.

Examples of the salt of the unsaturated monocarboxylic acid monomer or the salt of the unsaturated dicarboxylic acid monomer include metal salts, ammonium salts, and organic amine salts. Examples of the metal salt include alkali metal salts such as sodium salt, lithium salt, potassium salt, rubidium salt and cesium salt; alkaline earth metal salts such as magnesium salt, calcium salt, strontium salt and barium salt; aluminum and iron And the like; and the like. Examples of the organic amine salts include alkanolamine salts such as monoethanolamine salts, diethanolamine salts, and triethanolamine salts; alkylamine salts such as monoethylamine salts, diethylamine salts, and triethylamine salts; polyamines such as ethylenediamine salts and triethylenediamine salts; Of organic amines; and the like. Of these, the salt of the unsaturated monocarboxylic acid monomer or the salt of the unsaturated dicarboxylic acid monomer is highly effective in improving the ability to prevent recontamination of the resulting copolymer. Therefore, ammonium salts, sodium salts, and potassium salts are preferable, and sodium salts are more preferable.

Among the above carboxyl group-containing monomers (B), acrylic acid, acrylic acid, acrylic acid, maleic acid, maleic acid and maleic acid are preferred because they have a high effect of improving the ability to prevent recontamination. More preferably, the acid salt is essential.

Only one type of carboxyl group-containing monomer (B) may be used, or two or more types may be used. In this case, the copolymer of this invention has the sum total of the structural unit (b) derived from all the carboxyl group containing monomers (B) in a specific ratio.

The structural unit (b) has a form in which the polymerizable carbon-carbon unsaturated double bond of the monomer (B) is a single bond.

In the copolymer of the present invention, the structural unit (b) derived from the carboxyl group-containing monomer (B) is converted to 100% by mass of the structure derived from all monomers (structural units (a), (b), (c), And it is essential to have it in the ratio of 10 mass% or more and 98 mass% or less with respect to 100 mass% of total mass of the structural unit (e) mentioned later. When the structural unit (b) is within the above range, an excellent effect of improving the ability to prevent recontamination of the copolymer can be obtained. The ratio of the structural unit (b) to 100% by mass of the structure derived from all monomers is preferably 10% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 90% by mass or less. Preferably they are 10 mass% or more and 80 mass% or less.

When the copolymer of the present invention is used as a detergent builder, by having the structural unit (b) at a specific ratio, the water solubility of the polymer is improved, and the soil particles interacted by the structural unit (a) are removed. It is possible to exert the effect of dispersing.

In addition, in this invention, when calculating the mass ratio (mass%) with respect to the structure derived from all the monomers of the structural unit (b) derived from a carboxyl group-containing monomer (B), it calculates as a corresponding acid conversion. It shall be. For example, if the structural unit is —CH ₂ —CH (COONa) — derived from sodium acrylate, the structural unit —CH ₂ —CH (COOH) — derived from acrylic acid, which is the corresponding acid, is represented by a mass ratio (mass% ). Similarly, also when calculating the mass ratio (mass%) with respect to all the monomers of a carboxyl group-containing monomer (B), it shall calculate as a corresponding acid conversion. For example, if it is sodium acrylate, a mass ratio (mass%) is calculated as acrylic acid which is a corresponding acid.

Furthermore, the mass ratio of the structural unit derived from the acid group-containing monomer other than the carboxyl group-containing monomer (B) (for example, the sulfonic acid group-containing monomer (C)) to the structure derived from all monomers ( When calculating (mass%), it is calculated as the corresponding acid conversion, and the mass ratio (mass%) of the acid group-containing monomer other than the carboxyl group-containing monomer (B) to the total monomer is calculated. In this case, it is calculated as the corresponding acid conversion. When the structure derived from the other monomer described later is a structural unit derived from an amino group-containing monomer, the structural unit derived from the amino group-containing monomer is a structural unit derived from the corresponding unneutralized amine, The amino group-containing monomer is mass-calculated as the corresponding unneutralized amine. For example, when the other monomer is vinylamine hydrochloride, the mass ratio (% by mass) is calculated as vinylamine which is the corresponding unneutralized amine.
In the case where the structural unit derived from the amino group-containing monomer and the amino group in the amino group-containing monomer are quaternized, when calculating the mass ratio (mass%), the counter anion Shall be calculated without consideration.

<Sulphonic acid group-containing monomer (C)>
The copolymer of the present invention essentially has the structural unit (c) derived from the sulfonic acid group-containing monomer (C) at a specific ratio.

The sulfonic acid group-containing monomer (C) is a monomer that essentially contains 1) a polymerizable carbon-carbon unsaturated double bond and 2) a sulfonic acid group.

Specific examples of the sulfonic acid group-containing monomer (C) include 3-allyloxy-2-hydroxypropanesulfonic acid, 3-metaallyloxy-2-hydroxypropanesulfonic acid, sulfoethyl methacrylate, and (meth) allylsulfone. And acid, vinyl sulfonic acid, isoprene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, and salts thereof.

As a preferable form of the sulfonic acid group-containing monomer (C), a monomer represented by the following general formula (C1) is exemplified.

In General Formula (C1), R ₁ represents a single bond, CH ₂ , or CH ₂ CH ₂ structure, R ₂ represents a hydrogen atom or a methyl group, and X and Y represent a hydroxyl group or SO _3. M represents a group, and in the SO ₃ M group, M represents a hydrogen atom, Li, Na, K, provided that either X or Y represents a SO ₃ M group.
Here, in the present specification, the case where R ₁ is a single bond means that, for example, when it is represented as C—R ₁ —O, it becomes C—O.

When the copolymer has a structural unit derived from the monomer, the ability to prevent recontamination is improved. R ₁ is more preferably CH ₂ because the ability to prevent re-contamination of the copolymer tends to be further improved.

In the copolymer of the present invention, the structural unit (c) derived from the sulfonic acid group-containing monomer (C) is converted to 100% by mass of the structure derived from all monomers (structural units (a), (b), (c) And a total mass of 100 mass% of a structural unit (e) described later) is essential to have a ratio of 1 mass% to 89 mass%. When the structural unit (c) is within the above range, an effect of improving the hard water resistance of the copolymer can be obtained. The ratio of the structural unit (c) to 100% by mass of the structure derived from all monomers is preferably 2% by mass or more and 87% by mass or less, more preferably 3% by mass or more and 83% by mass or less. Preferably they are 4 mass% or more and 74 mass% or less.

When the copolymer of the present invention is used as a detergent builder, it has a specific proportion of the structural unit (c), thereby improving the water resistance of the polymer. It is possible to exhibit the effect of dispersing the acted dirt particles.

Although the sulfonic acid group-containing monomer of the present invention can be produced by an arbitrary production method, a monomer (composition) having few impurities and good polymerizability can be produced. Epoxy compounds having a carbon-carbon double bond such as allyl glycidyl ether, methallyl glycidyl ether, vinyl glycidyl ether, isoprenyl glycidyl ether, (2) bisulfite, isethionic acid (salt), p-phenolsulfonic acid ( It is preferable to produce by reacting a sulfonic acid group-containing compound such as a salt).

The copolymer of the present invention has a structure (c1) derived from a sulfonic acid group-containing monomer represented by the general formula (C1) as an essential feature. In the present invention, the structure (c1) derived from a sulfonic acid group-containing monomer is a structure formed by radical polymerization of a sulfonic acid group-containing monomer, and is represented by the following general formula (c1).

In the general formula (c1), R ₁ represents a single bond, CH ₂ or CH ₂ CH ₂ structure, R ₂ represents a hydrogen atom or a methyl group, and X and Y represent a hydroxyl group or SO _3. M represents a group, and in the SO ₃ M group, M represents a hydrogen atom, Li, Na, K, provided that either X or Y represents a SO ₃ M group.

<Other monomers>
The copolymer of the present invention is derived from other monomers (E) other than hydroxypropyl (meth) acrylate (A), carboxyl group-containing monomer (B), and sulfonic acid group-containing monomer (C). The structural unit (e) may be included.
The other monomer (E) when the copolymer of the present invention contains another monomer (E) can be copolymerized with the monomers (A), (B), and (C). There is no particular limitation as long as it is anything, and it is appropriately selected depending on the desired effect. Specifically, N-vinyl monomers such as N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-N-methylacetamide, N-vinyloxazolidone, etc. Amide monomers such as (meth) acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide; 3- (meth) allyloxy-1,2-dihydroxypropane, 3-allyloxy-1,2-dihydroxypropane, Allyl ether monomers such as (meth) allyl alcohol; Isoprene monomers such as isoprenol; (Meth) acrylic acid such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and dodecyl (meth) acrylate Alkyl ester monomers; hydroxyethyl (me ) Acrylate, 2-hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, α-hydroxymethylethyl (meth) acrylate, hydroxypentyl ( (Meth) acrylate, hydroxyneopentyl (meth) acrylate, hydroxyhexyl (meth) acrylate and other (meth) acrylic acid hydroxyalkyl monomers; vinyl aryls such as styrene, indene and vinylaniline Monomers, isobutylene, vinyl acetate; vinyl aromatic amino group-containing monomers having heterocyclic aromatic hydrocarbon groups and amino groups such as vinyl pyridine and vinyl imidazole, and quaternized products and salts thereof; dimethylamino Ethyla Aminoalkyl (meth) acrylates such as acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate and aminoethyl methacrylate and quaternized products and salts thereof; allylamines such as diallylamine and diallyldimethylamine and quaternized products and salts thereof (Ii) epoxy ring of (meth) allyl glycidyl ether, isoprenyl glycidyl ether, vinyl glycidyl ether, (ii) dialkylamine such as dimethylamine, diethylamine, diisopropylamine, di-n-butylamine, diethanolamine, diisopropanolamine, etc. Obtained by reacting an amine such as an aminocarboxylic acid such as alkanolamine, iminodiacetic acid or glycine, or a cyclic amine such as morpholine or pyrrole. And quaternized compounds and salts thereof; (meth) acrylic acid alkoxy polyalkylene glycol ester, maleic acid alkoxy polyalkylene glycol ester, alkylene glycol vinyl ether, alkoxy alkylene glycol vinyl ether, alkylene glycol (meth) allyl ether, alkoxy Polyalkylene glycol chain-containing monomers, such as (meth) allyl ether of alkylene glycol, (meth) isoprenyl ether of alkylene glycol, (meth) isoprenyl ether of alkoxyalkylene glycol, wherein the alcoholene glycol unit is 3 to 300 Examples thereof include polyalkylene glycol monomers such as monomers having a molarity (in the case of having an alkoxy group at the terminal, the alkoxy group has 1 to 20 carbon atoms).
Moreover, the said other monomer (E) may be only 1 type, and 2 or more types may be sufficient as it.

When the copolymer of the present invention contains the structural unit (e) derived from the other monomer (E), which is an optional component, the structural unit is derived from 100% by mass of the structural unit derived from all monomers (that is, the structural unit (a ), (B), (c) and (e) in a total of 100% by mass), it is preferably contained at a ratio of 0% by mass to less than 30% by mass. More preferably, it is less than 20 mass%, More preferably, it is less than 10 mass%.

<Other physical properties of copolymer>
In the copolymer of the present invention, the structural units (a), (b), (c) and, if necessary, the structural units (e) may be introduced at a specific ratio as described above. The structural unit may exist in any of alternating, block or random form. Moreover, the weight average molecular weight of the copolymer of this invention can be set suitably, and is not specifically limited. Specifically, the weight average molecular weight of the copolymer is preferably 1,800 to 200,000, more preferably 2,000 to 100,000, and still more preferably 3,000 to 50,000. . If the weight average molecular weight is within the above range, the ability to prevent recontamination tends to be improved. In addition, in this specification, a weight average molecular weight is a measured value by GPC (gel permeation chromatography), and the specific measuring method is computed according to the method described in an Example.
Since the copolymer of the present invention is excellent in compatibility with a surfactant in addition to the ability to prevent recontamination, it can be incorporated into a highly concentrated liquid detergent.

[Copolymer composition of the present invention]
The copolymer composition of the present invention contains the copolymer of the present invention as an essential component, and may contain only the copolymer of the present invention. Contains one or more selected from by-products and water during polymerization. The copolymer composition of the present invention preferably contains the copolymer of the present invention in a proportion of 1% by mass to 100% by mass with respect to 100% by mass of the copolymer composition of the present invention. One of the forms of a preferable copolymer composition is a form containing a copolymer in a proportion of 40% by mass or more and 60% by mass or less and containing water in a proportion of 40% by mass or more and 60% by mass or less. is there.

[Method for producing copolymer of the present invention]
The production method of the copolymer of the present invention is 1% by mass or more with respect to 100% by mass of all monomers (total of monomers (A), (B), (C) and (E)) used. , 89% by mass or less of hydroxypropyl (meth) acrylate (monomer (A)), 10% by mass or more and 98% by mass or less of the carboxyl group-containing single monomer with respect to 100% by mass of the total monomers used 1% by mass or more and 89% by mass or less of the sulfonic acid group-containing monomer (C) (single amount) with respect to 100% by mass of the monomer (B) (monomer (B)) and all monomers used The body (C)) is essential and is copolymerized.
In the method for producing a copolymer of the present invention, the monomer (A), monomer (B) and monomer (C) may be used alone or in combination of two or more. I do not care. In the method for producing a copolymer of the present invention, in addition to the monomer (A), the monomer (B), and the monomer (C), the other monomer (E) is added as necessary. Further, it may be copolymerized.
The proportion of the monomer (E) used in the method for producing a copolymer of the present invention is 100 masses of all monomers (total of monomers (A), (B), (C), and (E)). % Is preferably 0% by mass or more and 30% by mass or less. Also when using the monomer (E) which is the said arbitrary component, 1 type may be used or 2 types may be used.

The method for producing a copolymer of the present invention is such that each copolymer used in producing the above copolymer is from the viewpoint that the obtained copolymer exhibits more preferable recontamination preventing ability and compatibility with a surfactant. The composition ratio of the monomer is 3% by mass or more and 88% by mass or less of the hydroxypropyl (meth) acrylate (monomer (A)) with respect to 100% by mass of all monomers, and the carboxyl group-containing monomer ( B) (monomer (B)) is 10 mass% or more and 95 mass% or less, sulfonic acid group-containing monomer (C) (monomer (C)) is 2 mass% or more and 87 mass% or less, It is preferable that said other monomer (E) shall be 0-20 mass%. More preferably, the monomer (A) is 7% by mass or more and 87% by mass or less, the monomer (B) is 10% by mass or more and 90% by mass or less, the sulfonic acid group-containing monomer (C) (single The monomer (C)) is 3% by mass or more and 83% by mass or less, and the monomer (E) is 0 to 10% by mass, particularly preferably hydroxypropyl (meth) acrylate (monomer (A) ) Is 16 mass% or more and 86 mass% or less, the carboxyl group-containing monomer (B) is 10 mass% or more and 80 mass% or less, and the sulfonic acid group-containing monomer (C) (monomer (C)). 4 mass% or more and 74 mass% or less, and the said other monomer (E) is 0-10 mass%. The total amount of the monomers (A), (B), (C) and (E) is 100% by mass.

<Polymerization initiator>
The method for producing a copolymer of the present invention comprises the above monomers (A), (B), (C), (E) (monomer (A), (B), (C), and (E ) Are sometimes referred to as “monomer composition.”) Is preferably polymerized in the presence of a polymerization initiator.
As the initiator, those usually used as a polymer can be used. For example, hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; dimethyl 2,2′- Azobis (2-methylpropionate), 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethyl) Valeronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyric acid) dimethyl, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] n hydrate, 2,2′-azobis [ 2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 1,1′- Suitable are azo compounds such as azobis (cyclohexane-1-carbonitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydroperoxide, and the like. Of these polymerization initiators, hydrogen peroxide and persulfate 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. For example, a form in which hydrogen peroxide and persulfate are used in combination is a preferred form.

<Chain transfer agent>
In the method for producing a copolymer of the present invention, a chain transfer agent may be used as a molecular weight regulator of the polymer as long as it does not adversely affect polymerization. Specific examples of the chain transfer agent include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropion, 3-mercaptopropion, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2- Thiol chain transfer agents such as mercaptoethanesulfonic acid, n-dodecyl mercaptan, octyl mercaptan, butylthioglycolate; halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane; Secondary alcohol; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionic acid, metabisulfite, and salts thereof ( Sodium bisulfite, potassium bisulfite , Sodium dithionite, potassium dithionite, sodium metabisulfite, metabisulfite potassium, etc.) and the like, and the like lower oxides and salts thereof. The chain transfer agent may be used alone or in the form of a mixture of two or more.
The use of a chain transfer agent has the advantage that the copolymer to be produced can be prevented from having a higher molecular weight than necessary, and a low molecular weight copolymer can be produced efficiently. Among these, in the copolymerization reaction according to the present invention, bisulfite (salt) (bisulfite (salt), disulfite (salt), sulfurous acid (salt), dithionite (salt), thiosulfuric acid (salt) Is preferred. As a result, a sulfonic acid group can be introduced into the main chain terminal of the copolymer to be obtained, and the gel resistance can be improved. Further, it is preferable to use the above bisulfurous acid (salt) as a chain transfer agent because the color tone of the copolymer (composition) can be improved.

In the production method of the present invention, as described above, it is a preferred form to use the bisulfurous acid (salt) as a chain transfer agent. In that case, in addition to the bisulfurous acid (salt), an initiator is used. use. Furthermore, heavy metal ions may be used in combination as a reaction accelerator.
The bisulfite (salt) is as described above, but a form of bisulfite, disulfite, or sulfite is preferable.
The salt in the bisulfite (salt) is preferably a metal atom salt, an ammonium group salt or an organic amine group salt. Examples of the metal atom include monovalent metal atoms of alkali metals such as lithium, sodium and potassium; divalent metal atoms of alkaline earth metals such as calcium and magnesium; trivalent metal atoms such as aluminum and iron And the like are preferred. Moreover, as said organic ammonium (organic amine), alkanolamines, such as ethanolamine, diethanolamine, and triethanolamine, a triethylamine, etc. are suitable. Further, it may be ammonium. Therefore, examples of the bisulfite (salt) preferably used in the present invention include sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium sulfite, potassium sulfite, ammonium sulfite and the like. Particularly preferred. The above sulfurous acid (salt) may be used alone or in the form of a mixture of two or more.

<Reaction accelerator>
In the method for producing a copolymer of the present invention, a reaction accelerator may be added for the purpose of reducing the amount of initiator used. Examples of the reaction accelerator include heavy metal ions. In the present invention, the heavy metal ion means a metal having a specific gravity of 4 g / cm ³ or more. As said metal ion, iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium etc. are preferable, for example. These heavy metals can be used alone or in combination of two or more. Among these, iron is more preferable. The ionic valence of the heavy metal ions is not particularly limited. For example, when iron is used as the heavy metal, the iron ions in the initiator may be Fe ²⁺ or Fe ³⁺ , and these may be combined. May be.
The heavy metal ions are not particularly limited as long as they are included in the form of ions. However, it is preferable to use a method using a solution in which a heavy metal compound is dissolved because the handleability is excellent. The heavy metal compound used in that case should just contain the heavy metal ion desired to contain in an initiator, and can be determined according to the initiator to be used. 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 compound or the like. Moreover, when using manganese as a heavy metal ion, manganese chloride etc. can be used suitably. In the case of using these heavy metal compounds, since they are water-soluble compounds, they can be used in the form of an aqueous solution and have excellent handleability. The solvent of the solution obtained by dissolving the heavy metal compound is not limited to water, and does not interfere with the polymerization reaction in the production of the copolymer of the present invention, and dissolves the heavy metal compound. Anything is acceptable.

The method for adding the heavy metal ions is not particularly limited, but it is preferably added before the completion of the dropwise addition of the monomer, and it is particularly preferable to initially charge the entire amount. Further, the amount used is preferably 100 ppm or less, more preferably 70 ppm or less, still more preferably 50 ppm or less, and particularly preferably 30 ppm or less with respect to the total amount of the reaction solution. If it exceeds 100 ppm, the effect of the addition is no longer seen, and the resulting copolymer is unfavorably colored and cannot be used depending on the application.

The content of the heavy metal ions is preferably 0.1 to 10 ppm with respect to the total mass of the polymerization reaction solution at the completion of the polymerization reaction. If the content of heavy metal ions is less than 0.1 ppm, the effect of heavy metal ions may not be sufficiently exhibited. On the other hand, when the content of heavy metal ions exceeds 10 ppm, the color tone of the resulting copolymer may be deteriorated.

The time when the polymerization reaction is completed means the time when the polymerization reaction is substantially completed in the polymerization reaction solution and a desired polymer is obtained. For example, when the polymer polymerized in the polymerization reaction solution is neutralized with an alkali component, the content of heavy metal ions is calculated based on the total mass of the polymerization reaction solution after neutralization. When two or more kinds of heavy metal ions are included, the total amount of heavy metal ions may be in the above range.

In the method for producing a copolymer of the present invention, in the polymerization, a decomposition catalyst for the polymerization initiator or a reducing compound may be added to the reaction system in addition to the above-described compounds. Examples of the decomposition catalyst for the polymerization initiator include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid, nitric acid and the like. Metal salts of inorganic acids; carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid and benzoic acid, their esters and metal salts; heterocyclic amines such as pyridine, indole, imidazole and carbazole and their derivatives It is done. These decomposition catalysts may be used alone or in combination of two or more.

Examples of the reducing compound include organic metal compounds such as ferrocene; iron naphthenate, copper naphthenate, nickel naphthenate, cobalt naphthenate, manganese naphthenate, and the like, such as iron, copper, nickel, cobalt, and manganese. Inorganic compounds capable of generating metal ions; boron trifluoride ether adducts, potassium permanganate, perchloric acid and other inorganic compounds; sulfur dioxide, sulfite, sulfate, bisulfite, thiosulfate, sulfoxide, Sulfur-containing compounds such as benzenesulfinic acid and its substitutes, homologues of cyclic sulfinic acid such as para-toluenesulfinic acid; octyl mercaptan, dodecyl mercaptan, mercaptoethanol, α-mercaptopropionic acid, thioglycolic acid, thiopropionic acid, α -Sodium thiopropionate sulfopropyl es Tercap, mercapto compounds such as α-thiopropionic acid sodium sulfoethyl ester; nitrogen-containing compounds such as hydrazine, β-hydroxyethylhydrazine, hydroxylamine; formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, isovaleraldehyde Aldehydes such as L-ascorbic acid and the like. These reducing compounds may also be used alone or in combination of two or more. A reducing compound such as a mercapto compound may be added as a chain transfer agent.

In the method for producing a copolymer of the present invention, when the chain transfer agent, the initiator, and the reaction accelerator are used, the combination thereof is not particularly limited and can be appropriately selected from the above examples. For example, combinations of chain transfer agent, initiator and reaction accelerator include sodium bisulfite / hydrogen peroxide, sodium bisulfite / sodium persulfate, sodium bisulfite / iron ion, sodium bisulfite / hydrogen peroxide / iron ion. Sodium bisulfite / sodium persulfate / iron ions, sodium bisulfite / sodium persulfate / hydrogen peroxide, sodium bisulfite / oxygen / iron ions and the like are preferable. More preferred are sodium persulfate / hydrogen peroxide, sodium persulfate / hydrogen peroxide / iron ion, sodium hydrogen sulfite / sodium persulfate, sodium hydrogen sulfite / sodium persulfate / iron ion, most preferably sodium hydrogen sulfite. / Sodium persulfate / iron ions, sodium persulfate / hydrogen peroxide / iron ions.

<Amount of polymerization initiator used>
The amount of the initiator used is not particularly limited as long as it is an amount capable of initiating copolymerization of the monomer (A), (B), (C) and, if necessary, another monomer (E). It is preferable that it is 15 g or less with respect to 1 mol of all monomer components composed of the monomers (A), (B), (C) and, if necessary, other monomers (E). More preferably, it is 12 g.

When hydrogen peroxide is used as the initiator, the amount of hydrogen peroxide added is preferably 1.0 to 10.0 g with respect to 1 mol of all monomers, and 2.0 to 8.0 g. More preferably. When the amount of hydrogen peroxide added is less than 1.0 g, the polymerization average molecular weight of the resulting copolymer tends to increase. On the other hand, when the added amount exceeds 10.0 g, the effect of hydrogen peroxide cannot be obtained as the added amount increases, and the remaining hydrogen peroxide amount increases.

When persulfate is used as the initiator, the amount of persulfate added is preferably 1.0 to 5.0 g, based on 1 mol of all monomers, and is 2.0 to 4.0 g. More preferably. If the amount of persulfate added is less than 1.0 g, the molecular weight of the resulting copolymer tends to increase. On the other hand, if the addition amount exceeds 5.0 g, the effect of persulfate cannot be obtained as the addition amount increases, and further, the purity of the resulting copolymer is adversely affected.

When hydrogen peroxide and persulfate are used in combination as the initiator, the addition ratio of hydrogen peroxide and persulfate is the weight of persulfate when the weight of hydrogen peroxide added is 1 by weight. Is preferably 0.1 to 5.0, and more preferably 0.2 to 2.0. If the weight ratio of persulfate is less than 0.1, the weight average molecular weight of the resulting copolymer tends to be high. On the other hand, if the weight ratio of persulfate exceeds 5.0, the persulfate is wasted in the polymerization reaction system in a state where the effect of lowering the molecular weight due to the addition of persulfate cannot be obtained as much as the addition. It will be.

As the method for adding hydrogen peroxide, the amount dripped substantially continuously with respect to the total amount used is preferably 85% by weight or more of the required predetermined amount, particularly preferably 90% by weight or more, Most preferably, the entire amount is dropped. The dropping speed when hydrogen peroxide is continuously added appropriately can be set as appropriate.

The dropping of the hydrogen peroxide is preferably started after the start of dropping of the monomer (excluding the monomer to be initially charged) under the conditions of the polymerization temperature and pH at the time of polymerization described later. Preferably after 1 minute or more from the start of dropping of the carboxyl group-containing monomer (B), more preferably after 3 minutes, more preferably after 5 minutes, and most preferably after 10 minutes or more It is to start dropping hydrogen. By delaying the dropping start time of hydrogen peroxide, it is possible to smooth the initial polymerization start and narrow the molecular weight distribution.
The time for delaying the hydrogen peroxide dropping start time is preferably within 60 minutes, more preferably within 30 minutes after the start of dropping of the monomer.
It is possible to start the dropping of hydrogen peroxide at the same time as the dropping of the monomer, and to charge hydrogen peroxide in advance before the dropping of the monomer. It is preferably 10% or less, more preferably 7% or less, still more preferably 5% or less, and particularly preferably 3% or less.
If hydrogen peroxide exceeding 10% of the required predetermined amount is added by the time when the dropping of the monomer is started, for example, in the case of using persulfate together, the ratio of the concentration of hydrogen peroxide to persulfate increases, and polymerization is performed. May stop. On the other hand, if it starts later than 60 minutes from the start of dropping of the monomer, the chain transfer reaction due to hydrogen peroxide does not occur, so the molecular weight at the initial stage of polymerization increases.

The hydrogen peroxide dropping end time is preferably terminated simultaneously with the monomer dropping end time under the conditions of polymerization temperature and pH at the time of polymerization described later, and is 10 minutes or longer than the monomer dropping end time. It is more preferable to end early, and it is particularly preferable to end earlier than 30 minutes. In addition, even if it complete | finishes later than the dripping completion time of a monomer, it does not have a bad influence in a polymerization system especially. However, since the added hydrogen peroxide is not completely decomposed by the end of the polymerization, the effect as hydrogen peroxide is not obtained and is wasted, and a large amount of hydrogen peroxide may remain. This is not preferable because it may adversely affect the thermal stability of the obtained copolymer.

Further, the method for adding the persulfate is not particularly limited in view of its decomposability and the like, but the amount dripped substantially continuously with respect to the total amount used is 50% by mass or more of the required predetermined amount. It is preferable that the amount is 80% by mass or more, and it is most preferable to add the whole amount dropwise. The dropping speed when continuously adding the persulfate can be set as appropriate.

The persulfate dropping completion time is not particularly limited, but is relatively decomposed, such as persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate under the conditions of polymerization temperature and pH at the time of polymerization. In the case of an initiator with a short period of time, it is preferable to drop until the monomer dropping end time, more preferably within 30 minutes after the monomer dropping ends, and within 5 to 20 minutes after the monomer dropping. It is particularly preferable to finish the process. Thereby, the effect which can reduce the residual amount of the monomer in a copolymer remarkably can be found. It should be noted that, even if the addition of these initiators is completed before the completion of the monomer addition, it does not particularly adversely affect the polymerization, and is set according to the residual amount of monomer in the obtained copolymer. It is good.

For these initiators that are relatively quick to decompose, the preferred range is described only for the dropping end time, but the dropping start time is not limited at all and may be set as appropriate. For example, in some cases, the dropping of the initiator may be started before starting the dropping of the monomer, and particularly when two or more kinds of initiators are used in combination, the dropping of one initiator is started. Alternatively, the dropping of another initiator may be started after a certain period of time has elapsed or after completion. Any of these may be set as appropriate according to the decomposition rate of the initiator and the reactivity of the monomer.

The concentration of the radical polymerization initiator at the time of addition when the radical polymerization initiator is dissolved in a solvent such as water is not particularly limited, but is preferably 5 to 60% by weight with respect to the solution of the radical polymerization initiator. Particularly preferably, it is 10 to 50% by weight. If the concentration of the initiator is less than 5% by weight, the monomer concentration during the polymerization will be very low as a result. The remaining amount of the body becomes very large. Further, the efficiency and productivity of transportation and the like are lowered, which is not preferable from the economical aspect. On the other hand, if it exceeds 60% by weight, there is a problem in terms of safety and ease of dripping.

In the method of the present invention, the amount of the chain transfer agent added is such that the monomers (A), (B), (C) and, if necessary, other monomers (E) are polymerized satisfactorily. Although not limited, it is 1 to 20 g with respect to 1 mol of all the monomer components composed of the monomers (A), (B), (C) and, if necessary, other monomers (E). It is preferably 2 to 15 g. If the molecular weight is less than 1 g, the molecular weight may not be controlled. On the other hand, if it exceeds 20 g, a large amount of impurities may be generated and the polymer content may be reduced. When used, surplus bisulfite (salts) is decomposed in the reaction system, and toxic sulfurous acid gas may be generated. Moreover, there is a risk that it may be economically disadvantageous.

As a combination of the initiator and the chain transfer agent, it is most preferable to use one or more persulfates and bisulfites (salts). In this case, the mixing ratio of persulfate and bisulfite (salt) is not particularly limited, but 0.5 to 5 parts by mass of bisulfite (salt) is used per 1 part by mass of persulfate. Is preferred. More preferably, with respect to 1 part by mass of persulfate, the lower limit of the bisulfurous acid (salt) is 1 part by mass, and most preferably 2 parts by mass. Moreover, the upper limit of bisulfite (salt) is more preferably 4 parts by mass, and most preferably 3 parts by mass with respect to 1 part by mass of persulfate. Here, if the bisulfite (salt) is less than 0.5 parts by mass, the total amount of the initiator may increase when the molecular weight is lowered. Conversely, if it exceeds 5 parts by mass, side reactions increase. There is a risk that impurities due to this increase.

The total amount of the chain transfer agent, initiator, and reaction accelerator used is the total amount of monomer (A), (B), (C) and, if necessary, the other monomer (E). It is preferable that it is 2-20g with respect to 1 mol of body components. By setting it as such a range, the copolymer of this invention can be produced efficiently and the molecular weight distribution of a copolymer can be made into a desired thing. More preferably, it is 4-18g, More preferably, it is 6-15g.
As a method for adding the polymerization initiator and the chain transfer agent to the reaction vessel, a continuous charging method such as dropping or divided charging can be applied. In addition, a chain transfer agent may be introduced alone into the reaction vessel, and each monomer (A), (B), (C), other monomer (E), or solvent constituting the monomer component Etc. may be confused in advance.

<Polymerization solvent, raw material addition method, etc.>
In the present invention, monomers (A), (B), (C) and, if necessary, copolymerization of other monomers (E) use water in 50% by mass or more of the solvent used, and It is preferably carried out in the presence of a chain transfer agent, more preferably 50% by mass or more of the solvent used, and more preferably in the presence of a chain transfer agent. At this time, by using water in 50% by mass or more of the solvent to be used, the amount of the organic solvent used for the polymerization can be suppressed, so that there is an advantage that the organic solvent can be easily distilled off after the completion of the polymerization.
The solvent used in the above embodiment is not particularly limited as long as it contains water in a proportion of 50% by mass with respect to the total amount of the solvent used. From the viewpoint of improving the solubility of the monomer used for polymerization in a solvent, an organic solvent may be added as necessary. Even in this case, the content of water in the total mixed solvent is 50% by mass or more. Examples of organic solvents that can be used 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 and dioxane; and amides such as dimethylformaldehyde. . These solvents may be used alone or in the form of a mixture of two or more. In the present invention, the amount of water is preferably 80% by mass or more, and most preferably water alone (ie, 100% by mass) with respect to the total amount of solvent used. In the case of adding the organic solvent, from the viewpoint of the solubility of the monomer component and the resulting copolymer, one or more selected from the group consisting of water and a lower alcohol having 1 to 4 carbon atoms. It is preferable to use a solvent.
The amount of the solvent such as water used is preferably 40 to 200% by mass with respect to 100% by mass of the monomer component. More preferably, it is 45 mass% or more, More preferably, it is 50 mass% or more. Moreover, More preferably, it is 180 mass% or less, More preferably, it is 150 mass% or less. If the amount of the solvent used is less than 40% by mass, the resulting copolymer may have a high molecular weight. If it exceeds 200% by mass, the concentration of the obtained copolymer will be low, and solvent removal is required. There is a risk. The solvent may be partly or wholly charged in the reaction vessel in the initial stage of polymerization, but a part of the solvent may be added (dropped) into the reaction system during the polymerization reaction, or the monomer. Components, initiators, and the like may be added (dropped) into the reaction system during the polymerization reaction together with these components in a form in which the components and initiator are dissolved in advance.

In the above copolymerization method, monomer components, polymerization initiators, etc. can be added to the reaction vessel by charging all of the monomer components into the reaction vessel and adding the polymerization initiator into the reaction vessel. Method of performing polymerization: charging a part of the monomer component into the reaction vessel, and adding the polymerization initiator and the remaining monomer component continuously or stepwise (preferably continuously) into the reaction vessel. A method in which a polymerization solvent is charged into a reaction vessel, and a total amount of monomer components and a polymerization initiator is added; monomers (A), (B), (C) and in some cases (E) A method in which a part of one of them is charged into a reaction vessel and copolymerization is performed by adding (preferably continuously) a polymerization initiator and the remaining monomer components into the reaction vessel is preferable. Among these methods, since the molecular weight distribution of the obtained copolymer can be narrowed (sharpened) and the ability to prevent recontamination of the polymer can be improved, a polymerization initiator and a monomer It is preferable to carry out copolymerization by a method in which the components are successively added dropwise to the reaction vessel.

The copolymerization method can be carried out by commonly used methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization, and is not particularly limited, but solution polymerization is preferred. As described above, the solvent that can be used in this case is preferably a mixed solvent in which 50% by mass of water or water is based on the total solvent. When only water is used, it is preferable in that the solvent removal step can be omitted.
The copolymerization method can be carried out either batchwise or continuously.
In the above copolymerization method, the copolymerization conditions such as the copolymerization temperature are appropriately determined depending on the copolymerization method used, the solvent, and the polymerization initiator, but the copolymerization temperature is usually preferably 0 ° C. or higher. Moreover, it is preferable that it is 150 degrees C or less. More preferably, it is 40 degreeC or more, More preferably, it is 60 degreeC or more, Most preferably, it is 80 degreeC or more. Moreover, More preferably, it is 120 degrees C or less, More preferably, it is 110 degrees C or less. In particular, when bisulfurous acid (salt) is used, the copolymerization temperature is usually 60 ° C to 95 ° C, preferably 70 ° C to 95 ° C, and more preferably 80 ° C to 95 ° C. At this time, if the temperature is lower than 60 ° C., there is a possibility that a large amount of impurities derived from bisulfurous acid (salts) is generated. On the contrary, when it exceeds 95 ° C., toxic sulfurous acid gas may be released.
The copolymerization temperature need not always be kept substantially constant in the polymerization reaction. For example, the polymerization is started from room temperature, the temperature is increased to a set temperature at an appropriate temperature increase time or rate, and then the set temperature is reached. Depending on the dropping method of the monomer component, the initiator, etc., the temperature may be changed over time (temperature increase or decrease) during the polymerization reaction.

<Polymerization time, polymerization pressure, polymerization pH>
The polymerization time is not particularly limited, but is preferably 30 to 420 minutes, more preferably 45 to 390 minutes, still more preferably 60 to 360 minutes, and most preferably 90 to 300 minutes. In the present invention, “polymerization time” represents the time during which a monomer is added unless otherwise specified.
The pressure in the reaction system in the copolymerization method may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure, but in terms of the molecular weight of the resulting copolymer, The reaction system is preferably sealed and the reaction is carried out under pressure. Moreover, it is preferable to carry out under a normal pressure (atmospheric pressure) at the point of equipment, such as a pressurization apparatus, a pressure reduction apparatus, a pressure-resistant reaction container, and piping. The atmosphere in the reaction system may be an air atmosphere, but is preferably an inert atmosphere. For example, the inside of the system is preferably replaced with an inert gas such as nitrogen before the start of polymerization.

The pH during the polymerization in the copolymerization is preferably acidic. In particular, when a persulfate and bisulfite (salt) are used in combination as the initiator, it is preferably carried out under acidic conditions. By carrying out under acidic conditions, the increase in the viscosity of the aqueous solution of the polymerization reaction system can be suppressed, and the copolymer can be produced satisfactorily. In addition, since the polymerization reaction can proceed under high concentration conditions, the production efficiency can be greatly increased, and the final solid content concentration can be high concentration polymerization of 40% or more, and the residual contained A monomer having a total monomer concentration of 30,000 ppm or less can be obtained.
As said acidic condition, it is preferable that pH at 25 degreeC of the reaction solution in superposition | polymerization is 1-6. More preferably, it is 5 or less, More preferably, it is 3 or less. The copolymer obtained by the above copolymerization method can be used as it is as a main component of a scale inhibitor, but may be further neutralized with an alkaline substance if necessary. As the alkaline substance, it is preferable to use inorganic salts such as hydroxides, chlorides and carbonates of monovalent metals and divalent metals; ammonia; organic ammonium (organic amine) and the like.

The neutralization rate at the time of copolymerization can be appropriately changed depending on the initiator. For example, when persulfate and bisulfite (salts) are used in combination, the neutralization rate of the monomer with respect to the total amount of acid groups of the acid group-containing monomer such as a carboxyl group-containing monomer It is preferable to carry out the copolymerization of the monomer component at 0 to 60 mol%. The neutralization rate of the monomer is represented by mol% of the monomer forming the salt when the total number of moles of the monomer is 100 mol%. If the neutralization rate of the monomer exceeds 60 mol%, the polymerization rate in the copolymerization step does not increase, and the molecular weight of the resulting copolymer may decrease, or the production efficiency may decrease. More preferably, it is 50 mol% or less, more preferably 40 mol% or less, particularly preferably 30 mol% or less, more particularly preferably 20 mol% or less, and most preferably 10 mol%. It is as follows.
When persulfate and hydrogen peroxide are used in combination, 99 mol% or less, preferably 50 to 95 mol% or less, based on the total amount of acid groups of the acid group-containing monomer such as a carboxyl group-containing monomer. It is. If the degree of neutralization is less than 50 mol%, hydrogen peroxide is not sufficiently decomposed and the weight average molecular weight tends to be high. Also, if it exceeds 99 mol%, strong alkaline and corrosive conditions are required, so that the production equipment may be corroded at high temperatures, and furthermore, hydrogen peroxide is decomposed by alkali, so that the addition amount may increase. There is also. The degree of neutralization after completion of the polymerization (ie after completion of monomer addition) is determined by the acid content of the carboxyl group-containing monomer and other monomers, if applicable, to promote the decomposition of the remaining hydrogen peroxide. Preferably it is 80 mol% or more with respect to the total amount of quantity, More preferably, it is 90 mol% or more, More preferably, you may be 95 mol% or more.
Examples of a method for carrying out the copolymerization with the neutralization rate of the monomer being 0 to 60 mol% include, for example, when the monomer is an unsaturated carboxylic acid monomer, all of which are unsaturated acid carboxylic acid When neutralizing monomeric unsaturated carboxylic acid monomers into salt forms such as sodium salts and ammonium salts using alkaline substances A method in which a neutralization rate of 0 to 60 mol% is added to the copolymer is suitable.

[Use of the copolymer and copolymer composition of the present invention]
The copolymer (or copolymer composition) of the present invention comprises a water treatment agent, a fiber treatment agent, a dispersant, a detergent builder (or a detergent composition), a scale inhibitor (scale inhibitor), and a metal ion sealing agent. , Thickeners, various binders, emulsifiers, skin care agents, hair care agents and the like. As a detergent builder, it can be used by adding to detergents for various uses such as clothing, tableware, residential, hair, body, toothpaste, and automobile.

<Water treatment agent>
The copolymer (or copolymer composition) of the present invention can be used as a water treatment agent. If necessary, the water treatment agent may contain a polymerized phosphate, phosphonate, anticorrosive, slime control agent, and chelating agent as other compounding agents.

The water treatment agent is useful for scale prevention in a cooling water circulation system, a boiler water circulation system, a seawater desalination apparatus, a pulp digester, a black liquor concentration tank, and the like. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effects.

<Fiber treatment agent>
The copolymer (or copolymer composition) of the present invention can be used as a fiber treatment agent. The fiber treatment agent includes at least one selected from the group consisting of a dye, a peroxide, and a surfactant, and the copolymer (or copolymer composition) of the present invention.

The content of the copolymer of the present invention in the fiber treatment agent is preferably 1 to 100% by weight, more preferably 5 to 100% by weight, based on the entire fiber treatment agent. Further, any appropriate water-soluble polymer may be included as long as the performance and effects are not affected.

Below, the compounding example of the fiber processing agent which is closer to embodiment is shown. This fiber treatment agent can be used in the steps of refining, dyeing, bleaching and soaping in fiber treatment. Examples of dyeing agents, peroxides and surfactants include those usually used for fiber treatment agents.

The blending ratio of the copolymer of the present invention and at least one selected from the group consisting of a dye, a peroxide and a surfactant is, for example, for improving the whiteness, color unevenness, and dyeing tempering of the fiber. Includes 0.1 to 100 weight percent of at least one selected from the group consisting of a staining agent, a peroxide and a surfactant with respect to 1 weight part of the copolymer of the present invention in terms of a pure amount of the fiber treatment agent. It is preferable to use a composition blended at a ratio of parts as a fiber treatment agent.

Arbitrary appropriate fiber can be employ | adopted as a fiber which can use the said fiber processing agent. Examples thereof include cellulosic fibers such as cotton and hemp, chemical fibers such as nylon and polyester, animal fibers such as wool and silk, semi-synthetic fibers such as human silk, and woven fabrics and blended products thereof.

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

<Inorganic pigment dispersant>
The copolymer (or copolymer composition) of the present invention can be used as an inorganic pigment dispersant. If necessary, the inorganic pigment dispersant may contain condensed phosphoric acid and its salt, phosphonic acid and its salt, and polyvinyl alcohol as other compounding agents.

The content of the copolymer of the present invention in the inorganic pigment dispersant is preferably 5 to 100% by weight with respect to the whole inorganic pigment dispersant. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effect.

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

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

<Detergent Builder>
The copolymer and copolymer composition of the present invention can be used as a detergent builder. As a detergent builder, it can be used by adding to detergents for various uses such as clothing, tableware, residential, hair, body, toothpaste, and automobile.

<Detergent composition>
The copolymer (or copolymer composition) of the present invention can also be added to a detergent composition.

The content of the copolymer in the detergent composition is not particularly limited. However, from the viewpoint that excellent builder performance can be exhibited, the content of the copolymer is preferably 0.1 to 15% by mass, more preferably 0.3%, based on the total amount of the detergent composition. It is 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. It is above, More preferably, it is 70 mass% or more, Most preferably, it is 80 mass% or more.

Examples of the anionic surfactant 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 monoesters. 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, 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 copolymer (or copolymer composition) 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 builder for detergent 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%, Most preferably, it is 0.4-30 mass%, Most preferably, it is 0.5-20 mass% or less. It is. 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, even more preferably 0.7 to 60% by mass, particularly preferably 1 to 55% by mass, Preferably it is 1.5-50 mass%.

When the detergent composition is a liquid detergent composition, the detergent composition preferably has a kaolin turbidity of 200 mg / L or less, more preferably 150 mg / L or less, and even more preferably 120 mg / L or less. Especially preferably, it is 100 mg / L or less, Most preferably, it is 50 mg / L or less.
<Measurement method of kaolin turbidity>
A sample (liquid detergent) uniformly stirred in a 50 mm square cell having a thickness of 10 mm was removed and air bubbles were removed. Then, a NDU2000 manufactured by Nippon Denshoku Co., Ltd. Kaolin turbidity: mg / L) is measured.

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.

As the alkali builder, silicate, carbonate, sulfate and the like are preferable. As the chelate builder, diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), STPP (sodium tripolyphosphate), citric acid and the like are preferable. Other water-soluble polycarboxylic acid-based polymers other than the copolymer in the present invention may be used.

The above detergent composition should be a detergent with excellent dispersibility, extremely high quality agent performance and excellent stability that is less likely to cause performance degradation when stored for a long time and precipitation of impurities when held at low temperatures. Can do.

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. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
Moreover, the determination of the monomer and the measurement and evaluation of the weight average molecular weight of the copolymer were carried out according to the following methods.

<Quantitative method for hydroxypropyl (meth) acrylate>
Quantification of hydroxypropyl (meth) acrylate and the like was performed by high-speed chromatography under the following conditions.
Measuring device: 8020 series manufactured by Tosoh Corporation Column: CAPCELL PAK C1 UG120 manufactured by Shiseido Co., Ltd.
Temperature: 40.0 ° C
Eluent: 10 mmol / L Disodium hydrogen phosphate.12 hydrate aqueous solution (adjusted to pH 7 with phosphoric acid) / acetonitrile = 45/55 (volume ratio)
Flow rate: 1.0 ml / min
Detector: RI, UV (detection wavelength 215 nm)

<Method for quantifying carboxyl group-containing monomer and sulfonic acid group-containing monomer>
The content of the carboxyl group-containing monomer and the like was measured using liquid chromatography under the following conditions.
Apparatus: Hitachi L-7000 series detector: UV
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: POLYACRYLIC ACID STANDARD made by Soka Science Co., Ltd.
Eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio)

<Measurement conditions of weight average molecular weight>
Equipment: Hitachi L-7000 series detector: RI
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: POLYACRYLIC ACID STANDARD made by Soka Science Co., Ltd.
Eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio)

<Measurement of solid content>
The copolymer of the present invention (1.0 g of the copolymer composition of the present invention plus 1.0 g of water) was allowed to stand for 1 hour in an oven heated to 130 ° C. in a nitrogen atmosphere and dried. From the weight change before and after drying, the solid content (%) and the volatile component (%) were calculated.

<Recontamination prevention evaluation method>
The recontamination prevention test using carbon black was performed according to the following procedure.
(1) A polyester cloth obtained from Test fabric 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 meter SE2000 type manufactured by Nippon Denshoku Industries Co., Ltd. in advance.
(2) Pure water was added to 11.0 g of calcium chloride dihydrate to make 15 kg, and hard water was prepared.
(3) Polyethylene glycol (20) Pure water was added to 4.0 g of lauryl ether to make 100.0 g to prepare an aqueous surfactant solution. The pH was adjusted to 8.5 with sodium hydroxide.
(4) A targot meter is set at 25 ° C., 1 L of hard water, 5 g of a surfactant aqueous solution, 1 g of a 5.0% polymer aqueous solution in terms of solid content, and 1.0 g of carbon black are put in a pot and 150 minutes at 150 rpm. Stir. Then, 5 white cloths were put and stirred at 100 rpm for 10 minutes.
(5) The white cloth was drained by hand, 1 L of hard water brought to 25 ° C. was put in the pot, and stirred at 100 rpm for 2 minutes.
(6) 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.
(7) The recontamination prevention rate was calculated from the above measurement results using the following equation.
Recontamination prevention rate (%) = (whiteness after washing) / (whiteness of raw white cloth) × 100.

<Compatibility with liquid detergent (compatibility with surfactant)>
A detergent composition containing a test sample (polymer) was prepared with the following formulation.
SFT-70H (Nippon Shokubai Co., Ltd., polyoxyethylene alkyl ether); 40 g
Neoperex F-65 (manufactured by Kao Corporation, sodium dodecylbenzenesulfonate); 7.7 g (active ingredient 5 g)
Coatamine 86W (manufactured by Kao Corporation, stearyltrimethylammonium chloride); 17.9 g (active ingredient 5 g)
Diethanolamine; 5g
Ethanol; 5 g
Propylene glycol; 5g
Test sample (solid content conversion): 1.5 g
Ion-exchanged water; balance (the amount of ion-exchanged water is appropriately adjusted so that the total amount is 100 g, with the amount of test sample used as the actual usage)
Thoroughly stir so that each component becomes uniform, and the turbidity value at 25 ° C. is measured using a turbidimeter (“NDH2000” manufactured by Nippon Denshoku Co., Ltd.) with Turbidity (kaolin turbidity mg / l). It was measured.
The evaluation results were based on the following three stages.
○: Turbidity value (0 to 50 (mg / l)), visually separated, not precipitated or clouded.
(Triangle | delta): Turbidity value (50-200 (mg / l), and it is slightly cloudy visually.
X: Turbidity value (200 (mg / l) or more), visually turbid.

<Example 1>
A 300 mL glass separable flask equipped with a reflux condenser and a stirrer was charged with 45.0 g of pure water and 0.0058 g of a Mole salt and heated to 70 ° C. with stirring. 28.0 g, 40 wt% sodium 2-hydroxy-3-allyloxypropanesulfonate (hereinafter referred to as 40% HAPS) 23.3 g, 80% AA 70.0 g, pure water 15. 8 g, 20.7 g of 15% NaPS, and 12.7 g of 35% SBS were added dropwise from separate dropping ports. The dropping time was 150 minutes for HPA and 40% HAPS, 180 minutes for 80% AA, 35% SBS and pure water, and 200 minutes for 15% NaPS. The start of dropping was all simultaneous. The temperature was maintained at 70 ° C. until the end of dropping of HPA, 80%, 40% HAPS, 80% AA, 48% NaOH, 35% SBS, and pure water. Further, after the dropwise addition of 15% NaPS, the same temperature was maintained for 30 minutes for aging to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 57.5 g of a 48% aqueous sodium hydroxide solution (hereinafter referred to as 48% NaOH). Thus, a copolymer having a solid content concentration of 43% by weight and a final neutralization degree of 97 mol% was obtained.
The polymerization formulation is summarized in Table 1, and the polymerization results are summarized in Table 2.

<Example 2>
A 300-mL glass separable flask equipped with a reflux condenser and a stirrer was charged with 45.0 g of pure water and 0.0052 g of a Mole salt and heated to 70 ° C. with stirring. And 8.0%, 40% HAPS 40.0 g, 80% AA 70.0 g, 15% NaPS 19.6 g, and 35% SBS 12.6 g were added dropwise from separate dropping ports. The dropping times were 150 minutes for HPMA, 180 minutes for 80% AA and 35% SBS, and 200 minutes for 15% NaPS. The start of dropping was all simultaneous. The temperature was maintained at 70 ° C. until the end of dropping of HPMA, 80% AA, 48% NaOH, and 35% SBS. Further, after the dropwise addition of 15% NaPS, the same temperature was maintained for 30 minutes for aging to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 53.7 g of 48% NaOH. Thus, a copolymer having a solid content concentration of 42% by weight and a final neutralization degree of 97 mol% was obtained.
The polymerization formulation is summarized in Table 1, and the polymerization results are summarized in Table 2.

<Example 3>
A copolymer was obtained in the same manner as in Example 2 under the conditions shown in Table 2. The polymerization results are summarized in Table 2.

<Comparative Example 1>
A 45% by mass aqueous solution of polyacrylic acid having a weight average molecular weight of 13,000 was neutralized with a 48% by mass aqueous sodium hydroxide solution to adjust the pH to 6.5.

<Comparative example 2>
A 300 mL glass separable flask equipped with a reflux condenser and a stirrer was charged with 45.0 g of pure water and 0.0053 g of a Mole salt, heated to 70 ° C. with stirring, and then 2-hydroxyethyl methacrylate (hereinafter, 24.0 g, 80% by weight acrylic acid aqueous solution (hereinafter referred to as 80% AA) 70.0 g, 48% by weight sodium hydroxide aqueous solution (hereinafter referred to as 48% NaOH) 3.2 g, Separately, 22.7 g of pure water, 19.2 g of 15% by weight sodium persulfate (hereinafter referred to as 15% NaPS), and 8.2 g of 35% by weight sodium bisulfite (hereinafter referred to as 35% SBS) It was dripped from the dripping port. The dropping time of HEMA was 150 minutes, 80% AA, 48% NaOH, 35% SBS, and pure water were 180 minutes, and 15% NaPS was 200 minutes. The start of dropping was all simultaneous. The temperature was maintained at 70 ° C. until the end of dropping of HEMA, 80% AA, 48% NaOH, 35% SBS , and pure water. Further, after the dropwise addition of 15% NaPS, the same temperature was maintained for 30 minutes for aging to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 59.6 g of 48% NaOH. Thus, a copolymer having a solid content concentration of 41% by weight and a final neutralization degree of 97 mol% was obtained.
The polymerization formulation is summarized in Table 1, and the polymerization results are summarized in Table 2.

<Example 4>
The polymers obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated for their ability to prevent recontamination according to the above method. The results are summarized in Table 2.

From the above evaluation results, it has been clarified that the polymer of the present invention has a better anti-recontamination ability than conventional polymers.

The copolymer of the present invention has a high ability to prevent recontamination and compatibility with liquid detergents. Therefore, when it uses for additives, such as a water treatment agent, a builder for detergents, a detergent composition, a dispersing agent, a cleaning agent, it can exhibit the especially outstanding performance.

Claims (7)

1% by mass or more and 89% by mass or less of hydroxypropyl (meth) acrylate (A) -derived structural unit (a),
10% by mass or more and 98% by mass or less of the structural unit (b) derived from the carboxyl group-containing monomer (B),
And a structural unit (c) derived from the sulfonic acid group-containing monomer (C) represented by the following general formula (C1) of 1% by mass or more and 89% by mass or less as an essential structural unit, and having a weight average A copolymer having a molecular weight of 11,000 to 50,000 .

In General Formula (C1), R ₁ represents a single bond, CH ₂ , or CH ₂ CH ₂ structure, R ₂ represents a hydrogen atom or a methyl group, and X and Y represent a hydroxyl group or SO _3. M represents a group, and in the SO ₃ M group, M represents a hydrogen atom, Li, Na or K, provided that either X or Y represents a SO ₃ M group. The carboxyl group-containing monomer (B) is at least one selected from the group consisting of acrylic acid, acrylate, maleic acid and maleate,
The content ratio of the structural unit (a) is 7% by mass or more and 86% by mass or less,
The content ratio of the structural unit (b) is 10% by mass or more and 80% by mass or less,
2. The copolymer according to claim 1 , wherein a content ratio of the structural unit (c) is 4% by mass or more and 74% by mass or less. 1% by mass or more and 89% by mass or less of hydroxypropyl (meth) acrylate (A) with respect to 100% by mass of all monomers,
10% by mass or more and 98% by mass or less of the carboxyl group-containing monomer (B),
And a copolymer having a sulfonic acid group-containing monomer (C) represented by the following general formula (C1) of 1% by mass or more and 89% by mass or less as an essential component, and having a weight average molecular weight of 11,000 to 50,000. A method for producing a copolymer, comprising producing a polymer.

In General Formula (C1), R ₁ represents a single bond, CH ₂ , or CH ₂ CH ₂ structure, R ₂ represents a hydrogen atom or a methyl group, and X and Y represent a hydroxyl group or SO _3. M represents a group, and in the SO ₃ M group, M represents a hydrogen atom, Li, Na or K, provided that either X or Y represents a SO ₃ M group. 1% by mass or more and 89% by mass or less of the hydroxypropyl (meth) acrylate (A) derived structural unit (a), 10% by mass or more and 98% by mass or less of the carboxyl group-containing monomer (B) derived structural unit. (B) and 1% by mass or more and 89% by mass or less of the structural unit (c) derived from the sulfonic acid group-containing monomer (C) represented by the following general formula (C1) as an essential structural unit. And a detergent builder comprising a copolymer having a weight average molecular weight of 11,000 to 200,000 .

In General Formula (C1), R ₁ represents a single bond, CH ₂ , or CH ₂ CH ₂ structure, R ₂ represents a hydrogen atom or a methyl group, and X and Y represent a hydroxyl group or SO _3. M represents a group, and in the SO ₃ M group, M represents a hydrogen atom, Li, Na or K, provided that either X or Y represents a SO ₃ M group. The carboxyl group-containing monomer (B) is at least one selected from the group consisting of acrylic acid, acrylate, maleic acid and maleate,
The content ratio of the structural unit (a) is 7% by mass or more and 86% by mass or less,
The content ratio of the structural unit (b) is 10% by mass or more and 80% by mass or less,
The content rate of the said structural unit (c) is 4 mass% or more and 74 mass% or less, The detergent builder of Claim 4 characterized by the above-mentioned. A detergent composition containing 10 to 60% by mass of a surfactant,
As a detergent builder, 1 mass% or more and 89 mass% or less of hydroxypropyl (meth) acrylate (A) -derived structural unit (a), 10 mass% or more and 98 mass% or less of carboxyl group-containing monomer (B) The structural unit (b) derived from and the structural unit (c) derived from the sulfonic acid group-containing monomer (C) represented by the following general formula (C1) of 1% by mass or more and 89% by mass or less are essential. A detergent composition comprising a copolymer having a structural unit and a weight average molecular weight of 11,000 to 200,000 .

In General Formula (C1), R ₁ represents a single bond, CH ₂ , or CH ₂ CH ₂ structure, R ₂ represents a hydrogen atom or a methyl group, and X and Y represent a hydroxyl group or SO _3. M represents a group, and in the SO ₃ M group, M represents a hydrogen atom, Li, Na or K, provided that either X or Y represents a SO ₃ M group. The carboxyl group-containing monomer (B) is at least one selected from the group consisting of acrylic acid, acrylate, maleic acid and maleate,
The content ratio of the structural unit (a) is 7% by mass or more and 86% by mass or less,
The content ratio of the structural unit (b) is 10% by mass or more and 80% by mass or less,
The content rate of the said structural unit (c) is 4 mass% or more and 74 mass% or less, The detergent composition of Claim 6 characterized by the above-mentioned.