WO2020203694A1 - Detergent builder or detergent additive, and detergent composition - Google Patents

Abstract

Provided is a detergent builder or a detergent additive that exhibits superior clay dispersibility, superior compatibility with surfactants, and a superior solubilizing power, which is the ability to cause fats to dissolve. Additionally provided is a detergent composition containing a copolymer that can be suitably employed in such a detergent builder or detergent additive. A detergent builder or a detergent additive according to an embodiment of the present invention is a copolymer that contains a specific structural unit (I) and a specific structural unit (II), wherein a sulfide bond is included, and the average number of added moles n of an oxyalkylene group represented by AO is equal to or greater than 11.

Description

Detergent Builder or Detergent Additives and Detergent Compositions

The present invention relates to a detergent builder or a detergent additive and a detergent composition.

The water-soluble polymer is preferably used as a detergent builder or a detergent additive. Conventionally, as such a water-soluble polymer, an unsaturated carboxylic acid-based monomer such as acrylic acid, methacrylic acid, α-hydroxyacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and citraconic acid A polymer or copolymer using the above as a monomer component is used. Further, in order to improve the performance of detergent builders or detergent additives, improvement studies on the above polymers and copolymers have been actively conducted in recent years (for example, Patent Document 1).

As mentioned above, the performance of detergent builders or detergent additives has been improved by improved research, and those with excellent clay dispersibility, which is an index of mud detergency, and surfactants with the spread of liquid detergents. There is an increasing demand for compatibility with. In addition, from the viewpoint of reducing transportation costs and convenience, highly concentrated type detergents (types with a low water composition ratio) tend to be preferred as liquid detergents, and detergent builders or detergent additives have a surface activity with the polymer. There is an increasing demand for compatibility with other liquid detergent components such as agents. Furthermore, in recent years, from the viewpoint of reducing environmental load and cost, the amount of surfactant used in one washing has tended to decrease, and a detergent builder or a detergent builder who can sufficiently express the detergency of fats caused by body stains. Detergent additives are required.

Japanese Unexamined Patent Publication No. 2012-132007

As a result of diligent studies to solve the above problems, the applicant has excellent clay dispersibility, excellent compatibility with surfactants, and dissolution of fats in the copolymer having a specific structure. We have found that it is also excellent in solubilizing power, which is an ability, and have completed the present invention.

That is, an object of the present invention is to provide a detergent builder or a detergent additive having excellent clay dispersibility, excellent compatibility with a surfactant, and excellent solubilizing power, which is the ability to dissolve fats. It is in. Another object of the present invention is to provide a detergent composition containing a copolymer which can be suitably used for such a detergent builder or a detergent additive.

Detergent builders or detergent additives according to embodiments of the present invention
A copolymer containing a structural unit (I) represented by the general formula (I) and a structural unit (II) represented by the general formula (II).
Has a sulfide bond and
The average number of moles n of oxyalkylene groups represented by AO in the general formula (II) is 11 or more.

(In the general formula ^{(I), R 1 ~ R} 3 are each independently a hydrogen atom, a methyl group, or _- represents a _(CH 2) z COOM groups, _{- (CH} 2) z COOM group -COOX group Alternatively, it may form an anhydride with another − (CH ₂ ) _z COOM group, z is an integer of 0 to 2, and M is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an organic substance. Represents an ammonium group or an organic amine group, where X represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.)

(In the general formula (II), R ⁴ and R ⁵ independently represent a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and AO represents a hydrocarbon group. , Represents an oxyalkylene group having 2 to 18 carbon atoms, and x is an integer of 0 to 2.)

The detergent composition according to the embodiment of the present invention
A detergent composition containing 0.01% by weight to 10% by weight of a copolymer, 1% by weight to 70% by weight of a surfactant, and alcohol.
The copolymer is a copolymer containing a structural unit (I) represented by the general formula (I) and a structural unit (II) represented by the general formula (II).
Has a sulfide bond and
The average number of moles n of oxyalkylene groups represented by AO in the general formula (II) is 11 or more.
Detergent composition.

(In the general formula ^{(I), R 1 ~ R} 3 are each independently a hydrogen atom, a methyl group, or _- represents a _(CH 2) z COOM groups, _{- (CH} 2) z COOM group -COOX group Alternatively, it may form an anhydride with another − (CH ₂ ) _z COOM group, z is an integer of 0 to 2, and M is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an organic substance. Represents an ammonium group or an organic amine group, where X represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.)

(In the general formula (II), R ⁴ and R ⁵ independently represent a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and AO represents a hydrocarbon group. , Represents an oxyalkylene group having 2 to 18 carbon atoms, and x is an integer of 0 to 2.)

According to an embodiment of the present invention, there is provided a detergent builder or a detergent additive having excellent clay dispersibility, excellent compatibility with a surfactant, and excellent solubilizing power, which is the ability to dissolve fats. be able to. In addition, it is possible to provide a detergent composition containing a copolymer that can be suitably used for such a detergent builder or a detergent additive.

In the present specification, the expression "(meth) acrylic" means "acrylic and / or methacrolein", and the expression "(meth) acrylate" means "acrylate and / or methacrylate". When the expression "(meth) allyl" is used, it means "allyl and / or methacrolein", and when the expression "(meth) acrolein" is used, "acrolein and / or methacrolein" is used. It means "rain". In addition, when the expression "acid (salt)" is used in the present specification, it means "acid and / or a salt thereof". In addition, when the expression "mass" is used in the present specification, it may be read as "weight" which is generally used as a unit of weight, and conversely, "weight" is used in the present specification. When there is an expression of, it may be read as "mass" which is commonly used as an SI system unit indicating weight.

In the present specification, the content ratio of the structural unit (I) represented by the general formula (I) is-even when it is in the form of an acid type (that is, a carboxylate such as -COONa-". Calculated as the carboxylic acid form of COOH). However, in the ratio (content ratio) of the structural units of the copolymer structure shown in the tables of Examples and Comparative Examples, the content ratio of the structural unit (I) represented by the general formula (I) is the salt type (-). Calculated as a form of carboxylate such as COONa).

Further, in the present specification, the content ratio of the structural unit derived from various monomers is the ratio of the amount used (charged amount) of each of the various monomers, as it is, of the structural unit derived from the various monomers. The content ratio.

≪Detergent builder or detergent additive≫
The detergent builder or detergent additive according to the embodiment of the present invention has a copolymer weight including a structural unit (I) represented by the general formula (I) and a structural unit (II) represented by the general formula (II). It is a coalescence, has a sulfide bond, and has an average number of moles n of oxyalkylene groups represented by AO in the general formula (II) of 11 or more.

The detergent builder or detergent additive is a copolymer containing a structural unit (I) and a structural unit (II). As such a copolymer, a copolymer obtained by any suitable method can be adopted as long as the effect of the present invention is not impaired.

The structural unit (I) may be only one type or two or more types. The unsaturated carboxylic acid-based monomer represented by the general formula (1) may be only one kind or two or more kinds.

The structural unit (II) may be of only one type or of two or more types. The unsaturated polyalkylene glycol ether-based monomer represented by the general formula (2) may be of only one type or of two or more types.

As described above, the detergent builder or detergent additive is a copolymer containing the structural unit (I) and the structural unit (II), and any suitable method is used as long as the effects of the present invention are not impaired. The copolymer obtained by can be adopted. For example, a monomer component containing an unsaturated carboxylic acid-based monomer represented by the general formula (1) and an unsaturated polyalkylene glycol ether-based monomer represented by the general formula (2) is copolymerized. The obtained copolymer can be adopted. In this case, the structural unit (I) is a structural unit derived from an unsaturated carboxylic acid-based monomer represented by the general formula (1), and the structural unit (II) is represented by the general formula (2). It is a structural unit derived from an unsaturated polyalkylene glycol ether-based monomer. However, the detergent builder or detergent additive may be a copolymer obtained by such a non-copolymerization method.

In the general formula (I) and the general formula (1), R ¹ to R ³ represent the same or different hydrogen atom, methyl group, or-(CH ₂ ) _z COM group. - _{(CH 2)} z COOM group -COOX groups or other _- may form a _(CH 2) z COOM groups and anhydride. z is an integer of 0 to 2.

R ¹ to R ³ are preferably hydrogen atoms or methyl groups independently of each other.

M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.

X represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.

Examples of the unsaturated carboxylic acid-based monomer represented by the general formula (1) include monocarboxylic acid-based monomers such as (meth) acrylic acid and crotonic acid or salts thereof; maleic acid, itaconic acid, and the like. Dicarboxylic acid-based monomers such as fumaric acid or salts thereof; anhydrides of dicarboxylic acid-based monomers such as maleic acid, itaconic acid, and fumaric acid or salts thereof; and the like. Examples of the salt referred to here include alkali metal salts, alkaline earth metal salts, ammonium salts, organic ammonium salts, and organic amine salts.

The content ratio of the monocarboxylic acid-based monomer or a salt thereof in the unsaturated carboxylic acid-based monomer represented by the general formula (1) is preferably 30 in that the effect of the present invention can be more exhibited. It is from mass% to 100% by mass, more preferably 50% by mass to 100% by mass, further preferably 70% by mass to 100% by mass, particularly preferably 90% by mass to 100% by mass, and most preferably. Is substantially 100% by mass.

Examples of the alkali metal salt include lithium salt, sodium salt, potassium salt and the like. Examples of the alkaline earth metal salt include calcium salt and magnesium salt.

Examples of the organic ammonium salt include methylammonium salt, ethylammonium salt, dimethylammonium salt, diethylammonium salt, trimethylammonium salt, triethylammonium salt and the like.

Examples of the organic amine salt include ethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt, triisopropanolamine salt, hydroxyethyldiisopropanolamine salt, dihydroxyethylisopropanolamine salt, and tetrakis (dihydroxyethylisopropanolamine salt). Examples thereof include alkanolamine salts such as 2-hydroxypropyl) ethylenediamine and pentax (2-hydroxypropyl) diethylenetriamine. Among these, preferably diisopropanolamine salt, triisopropanolamine salt, hydroxyethyldiisopropanolamine salt, tetrakis (2-hydroxypropyl) ethylenediamine salt, pentakis (2-hydroxypropyl) diethylenetriamine salt are preferable. Triisopropanolamine salt and hydroxyethyldiisopropanolamine salt.

The unsaturated carboxylic acid-based monomer represented by the general formula (1) is preferably (meth) acrylic acid, maleic acid, or maleic anhydride in that the effects of the present invention can be further exhibited. More preferably, it is acrylic acid or methacrylic acid.

In structural unit (II) and general formula (2), R ⁴ and R ⁵ represent the same or different hydrogen atoms or methyl groups.

In the structural unit (II) and the general formula (2), R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms (aliphatic alkyl group and alicyclic alkyl group), an alkenyl group having 1 to 30 carbon atoms, and a carbon atom number. Examples thereof include an alkynyl group having 1 to 30 and an aromatic group having 6 to 30 carbon atoms. The effect of the present invention in terms which can be further expressed, R ³ is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably, carbon hydrogen atom or 1 to 12 carbon atoms It is a hydrogen group, more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

In the structural unit (II) and the general formula (2), AO is an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 8 carbon atoms, and more preferably an oxyalkylene group having 2 to 8 carbon atoms. It is 2 to 4 oxyalkylene groups. When the AO is any two or more types selected from an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxystyrene group, etc., the addition form of AO is random addition, block addition, alternate addition, etc. It may be in any form of. From the viewpoint of further exhibiting the effects of the present invention, it is preferable that the oxyethylene group contains an oxyethylene group as an essential component, and 50 mol% or more of the total oxyalkylene group is an oxyethylene group. It is more preferable that 90 mol% or more of the total oxyalkylene group is an oxyethylene group, and 100 mol% or more of the total oxyalkylene group is particularly preferably an oxyethylene group.

In the structural unit (II) and the general formula (2), n represents the average number of moles of oxyalkylene group represented by AO (sometimes referred to as "chain length"). In the detergent builder or detergent additive, n is 11 or more, preferably 11 to 500, preferably 13 to 200, more preferably 15 to 200, and further. The number is preferably 18 to 100, particularly preferably 20 to 74, and most preferably 40 to 60. When n is within the above range, the clay dispersibility can be improved, the compatibility with the surfactant can be improved, and the solubilizing power, which is the ability to dissolve fats, can be improved. Detergent builder or detergent additive Can be obtained.

In the structural unit (II) and the general formula (2), x is an integer of 0 to 2.

Examples of the unsaturated polyalkylene glycol ether-based monomer represented by the general formula (2) include vinyl alcohol, (meth) allyl alcohol, 3-methyl-3-butene-1-ol, and 3-methyl-2. Average alkylene oxide to any of -butene-1-ol, 2-methyl-3-butene-2-ol, 2-methyl-2-butene-1-ol, and 2-methyl-3-butene-1-ol It is a compound in which 1 mol to 500 mol is added, preferably a compound in which an average of 1 mol to 500 mol of alkylene oxide is added to 3-methyl-3-butene-1-ol, and an average of 1 mol to 1 mol to alkylene oxide is added to metallic alcohol. It is a compound to which 500 mol is added.

In the detergent builder or detergent additive, the content ratio of the structural unit (I) in the copolymer which is the detergent builder or detergent additive is preferably 1% by mass to 50% by mass, more preferably. Is 1% by mass to 40% by mass, more preferably 1% by mass to 35% by mass, and particularly preferably 2% by mass to 30% by mass. When the content ratio of the structural unit (I) in the detergent builder or the copolymer which is an additive for detergent is within the above range, the clay dispersibility can be improved, the compatibility with the surfactant can be improved, and the fat. Detergent builders or detergent additives may be obtained that may be superior to the solubilizing power, which is the ability of the minutes to dissolve.

In the detergent builder or detergent additive, the content ratio of the structural unit (II) in the copolymer which is the detergent builder or detergent additive is preferably 50% by mass to 99% by mass, more preferably. Is 60% by mass to 99% by mass, more preferably 65% by mass to 99% by mass, and particularly preferably 70% by mass to 98% by mass. The content ratio of the structural unit (II) derived from the unsaturated polyalkylene glycol ether-based monomer represented by the general formula (2) in the detergent builder or the detergent additive is within the above range. For example, a detergent builder or a detergent additive can be obtained which can be excellent in clay dispersibility, can be excellent in compatibility with a surfactant, and can be excellent in solubilizing power which is the ability to dissolve fats.

In the detergent builder or detergent additive, the total content ratio of the structural unit (I) and the structural unit (II) in the copolymer which is the detergent builder or the detergent additive is preferably 50% by mass. It is ~ 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 90% by mass to 100% by mass, particularly preferably 95% by mass to 100% by mass, and most preferably substantial. It is 100% by mass. If the total content ratio of the structural unit (I) and the structural unit (II) in the detergent builder or the copolymer which is the detergent additive is within the above range, the clay dispersibility can be improved and the surfactant can be obtained. It is possible to obtain a detergent builder or a detergent additive which can be excellent in compatibility with and can be excellent in solubilizing power which is the ability to dissolve fats.

A copolymer that is a detergent builder or a detergent additive may have a structural unit (III) derived from another monomer (3) in addition to the structural unit (I) and the structural unit (II). Good.

Examples of the other monomer (3) include the unsaturated carboxylic acid-based monomer represented by the general formula (1) and the unsaturated polyalkylene glycol ether-based monomer represented by the general formula (2). It is a polymerizable monomer. The other monomer (3) may be only one kind or two or more kinds.

As the other monomer (3), any suitable monomer can be adopted as long as the effect of the present invention is not impaired. Examples of such other monomer (3) include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; methyl (meth) acrylate and glycidyl (meth) acrylate. Esters of unsaturated monocarboxylic acids such as, and alcohols having 1 to 30 carbon atoms; various (alkoxy) (poly) alkylenes such as polyethylene glycol mono (meth) acrylate and methoxy (poly) ethylene glycol mono (meth) acrylate. Glycol mono (meth) acrylates; Half esters of unsaturated dicarboxylic acids such as (anhydrous) maleic acid, fumaric acid, and itaconic acid with alcohols having 1 to 30 carbon atoms; (anhydrous) maleic acid, fumaric acid, itacone. Diesters of unsaturated dicarboxylic acids such as acids and alcohols having 1 to 30 carbon atoms; halfamides of the unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms; the unsaturated dicarboxylic acids and carbon atoms. Diamides with 1 to 30 amines; half esters of alkyl (poly) alkylene glycols with an average of 1 to 500 mol of alkylene oxides with 2 to 18 carbon atoms added to the alcohols and amines and unsaturated dicarboxylic acids. Diesters of alkyl (poly) alkylene glycols obtained by adding an average of 1 to 500 mol of an alkylene oxide having 2 to 18 carbon atoms to the alcohol or amine; the unsaturated dicarboxylic acids and the number of carbon atoms; Half esters of 2 to 18 glycols or polyalkylene glycols having an average addition molar number of 2 to 500 of these glycols; the unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or the average addition moles of these glycols. Diesters with 2 to 500 polyalkylene glycols; halfamides of maleamic acid with glycols with 2 to 18 carbon atoms or polyalkylene glycols with an average addition molar number of 2 to 500 of these glycols; (poly) ethylene glycol (Poly) alkylene glycol di (meth) acrylates such as di (meth) acrylate and (poly) propylene glycol di (meth) acrylate; polyfunctional such as hexanediol di (meth) acrylate and trimethyl propantri (meth) acrylate. (Meta) acrylates; (Poly) alkylene glycol dimalay such as polyethylene glycol dimalate G: Vinyl sulfonate, (meth) allyl sulfonate, 2-methylpropanesulfonic acid (meth) acrylamide, unsaturated sulfonic acid (salt) such as styrenesulfonic acid; and unsaturated monocarboxylic acid such as methyl (meth) acrylamide. Amides with amines having 1 to 30 carbon atoms; Vinyl aromatics such as styrene, α-methylstyrene and vinyltoluene; Alcandiol mono (meth) acrylates such as 1,4-butanediol mono (meth) acrylate Dienes such as butadiene and isoprene; unsaturated amides such as (meth) acrylic (alkyl) amides, N-methylol (meth) acrylamides, N, N-dimethyl (meth) acrylamides; unsaturated amides such as (meth) acrylonitrile Cyanides; unsaturated esters such as vinyl acetate; unsaturated amines such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, vinyl pyridine; divinyl aromatics such as divinylbenzene; (meth) Allyls such as allyl alcohol and glycidyl (meth) allyl ether; vinyl ethers such as (methoxy) polyethylene glycol monovinyl ether; (meth) allyl ethers such as (methoxy) polyethylene glycol mono (meth) allyl ether; and the like. ..

In the detergent builder or the detergent additive, the content ratio of the structural unit (III) derived from the other monomer (3) in the copolymer which is the detergent builder or the detergent additive is preferably 0% by mass. % To 50% by mass, more preferably 0% by mass to 40% by mass, further preferably 0% by mass to 30% by mass, particularly preferably 0% by mass to 20% by mass, and most preferably. It is 0% by mass to 10% by mass. If the content ratio of the structural unit (III) derived from the other monomer (3) in the detergent builder or the copolymer which is the detergent additive is within the above range, the clay dispersibility can be improved and the surface activity can be improved. Detergent builders or detergent additives may be obtained that may be superior in compatibility with the agent and in solubilizing power, which is the ability to dissolve fats.

Detergent builders or detergent additives have sulfide bonds in their structure. Here, the sulfide bond is a bond represented by —S—. Detergent builder or detergent additive has a sulfide bond in its structure, so that it can be more excellent in clay dispersibility, more excellent in compatibility with surfactants, and solubilizing power which is the ability to dissolve fats. A better detergent builder or detergent additive may be obtained.

The number of sulfide bonds in the structure of the detergent builder or the detergent additive may be only one or two or more.

The sulfide bond in the structure of the detergent builder or detergent additive is preferably obtained through a polymerization step in the presence of a mercapto group-containing compound.

The mercapto group-containing compound may have a carboxylic acid group, a hydroxyl group, a sulfonic acid group, an amino group, a cationic group, or the like as a functional group. The functional group is preferably a carboxylic acid group. The functional group may be only one kind or two or more kinds.

Examples of the mercapto group-containing compound include thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiosuccinic acid, thioalinic acid, mercaptoacetic acid, 2-mercaptoethanol, and sodium 3-mercapto-1-propanesulfonate. Examples include cysteine and salts thereof. The mercapto group-containing compound may be only one kind or two or more kinds.

The content ratio of various structural units in the copolymer can be known, for example, by various structural analyzes of the copolymer (for example, NMR). Further, it may be calculated based on the content ratio of various monomers used in producing the copolymer without performing various structural analyzes as described above. In this case, the reaction rate may be considered if necessary.

The polyethylene glycol-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography of a detergent builder or a copolymer as a detergent additive is preferably 5000 or more, more preferably 7000 to 200,000. , More preferably 8000 to 180,000, particularly preferably 8000 to 100,000, further preferably 8000 to 80,000, and most preferably 8000 to 60000. If the weight average molecular weight (Mw) in terms of polyethylene glycol obtained by gel permeation chromatography of a detergent builder or a copolymer as a detergent additive is within the above range, the clay dispersibility can be improved and the surface activity can be improved. Detergent builders or detergent additives may be obtained that may be superior in compatibility with the agent and in solubilizing power, which is the ability to dissolve fats.

The builder for detergent or the copolymer as an additive for detergent can be obtained by any appropriate method as long as the effect of the present invention is not impaired. Such a method preferably includes an unsaturated carboxylic acid-based monomer represented by the general formula (1) and an unsaturated polyalkylene glycol ether-based monomer represented by the general formula (2). It is obtained by copolymerizing a monomer component in the presence of a mercapto group-containing compound. According to such a method, it is a copolymer containing the structural unit (I) represented by the general formula (I) and the structural unit (II) represented by the general formula (II), and has a sulfide bond. A detergent builder or a detergent additive having an average addition mole number n of an oxyalkylene group represented by AO in the general formula (II) of 11 or more can be easily obtained.

The mercapto group-containing compound can mainly act as a chain transfer agent in the polymerization step. Examples of the mercapto group-containing compound include thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiosuccinic acid, thioalinic acid, mercaptoacetic acid, 2-mercaptoethanol, and sodium 3-mercapto-1-propanesulfonate. Examples include cysteine and salts thereof. The mercapto group-containing compound may be only one kind or two or more kinds.

The mercapto group-containing compound is preferably a mercapto group-containing compound having a carboxyl group. By using a mercapto group-containing compound having a carboxyl group as the mercapto group-containing compound, it is possible to obtain excellent clay dispersibility, excellent compatibility with a surfactant, and excellent solubilization ability, which is the ability to dissolve fats. Obtaining Detergent Builders or Detergent Additives can be obtained.

When a mercapto group-containing compound having a carboxyl group is used as the mercapto group-containing compound, the mercapto group-containing compound can mainly act as a chain transfer agent, and therefore is preferably a builder for detergents or a copolymer which is an additive for detergents. One of the ends of the main chain of can be a carboxyl group via a sulfide bond.

The amount of the mercapto group-containing compound used is preferably 0.3 mol to 30 mol, more preferably 0.4 mol to 25 mol, based on 100 mol of the monomer (total monomer) used. Yes, more preferably 0.5 mol to 20 mol, most preferably 0.7 mol to 10 mol. When the amount of the mercapto group-containing compound used is within the above range, the detergent dispersibility can be improved, the compatibility with the surfactant can be improved, and the solubilizing power, which is the ability to dissolve fats, can be obtained. Alternatively, detergent additives can be obtained.

In the polymerization step in the presence of the mercapto group-containing compound, another chain transfer agent may be used in combination in addition to the mercapto group-containing compound. Examples of such other chain transfer agents include thiol-based chain transfer agents other than the above-mentioned mercapto group-containing compounds such as n-dodecyl mercaptan and octyl mercaptan; and carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane and the like. Halogens; secondary alcohols such as isopropanol and glycerin; phosphite, hypophosphate, hypophosphate (sodium bisulfite, potassium hypophosphate, etc.), hydrates thereof, etc. , Phosphates (salts); sodium bisulfite, bisulfite, metabisulfite, these salts (sodium bisulfite, potassium bisulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, meta Sodium bisulfite (salts) such as potassium bisulfite; etc.; The other chain transfer agent may be only one kind or two or more kinds.

The amount of the other chain transfer agent used is preferably 0 g to 10 g with respect to 1 mol of all the monomer components. When the amount of the other chain transfer agent used is within the above range, the clay dispersibility can be improved, the compatibility with the surfactant can be improved, and the solubilizing power, which is the ability to dissolve fats, can be obtained. Additives for builders or detergents may be obtained.

When obtaining a copolymer for a detergent builder or a detergent additive by copolymerization, a polymerization initiator is preferably used. The polymerization initiator may be only one kind or two or more kinds.

Examples of the polymerization initiator include hydrogen peroxide; persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; 2,2'-azobis (2-amidinopropane) hydrochloride, and 4,4'-azobis-. Azo compounds such as 4-cyanopalelic acid, azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, peracetic acid, di- Organic peroxides such as t-butyl peroxide and cumene hydroperoxide; and the like can be mentioned.

When a copolymer which is a builder for a detergent or an additive for a detergent is obtained by copolymerization, hydrogen peroxide, a persulfate, and an azo compound are used as a polymerization initiator in that the effects of the present invention can be further exhibited. It is preferable to employ at least one selected from the group consisting of compounds, and it is more preferable to employ persulfate and hydrogen peroxide.

The content of at least one selected from the group consisting of hydrogen peroxide, persulfate, and azo compounds in the total amount of the polymerization initiator used to obtain the copolymer for the detergent builder or the additive for the detergent. The ratio is preferably 80% by mass to 100% by mass, more preferably 85% by mass to 100% by mass, further preferably 90% by mass to 100% by mass, and particularly preferably 95% by mass to 100% by mass. %, Most preferably substantially 100% by mass.

Hydrogen peroxide can be used in any suitable form, for example, in the form of an aqueous solution or in the form of a complex with another compound. In producing a detergent builder or a copolymer as a detergent additive, it is preferable to use hydrogen peroxide in the form of an aqueous solution. By using hydrogen peroxide in the form of an aqueous solution, it is possible to obtain better clay dispersibility, better compatibility with surfactants, and better solubilizing power, which is the ability to dissolve fats. For detergent builders or detergents. Additives can be obtained.

When hydrogen peroxide is used in the polymerization step in the presence of a mercapto group-containing compound, the hydrogen peroxide can act as a polymerization initiator, and thus is preferably a detergent builder or a copolymer which is an additive for detergent. One of the ends of the main chain can be a hydroxyl group. In addition, when hydrogen peroxide is used in the polymerization step in the presence of a mercapto group-containing compound, the hydrogen peroxide does not contain a dispersibility inhibitor (for example, sulfate ion). The copolymer, which is an additive for use, can be excellent in stability at low temperatures.

The amount of the polymerization initiator used to obtain the builder for detergent or the copolymer as an additive for detergent may be any appropriate amount as long as the copolymerization of the monomer component can be initiated. .. Such an amount is preferably 0.1 mol to 30 mol, more preferably 0.1 mol to 20 mol, still more preferably 0.1 mol, based on 100 mol of the total monomer component. ~ 10 mol.

The polymerization initiator may be used in combination with a reducing agent. The reducing agent may be only one kind or two or more kinds.

Examples of the reducing agent include ascorbic acid, ascorbic acid salt, erythorbic acid, erythorbic acid salt, ascorbic acid ester, formic acid, formate, oxalic acid, oxalate, and hydroquinone. The "salt" here is a carboxyl group salt represented by COOM, and M is a hydrogen atom, a metal atom, an ammonium group (consisting of an ammonium salt), or an organic amino group (consisting of an organic amine salt). is there. Examples of the metal atom include alkali metals such as sodium and potassium, alkaline earth metals such as calcium, and transition metals such as iron. Examples of the organic amine salt include primary to quaternary amine salts such as methylamine salt, n-butylamine salt, monoethanolamine salt, dimethylamine salt, diethanolamine salt, morpholine salt and trimethylamine salt. Among these, the reducing agent is preferably ascorbic acid, ascorbic acid salt, erythorbic acid, or erythorbic acid salt, and more preferably L-ascorbic acid or L-ascorbic acid salt.

As the reducing agent, an inorganic compound reducing agent may be used. Examples of the reducing agent for the inorganic compound include heavy metal ions (heavy metal salts). Examples of such heavy metal ions (heavy metal salts) include ions such as iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, and ruthenium; sodium sulfite. Sulfites such as sodium; Heavy sulfites such as sodium hydrogen sulfite; Dithionate such as sodium dithionite; Hypophosphorous acid such as sodium hypophosphate; Hypophosphates such as sodium bisulfite; Boron Compounds; and the like.

By using the reducing agent in combination with the polymerization initiator, the clay dispersibility can be improved, the compatibility with the surfactant can be improved, and the solubilizing power, which is the ability to dissolve fats, can be improved. For detergent builders or detergents. Additives can be obtained.

The amount of the reducing agent used is preferably 0 mol to 20 mol, more preferably 0.1 mol to 15 mol, and further 0, based on 100 mol of the total monomer component. . 1 mol to 10 mol. When the amount of the reducing agent used is within the above range, the clay dispersibility can be improved, the compatibility with the surfactant can be improved, and the solubilizing power, which is the ability to dissolve fats, can be improved. Detergents can be obtained.

An unsaturated carboxylic acid-based monomer represented by the general formula (1) and an unsaturated polyalkylene represented by the general formula (2), which can be used in the production of a detergent builder or a copolymer as a detergent additive. The amount of the glycol ether-based monomer and, if necessary, the other monomer (3) used is each unit in the total structural unit constituting the copolymer for the detergent builder or the detergent additive. It may be appropriately adjusted so that the ratio of the structural unit derived from the polymer is as described above. Preferably, assuming that the polymerization reaction proceeds quantitatively, at the same ratio as the ratio of the structural units derived from each monomer in the total structural units constituting the above-mentioned detergent builder or the copolymer which is an additive for detergent. , Each monomer may be used.

Copolymerization of monomer components can be performed by any suitable method. For example, solution polymerization and bulk polymerization can be mentioned, and solution polymerization is preferable. Examples of the solution polymerization method include batch type and continuous type.

Solvents that can be used in solution polymerization include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane; and esters such as ethyl acetate. Compounds; ketone compounds such as acetone and methyl ethyl ketone; cyclic ether compounds such as tetrahydrofuran and dioxane; and the like. Among these solvents, from the viewpoint of environmental pollution and the like, it is preferable that 50% by mass or more of the solvent used is water, and the content ratio of water in the solvent used is more preferably 70% by mass to 100% by mass. It is more preferably 90% by mass to 100% by mass, particularly preferably 95% by mass to 100% by mass, and most preferably substantially 100% by mass.

The amount of the solvent used is preferably 20% by mass to 500% by mass, and more preferably 50% by mass to 300% by mass with respect to 100% by mass of the monomer component.

In the production of a detergent builder or a copolymer as a detergent additive, heavy metal ions may be used as a reaction accelerator. The heavy metal ion may be only one kind or two or more kinds.

The heavy metal ion used as a reaction accelerator means a metal having a specific gravity of 4 g / cm ³ or more. Examples of such heavy metal ions include iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium and the like. Among these, the heavy metal ion is preferably iron.

The amount of heavy metal ions that can be used to obtain a detergent builder or a copolymer as a detergent additive is preferably 0.1 ppm to 10 ppm with respect to the total mass of the polymerization reaction solution at the completion of the polymerization reaction. ..

The reaction temperature at the time of copolymerization of the monomer components is appropriately determined depending on the polymerization method, solvent, polymerization initiator, chain transfer agent, etc. used. Such a reaction temperature is preferably 0 ° C. or higher, more preferably 30 ° C. or higher, further preferably 50 ° C. or higher, and preferably 150 ° C. or lower, more preferably 120 ° C. or lower. It is more preferably 100 ° C. or lower.

The copolymerization time at the time of copolymerization of the monomer components is preferably 30 minutes to 800 minutes, more preferably 60 minutes to 700 minutes, and further preferably 120 to 500 minutes.

The pressure in the reaction system during copolymerization of the monomer components may be under normal pressure (atmospheric pressure), under reduced pressure, or under pressure, and may be a combination of two or more of these. Good.

The atmosphere in the reaction system during the copolymerization of the monomer components may be an air atmosphere or an inert atmosphere. The atmosphere in the reaction system during the copolymerization of the monomer components is preferably an inert atmosphere in which the inside of the system is replaced with an inert gas such as nitrogen before the start of polymerization.

Any appropriate method can be adopted as the method for charging the monomer component into the reaction vessel. Examples of such a charging method include a method in which the entire amount is initially charged into the reaction vessel, a method in which the entire amount is divided or continuously charged into the reaction vessel, a part is initially charged into the reaction vessel, and the rest is charged into the reaction vessel. Examples thereof include a method of dividing or continuously feeding. Specifically, a method in which the entire amount of the monomer (a) and the total amount of the monomer (b) are continuously charged into the reaction vessel, and a part of the monomer (a) is initially charged into the reaction vessel. A method in which the rest of the monomer (a) and the total amount of the monomer (b) are continuously charged into the reaction vessel, a part of the monomer (a) and a part of the monomer (b) are put into the reaction vessel. Examples thereof include a method in which the residue of the monomer (a) and the residue of the monomer (b) are alternately charged into the reaction vessel in several batches. Further, by continuously or stepwise changing the charging rate of each polymer into the reaction vessel during the reaction, the charging mass ratio of each monomer per unit time is continuously or stepwise changed. Two or more kinds of copolymers having different ratios of the structural unit (I) and the structural unit (II) may be synthesized at the same time during the polymerization reaction. The polymerization initiator may be charged into the reaction vessel from the beginning, may be added dropwise to the reaction vessel, or these may be combined depending on the intended purpose.

The copolymer, which is a detergent builder or a detergent additive, may be used as it is after being obtained by the above-mentioned production method, or the pH of the reaction solution after production may be 5 or more from the viewpoint of handleability. It may be adjusted to. In the latter case, in order to improve the polymerization rate, it is preferable to carry out the copolymerization at a pH of less than 5, and adjust the pH to 5 or more after the copolymerization. The pH can be adjusted, for example, by using an inorganic salt such as a hydroxide or carbonate of a monovalent metal or a divalent metal; an alkaline substance such as ammonia; an organic amine;

The concentration of the obtained detergent builder or the copolymer as a detergent additive may be adjusted as necessary.

The detergent builder or detergent additive may be a powder detergent builder or a powder detergent additive, or a liquid detergent builder or a liquid detergent additive. The detergent builder or detergent additive is preferably a liquid detergent builder or liquid detergent additive in that the effects of the present invention can be more exhibited.

The above-mentioned copolymer disclosed in the present specification can be used as an additive for various detergents. Detergent builders or detergent additives can be used as additives for various detergents. The term "detergent" as used herein is a concept including a cleaning agent, and the field of use is not limited to household, industrial, medical, agricultural, and the like.

Detergent additives include, for example, anti-adhesion agents, stain inhibitors, soil release agents, color transfer inhibitors, fabric softeners, solubilizers, fluorescent agents, and foaming agents to prevent re-deposition of contaminants. , Foam stabilizers, polishes, bactericides and the like.

≪Detergent composition≫
The detergent composition according to the embodiment of the present invention is a detergent composition containing 0.01% by weight to 10% by weight of a copolymer, 1% by weight to 70% by weight of a surfactant, and alcohol. The copolymer is a copolymer containing a structural unit (I) represented by the general formula (I) and a structural unit (II) represented by the general formula (II), and has a sulfide bond. The average number of moles n of the oxyalkylene group represented by AO in the general formula (II) is 11 or more.

(In the general formula ^{(I), R 1 ~ R} 3 are each independently a hydrogen atom, a methyl group, or _- represents a _(CH 2) z COOM groups, _{- (CH} 2) z COOM group -COOX group Alternatively, it may form an anhydride with another − (CH ₂ ) _z COOM group, z is an integer of 0 to 2, and M is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an organic substance. Represents an ammonium group or an organic amine group, where X represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.)

(In the general formula (II), R ⁴ and R ⁵ independently represent a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and AO represents a hydrocarbon group. , Represents an oxyalkylene group having 2 to 18 carbon atoms, and x is an integer of 0 to 2.)

As the explanation of the copolymer contained in the detergent composition, the explanation of the copolymer mentioned in the section << Detergent builder or detergent additive >> can be used as it is.

The concept of detergent composition is used only for specific applications such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance one of its components. Detergent is also included.

The detergent composition may be a powder detergent composition or a liquid detergent composition. The detergent composition is preferably a liquid detergent composition in that the effects of the present invention can be more exhibited.

The content of the copolymer in the detergent composition is 0.01% by mass to 10% by mass, preferably 0.01, based on the total amount of the detergent composition, from the viewpoint of exhibiting excellent builder performance. It is from mass% to 8% by mass, particularly preferably 0.05% by mass to 6% by mass, and most preferably 0.1% by mass to 5% by mass.

As the copolymer contained in the detergent composition, a detergent builder or a detergent additive according to the embodiment of the present invention may be used.

The detergent composition may contain a surfactant that is usually used in detergents. As the surfactant, any suitable surfactant can be adopted as long as the effects of the present invention are not impaired.

The surfactant may be only one kind or two or more kinds.

The surfactant is typically at least one selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

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, and alkane sulfone. Acid salt, saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acylamino acid type surfactant, alkyl phosphate ester or its salt, alkenyl phosphate Examples include esters or salts thereof. The alkyl group and alkenyl group that the anionic surfactant may have may have an alkyl group such as a methyl group branched.

Examples of nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycolides, and fatty acids. Examples thereof include glycerin monoester and alkylamine oxide. The alkyl group and alkenyl group that the nonionic surfactant may have may have an alkyl group such as a methyl group branched.

Examples of the cationic surfactant include a quaternary ammonium salt and the like. The alkyl group and alkenyl group that the cationic surfactant may have may have an alkyl group such as a methyl group branched.

Examples of the amphoteric surfactant include a carboxyl type amphoteric surfactant and a sulfobetaine type amphoteric surfactant. As the alkyl group and alkenyl group that the amphoteric surfactant can have, an alkyl group such as a methyl group may be branched.

The blending ratio of the surfactant is usually preferably 10% by mass to 70% by mass, more preferably 15% by mass to 65% by mass, still more preferably 18% by mass, based on the total amount of the detergent composition. It is about 60% by mass, and particularly preferably 20% by mass to 55% by mass. If the blending ratio of the surfactant is too small, sufficient detergency may not be exhibited, and if the blending ratio of the surfactant is too large, the economic efficiency may be lowered.

Detergent compositions include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol. Contains alcohols such as monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol. May be good.

The blending ratio of the alcohol as described above is usually preferably 5% by mass to 40% by mass, more preferably 5% by mass to 35% by mass, and further preferably 5 with respect to the total amount of the detergent composition. It is by mass% to 30% by mass, and particularly preferably 10% by mass to 30% by mass.

The detergent composition may contain additives usually used in detergents. As the additive, any suitable additive can be adopted as long as the effect of the present invention is not impaired.

The additive may be only one type or two or more types.

Additives include, for example, anti-redeposition agents for preventing re-deposition of contaminants such as sodium carboxymethyl cellulose, stain inhibitors such as benzotriazole and ethylene-thiourea, soil release agents, anti-color transfer agents, and fabric softeners. Agents, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents, bleaching aids, enzymes, dyes, solvents, etc. Can be mentioned. Further, in the case of a powder detergent composition, it is preferable to add zeolite.

The detergent composition may include any suitable detergent builder (other than that if the copolymer is used as a detergent builder). Examples of such detergent builders include alkali builders such as carbonates, bicarbonates and silicates; tripoliphosphate, pyrophosphate, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, citrate, (meth). ) Chelate builder such as copolymer salt of acrylic acid, acrylic acid-maleic acid copolymer, fumarate, zeolite; carboxyl derivative of polysaccharide such as carboxymethyl cellulose; and the like. Examples of the anti-salt used in the above-mentioned other detergent builders include alkali metals such as sodium and potassium, ammonium and amines.

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

When the detergent composition is a liquid detergent composition, the amount of water contained in the liquid detergent composition is usually 0.1% by mass to 60% by mass, more preferably 0.1% by mass, based on the total amount of the liquid detergent composition. It is preferably 0.2% by mass to 55% by mass, more preferably 0.5% by mass to 50% by mass, still more preferably 0.7% by mass to 40% by mass, and particularly preferably 1% by mass. It is about 35% by mass, and most preferably 1.5% by mass to 30% by mass.

The detergent composition may contain an enzyme. Examples of such an enzyme include protease, lipase, cellulase, amylase and the like.

The blending ratio of the enzyme is usually 5% by mass or less with respect to the total amount of the detergent composition.

Even when the detergent composition is used in a region 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 an excellent cleaning effect can be obtained. This effect is particularly noticeable when the detergent composition contains an anionic surfactant such as LAS.

Detergent compositions can usually be produced with the step of blending the copolymer as essential.

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

<Weight average molecular weight analysis conditions>
The weight average molecular weight was measured under the following measurement conditions.
Equipment: Waters Alliance (2695)
Analysis software: Waters, Emper Professional + GPC option Column used: Tosoh, TSKgel guard column (inner diameter 6.0 mm x 40 mm) + TSKgel G4000SWXL (inner diameter 7.8 mm x 300 mm) + G3000SWXL (inner diameter 7.8 mm x 300 mm) + G2000SWXL (inner diameter 7.8 mm x 300 mm) Inner diameter 7.8 mm x 300 mm)
Detectors: Differential Refractometer (RI) Detector (Waters 2414), Photodiode Array (PDA) Detector (Waters 2996)
Eluent: 115.6 g of sodium acetate trihydrate dissolved in a mixed solvent of 10999 g of water and 6001 g of acetonitrile, and the pH was adjusted to 6.0 with acetic acid. GPC standard sample: Polyethylene glycol manufactured by GL Science (peak top molecular weight (peak top molecular weight (peak top molecular weight)) Mp) 272500, 219300, 107000, 50000, 24000, 11840, 6450, 4250, 1470)
Calibration curve: Prepared by a cubic formula using the Mp value of the above polyethylene glycol.
Flow rate: 1.0 mL / min Column temperature: 40 ° C
Measurement temperature: 40 ° C
Measurement time: 45 minutes Sample solution injection volume: 100 μL (eluent solution with a sample concentration of 0.5% by mass)
Standard sample injection volume: 100 μL (eluent solution with a concentration of 0.1% by mass)

<Clay dispersibility test>
Calcium chloride dihydrate: 5.90 g and magnesium chloride hexahydrate: 2.72 g were weighed in a beaker, and pure water was added to make 1000 g (buffer (1)). Next, sodium hydrogen carbonate: 0.077 g, 0.1 N hydrogen chloride, and buffer (1): 50 g were placed in a beaker and diluted with ion-exchanged water to make 1000 g (buffer (2)).
The polymer solutions obtained in Examples and Comparative Examples were diluted to 0.1% by mass to prepare a 0.1% by mass polymer aqueous solution (diluted solution). Clay in a test tube (manufactured by Japan Powder Industry Technology Association, 11 types of JIS test powder Kanto loam): 0.075 g, 0.1 mass% polymer aqueous solution: 0.25 g, buffer (2): 29.75 g After putting in, it was sealed. The test tube was shaken 30 times to evenly disperse the clay. Then, the mixture was left to stand for 1 hour, 4 cc of the supernatant of the dispersion was weighed, and the absorbance was measured with a UV spectroscope (Shimadzu Corporation, UV-1200, 1 cm cell, wavelength 575 nm).
The judgment criteria were as follows.
◯: Absorbance 2 or more ×: Absorbance less than 2

<Evaluation of compatibility with surfactant solution>
Emargen 108 (manufactured by Kao Corporation) and Neoperex G-65 (manufactured by Kao Corporation) were used as surfactants to prepare a surfactant solution having the following composition.

The polymer solutions obtained in Examples and Comparative Examples were added to 10 g of the above-mentioned surfactant solution so as to have a concentration of 3.9% by mass, the appearance was confirmed, and the compatibility was judged according to the following criteria.
◯: Transparent ×: White turbidity or precipitation

<Solubilization test>
Sudan III: 0.01 g, 1 mass% polymer solution: 0.1 g, 3% Emargen 108 (manufactured by Kao Corporation) solution: 0.833 g was weighed. It was diluted with ion-exchanged water so that the total amount was 50 g. After leaving it for 24 hours, the absorbance was measured with a UV spectroscope (Shimadzu Corporation, UV-1200, 1 cm cell).
The judgment criteria were as follows.
◯: Absorbance 1.05 or more ×: Absorbance less than 1.05

[Example 1]
An unsaturated flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel with an average of 50 mol of ethylene oxide added to 80% by mass of 3-methyl-3-butene-1-ol. An aqueous solution of polyalkylene glycol ether (MB-50): 221.24 g and ion-exchanged water: 102.9 g were charged, and after nitrogen substitution, the temperature was raised to 58 ° C. with stirring. When the temperature reached a predetermined temperature, 3.8% by mass of ammonium persulfate (APS) aqueous solution: 20 g, 100% by mass of acrylic acid (AA): 10.2 g, 1.36% by mass of L-ascorbic acid (L). -As) Aqueous solution: 11.4 g, 5% by mass of mercaptopropionic acid (MPA) aqueous solution: 9.9 g was added dropwise. However, the AA, L-As aqueous solution, and APS aqueous solution were added dropwise over 300 minutes, and the MPA was added dropwise over 330 minutes. After the completion of dropping the MPA aqueous solution, the mixture is aged at the same temperature for 30 minutes to complete the polymerization, and after the polymerization, 49% by mass of KOH aqueous solution: 4.56 g is added to obtain an aqueous solution of the water-soluble copolymer (1). It was. The weight average molecular weight of the obtained water-soluble copolymer (1) was 29000, the solid content was 50.1% by mass, and the pH was 5.6.
Various evaluations were carried out using the obtained water-soluble copolymer (1) as a detergent builder or a detergent additive.
The results are shown in Table 2. In Table 2, "SA" means a salt of acrylic acid (AA) (hereinafter, the same applies).

[Example 2]
In a 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel, 181.72 g of an 80 mass% MB-50 aqueous solution and 118.4 g of ion-exchanged water were charged, and after nitrogen substitution. The temperature was raised to 60 ° C. with stirring. When the temperature reached a predetermined temperature, 0.65 g of 35% by mass hydrogen peroxide solution (H ₂ O ₂ ) was added all at once. Then, 100% by mass of AA: 19.7 g, 2.3% by mass of L'As aqueous solution: 13.2 g, and 2.9% by mass of MPA acid aqueous solution: 28.8 g were added dropwise. However, AA was added dropwise over 180 minutes, and the L'As aqueous solution and the MPA aqueous solution were added dropwise over 210 minutes. After the completion of dropping the L-As aqueous solution, the mixture is aged at the same temperature for 60 minutes to complete the polymerization. After the polymerization, 49% by mass of the NaOH aqueous solution: 17.5 g is added to obtain an aqueous solution of the water-soluble copolymer (2). Got The weight average molecular weight of the obtained water-soluble copolymer (2) was 34,000, the solid content was 45.6% by mass, and the pH was 6.6.
Various evaluations were carried out using the obtained water-soluble copolymer (2) as a detergent builder or a detergent additive. The results are shown in Table 2.

[Example 3]
80% by mass MB-50 aqueous solution: 260.2 g and ion-exchanged water: 66.6 g were charged in a 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel, and after nitrogen replacement. The temperature was raised to 58 ° C. with stirring. When the temperature reached a predetermined temperature, 0.57 g of 35% by mass hydrogen peroxide solution (H ₂ O ₂ ) was added all at once. Then, 100% by mass of AA: 14.8 g, 1.6% by mass of L'As aqueous solution: 16.7 g, and 3.5% by mass of MPA aqueous solution: 17.4 g were added dropwise. However, AA was added dropwise over 180 minutes, and the L'As aqueous solution and the MPA aqueous solution were added dropwise over 210 minutes. After the completion of dropping the L-As aqueous solution, the mixture is aged at the same temperature for 60 minutes to complete the polymerization. After the polymerization, a 49% by mass NaOH aqueous solution: 3.69 g is added to obtain an aqueous solution of the water-soluble copolymer (3). Got The weight average molecular weight of the obtained water-soluble copolymer (3) was 32,000, the solid content was 59.7% by mass, and the pH was 6.3.
Various evaluations were carried out using the obtained water-soluble copolymer (3) as a detergent builder or a detergent additive. The results are shown in Table 2.

[Example 4]
80% by mass MB-50 aqueous solution: 235.4 g and ion-exchanged water: 81.6 g were placed in a 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel, and after nitrogen replacement. The temperature was raised to 57 ° C. with stirring. When the temperature reached a predetermined temperature, 35% by mass of hydrogen peroxide solution (H ₂ O ₂ ): 0.38 g was added all at once. Then, 100% by mass of AA: 5.62 g, 2-hydroxyethyl acrylate (HEA): 13.6 g, 0.98% by mass of L'As aqueous solution: 19.4 g, 1.6% by mass of MPA aqueous solution: 21.0 g of each was added dropwise. However, AA and HEA were added dropwise over 180 minutes, and the L'As aqueous solution and the MPA aqueous solution were added dropwise over 240 minutes. After the completion of dropping the L-AS aqueous solution, the mixture is aged at the same temperature for 60 minutes to complete the polymerization. After the polymerization, a 49% by mass NaOH aqueous solution: 3.10 g is added to obtain an aqueous solution of the water-soluble copolymer (4). Got The weight average molecular weight of the obtained water-soluble copolymer (4) was 46000, the solid content was 55.6% by mass, and the pH was 6.7.
Various evaluations were carried out using the obtained water-soluble copolymer (4) as a detergent builder or a detergent additive. The results are shown in Table 2.

[Example 5]
In a 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel, 80% by mass of MB-50 aqueous solution: 220.1 g, ion-exchanged water: 81.9 g, molle salt: 0. After charging 0017 g and replacing with nitrogen, the temperature was raised to 60 ° C. with stirring. When the temperature reached a predetermined temperature, 35% by mass of hydrogen peroxide solution (H ₂ O ₂ ): 0.49 g was added all at once. Then, 100% by mass of AA: 23.8 g, 0.6% by mass of L'As aqueous solution: 13.1 g, and 13.8% by mass of MPA aqueous solution: 16.2 g were added dropwise. However, AA was added dropwise over 150 minutes, the L'As aqueous solution was added dropwise over 270 minutes, and the MPA aqueous solution was added dropwise over 210 minutes. After the completion of dropping the L—As aqueous solution, it is aged at the same temperature for 60 minutes to complete the polymerization, and after the polymerization, a 49% by mass NaOH aqueous solution: 23.3 g is added to obtain an aqueous solution of the water-soluble copolymer (5). Obtained. The weight average molecular weight of the obtained water-soluble copolymer (5) was 15,000, the solid content was 55.5% by mass, and the pH was 6.9.
Various evaluations were carried out using the obtained water-soluble copolymer (5) as a detergent builder or a detergent additive. The results are shown in Table 2.

[Example 6]
250 g of ion-exchanged water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube, and a reflux condenser, and the inside of the reaction vessel was replaced with nitrogen under stirring to raise the temperature to 58 ° C. .. Next, an aqueous solution obtained by diluting 80% by mass of MB-50 aqueous solution: 435.6 g and 100% by mass of AA: 51.5 g with ion-exchanged water: 155 g was added dropwise to the reaction vessel over 5 hours. At the same time, an aqueous solution prepared by dissolving 3.19 g of ammonium persulfate in 50.0 g of ion-exchanged water and an aqueous solution prepared by dissolving 0.62 g of LAs and 2.67 g of MPA in 52.9 g of ion-exchanged water. It was added dropwise over 5 hours. Then, the temperature was maintained at 58 ° C. for 1 hour continuously, and the polymerization reaction was completed. Then, the reaction solution was neutralized to pH = 7 with an aqueous sodium hydroxide solution at a temperature equal to or lower than the polymerization reaction temperature to obtain an aqueous solution of the water-soluble copolymer (6) copolymer having a weight average molecular weight of 24,000. ..
Various evaluations were carried out using the obtained water-soluble copolymer (6) as a detergent builder or a detergent additive. The results are shown in Table 2.

[Example 7]
In a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen introduction tube, and reflux condenser, 300 parts of ion-exchanged water, 10 mol of ethylene oxide in 3-methyl-3-buten-1-ol on average. Add 165 parts of unsaturated polyalkylene glycol ether (MB-10) and 430 parts of MB-50: 430 parts, and after raising the temperature to 65 ° C., hydrogen peroxide: 3.3 parts and ion-exchanged water: 6 parts. A hydrogen peroxide aqueous solution containing 2 parts was added. Next, 105 parts of 100% by mass of AA was added dropwise into the reaction vessel over 5 hours, and at the same time, 4.3 parts of LAs and 14.6 parts of MPA were dissolved in 151 parts of ion-exchanged water. The aqueous solution was added dropwise over 5.5 hours. Then, the temperature was maintained at 65 ° C. for 1 hour to complete the polymerization reaction, and an aqueous solution of the water-soluble copolymer (7) was obtained. The weight average molecular weight of the obtained water-soluble copolymer (7) was 8900.
Various evaluations were carried out using the obtained water-soluble copolymer (7) as a detergent builder or a detergent additive. The results are shown in Table 2.

[Example 8]
85 parts of ion-exchanged water, MB-10: 26.4 parts, and MB-50: 172 parts were charged in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube, and a reflux condenser. After raising the temperature to 65 ° C., an aqueous hydrogen peroxide solution containing 1.3 parts of hydrogen peroxide and 2.3 parts of ion-exchanged water was added thereto. Next, 100% by mass of AA: 26.3 parts was added dropwise into the reaction vessel over 5 hours, and at the same time, ion-exchanged water: 68 parts, LAs: 1.0 part and MPA: 3.6 parts. Was added dropwise over 5.5 hours. Then, the temperature was maintained at 65 ° C. for 1 hour to complete the polymerization reaction, and an aqueous solution of the water-soluble copolymer (8) was obtained. The weight average molecular weight of the obtained water-soluble copolymer (8) was 11,300.
Various evaluations were carried out using the obtained water-soluble copolymer (8) as a detergent builder or a detergent additive. The results are shown in Table 2.

[Example 9]
Ion-exchanged water: 86 parts, MB-10: 5.8 parts, MB-50: 176 parts were charged in a glass reaction vessel equipped with a thermometer, agitator, a dropping funnel, a nitrogen introduction tube, and a reflux condenser. After raising the temperature to 65 ° C., an aqueous hydrogen peroxide solution containing 0.6 part of hydrogen peroxide and 1.1 parts of ion-exchanged water was added thereto. Next, 100% by mass of AA: 18.4 parts was added dropwise into the reaction vessel over 5 hours, and at the same time, ion-exchanged water: 59.4 parts, L-As: 0.8 parts and MPA: 2. An aqueous solution in which 6 parts were dissolved was added dropwise over 5.5 hours. Then, the temperature was maintained at 65 ° C. for 1 hour to complete the polymerization reaction, and an aqueous solution of the water-soluble copolymer (9) was obtained. The weight average molecular weight of the obtained water-soluble copolymer (9) was 10900.
Various evaluations were carried out using the obtained water-soluble copolymer (9) as a detergent builder or a detergent additive. The results are shown in Table 2.

[Example 10]
Ion-exchanged water: 104 parts, MB-10: 28.3 parts, MB-50: 166 parts were charged in a glass reaction vessel equipped with a thermometer, agitator, a dropping funnel, a nitrogen introduction tube, and a reflux condenser. After raising the temperature to 65 ° C., an aqueous hydrogen peroxide solution containing 0.9 part of hydrogen peroxide and 1.7 parts of ion-exchanged water was added thereto. Next, 100% by mass of AA: 30.4 parts was added dropwise into the reaction vessel over 5 hours, and at the same time, ion-exchanged water: 81 parts, L-As: 1.2 parts and MPA: 3.0 parts. Was added dropwise over 5.5 hours. Then, the temperature was maintained at 65 ° C. for 1 hour to complete the polymerization reaction, and an aqueous solution of the water-soluble copolymer (10) was obtained. The weight average molecular weight of the obtained water-soluble copolymer (10) was 16000.
Various evaluations were carried out using the obtained water-soluble copolymer (10) as a detergent builder or a detergent additive. The results are shown in Table 2.

[Comparative Example 1]
A 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel is charged with 98 g of ion-exchanged water and 0.003 g of molle salt, and after nitrogen replacement, reaches 85 ° C. with stirring. The temperature was raised. When the temperature reached a predetermined temperature, 80% by mass of AA aqueous solution: 111 g, 80% by mass of MB-10 aqueous solution: 74 g, 12% by mass of NaOH aqueous solution: 20.5 g, 5% by mass of sodium persulfate (NaPS). Aqueous solution: 26.9 g, 3% by mass sodium hydrogen sulfite (SBS) aqueous solution: 13.5 g were added dropwise. The AA aqueous solution and the NaOH aqueous solution were added dropwise over 180 minutes, the MB-10 aqueous solution was added dropwise over 110 minutes, the NaPS aqueous solution was added dropwise over 220 minutes, and the SBS aqueous solution was added dropwise over 210 minutes. The polymer was aged at the same temperature for 30 minutes to complete the polymerization, and after the polymerization, 36 g of a 49% by mass NaOH aqueous solution was added to obtain a water-soluble copolymer (C1). The weight average molecular weight of the obtained water-soluble copolymer (C1) was 90500, and the solid content was 44.1% by mass.
Various evaluations were carried out using the obtained water-soluble copolymer (C1) as a detergent builder or a detergent additive. The results are shown in Table 2.

[Comparative Example 2]
Ion-exchanged water: 104.9 g was charged into a 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel, and after nitrogen substitution, the temperature was raised to 80 ° C. with stirring. When the temperature reaches a predetermined temperature, 80% by mass of AA aqueous solution: 33.8 g, 50% by mass of MB-10 aqueous solution: 126 g, 2% by mass of NaOH aqueous solution: 75 g, 1% by mass of 2,2'-azobis Aqueous solution of (2-methylpropion amidine) dihydrochloride (V-50, manufactured by Wako Co., Ltd.): 24.7 g was added dropwise. The AA aqueous solution and the NaOH aqueous solution were added dropwise over 180 minutes, the MB-10 aqueous solution was added dropwise over 110 minutes, and the V-50 aqueous solution was added dropwise over 210 minutes. The polymer was aged at the same temperature for 30 minutes to complete the polymerization, and after the polymerization, 15.6 g of a 49% by mass NaOH aqueous solution was added to obtain a water-soluble copolymer (C2). The weight average molecular weight of the obtained water-soluble copolymer (C2) was 77400, and the solid content was 25.9% by mass.
Various evaluations were carried out using the obtained water-soluble copolymer (C2) as a detergent builder or a detergent additive. The results are shown in Table 2.

[Comparative Example 3]
Ion-exchanged water: 140 g was charged into a 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel, and after nitrogen substitution, the temperature was raised to 100 ° C. with stirring. When the temperature reaches a predetermined temperature, 80% by mass of AA aqueous solution: 55.9 g, 60% by mass of MB-50 aqueous solution: 74.5 g, 4% by mass of NaOH aqueous solution: 62.1 g, 1% by mass of 2, An aqueous solution of 2'-azobis (2-methylpropionamidine) dihydrochloride (manufactured by Wako Co., Ltd., V-50): 32 g was added dropwise. The AA aqueous solution and the NaOH aqueous solution were added dropwise over 90 minutes, the MB-50 aqueous solution was added dropwise over 55 minutes, and the V-50 aqueous solution was added dropwise over 210 minutes. The polymer was aged at the same temperature for 30 minutes to complete the polymerization, and after the polymerization, 15.5 g of a 49% by mass NaOH aqueous solution was added to obtain a water-soluble copolymer (C3). The weight average molecular weight of the obtained water-soluble copolymer (C3) was 132,000, and the solid content was 25.9% by mass.
Various evaluations were carried out using the obtained water-soluble copolymer (C3) as a detergent builder or a detergent additive. The results are shown in Table 2.

[Comparative Example 4]
In a 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel, 68.7 g of ion-exchanged water and 0.003 g of molle salt were charged, and after nitrogen substitution, 85 while stirring. The temperature was raised to ° C. When the temperature reaches a predetermined temperature, 80% by mass of AA aqueous solution: 64.5 g, 80% by mass of MB-10 aqueous solution: 64.5 g, 2% by mass of NaOH aqueous solution: 71.7 g, 5% by mass of NAPS aqueous solution. : 48.9 g, 3% by mass SBS aqueous solution: 40.7 g were added dropwise. The AA aqueous solution and the NaOH aqueous solution were added dropwise over 180 minutes, the MB-10 aqueous solution was added dropwise over 110 minutes, the NaPS aqueous solution was added dropwise over 220 minutes, and the SBS aqueous solution was added dropwise over 210 minutes. The polymer was aged at the same temperature for 30 minutes to complete the polymerization, and after the polymerization, a 49% by mass NaOH aqueous solution: 20.9 g was added to obtain a water-soluble copolymer (C4). The weight average molecular weight of the obtained water-soluble copolymer (C4) was 23,700, and the solid content was 30.7% by mass.
Various evaluations were carried out using the obtained water-soluble copolymer (C4) as a detergent builder or a detergent additive. The results are shown in Table 2.

[Comparative Example 5]
Ion-exchanged water: 135.5 g was charged into a 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel, and after nitrogen substitution, the temperature was raised to 100 ° C. with stirring. When the temperature reached a predetermined temperature, 80% by mass of AA aqueous solution: 50.2 g, 80% by mass of MB-10 aqueous solution: 50.2 g, 1% by mass of 2,2'-azobis (2-methylpropion amidine). Aqueous solution of dihydrochloride (Wako Co., Ltd., V-50): 95.1 g was added dropwise. The AA aqueous solution was added dropwise over 180 minutes, the MB-10 aqueous solution was added dropwise over 110 minutes, and the V-50 aqueous solution was added dropwise over 210 minutes. The polymer was aged at the same temperature for 30 minutes to complete the polymerization, and after the polymerization, 18.6 g of a 49% by mass NaOH aqueous solution was added to obtain a water-soluble copolymer (C5). The weight average molecular weight of the obtained water-soluble copolymer (C5) was 36,800, and the solid content was 23.9% by mass.
Various evaluations were carried out using the obtained water-soluble copolymer (C5) as a detergent builder or a detergent additive. The results are shown in Table 2.

[Comparative Example 6]
Various evaluations were performed without using detergent builders or detergent additives. The results are shown in Table 2.

The detergent builder or detergent additive according to the embodiment of the present invention can be used in various detergent compositions.

Claims (2)

1. A copolymer containing a structural unit (I) represented by the general formula (I) and a structural unit (II) represented by the general formula (II).
   Has a sulfide bond and
   A detergent builder or a detergent additive having an average addition mole number n of an oxyalkylene group represented by AO in the general formula (II) of 11 or more.
   

   

   (In the general formula ^{(I), R 1 ~ R} 3 are each independently a hydrogen atom, a methyl group, or _- represents a _(CH 2) z COOM groups, _{- (CH} 2) z COOM group -COOX group Alternatively, it may form an anhydride with another − (CH ₂ ) _z COOM group, z is an integer of 0 to 2, and M is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an organic substance. Represents an ammonium group or an organic amine group, where X represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.)
   

   

   (In the general formula (II), R ⁴ and R ⁵ independently represent a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and AO represents a hydrocarbon group. , Represents an oxyalkylene group having 2 to 18 carbon atoms, and x is an integer of 0 to 2.)
2. A detergent composition containing 0.01% by weight to 10% by weight of a copolymer, 1% by weight to 70% by weight of a surfactant, and alcohol.
   The copolymer is a copolymer containing a structural unit (I) represented by the general formula (I) and a structural unit (II) represented by the general formula (II).
   Has a sulfide bond and
   The average number of moles n of oxyalkylene groups represented by AO in the general formula (II) is 11 or more.
   Detergent composition.
   

   

   (In the general formula ^{(I), R 1 ~ R} 3 are each independently a hydrogen atom, a methyl group, or _- represents a _(CH 2) z COOM groups, _{- (CH} 2) z COOM group -COOX group Alternatively, it may form an anhydride with another − (CH ₂ ) _z COOM group, z is an integer of 0 to 2, and M is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an organic substance. Represents an ammonium group or an organic amine group, where X represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.)
   

   

   (In the general formula (II), R ⁴ and R ⁵ independently represent a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and AO represents a hydrocarbon group. , Represents an oxyalkylene group having 2 to 18 carbon atoms, and x is an integer of 0 to 2.)