JP2010111792A - Sulfonic acid group-containing copolymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer composition having improved resoil-preventing capacity in the case of being used as a detergent, and a method for producing the same. <P>SOLUTION: The sulfonic acid group-containing copolymer comprises 5 to 45 mass% of a specific sulfonic acid group-containing monomer-derived structure, 5 to 45 mass% of a specific polyoxyalkylene-based monomer-derived structure and 10 to 90 mass% carboxyl group-containing monomer-derived structure. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a sulfonic acid group-containing copolymer 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 addition to the above various detergent builders, in recent years, polymers have been blended into detergent compositions as detergent builders.
For example, it is disclosed that a water-soluble copolymer obtained from an unsaturated monocarboxylic acid monomer or an unsaturated polyalkylene glycol monomer is used as a detergent builder (see Patent Document 1). Patent Document 1 discloses that the water-soluble copolymer has a sulfonic acid group as required in addition to the unsaturated monocarboxylic acid monomer and the unsaturated polyalkylene glycol monomer. It is disclosed that it may be obtained by copolymerizing a monomer component containing a monomer.
Here, with the recent increase in consumers' awareness of environmental issues, the performance required of detergent builders is changing. In other words, consumers like to save water by using the remaining hot water from the bath for washing, or prefer detergents with a small amount of use (compact detergent composition) by reducing the amount of detergent components to be drained. It has become.
The use of the remaining hot water causes a problem that the laundry must be washed under conditions where there are many dirt components and hardness components. In order to cope with the above problems, there is a demand for an agent having a higher anti-recontamination ability than before, which suppresses reattachment of soil components to fibers during washing.
Furthermore, the liquid detergent composition can be added to the liquid detergent composition as the tendency of the liquid detergent composition to be preferred in order to avoid the residue of the detergent composition remaining on clothes, etc. (good compatibility) ) The demand for detergent builders is even greater.

JP 2004-75971 A

Thus, although various polymers have been reported in the past, there is a need for the development of a detergent builder that is further adapted to the current consumer needs described above.
Therefore, an object of the present invention is to provide a polymer having improved compatibility and recontamination preventing ability when used in detergent applications and a method for producing the same.

The present inventors have intensively studied to solve the above problems. As a result, the present inventors have obtained a copolymer having a structure derived from a specific sulfonic acid group-containing monomer, a structure derived from a specific polyoxyalkylene compound, and a structure derived from a carboxyl group-containing monomer. The present inventors have found that it has a high compatibility with liquid detergents and remarkably improves the ability to prevent recontamination, thereby completing the present invention.
That is, the copolymer according to the present invention has a structure derived from a sulfonic acid group-containing monomer represented by the following general formula (s-1) (S1), the following general formula (p-1) and / or the following general formula. A structure derived from a polyoxyalkylene monomer represented by formula (p-3) (respectively P1 and P3),
A sulfonic acid group-containing copolymer having a structure (C1) derived from a carboxyl group-containing monomer, the sulfonic acid group-containing monomer based on 100% by mass of the structure derived from all monomers of the copolymer The structure derived from the polyoxyalkylene monomer has a composition of the derived structure (S1) of 5 to 45% by mass (converted to acid type) and is 100% by mass of the structure derived from all monomers of the copolymer. The composition of (the sum of P1 and P2) is 5 to 45% by mass, and the composition of the structure (C1) derived from the carboxyl group-containing monomer with respect to 100% by mass of the structure derived from all monomers of the copolymer is It is a sulfonic acid group containing copolymer which is 10-90 mass%.

In General Formula (s-1), 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 It represents SO ₃ M group, in SO ₃ M group, M represents hydrogen atom, Li, Na, and K, however, X, is either Y, represents a SO ₃ M group.

In the general formula (p-1), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a single bond, CH ₂ , CH ₂ CH ₂ , and X ₀ are represented by the following general formula (p-2). Represents the structure

In the general formula (P2), Z represents a structure derived from an alkylene oxide having 2 to 20 carbon atoms, R ₀ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, and n represents a structure derived from an alkylene oxide. It is the number of repeating units, and is a number from 1 to 200.

In the general formula (p-3), R ₁ represents a hydrogen atom or a methyl group, X ₁ and X ₂ represent a hydroxyl group or a structure represented by the following general formula (P4), and at least X ₁ , X Any one of ₂ represents the structure represented by the following general formula (P4),

In the general formula (4), Z represents a structure derived from an alkylene oxide having 2 to 20 carbon atoms, R ₀ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, and n represents a structure derived from an alkylene oxide. It is the number of repeating units, and is a number from 1 to 200.

When the copolymer of the present invention (also referred to as the polymer of the present invention) is used as a detergent builder, the detergency is improved because the copolymer of the present invention has an excellent anti-recontamination ability. Therefore, it can be preferably used as a detergent additive. In addition, since the copolymer of the present invention has high compatibility with a liquid detergent, it can be blended more into the liquid detergent, so that the detergency of the liquid detergent composition is synergistic. improves.

Hereinafter, the present invention will be described in detail.
The copolymer of the present invention has a structure derived from a specific sulfonic acid group-containing monomer (also referred to as a monomer having the structure of the general formula (s-1)), a specific polyoxyalkylene monomer ( It is a copolymer having a structure derived from the general formula (p-1) or (p-3) and a structure derived from a carboxyl group-containing monomer.
[Sulfonic acid group-containing unsaturated monomer]
The sulfonic acid group-containing monomer of the present invention is characterized by having a structure represented by the following general formula (s-1).

In General Formula (s-1), 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 It represents SO ₃ M group, in SO ₃ M group, M represents hydrogen atom, Li, Na, and K, however, X, is either 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 the above structure, 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.

The composition of the structure derived from the sulfonic acid group-containing monomer (S1) with respect to 100% by mass of the structure derived from all monomers of the copolymer is 5 to 45% by mass (in terms of acid type), more preferably. It is 10-40 mass% (acid type conversion), More preferably, it is 15-30 mass% (acid type conversion).
In the present invention, “acid type conversion” means the mass of the monomer with respect to all monomer components in the sulfonic acid group-containing monomer, carboxyl group-containing monomer, and other acid group-containing monomers. When calculating a ratio (composition ratio), it means calculating as a corresponding acid type monomer. The same applies when calculating the mass ratio of the copolymer derived from the monomer to the structure derived from all monomers. For example, when calculating the mass ratio of sodium acrylate to all monomer components, it means calculating the mass as the corresponding acid acrylic acid, and the structure derived from all monomer components of the structure derived from sodium acrylate When calculating the mass ratio with respect to, it means calculating the mass as a structure derived from acrylic acid which is the corresponding acid type structure. Similarly, structural units having an amine base-containing monomer and an amine salt structure similarly have a corresponding amine (amino group) -containing monomer and amine structure (amino group structure) when calculating the mass ratio. The mass is calculated as

  The copolymer of the present invention has a structure (S1) derived from the sulfonic acid group-containing monomer represented by the general formula (s-1) as an essential feature. In the present invention, the structure derived from a sulfonic acid group-containing monomer (S1) is a structure in which a sulfonic acid group-containing monomer is copolymerized by radical polymerization, and is represented by the following general formula (S1).

In General Formula (S1), 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.
[Polyoxyalkylene monomer]
The polyoxyalkylene monomer of the present invention is characterized by having a structure represented by any of the following general formulas (P1) or (P3).

In the general formulas (p-1) and (p-3), R ₁ is a hydrogen atom or a methyl group. In General Formula (p-1), R ₂ represents any structure of a single bond, a CH ₂ group (methylene group), and a CH ₂ CH ₂ group (ethylene group). Since the ability to prevent recontamination of the obtained polymer is improved, a CH ₂ group or a CH ₂ CH ₂ group is preferable.
In the general formula (p-1), X ₀ represents a structure represented by the following general formula (P2).

In the general formula (p-3), X ₁ and X ₂ represent a hydroxyl group or a structure represented by the following general formula (P4), and at least _one of X ₁ and X ₂ represents the following general formula (P4) Represents a structure represented by “Either one” means that either X ₁ or X ₂ has a structure represented by the following general formula (P4), and both X ₁ and X ₂ have the following general formula ( This includes the case where the structure is represented by P4). Preferably, one of X ₁ and X ₂ is a structure represented by the following general formula (P4).

In the general formulas (P2) and (P4), Z represents a structure derived from an alkylene oxide having 2 to 20 carbon atoms, R ₀ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, and n represents an alkylene. It is the number of repeating structural units derived from oxide, and is a number from 1 to 200.

  In the general formulas (P2) and (P4), examples of the organic group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and an aryl having 6 to 30 carbon atoms. Groups and the like. These may further have a substituent. Further substituents include heterocyclic groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkoxycarbonyl groups, aryloxycarbonyl groups, sulfamoyl groups, acyl groups, acyloxy groups, amide groups, carbamoyl groups, ureido groups, Examples thereof include an alkylsulfonyl group, an arylsulfonyl group, an amino group, a halogen atom, a fluorinated hydrocarbon group, a cyano group, a nitro group, a hydroxy group, a mercapto group, and a silyl group. Specific examples of the organic group having 1 to 30 carbon atoms include methyl group, ethyl group, butyl group, octyl group, lauryl group, cyclohexyl group, phenyl group, naphthyl group, pyridyl group, pyrimidyl group, imidazolidyl group, and morpholyl. Examples thereof include a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, a methylcarbonyl group, and an ethylcarbonyl group.

In the above general formulas (P2) and (P4), the “structure derived from alkylene oxide” indicates an oxyalkylene structure in which the alkylene oxide is opened. For example, when the alkylene oxide is ethylene oxide (EO), the “structure derived from alkylene oxide” is an —OCH ₂ CH ₂ — group (oxyethylene group), which is an oxyalkylene structure in which ethylene oxide is opened.

The oxyalkylene group as the structure derived from the alkylene oxide has 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 2 to 5 carbon atoms. Particularly preferably, it is 2 to 3, and most preferably 2.
Examples of the structure derived from alkylene oxide include ethylene oxide (EO), propylene oxide (PO), isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, and butadiene mono Examples include groups derived from compounds such as oxide, octylene oxide, styrene oxide, and 1,1-diphenylethylene oxide.
Among them, the alkylene oxide-derived structure (oxyalkylene group) is preferably a group derived from EO or PO (that is, an oxyethylene group or oxypropylene group), and more preferably an oxyethylene group. In addition, as an oxyalkylene group, only 1 type may exist independently and 2 or more types may be mixed.

  The polyalkylene glycol chain (group formed by an oxyalkylene group) of the polyoxyalkylene monomer of the present invention is preferably mainly composed of an oxyethylene group (—O—CH 2 —CH 2 —). . In this case, “mainly composed of oxyethylene groups” means that when two or more oxyalkylene groups are present in the monomer, the oxyethylene groups occupy most of the total number of oxyalkylene groups present. It means that. Thereby, the superposition | polymerization at the time of manufacture advances smoothly, and the outstanding effect that water solubility and the ability to prevent recontamination improve is acquired.

  In the polyalkylene glycol chain of the polyoxyalkylene monomer of the present invention, when expressed as “mol% of oxyethylene groups in 100 mol% of all oxyalkylene groups”, It is preferable that it is 100 mol%. When the content of the oxyethylene group is less than 50 mol%, the hydrophilicity of the group formed from the oxyalkylene group may be lowered. More preferably, it is 60 mol% or more, more preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more.

  In the said general formula (P2) and (P4), n is the number of repetition of the structural unit derived from alkylene oxide, and is the number of 1-200. Preferably it is 5-100 mol, More preferably, it is 10-60 mol. If it is the said range, it exists in the tendency for the re-staining prevention ability of the sulfonic acid group containing copolymer obtained to improve.

  The content of the structure derived from an oxyalkylene group per mole of the polyoxyalkylene monomer of the present invention (added mole number of oxyalkylene group) is more preferably 1 to 200 mol. That is, when the polyoxyalkylene monomer has two structures of the general formula (P4) in one molecule, the total of both n is preferably 1 to 200. If the content of the structure derived from the oxyalkylene group per mole of the polyoxyalkylene monomer is within the above range, the ability to prevent recontamination tends to be improved. More preferably, the polyoxyalkylene monomer preferably has one or two polyalkylene glycol chains having 5 to 100 structures derived from oxyalkylene groups, and more preferably has one.

  The composition of the structure derived from the polyoxyalkylene monomer (P1 and / or P3) (the sum of P1 and P3) with respect to 100% by mass of the structure derived from all monomers of the copolymer is 5 to 45% by mass. More preferably, it is 10-40 mass%, More preferably, it is 15-30 mass%.

  The copolymer of the present invention essentially comprises the structure (P1) and / or (P3) derived from the polyoxyalkylene monomer represented by the general formula (p-1) and / or (p-3). It is characterized by having. In the present invention, the structure (P1) and / or (P3) derived from a polyoxyalkylene monomer is a structure in which a polyoxyalkylene monomer is copolymerized by radical polymerization, and is represented by the following general formula. The

In the general formula (P1), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a single bond, CH ₂ , CH ₂ CH ₂ , and X ₀ represent a structure represented by the general formula (P2). To express.

In the general formula (P3), R ₁ represents a hydrogen atom or a methyl group, X ₁ and X ₂ represent a hydroxyl group or a structure represented by the general formula (P4), and at least X ₁ and X ₂ Either one represents the structure represented by the general formula (P4).

(Method for producing polyoxyalkylene monomer)
The method for producing the polyoxyalkylene monomer is not limited.
As a preferable production method of the polyoxyalkylene monomer having the structure of the general formula (p-1), (i) alcohols having carbon-carbon double bonds such as allyl alcohol, methallyl alcohol, and isoprenol are used. A production method of adding an alkylene oxide, (ii) a production method of adding a polyalkylene glycol to a halide having a carbon-carbon double bond such as allyl chloride, methallyl chloride, isoprenyl chloride, and vinyl chloride. .

In the production method of (i) above, examples of the method of adding alkylene oxide to alcohol having a carbon-carbon double bond include 1) strong alkali such as alkali metal hydroxide, alkoxide, alkylamine, etc. 2) Cationic polymerization using metal and metalloid halides, mineral acids, acetic acid and the like as catalysts 3) Alkoxides of metals such as aluminum, iron and zinc, alkaline earth compounds, Lewis acids And a method of adding the above-described alkylene oxide to the hydroxyl group of the alcohol using a method such as coordination polymerization using a combination of the above.
As a preferable production method of the polyoxyalkylene monomer having the structure of the general formula (p-3), (iii) carbon-carbon double bonds such as allyl glycidyl ether, methallyl glycidyl ether, and isoprenyl glycidyl ether This is a production method in which polyalkylene glycol is added to an epoxy compound having the following formula.

Since the polyoxyalkylene monomer of the present invention has a structure represented by any one of the above general formulas (p-1) and (p-3), it has good stability during polymerization, and thus is obtained. The ability to prevent recontamination of the polymer is improved. In addition, the polyoxyalkylene monomer of the present invention has a structure represented by any one of the above general formulas (p-1) and (p-3), so that the obtained polymer has stability over time. Is preferred. In addition, since it exhibits excellent stability when producing a product (composition) containing the polymer of the present invention (a sulfonic acid group-containing copolymer) for application in various applications, It is preferable because the performance is stable.
[Carboxyl group-containing monomer (also called carboxyl group-containing unsaturated monomer)]
The carboxyl group-containing monomer is a monomer having a carboxyl group and a carbon-carbon double bond. Examples of such a carboxyl group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 2-methyleneglutaric acid, and the like. Among these, from the viewpoint that the copolymer having high polymerizability has a high ability to prevent recontamination, the carboxyl group-containing monomer is more preferably (meth) acrylic acid or maleic acid, and acrylic acid, Maleic acid is more preferable, and acrylic acid is particularly preferable. These carboxyl group-containing monomers may be used alone or in combination of two or more.
In terms of structure, the carboxyl group-containing monomer corresponding to the polyoxyalkylene monomer of the present invention is calculated as a polyoxyalkylene monomer when calculating the mass ratio.

  The composition of the structure derived from the carboxyl group-containing monomer (C1) with respect to 100% by mass of the structure derived from all monomers of the copolymer is 10 to 90% by mass (as acid type), more preferably 20%. It is -80 mass% (acid type conversion), More preferably, it is 40-70 mass% (acid type conversion).

The copolymer of the present invention is characterized by having a structure derived from a carboxyl group-containing monomer as an essential component. In the present invention, the structure derived from a carboxyl group-containing monomer is a structure in which the carboxyl group-containing monomer is copolymerized by radical polymerization. For example, when the carboxyl group-containing monomer is acrylic acid, -CH ₂ A structure represented by —CH (COOH) —.
[Other monomers]
In addition to the sulfonic acid group-containing unsaturated monomer, polyoxyalkylene monomer, and carboxyl group-containing monomer, other monomers copolymerizable with any of the monomers are included. Also good. Other monomers are not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Hydroxyl group-containing alkyl (meth) acrylates such as acrylate, 4-hydroxybutyl (meth) acrylate, α-hydroxymethylethyl (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid Alkyl (meth) acrylates obtained by esterification of (meth) acrylic acid such as butyl, cyclohexyl (meth) acrylate, lauryl (meth) acrylate and alcohols having 1 to 18 carbon atoms; dimethylaminoethyl (meth) Ami such as acrylate or its quaternized product Group-containing acrylates; Amide group-containing monomers such as (meth) acrylamide, dimethylacrylamide and isopropylacrylamide; Vinyl esters such as vinyl acetate; Alkenes such as ethylene and propylene; Aromatic vinyl monomers such as styrene Maleimide derivatives such as maleimide, phenylmaleimide and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as (meth) acrylonitrile; 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, vinylsulfonic acid, etc. Monomers having a sulfonic acid group; monomers having a phosphonic acid group such as vinyl phosphonic acid and (meth) allylphosphonic acid; aldehyde group-containing vinyl monomers such as (meth) acrolein; methyl vinyl ether, ethyl Vinyl ether, butyl And alkyl vinyl ethers such as vinyl ether; vinyl chloride, vinylidene chloride, allyl alcohol: other functional group-containing monomers such as vinyl pyrrolidone; and the like. Also about these other monomers, only 1 type may be used independently and 2 or more types may be used together.

  The composition of the structure derived from another monomer (E1) with respect to 100% by mass of the structure derived from all monomers of the copolymer is preferably 0 to 30% by mass. The structure (E1) is an optional component and may have the structure (E1) or not at all depending on the application.

In the present invention, the structure derived from another monomer is a structure in which another monomer is copolymerized by radical polymerization. For example, when the other monomer is methyl acrylate, —CH ₂ —CH (COOCH ₃₎ - refers to a structure represented by.
The entire sulfonic acid group-containing monomer, polyoxyalkylene monomer, carboxyl group-containing monomer and other monomers (“total amount of monomer components” or “total monomer composition” The proportion of the sulfonic acid group-containing monomer is not particularly limited, but from the viewpoint of sufficiently exerting the effects of the present invention, the sulfonic acid group-containing unsaturated monomer with respect to the total amount of the monomer component The ratio is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 30% by mass.
The proportion of the polyoxyalkylene monomer in the total amount of the monomer component is not particularly limited, but from the viewpoint of sufficiently exerting the effects of the present invention, the polyoxyalkylene monomer relative to the total amount of the monomer component The proportion of the body is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 30% by mass.
The ratio of the carboxyl group-containing monomer in the total amount of the monomer component is not particularly limited, but from the viewpoint of sufficiently exerting the effects of the present invention, the carboxyl group-containing monomer with respect to the total amount of the monomer component. A ratio becomes like this. Preferably it is 10-90 mass%, More preferably, it is 20-80 mass%, More preferably, it is 40-70 mass%.
The ratio of other monomers in the total amount of monomer components is not particularly limited, but is preferably 0 to 30% by mass.

[Sulfonic acid group-containing copolymer]
As described above, the sulfonic acid group-containing copolymer of the present invention has a structure derived from the above-described sulfonic acid group-containing copolymer, a structure derived from a polyoxyalkylene monomer, and a structure derived from a carboxyl group-containing monomer. Is included as essential.
The sulfonic acid group-containing copolymer of the present invention is obtained by copolymerizing a monomer component containing a sulfonic acid group-containing monomer, a polyoxyalkylene monomer, and a carboxyl group-containing monomer. Preferably there is.

  The weight average molecular weight of the sulfonic acid group-containing copolymer of the present invention is not particularly limited because it can be appropriately set in consideration of the desired performance as a detergent builder, etc., but the sulfonic acid group-containing copolymer of the present invention Specifically, the weight average molecular weight is preferably 100 to 50000, more preferably 500 to 30000, and still more preferably 1000 to 20000. When the value of the weight average molecular weight is too large, the viscosity becomes high and handling may be complicated. On the other hand, if the value of the weight average molecular weight is too small, the ability to prevent recontamination is lowered, and there is a possibility that sufficient performance as a detergent builder may not be exhibited. In addition, the value measured by the method as described in the Example mentioned later shall be employ | adopted as a value of the weight average molecular weight of the sulfonic acid group containing copolymer of this invention.

  The number average molecular weight of the sulfonic acid group-containing copolymer of the present invention is not particularly limited because it can be appropriately set in consideration of desired performance as a detergent builder and the like. However, the sulfonic acid group-containing copolymer of the present invention is not particularly limited. Specifically, the number average molecular weight of the polymer is preferably 100 to 20000, more preferably 200 to 15000, and still more preferably 500 to 10,000. When the value of the number average molecular weight is too large, the viscosity becomes high and handling may be complicated. On the other hand, if the value of the number average molecular weight is too small, the ability to prevent recontamination is lowered, and there is a possibility that sufficient performance as a detergent builder may not be exhibited. In addition, the value measured by the method as described in the Example mentioned later shall be employ | adopted as a value of the number average molecular weight of the sulfonic acid group containing copolymer of this invention.

  The sulfonic acid group-containing copolymer of the present invention is preferably obtained by the method described in the section of [Method for producing sulfonic acid group-containing copolymer] described later.

[Method for producing sulfonic acid group-containing copolymer]
As long as there is no notice in particular, the manufacturing method of the sulfonic acid group containing copolymer of this invention can use the method which modified the well-known polymerization method or a well-known method.

  In the production method of the present invention, the monomer component may be copolymerized using a polymerization initiator. Known initiators can be used such as hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; dimethyl 2,2′-azobis (2-methylpropio Nate), 2,2′-azobis (2-amidinopropane) hydrochloride, 4,4′-azobis-4-cyanoparerenic acid, azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2, Preferred are azo compounds such as 4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide and cumene hydroperoxide. 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.

  The amount of the polymerization initiator used in the polymerization reaction may be appropriately adjusted according to the amount of the monomer component used, and is not particularly limited. It is 0.001 mass part or more and 20 mass parts or less, More preferably, it is 0.005 mass part or more and 15 mass parts or less, More preferably, it is 0.01 mass part or more and 10 mass parts or less.

  In the method for producing a sulfonic acid group-containing copolymer of the present invention, it is preferable to use a chain transfer agent in addition to the polymerization initiator. The chain transfer agent that can be used in this case is not particularly limited as long as it is a compound capable of adjusting the molecular weight, and a known chain transfer agent can be used. Specifically, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropion, 3-mercaptopropion, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, n Thiol chain transfer agents such as dodecyl mercaptan, octyl mercaptan, butyl thioglycolate; halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane; secondary alcohols such as isopropanol, glycerin; Acids, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, and salts thereof (sodium hydrogen sulfite, hydrogen bisulfite) Potassium, sodium dithionite Um, 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.

In the method for producing a sulfonic acid group-containing copolymer of the present invention, a reaction accelerator may be added for the purpose of reducing the amount of an 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 hinder the polymerization reaction in the production of the hydrophobic group-containing copolymer of the present invention, and is a heavy metal compound. As long as it dissolves.

  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, if the content of heavy metal ions exceeds 10 ppm, the color tone of the resulting polymer may be deteriorated. Moreover, when there is much content of heavy metal ion, when using the polymer which is a product as a detergent builder, there exists a possibility of causing the stain | pollution | contamination of a builder for detergents.

  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.

  As a combination of the initiator and the chain transfer agent, it is most preferable to use one or more persulfates and sulfites. In this case, the mixing ratio of persulfate and sulfite is not particularly limited, but it is preferable to use 0.5 to 8 parts by mass of sulfite with respect to 1 part by mass of persulfate. More preferably, with respect to 1 part by mass of persulfate, the lower limit of sulfite is 1 part by mass, and most preferably 2 parts by mass. Further, the upper limit of the sulfite is more preferably 7 parts by mass and most preferably 6 parts by mass with respect to 1 part by mass of the persulfate. Here, if the amount of sulfite is less than 0.5 parts by mass, the total amount of initiator may increase when the molecular weight is lowered. Conversely, if the amount exceeds 8 parts by mass, side reactions increase and impurities due to it. May increase.

The combination of the chain transfer agent, the initiator, and the reaction accelerator is not particularly limited, and can be appropriately selected from the above examples. For example, a combination of a chain transfer agent, an initiator, and a reaction accelerator includes sodium bisulfite (SBS) / hydrogen peroxide (H ₂ O ₂ ), sodium bisulfite (SBS) / sodium persulfate (NaPS), and bisulfite. Sodium (SBS) / Fe, Sodium bisulfite (SBS) / Hydrogen peroxide (H ₂ O ₂ ) / Fe, Sodium bisulfite (SBS) / Sodium persulfate (NaPS) / Fe, Sodium bisulfite (SBS) / Over Forms such as sodium sulfate (NaPS) / hydrogen peroxide (H ₂ O ₂ ) and sodium bisulfite (SBS) / oxygen / Fe are preferred. More preferred are sodium bisulfite (SBS) / sodium persulfate (NaPS), sodium bisulfite (SBS) / sodium persulfate (NaPS) / Fe, and most preferred sodium bisulfite (SBS) / sodium persulfate ( NaPS) / Fe.

  In the method for producing a sulfonic acid group-containing copolymer of the present invention, a polymerization catalyst decomposition catalyst or a reducing compound may be added to the reaction system in addition to the above-described polymerization initiator. 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, lactic acid, isolacic acid, benzoic acid, their esters and their metal salts; heterocyclic amines such as pyridine, indole, imidazole, carbazole and their derivatives Can be mentioned. 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, and homologues of cyclic sulfinic acid such as p-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-hydroxyethyl hydrazine, hydroxylamine; formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, isovaleraldehyde Aldehydes such as 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.

  The total amount of the chain transfer agent, initiator, and reaction accelerator used is sulfonic acid group-containing monomer, polyoxyalkylene monomer, carboxyl group-containing monomer, and other monomers if necessary. It is preferable that it is 2-20g with respect to 1 mol of all the monomer components which consist of. By setting it as such a range, the hydrophobic group containing copolymer of this invention can be produced efficiently, and the molecular weight distribution of a hydrophobic group containing 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. Further, the chain transfer agent may be introduced alone into the reaction vessel, or may be confused in advance with each monomer, solvent, etc. constituting the monomer component.

  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 in a reaction vessel and the whole amount of monomer components and a polymerization initiator is added; one of monomers (for example, a polyoxyalkylene monomer) A method of carrying out copolymerization by charging a portion into a reaction vessel and adding (preferably continuously) a polymerization initiator and the remaining monomer components to the reaction vessel is suitable. Among such methods, the molecular weight distribution of the obtained copolymer can be narrowed (sharpened), and the dispersibility when used as a detergent builder can be improved. It is preferable to carry out copolymerization by a method in which body components are successively dropped into a 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 addition, a known solvent can be used as needed during copolymerization, and water; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol; glycerin; polyethylene glycol; benzene, toluene, xylene Aromatic or aliphatic hydrocarbons such as cyclohexane and n-heptane; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Amides such as dimethylformaldehyde; Ethers such as diethyl ether and dioxane It is. These may be used alone or in combination of two or more. Among these, from the viewpoint of the solubility of the monomer component and the resulting copolymer, one or more solvents selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms may be used. preferable.

In the method for producing the sulfonic acid group-containing copolymer of the present invention, any chain transfer agent, pH adjuster, buffering agent, and the like can be used as necessary.
The temperature during the polymerization is preferably 70 ° C or higher, more preferably 75 to 110 ° C, and still more preferably 80 to 100 ° C. If the temperature at the time of polymerization is in the above range, the residual monomer component is decreased, and the ability to prevent re-contamination of the polymer tends to be improved. The temperature at the time of polymerization need not always be kept constant during the progress of the polymerization reaction. For example, the polymerization is started from room temperature, and the temperature is increased to a set temperature at an appropriate temperature increase time or temperature increase rate. Thereafter, the set temperature may be maintained, or the polymerization temperature may be varied (increased or decreased) over time during the course of the polymerization reaction, depending on the dropping method of the monomer component, initiator, and the like. Also good.
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 240 minutes. In the present invention, “polymerization time” represents the time during which a monomer is added.
The pressure in the reaction system may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure, but from the viewpoint of the molecular weight of the polymer obtained, the reaction system is sealed under normal pressure. However, it is preferably performed under pressure. Moreover, it is preferable to carry out under normal pressure (atmospheric pressure) in terms of equipment such as a pressurizing device, a decompressing device, a pressure-resistant reaction vessel, 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.

[Sulfonic acid group-containing copolymer composition (polymer composition)]
The sulfonic acid group-containing copolymer of the present invention is essential in the polymer composition of the present invention. In addition, unreacted sulfonic acid group-containing monomer, unreacted polyoxyalkylene monomer, unreacted carboxyl group-containing monomer, unreacted polymerization initiator, polymerization initiator decomposition product, sulfonic acid A binary copolymer of a group-containing monomer and a carboxyl group-containing monomer may be included. Since the polymer composition of the present invention is polymerized with the sulfonic acid group-containing monomer as an essential component according to the configuration of the present invention, the by-product of the homopolymer of the carboxyl group-containing monomer can be kept low. Therefore, there is an effect that the polymer precipitation can be remarkably suppressed even in cleaning under high hardness. Moreover, since the by-product of the homopolymer of a carboxyl group-containing monomer is suppressed, there is also a secondary effect that stability with time (suppression of layer separation) is improved when blended with a liquid detergent or the like.
The contents of the unreacted polyoxyalkylene monomer and the unreacted sulfonic acid group-containing unsaturated monomer present in the polymer composition are each 100% by mass of the solid content of the polymer composition. Less than 3% by mass is preferred. More preferably, it is less than 2% by mass. The content of the polymer composed of an acid group-containing unsaturated monomer present in the polymer composition is preferably less than 1% by mass with respect to 100% by mass of the solid content of the polymer composition. More preferably, it is less than 0.5 mass%. The content of the unreacted carboxyl group-containing monomer present in the polymer composition is preferably 1000 ppm by mass or less, more preferably 100 masses with respect to 100 mass% of the solid content of the polymer composition. ppm or less, and most preferably 0 ppm by mass.
The polymer composition referred to in the present application is not particularly limited, but is preferably obtained without a purification step such as impurity removal from the viewpoint of production efficiency. Further, after the polymerization step, the polymer composition referred to in the present application is obtained by diluting the obtained polymerization composition with a small amount of water for handling convenience (about 1 to 400% by mass with respect to the obtained mixture). Included in the composition.
The polymer and polymer composition of the present invention can be used as a water treatment agent, fiber treatment agent, dispersant, detergent builder (or detergent composition) 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 polymer 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 polymer 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 polymer composition of the present invention.

  The content of the polymer composition 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 polymer composition of the present invention to at least one selected from the group consisting of a dye, a peroxide, and a surfactant is, for example, an improvement in whiteness, uneven color, and dyeing tempering of the fiber. For this purpose, at least one selected from the group consisting of a dye, a peroxide and a surfactant is 0.1 to 0.1 part by weight of the polymer composition 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 100 parts by weight 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 polymer composition of the present invention with an alkali agent and a surfactant. In the case of applying to the bleaching step, it is preferable to blend the polymer composition 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 polymer 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 polymer composition 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 composition>
The polymer composition of the present invention can also be added to a detergent composition.
Although the polymer composition of the present invention includes the sulfonic acid group-containing copolymer described above, the content of the sulfonic acid group-containing copolymer in the detergent composition is not particularly limited. However, from the viewpoint of exhibiting excellent builder performance, the content of the sulfonic acid group-containing copolymer is preferably 0.1 to 15% by mass, more preferably based on the total amount of the detergent composition. 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. 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 alkylphenyl ethers, higher fatty acid alkanolamides or their alkylene oxide adducts, 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 agents to prevent redeposition of contaminants such as alkali builders, chelate builders, sodium carboxymethylcellulose, stain inhibitors such as benzotriazole and ethylene-thiourea, soil release agents, and 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 include other detergent builders in addition to the polymer composition of the present invention. Other detergent builders are not particularly limited, but include, for example, alkali builders such as carbonates, hydrogen carbonates, silicates, tripolyphosphates, pyrophosphates, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, citrate. 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 uses such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface cleaners, and bleach 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.
Further, the change (difference) in kaolin turbidity with and without adding the polymer composition of the present invention as a detergent builder to the liquid detergent composition is preferably 500 mg / L or less, more preferably It is 400 mg / L or less, more preferably 300 mg / L or less, particularly preferably 200 mg / L or less, and most preferably 100 mg / L or less. As the kaolin turbidity value, a value measured by the following method is adopted.

<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, the NDU2000 (trade name, turbidimeter) manufactured by Nippon Denshoku Co., Ltd. was used at 25 ° C. 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.
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 present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
Further, the weight average molecular weight, number average molecular weight, anti-recontamination ability of the sulfonic acid group-containing copolymer of the present invention, determination of unreacted monomer, solid content of the polymer composition and the aqueous polymer solution are as follows: Measured according to the method.

<Measurement conditions of weight average molecular weight and number average molecular weight (GPC)>
Apparatus: L-7000 series detector manufactured by Hitachi, Ltd. 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: POLYETHYLENGLYCOL STANDARD made by Soka Science Co., Ltd.
Eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio)
<Quantification method of unreacted polyoxyalkylene monomer>
The unreacted polyoxyalkylene monomer in the polymer composition was quantified by high-speed chromatography under the following conditions.
High-performance liquid chromatography 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)
<Polymer composition, method for measuring solid content of copolymer aqueous solution>
In a nitrogen atmosphere, the polymer composition (polymer composition 1.0 g + water 3.0 g) was left to dry for 1 hour in an oven heated to 130 ° C. From the weight change before and after drying, the solid content (%) and the volatile component (%) were calculated.

<Measurement of content of carboxyl group-containing monomer and sulfonic acid group-containing monomer in polymer composition>
The monomer was measured using liquid chromatography under the conditions shown in Table 1 below.
Measuring device: L-7000 series detector manufactured by Hitachi, Ltd .: UV detector L-7400 manufactured by Hitachi, Ltd.
Column: SHODEX RSpak DE-413 manufactured by Showa Denko Co., Ltd.
Temperature: 40.0 ° C
Eluent: 0.1% phosphoric acid aqueous solution Flow rate: 1.0 ml / min
<Measurement of polymer not containing polyoxyalkylene monomer>
The polymer containing no by-product polyoxyalkylene monomer was quantified by capillary electrophoresis measurement under the following conditions.

<Electrophoretic measurement conditions>
Device name: Photo OTSUKA ELECTRONICS CAPI-3300
CAPILLARY ELECTROPHORESIS SYSTEM
Column: Otsuka Electronics Co., Ltd. GL capillary tube 75μ × 50cm
Voltage: 15kV
Developing solvent: 50 mmol / L Sodium 4-borate aqueous solution Migration time: 30 minutes Detection: UV 210 nm
<Measurement method of recontamination prevention rate>
(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) Hard water was prepared by adding pure water to 4.41 g of calcium chloride dihydrate to 15 kg.
(3) Pure water was added to 4.0 g of sodium linear alkylbenzene sulfonate, 6.0 g of sodium carbonate, and 2.0 g of sodium sulfate to make 100.0 g to prepare an aqueous surfactant solution.
(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 2% polymer aqueous solution in terms of solid content, 0.15 g of zeolite, and 0.25 g of carbon black are put in a pot, and 100 rpm For 1 minute. Then, 10 white cloths were put and stirred at 100 rpm for 10 minutes.
(5) The white cloth was drained by hand, 1 L of tap water adjusted to 25 ° C. was placed in the pot, and stirred at 100 rpm for 2 minutes. This was done twice.
(6) A white cloth was applied and dried while stretching the wrinkle 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 formula.

<Compatibility test for liquid detergent>
Various detergents were prepared using the novel copolymer obtained in the Examples and the following components. The components were sufficiently stirred so that each component was uniform, and the turbidity value at 25 ° C. was measured. Turbidity value measured Turbidity (kaolin turbidity mg / l) using NDH2000 (turbidimeter) made by Nippon Denshoku Co., Ltd.
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)), it is slightly cloudy visually.

X: Turbidity value (200 (mg / l) or more), visually turbid.
Detergent formulation:
SFT-70H (softanol 70H, manufactured by Nippon Shokubai Co., Ltd., polyoxyethylene alkyl ether); 11 g
Neoperex F-65 (manufactured by Kao Corporation, sodium dodecylbenzenesulfonate); 32 g
Diethanolamine; 10g
Ethanol; 5 g
Propylene glycol; 15 g
New copolymer and comparative polymer obtained in Examples; 1.5 g as solid content
Pure water; total over balance: 100g
<Example 1>
A 500 mL glass separable flask equipped with a reflux condenser and a stirrer was charged with 11.2 g of pure water and 0.0122 g of Mole salt, heated to 85 ° C. with stirring, and then 80% acrylic acid (hereinafter, 80% Abbreviated as AA.) 144.0 g, 40% aqueous solution of sodium 3-allyloxy-2-hydroxypropanesulfonate (hereinafter also referred to as “40% HAPS”) 144.0 g, 80 of 50 moles of isoprenol ethylene oxide adduct % Aqueous solution (hereinafter referred to as 80% IPN50) 96.0 g, 15% sodium persulfate (hereinafter abbreviated as 15% NaPS) 38.0 g, 35% sodium bisulfite (hereinafter abbreviated as 35% SBS) 32.0 g was dripped from another dripping port, respectively. The dropping time was 80 minutes for 80% AA, 150 minutes for 40% HAPS, 150 minutes for 80% IPN50, 190 minutes for 15% NaPS, and 175 minutes for 35% SBS. The start of dropping was all simultaneous. The temperature was maintained at 85 ° C. until the end of dropping 80% AA. Furthermore, the same temperature was maintained for 30 minutes after the completion of dropping of 80% AA, and aging was performed to complete the polymerization. After the completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 113.3 g of 48% sodium hydroxide (hereinafter abbreviated as 48% NaOH). Thus, an aqueous copolymer solution (1) having a solid content concentration of 48 mass% and a final neutralization degree of 85 mol% was obtained (the copolymer is referred to as polymer (1)).

<Example 2>
A 500 mL glass separable flask equipped with a reflux condenser and a stirrer was charged with 12.9 g of pure water and 0.0121 g of Mole salt, heated to 85 ° C. with stirring, then 180.0 g of 80% AA, 40% HAPS138. 0.5 g, 80% IPN5036.9 g, 15% NaPS 30.2 g, and 35% SBS 32.2 g were added dropwise from separate dropping ports. The dropping time was 80 minutes for 80% AA, 150 minutes for 40% HAPS, 150 minutes for 80% IPN50, 190 minutes for 15% NaPS, and 175 minutes for 35% SBS. The start of dropping was all simultaneous. The temperature was maintained at 85 ° C. until the end of dropping 80% AA. Furthermore, the same temperature was maintained for 30 minutes after the completion of dropping of 80% AA, and aging was performed to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 141.7 g of 48% NaOH. Thus, a copolymer aqueous solution (2) having a solid content concentration of 48% by mass and a final neutralization degree of 85 mol% was obtained (the copolymer is referred to as polymer (2)).

<Example 3>
A 500 mL glass separable flask equipped with a reflux condenser and a stirrer was charged with 10.5 g of pure water and 0.0113 g of a Mole salt, heated to 85 ° C. with stirring, then 135.0 g of 80% AA, 40% HAPS135. 0.0 g, 60% aqueous solution (hereinafter referred to as 60% IPN25) of 25 mol of an isoprenol ethylene oxide 25 mol adduct, and 95.0 g of 15% NaPS, 36.2 g, and 25.0 g of 35% SBS were added dropwise from separate dropping ports. The dropping time was 80 minutes for 80% AA, 120 minutes for 40% HAPS, 120 minutes for 60% IPN25, 190 minutes for 15% NaPS, and 175 minutes for 35% SBS. The start of dropping was all simultaneous. The temperature was maintained at 85 ° C. until the end of dropping 80% AA. Furthermore, the same temperature was maintained for 30 minutes after the completion of dropping of 80% AA, and aging was performed to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 106.3 g of 48% NaOH. Thus, a copolymer aqueous solution (3) having a solid content concentration of 48 mass% and a final neutralization degree of 85 mol% was obtained (the copolymer is referred to as polymer (3)).

<Example 4>
A 500 mL glass separable flask equipped with a reflux condenser and a stirrer was charged with 45.0 g of pure water and 0.0114 g of a Mole salt, heated to 85 ° C. with stirring, then 135.0 g of 80% AA, 40% HAPS135. 0.04 g of an isoprenol ethylene oxide 10 mol adduct (hereinafter referred to as IPN10) 54.0 g, 15% NaPS 36.6 g, and 35% SBS 30.0 g were added dropwise from separate dripping ports. The drop times were 180 minutes for 80% AA, 150 minutes for 40% HAPS, 120 minutes for IPN10, 190 minutes for 15% NaPS, and 175 minutes for 35% SBS. The start of dropping was all simultaneous. The temperature was maintained at 85 ° C. until the end of dropping 80% AA. Furthermore, the same temperature was maintained for 30 minutes after the completion of dropping of 80% AA, and aging was performed to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 106.3 g of 48% NaOH. Thus, a copolymer aqueous solution (4) having a solid content concentration of 48 mass% and a final neutralization degree of 85 mol% was obtained (the copolymer is referred to as polymer (4)).

<Example 5>
A 500 mL glass separable flask equipped with a reflux condenser and a stirrer was charged with 17.0 g of pure water and 0.0123 g of Mole salt, heated to 85 ° C. with stirring, then 180.0 g of 80% AA, 40% HAPS 138. 0.5 g, IPN 1022.2 g, 15% NaPS 45.8 g, and 35% SBS 38.7 g were added dropwise from separate dropping ports. The drop times were 180 minutes for 80% AA, 150 minutes for 40% HAPS, 120 minutes for IPN10, 190 minutes for 15% NaPS, and 175 minutes for 35% SBS. The start of dropping was all simultaneous. The temperature was maintained at 85 ° C. until the end of dropping 80% AA. Furthermore, the same temperature was maintained for 30 minutes after the completion of dropping of 80% AA, and aging was performed to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 141.7 g of 48% NaOH. Thus, a copolymer aqueous solution (5) having a solid content concentration of 48% by mass and a final neutralization degree of 85 mol% was obtained (the copolymer is referred to as polymer (5)).

<Example 6>
A 500 mL glass separable flask equipped with a reflux condenser and a stirrer was charged with 11.2 g of pure water and 0.0122 g of Mole salt, heated to 85 ° C. with stirring, and then 80% AA 144.0 g and 40% HAPS 144. 0.06 g, 80% aqueous solution of allyl alcohol ethylene oxide 50 mol adduct (hereinafter referred to as 80% PEA50) 96.0 g, 15% NaPS 38.0 g, and 35% SBS 32.0 g were dropped from separate dripping ports. . The dropping time was 80 minutes for 80% AA, 150 minutes for 40% HAPS, 150 minutes for 80% PEA50, 190 minutes for 15% NaPS, and 175 minutes for 35% SBS. The start of dropping was all simultaneous. The temperature was maintained at 85 ° C. until the end of dropping 80% AA. Furthermore, the same temperature was maintained for 30 minutes after the completion of dropping of 80% AA, and aging was performed to complete the polymerization. After the completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 113.3 g of 48% sodium hydroxide (hereinafter abbreviated as 48% NaOH). Thus, a copolymer aqueous solution (6) having a solid content concentration of 48 mass% and a final neutralization degree of 85 mol% was obtained (the copolymer is referred to as polymer (6)).

<Comparative Example 1>
A 500 mL glass separable flask equipped with a reflux condenser and a stirrer was charged with 54.0 g of pure water and 0.0110 g of Mole salt, heated to 85 ° C. with stirring, and then 18% of 80% AA and 60% IPN 5083. .3 g, 15% NaPS 28.1 g, and 35% SBS 23.8 g were added dropwise from separate dropping ports. Each drop time was 180 minutes for 80% AA, 150 minutes for 60% IPN50, 190 minutes for 15% NaPS, and 175 minutes for 35% SBS. The start of dropping was all simultaneous. The temperature was maintained at 85 ° C. until the end of dropping 80% AA. Furthermore, the same temperature was maintained for 30 minutes after the completion of dropping of 80% AA, and aging was performed to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 147.6 g of 48% NaOH. In this way, a comparative polymer aqueous solution (1) having a solid content concentration of 48 mass% and a final neutralization degree of 85 mol% was obtained (the copolymer is referred to as a comparative polymer (1)).

<Comparative example 2>
A 500 mL glass separable flask equipped with a reflux condenser and a stirrer was charged with 9.0 g of pure water and 0.0111 g of Mole salt, heated to 85 ° C. with stirring, then 187.5 g of 80% AA, 40% HAPS125. 0.0 g, 30.8 g of 15% NaPS, and 26.4 g of 35% SBS were dropped from separate dripping ports. Each drop time was 180 minutes for 80% AA, 150 minutes for 40% HAPS, 190 minutes for 15% NaPS, and 175 minutes for 35% SBS. The start of dropping was all simultaneous. The temperature was maintained at 85 ° C. until the end of dropping 80% AA. Furthermore, the same temperature was maintained for 30 minutes after the completion of dropping of 80% AA, and aging was performed to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 147.6 g of 48% NaOH. In this way, a comparative polymer aqueous solution (2) having a solid content concentration of 48 mass% and a final neutralization degree of 85 mol% was obtained (the copolymer is referred to as a comparative polymer (2)).

Regarding the polymers obtained in Table 1, the weight average molecular weight (Mw), the number average molecular weight (Mn), the compatibility of the polymer measured by the above-described method with a liquid detergent, and the polymer having good compatibility, The results of the anti-recontamination ability measured by the above method are shown. In the table, “impossible” means unmeasured.
From the results shown in Table 1, it was demonstrated that the polymer of the present invention has excellent compatibility with liquid detergents as compared to conventional sulfonic acid group-containing polymers. In addition, it was demonstrated that the polymer of the present invention has an excellent ability to prevent recontamination as compared with conventional polymers.
Therefore, when the polymer of the present invention is used as a detergent builder, it is expected that recontamination of dirt can be effectively prevented even if washing is performed using the remaining bath water. Moreover, since the polymer of the present invention has excellent compatibility with liquid detergents, a wider range of detergent blending becomes possible.

Claims (3)

A structure (S1) derived from a sulfonic acid group-containing monomer represented by the following general formula (s-1),
A structure derived from a polyoxyalkylene monomer represented by the following general formula (p-1) and / or the following general formula (p-3) (respectively P1, P3),
Structure derived from a carboxyl group-containing monomer (C1),
A sulfonic acid group-containing copolymer having
The composition of the sulfonic acid group-containing monomer-derived structure (S1) with respect to 100% by mass of the structure derived from all monomers of the copolymer is 5 to 45% by mass (in terms of acid type),
The composition of the structure derived from the polyoxyalkylene monomer (total of P1 and P3) with respect to 100% by mass of the structure derived from all monomers of the copolymer is 5 to 45% by mass,
The composition of the structure derived from the carboxyl group-containing monomer (C1) with respect to 100% by mass of the structure derived from all monomers of the copolymer is 10 to 90% by mass (in terms of acid type).
A sulfonic acid group-containing copolymer.

In General Formula (s-1), 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 represents SO ₃ M group, in SO ₃ M group, M represents hydrogen atom, Li, Na, and K, however, X, is either Y, represents a SO ₃ M group,

In the general formula (p-1), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a single bond, CH ₂ , CH ₂ CH ₂ , and X ₀ are represented by the following general formula (P2). Representing the structure,

In the general formula (P2), Z represents a structure derived from an alkylene oxide having 2 to 20 carbon atoms, R ₀ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, and n represents a structure derived from an alkylene oxide. It is the number of repeating units, and is a number from 1 to 200.

In the general formula (p-3), R ₁ represents a hydrogen atom or a methyl group, X ₁ and X ₂ represent a hydroxyl group or a structure represented by the following general formula (P4), and at least X ₁ , X Any one of ₂ represents the structure represented by the following general formula (P4),

In the general formula (P4), Z represents a structure derived from an alkylene oxide having 2 to 20 carbon atoms, R ₀ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, and n represents a structure derived from an alkylene oxide. It is the number of repeating units, and is a number from 1 to 200. Sulfonic acid group-containing monomer represented by the following general formula (s-1),
A polyoxyalkylene monomer represented by the following general formula (p-1) and / or the following general formula (p-3),
A carboxyl group-containing monomer,
2. The method for producing a sulfonic acid group-containing copolymer according to claim 1, wherein the copolymer is copolymerized.

In General Formula (s-1), 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 represents SO ₃ M group, in SO ₃ M group, M represents hydrogen atom, Li, Na, and K, however, X, is either Y, represents a SO ₃ M group,

In the general formula (p-1), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a single bond, CH ₂ , CH ₂ CH ₂ , and X ₀ are represented by the following general formula (p-2). Represents the structure

In the general formula (P2), Z represents a structure derived from an alkylene oxide having 2 to 20 carbon atoms, R ₀ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, and n represents a structure derived from an alkylene oxide. It is the number of repeating units, and is a number from 1 to 200.

In the general formula (p-3), R ₁ represents a hydrogen atom or a methyl group, X ₁ and X ₂ represent a hydroxyl group or a structure represented by the following general formula (P4), and at least X ₁ , X Any one of ₂ represents the structure represented by the following general formula (P4),

In the general formula (4), Z represents a structure derived from an alkylene oxide having 2 to 20 carbon atoms, R ₀ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, and n represents a structure derived from an alkylene oxide. It is the number of repeating units, and is a number from 1 to 200. A detergent composition comprising the sulfonic acid group-containing copolymer according to claim 1.