JP2010229268A - Lactam ring-containing copolymer, and manufacturing method for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copolymer having a more improved anti-soil redeposition capability than conventional detergents when used for detergent application, and having an excellent compatibility with a surfactant; and to provide a method for manufacturing the same. <P>SOLUTION: The copolymer includes a structure originated from a specific lactam ring-containing monomer, and a structure originated from a monomer represented by the formula in the figure, wherein R<SB>1</SB>is hydrogen or a methyl group; R<SB>2</SB>is a 2-20C alkylene group; n is 1 to 200; and R<SB>3</SB>is hydrogen or a 1-20C organic group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a lactam ring-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 of a specific monoethylenically unsaturated polyalkylene oxide monomer and at least one amphoteric monomer containing at least one nitrogen atom is used as a detergent builder (Patent Document 1). reference). Patent Document 1 discloses that the water-soluble copolymer has the ability to remove grass and tea stains from cotton cloth or the like.
Here, with the recent increase in consumers' awareness of environmental issues, the performance required of detergent builders is changing. In other words, consumers prefer to save water by using a water-saving washing machine, and prefer detergents with a small amount of use (downsizing detergent composition) to reduce the amount of detergent components to be drained. I came.
Washing under water-saving conditions will cause problems such as facilitating color transfer between laundry, but in order to deal with the problem, dyes etc. will adhere to the fibers being washed, etc. There is a demand for agents that have higher dye transfer prevention ability (color transfer prevention ability) than ever before.
Furthermore, in order to avoid the remaining undissolved detergent composition remaining on clothes, etc., it can be added to liquid detergent compositions as the tendency to favor liquid detergent compositions increases (with surfactants) The demand for detergent builders with good compatibility is even greater.

Japanese translation of PCT publication No. 2007-511652

Although various polymers have been reported in the past, there is a need to develop a detergent builder that is more adapted to the current consumer needs described above.
Accordingly, an object of the present invention is to provide a polymer having improved compatibility with a surfactant and ability to prevent migration when used in a detergent application, 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 found that a copolymer having a structure derived from a specific lactam ring-containing monomer and a structure derived from a specific polyoxyalkylene compound has high compatibility with a surfactant. As a result, the present inventors have found that it has high compatibility with liquid detergents and has a significantly improved ability to prevent dye transfer, thereby completing the present invention.
That is, the copolymer of the present invention has a structure derived from a lactam ring-containing monomer represented by the following general formula (r-1) (R1) and a polyoxyalkylene type represented by the following general formula (p-1). A lactam ring-containing copolymer having a monomer-derived structure (P1), wherein the structure is derived from a lactam ring-containing monomer with respect to 100% by mass of the structure derived from all monomers of the copolymer (R1). ) Is 30 to 90% by mass, and the composition of the polyoxyalkylene monomer structure (P1) is 10 to 70% by mass with respect to 100% by mass of the structure derived from all monomers of the copolymer. % Of the structure derived from the lactam ring-containing monomer and the structure derived from the polyoxyalkylene monomer (P1) with respect to 100% by mass of the structure derived from all monomers of the copolymer. Containing a lactam ring having a composition of 50 to 100% by mass A copolymer.

In the general formula (r-1), R ₁ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6.

In the general formula (p-1), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 20 carbon atoms, n is a number from 1 to 200, and R ₃ is A hydrogen atom or a C1-C20 organic group is represented.

  According to another aspect of the present invention, a method for producing a copolymer is provided. In the production method of the present invention, a lactam ring-containing monomer represented by the following general formula (r-1) and a polyoxyalkylene monomer represented by the following general formula (p-1) are copolymerized. 2. The method for producing a lactam ring-containing copolymer according to claim 1, wherein:

In the general formula (r-1), R ₁ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6.

In the general formula (p-1), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 20 carbon atoms, n is a number from 1 to 200, and R ₃ is A hydrogen atom or a C1-C20 organic group is represented.

If 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 due to the excellent ability of the copolymer of the present invention to prevent dye transfer. Therefore, it can be preferably used as a detergent additive. In addition, since the copolymer of the present invention has a high compatibility with a surfactant, it can be blended more into a liquid detergent, so the detergency of the liquid detergent composition is synergistic. To improve.

Hereinafter, the present invention will be described in detail.
The copolymer of the present invention has a structure derived from a specific lactam ring-containing monomer (also referred to as a monomer having the structure of the general formula (r-1)), a specific polyoxyalkylene monomer (general It is a copolymer having a structure derived from (also referred to as a monomer having the structure of formula (p-1)).
[Lactam ring-containing unsaturated monomer]
In the present invention, the lactam ring-containing monomer has a structure represented by the following general formula (r-1).

In the general formula (r-1), R ₁ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6.

When the copolymer has the above structure, the ability to prevent dye transfer is improved. In the general formula (r-1), R ₁ is more preferably a hydrogen atom because the ability of the copolymer to prevent dye transfer tends to be further improved.
In the above general formula (r-1), n is more preferably 3 to 6 and most preferably 3 because the dye transfer prevention ability of the copolymer tends to be further improved.
In the general formula (r-1), the lactam ring-containing monomer in which n is 3 has a structure represented by the following general formula (r-2).

In the above general formula (r-2), R ₁ represents a hydrogen atom or a methyl group.

  In the present invention, preferred lactam ring-containing monomers include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyl-ε-caprolactam, N-vinyl-o-valerolactam and the like. Most preferred is N-vinylpyrrolidone.

  The composition of the structure derived from the lactam ring-containing monomer (R1) with respect to 100% by mass of the structure derived from all monomers of the copolymer is 30 to 90% by mass, more preferably 35 to 85% by mass. Yes, more preferably 40 to 80% by mass. By setting it within the above range, good dye transfer prevention ability and compatibility with a surfactant are expressed.

  The composition of the structure derived from the lactam ring-containing monomer (R1) with respect to 100 mol% of the structure derived from all monomers of the copolymer is 90 to 99.7 mol%, more preferably 93 to 99.6 mass. %, More preferably 95 to 99.5 mol%. By setting it within the above range, the remaining polyoxyalkylene monomer can be remarkably reduced.

  The copolymer of the present invention has a structure (R1) derived from a lactam ring-containing monomer represented by the general formula (r-1) as an essential feature. In the present invention, the structure derived from a lactam ring-containing monomer (R1) is a structure in which the lactam ring-containing monomer represented by the general formula (r-1) is copolymerized by radical polymerization. It is represented by the formula (R1).

In the general formula (R1), _{R 1} represents a hydrogen atom or a methyl group, n represents an integer of 1-6.
[Polyoxyalkylene monomer]
The polyoxyalkylene monomer of the present invention is characterized by having a structure represented by the following general formula (p-1). By having the structure of the following general formula (p-1), the amount of the polyoxyalkylene monomer remaining when copolymerized with the lactam ring-containing unsaturated monomer can be reduced. In addition, due to the good copolymerizability, the storage stability when the obtained copolymer is stored in an aqueous solution is good. Furthermore, by having the structure of the following general formula (p-1), it does not have an ester group or the like between the main chain of the resulting polymer and the polyalkylene glycol group, so that it does not undergo hydrolysis in the production process. Therefore, the polyalkylene glycol content in the polymer between lots can be kept uniform. Therefore, for example, the stability of quality (preventing lottery) can be ensured when added to a product such as a detergent composition. Moreover, hydrolysis after liquid detergent blending can also be suppressed.

In the general formula (p-1), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 20 carbon atoms, n is a number from 1 to 200, and R ₃ is A hydrogen atom or a C1-C20 organic group is represented. R ₁ is preferably a methyl group because the polymerization rate of the copolymer is improved.

In the above general formula (p-1), R ₂ represents an alkylene group having 2 to 20 carbon atoms.
As said alkylene group, carbon number is 2-20, Preferably it is 2-15, More preferably, it is 2-10, More preferably, it is 2-5, Most preferably, it is 2-3. And most preferably 2.
Examples of the alkylene group include ethylene, isopropylene, isobutylene, isooctylene, phenylethylene, and diphenylethylene groups.
Among these, the oxyalkylene group is preferably an ethylene group or an isopropylene group. In addition, as an alkylene 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 —). . That is, in the general formula (p-1), R ₂ is preferably mainly composed of an ethylene group. 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 the water solubility of a copolymer and the dye transfer prevention property which are obtained 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 70 mol% or more, More preferably, it is 80 mol% or more, Especially preferably, it is 90 mol% or more, Most preferably, it is 100 mol%.

  In the above general formula (P1), n is a number of 1 to 200, but n is preferably 3 or more because compatibility of the resulting polymer with the surfactant is improved. It is preferable. In addition, n is preferably less than 150, more preferably less than 100, because the ability to prevent dye transfer of the resulting polymer tends to be improved.

In the above general formula (P1), R ₃ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. Examples of the organic group having 1 to 20 carbon atoms include an alkyl group, alkenyl group, and aryl group having 1 to 20 carbon atoms, an alkyl group substituted with a functional group, an alkenyl group, and an aryl group (provided by R ₃ ). The group as a whole has 1 to 20 carbon atoms.). The functional group can be arbitrarily adopted as long as it does not have a significant adverse effect on the polymerization of the polyoxyalkylene monomer represented by the general formula (P1) and the lactam ring-containing monomer, For example, hydroxyl groups; acid groups such as carboxyl groups and sulfonic acid groups and salts thereof; ester groups, amide groups, amino groups, ether groups, acyl groups, thiol groups, carbonyl groups, and the like.

  The copolymer of the present invention has a structure (P1) derived from the polyoxyalkylene monomer represented by the general formula (p-1) as an essential feature. In the present invention, the polyoxyalkylene monomer-derived structure (P1) is a structure in which a polyoxyalkylene monomer is copolymerized by radical polymerization, and is represented by the following general formula (P1).

In the general formula (P1), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 20 carbon atoms, n is a number from 1 to 200, and R ₃ represents a hydrogen atom. Or represents a C1-C20 organic group.

  The composition of the structure derived from the polyoxyalkylene monomer (P1) with respect to 100% by mass of the structure derived from all monomers of the copolymer of the present invention is 10 to 70% by mass, more preferably 15 to It is 65 mass%, More preferably, it is 20-60 mass%. If the composition of the structure derived from the polyoxyalkylene monomer (P1) is 10% by mass or more, for example, when the copolymer is added to the liquid detergent composition, the compatibility with the surfactant tends to be improved. As a result, more diverse detergent formulations are possible. If it is 70 mass% or less, the ability to prevent dye transfer tends to be improved.

  The composition of the structure derived from the polyoxyalkylene monomer (P1) with respect to 100 mol% of the structure derived from all monomers of the copolymer is 0.3 to 10 mol%, more preferably 0.4 to 7%. It is mass%, More preferably, it is 0.5-5 mol%. By setting it within the above range, the remaining polyoxyalkylene monomer can be remarkably reduced.

(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) a production method of adding an alkylene oxide to an alcohol having a carbon-carbon double bond such as isoprenol (Ii) a production method of adding a polyalkylene glycol to a halide having a carbon-carbon double bond such as isoprenyl chloride, (iii) the terminal hydroxyl group of the monomer obtained in (i) has a carbon number It is preferably produced by a production method of reacting 1 to 20 halogenated alkyls, acid chlorides, chloroformates, carboxyl group-containing compounds, carboxylic acid ester group-containing compounds, isocyanate group-containing compounds, and the like.

  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.

  In the production method (ii), the polyalkylene glycol to be added to the halide is a compound in which an alkylene oxide having 1 to 20 carbon atoms is added to a hydroxyl group of an alcohol or phenol having 1 to 20 carbon atoms. preferable.

  In the production method (iii), usable alkyl halides are alkyl halides having 1 to 20 carbon atoms, and examples thereof include iodomethane, iodobutane, iodooctane, chloromethane, and chloroisopropane. Examples of usable acid chlorides and chloroformates include isopropyl chloroformate, benzyl chloroformate, butyric acid chloride and the like. Examples of usable carboxyl group-containing compounds and carboxylic acid ester group-containing compounds include acetic acid having 1 to 20 carbon atoms, butyric acid, oleic acid, benzoic acid, and methyl and ethyl esters thereof. Examples of the isocyanate group-containing compound that can be used include phenyl isocyanate and octyl isocyanate.

In the present invention, since the polyoxyalkylene monomer has a structure represented by the above general formula (P1) and has good stability at the time of polymerization, the compatibility of the surfactant of the obtained copolymer is good. Will improve. In addition, the polyoxyalkylene compound of the present invention has a structure represented by the above general formula (P1), so that the obtained polymer is preferably stable over time. Moreover, since it shows the outstanding stability when manufacturing the product (composition) containing the copolymer (lactam ring containing copolymer) of this invention for applying to various uses, It is preferable because the performance is stable.
[Other monomers]
In addition to the lactam ring-containing unsaturated monomer and the polyoxyalkylene monomer, other monomers copolymerizable with any of the monomers may be included. Other monomers are not particularly limited, but examples thereof include carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 2-methyleneglutaric acid, and salts thereof. 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, α- Hydroxyl-containing alkyl (meth) acrylates such as hydroxymethylethyl (meth) acrylate; (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate By esterification of acrylic acid with C1-C18 alcohol Obtained alkyl (meth) acrylates; amino group-containing acrylates such as dimethylaminoethyl (meth) acrylate or quaternized products thereof; amide group-containing monomers such as (meth) acrylamide, dimethylacrylamide, and isopropylacrylamide; vinyl acetate Vinyl esters such as ethylene; alkenes such as ethylene and propylene; aromatic vinyl monomers such as styrene; maleimide derivatives such as maleimide, phenylmaleimide and cyclohexylmaleimide; vinyl-based monomers containing nitrile groups such as (meth) acrylonitrile; 3-mersyloxy-2-hydroxypropanesulfonic acid, (meth) allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, isoprenesulfonic acid, styrenesulfonic acid, vinylsulfonic acid and these A monomer having a sulfonic acid group such as a salt of aldehyde; a vinyl monomer containing an aldehyde group such as (meth) acrolein, such as a monomer having a phosphonic acid group such as vinylphosphonic acid or (meth) allylphosphonic acid; Alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether; monomers containing other functional groups such as vinyl chloride, vinylidene chloride and allyl alcohol; alkylene oxides for unsaturated alcohols such as (meth) allyl alcohol and vinyl hydroxyalkyl ether And a polyoxyalkylene monomer other than the polyoxyalkylene monomer represented by the general formula (p-1), such as a compound added with a polyalkylene glycol ester of (meth) acrylic acid. . Also about these other monomers, only 1 type may be used independently and 2 or more types may be used together.
In the present invention, the “salt” of the carboxyl group-containing monomer or the monomer having a sulfonic acid group is an alkali metal salt such as sodium salt or potassium salt, or an alkaline earth metal salt such as calcium salt or magnesium salt. , Ammonium salt, quaternary ammonium salt and the like. When these “salts” are used, alkali metal salts are preferable because dispersibility of clay and the like is improved.

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.
That is, the structure derived from the lactam ring-containing monomer represented by the general formula (r-1) and the structure represented by the general formula (p-1) with respect to 100% by mass of the structure derived from all monomers of the copolymer. The total structure derived from the polyoxyalkylene monomer is 70 to 100% by mass.

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.
In addition, the lactam ring-containing monomer represented by the general formula (r-1), the polyoxyalkylene monomer represented by the general formula (p-1), and all other monomers (“single The ratio of the lactam ring-containing monomer in the “total amount of the monomer component” or “total monomer composition”) is not particularly limited, but from the viewpoint of sufficiently exerting the effects of the present invention, the monomer The ratio of the lactam ring-containing monomer represented by the general formula (r-1) to the total amount of the components is 30 to 90% by mass, more preferably 35 to 85% by mass, and further preferably 40 to 80%. % By mass.
The ratio of the lactam ring-containing monomer represented by the general formula (r-1) with respect to the total amount of the monomer components is 90 to 99.7 mol%, and more preferably 93 to 99.6 mass%. More preferably, it is 95-99.5 mol%.
The proportion of the polyoxyalkylene monomer represented by the general formula (p-1) in the total amount of the monomer components is not particularly limited, but from the viewpoint of sufficiently exerting the effects of the present invention, the single amount The ratio of the polyoxyalkylene monomer to the total amount of the body components is 10 to 70% by mass, more preferably 15 to 65% by mass, and still more preferably 20 to 60% by mass.
Moreover, the ratio of the polyoxyalkylene monomer with respect to the total amount of the monomer components is 0.3 to 10 mol%, more preferably 0.4 to 7 mass%, still more preferably 0.5 to 5 mol%.
The ratio of other monomers in the total amount of monomer components is not particularly limited, but is preferably 0 to 30% by mass.

[Lactam ring-containing copolymer]
As described above, the sulfonic acid group-containing copolymer of the present invention is represented by the structures (R1) and (p-1) derived from the lactam ring-containing monomer represented by (r-1) described above. A structure derived from a polyoxyalkylene monomer (P1) is included as an essential component.
The lactam ring-containing copolymer of the present invention comprises a monomer component comprising a lactam ring-containing monomer represented by (r-1) and a polyoxyalkylene monomer represented by (p-1). It is preferable to be obtained by copolymerization.

  The weight average molecular weight of the lactam ring-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 weight of the lactam ring-containing copolymer of the present invention is not particularly limited. Specifically, the average molecular weight is preferably 100 to 50000, more preferably 500 to 40000, and still more preferably 1000 to 30000. 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 dye transfer 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 lactam ring containing copolymer of this invention.

  Further, the number average molecular weight of the lactam ring-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, etc., but the lactam ring-containing copolymer of the present invention is not particularly limited. Specifically, the number average molecular weight is preferably 100 to 25000, more preferably 200 to 20000, and still more preferably 500 to 15000. 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, when the value of the number average molecular weight is too small, the dye transfer preventing ability 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 lactam ring containing copolymer of this invention.

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

[Method for producing lactam ring-containing copolymer]
As long as there is no notice in particular, the manufacturing method of the lactam ring containing copolymer of this invention can use the method which modified the well-known polymerization method or a well-known method. From the viewpoint of producing a high-performance copolymer with few impurities, the polymerization is preferably performed near neutrality or under alkaline conditions. Specifically, the pH is preferably 5.5 or more, more preferably 6 or more, and still more preferably 6.5 or more. The upper limit of the preferred pH is 13.

  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 and ammonium persulfate; 2,2′-azobis (2-methylpropionamidine). Hydrochloride, dimethyl 2,2′-azobis (2-methylpropionate), 2,2′-azobis (2-amidinopropane) hydrochloride, 4,4′-azobis-4-cyanoparerenic acid, azobisisobutyrate Azo compounds such as rhonitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydroper An organic peroxide such as oxide is preferable. Of these polymerization initiators, hydrogen peroxide, persulfate, and water-soluble azo compounds are preferred, and 2,2'-azobis (2-methylpropionamidine) hydrochloride is most preferred. 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 10 mass parts or less, More preferably, it is 0.005 mass part or more and 8 mass parts or less, More preferably, it is 0.01 mass part or more and 5 mass parts or less.

  The method for producing a lactam ring-containing copolymer of the present invention preferably uses 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 lactam ring-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 lactam ring-containing copolymer of the present invention, in the polymerization, in addition to the polymerization initiator described above, a decomposition catalyst for the polymerization initiator or a reducing compound may be added to the reaction system. 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, the initiator, and the reaction accelerator is preferably 0.5 to 10 g with respect to 1 mol of all monomer components. 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 1-8g, More preferably, it is 2-7g.

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 a lactam ring-containing copolymer of the present invention, any chain transfer agent, pH adjusting agent, 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.

[Lactam ring-containing copolymer composition (polymer composition)]
In the polymer composition of the present invention, the lactam ring-containing copolymer of the present invention is essential. In addition, an unreacted lactam ring group-containing monomer, an unreacted polyoxyalkylene monomer, an unreacted polymerization initiator, a polymerization initiator decomposition product, and the like may be included.
The content of the unreacted polyoxyalkylene monomer present in the polymer composition is preferably less than 3% by mass with respect to 100% by mass of the solid content of the polymer composition. 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 lactam ring-containing unsaturated monomer is preferably 1000 ppm by mass or less, more preferably 100 ppm by mass or less, and most preferably 0 ppm by mass with respect to 100% by mass of the solid content of the polymer composition. is there.
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 copolymer 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 this invention contains the lactam ring containing copolymer mentioned above, content of the said lactam ring containing copolymer in a detergent composition is not restrict | limited in particular. However, from the viewpoint that excellent builder performance can be exhibited, the content of the lactam ring-containing copolymer is preferably 0.1 to 15% by mass, more preferably based on the total amount of the detergent composition. It is 0.3-10 mass%, More preferably, it is 0.5-5 mass%.
Detergent compositions used in detergent applications usually include surfactants and additives used in detergents. Specific forms of these surfactants and additives are not particularly limited, and conventionally known knowledge can be appropriately referred to in the detergent field. The detergent composition may be a powder detergent composition or a liquid detergent composition.
The surfactant is one or more selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant. When two or more kinds are used in combination, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 60% by mass with respect to the total amount of the surfactant. 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%.
Since the lactam ring-containing copolymer of the present invention has excellent compatibility with a surfactant, the water content can be reduced.
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”.
In addition, the weight average molecular weight, number average molecular weight, anti-recontamination ability, quantification of unreacted monomer, polymer composition, and solid content of the aqueous polymer solution of the lactam ring-containing copolymer of the present invention are as follows: Measured according to

<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)
<Measurement of solid content of polymer composition, aqueous copolymer solution, etc.>
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 lactam ring group-containing monomer in polymer composition>
The monomer was measured using liquid chromatography under the conditions shown in Table 1 below.
Measurement conditions column for liquid chromatography: CAPCELL PAC C18 TYPE UG120 5 μm, 1.5 mmΦ × 250 mm, manufactured by Shiseido Co., Ltd.
Eluent: methanol / water = 1/24 (containing 0.4% by mass of sodium 1-heptanesulfonate)
Flow rate: 100 μL / min
Column oven: 20 ° C
Injection volume: 10 μL
UV detector: 235 nm
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 method of dye transfer prevention ability>
(I) JIS cotton cloth (5 cm × 5 cm, obtained from the Japan Standards Association) was measured in advance by using a colorimetric color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. (before the test) The whiteness of the test cloth).
(Ii) Hard water was prepared by adding pure water to calcium chloride dihydrate and magnesium chloride (hexahydrate) (calcium ions 150 ppm (calcium carbonate equivalent), magnesium ions (magnesium carbonate equivalent) 50 ppm)).
(Iii) Polyoxyethylene (2) Sodium lauryl ether sulfate 3.2 g, Polyoxyethylene (7) Lauryl ether 0.4 g, Sodium borate 0.4 g, Citric acid 1.0 g 0.0 g, and an aqueous surfactant solution was prepared. The pH was adjusted to 8.5 with sodium hydroxide.
(Iv) A targot meter is set at 40 ° C., 500 mL of hard water, 0.7 g of zeolite, 7.7 g of 5% by mass sodium carbonate aqueous solution, 3.5 g of 5% by mass LAS (obtained from Kao Corporation), 3.5 g solid In a minute conversion, 3.5 g of a 1% polymer aqueous solution and 2 g of a 0.25 mass% aqueous solution of chlorazole black LF (reagent obtained from Tokyo Chemical Industry Co., Ltd.) as a dye were put in a pot and stirred at 100 rpm for 1 minute. Then, 10 white cloths were put and stirred at 100 rpm for 30 minutes.
(V) The white cloth was drained by hand, and 500 mL of tap water adjusted to 40 ° C. was placed in the pot and stirred at 100 rpm for 2 minutes. This was done twice.
(Vi) After applying the cloth to a white cloth and drying it while stretching the wrinkles with an iron, the whiteness of the white cloth was measured again with the above colorimetric color difference meter (the whiteness of the test cloth after washing). Called degrees).
(Vii) From the above measurement results, the ability to prevent dye transfer was determined by the following equation.
(Viii) Transfer prevention ability (%) = [(whiteness of test cloth after washing) / (whiteness of test cloth before test)] × 100
<Compatibility test with surfactant>
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 copolymers and comparative polymers obtained in the examples; 1.5 g
Pure water; balance <Example 1>

16.7 g of a 60% aqueous solution (hereinafter also referred to as “60% IPN50”) of a 50-mol adduct of ethylene oxide of isoprenol in a 300 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade). 79.5 g of pure water was charged, and the temperature was raised to 90 ° C. while stirring to obtain a polymerization reaction system. Next, 40.0 g of N-vinylpyrrolidone (hereinafter also referred to as “NVP”), 2,2′-azobis (2-methylpropionamidine) dihydro hydride in a polymerization reaction system maintained at 90 ° C. with stirring. 36.5 g of a 5% aqueous chloride solution (hereinafter also referred to as “5% V50”) was dropped from separate nozzles. The dropping time of each solution was 120 minutes for NVP and 130 minutes for 5% V50. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After completion of the dropwise addition of NVP, the reaction solution was kept at 90 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool.
Thus, an aqueous solution (copolymer composition (1)) containing a copolymer and having a solid content concentration of 30% was obtained (the obtained copolymer was referred to as copolymer (1)).

<Example 2>
A 300 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 16.7 g of 60% IPN50 and 80.0 g of pure water, and the temperature was raised to 90 ° C. while stirring to polymerize. The reaction system was used. Next, 35.0 g of NVP and 32.2 g of 5% V50 were dropped from separate nozzles into the polymerization reaction system maintained at 90 ° C. with stirring. The dropping time of each solution was 120 minutes for NVP and 130 minutes for 5% V50. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After completion of the dropwise addition of NVP, the reaction solution was kept at 90 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool.
Thus, an aqueous solution (copolymer composition (2)) containing a copolymer and having a solid content concentration of 30% was obtained (the obtained copolymer was referred to as copolymer (2)).
<Example 3>
A glass separable flask having a capacity of 300 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 25.0 g of 60% IPN50 and 51.0 g of pure water, and the temperature was raised to 90 ° C. while stirring to polymerize. The reaction system was used. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 35.0 g of NVP, 32.2 g of a 5% aqueous solution of sodium persulfate (hereinafter also referred to as “5% NaPS”), and sodium hydroxide 27.0 g of a 2% aqueous solution (hereinafter also referred to as “2% NaOH”) was dropped from separate nozzles. The dropping time of each solution was 120 minutes for NVP and 130 minutes for 5% NaPS and 2% NaOH. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After completion of the dropwise addition of NVP, the reaction solution was kept at 90 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool.
In this way, an aqueous solution (copolymer composition (3)) containing a copolymer and having a solid content concentration of 30% was obtained (the obtained copolymer was referred to as copolymer (3)).

<Example 4>
A 300 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 25.0 g of 60% IPN50 and 53.0 g of pure water, and the temperature was raised to 90 ° C. while stirring to polymerize. The reaction system was used. Next, 35.0 g of NVP, 32.2 g of 5% V50, and a 5% aqueous solution of sodium sulfite (hereinafter also referred to as “5% SS”) in a polymerization reaction system maintained at 90 ° C. with stirring. ) 32.2 g was dropped from separate nozzles. The dropping time of each solution was 120 minutes for NVP and 5% SS and 130 minutes for 5% V50. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After completion of the dropwise addition of NVP, the reaction solution was kept at 90 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool.
In this way, an aqueous solution (copolymer composition (4)) containing a copolymer and having a solid content concentration of 30% was obtained (the obtained copolymer was referred to as copolymer (4)).

<Example 5>
In a glass separable flask having a capacity of 300 mL equipped with a reflux condenser and a stirrer (paddle blade), 20.8 g of a 48% aqueous solution (hereinafter also referred to as “48% IPN25”) of a 25 mol adduct of isoprenol in ethylene oxide. Then, 75.0 g of pure water was charged, and the temperature was raised to 90 ° C. while stirring to obtain a polymerization reaction system. Next, 40.0 g of NVP and 36.9 g of 5% V50 were dropped from separate nozzles into the polymerization reaction system maintained at 90 ° C. with stirring. The dropping time of each solution was 120 minutes for NVP and 130 minutes for 5% V50. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After completion of the dropwise addition of NVP, the reaction solution was kept at 90 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool.
In this way, an aqueous solution (copolymer composition (5)) having a solid content concentration of 30% containing the copolymer was obtained (the obtained copolymer was referred to as copolymer (5)).

<Example 6>
A 300 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 33.3 g of 60% IPN50 and 57.0 g of pure water, and the temperature was raised to 90 ° C. while stirring to polymerize. The reaction system was used. Next, 35.8 g of NVP and 55.8 g of 5% V50 were dropped from separate nozzles into the polymerization reaction system maintained at 90 ° C. with stirring. The dropping time of each solution was 120 minutes for NVP and 130 minutes for 5% V50. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After completion of the dropwise addition of NVP, the reaction solution was kept at 90 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool.
Thus, an aqueous solution (copolymer composition (6)) containing a copolymer and having a solid content concentration of 30% was obtained (the obtained copolymer was referred to as copolymer (6)).

<Comparative Example 1>
A glass separable flask having a capacity of 300 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 58.0 g of pure water and heated to 90 ° C. while stirring to prepare a polymerization reaction system. Next, under stirring, NVP 70.0 g, 5% V5063.1 g, and 5% SS 63.1 g were dropped from separate nozzles into the polymerization reaction system maintained at 90 ° C. The dropping time of each solution was 120 minutes for NVP and 5% SS and 130 minutes for 5% V50. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After completion of the dropwise addition of NVP, the reaction solution was kept at 90 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool.
In this way, a comparative polymer having a solid content concentration of 30% was obtained.

<Comparative example 2>
A glass separable flask having a capacity of 300 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 80.0 g of pure water and heated to 90 ° C. while stirring to prepare a polymerization reaction system. Next, in a polymerization reaction system maintained at 90 ° C. under stirring, 25.0 g of a 60% aqueous solution of methanol ethylene oxide 25 mol adduct methacrylate (hereinafter also referred to as “60% PGM25E”), NVP35. 0.02 g and 52.8% V50, 32.8 g, were added dropwise from separate nozzles. The dropping time of each solution was 90 minutes for 60% PGM25E, 120 minutes for NVP, and 130 minutes for 5% V50. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously.
After completion of the dropwise addition of NVP, the reaction solution was kept at 90 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool.
In this way, a comparative polymer (2) having a solid content concentration of 30% was obtained.

From the results shown in Table 1, it was demonstrated that the copolymer of the present invention has excellent compatibility with a surfactant as compared with a conventional polymer. In addition, it was demonstrated that the polymer of the present invention has an excellent ability to prevent dye transfer as compared with conventional polymers.
Therefore, when the polymer of the present invention is used as a detergent builder, it is expected that color transfer can be effectively prevented even under water-saving conditions. In addition, since the polymer of the present invention has excellent compatibility with a surfactant, a wider range of detergent blending, such as blending into a liquid detergent, becomes possible.

Claims (3)

A structure derived from a lactam ring-containing monomer represented by the following general formula (r-1) (R1),
A structure (P1) derived from a polyoxyalkylene monomer represented by the following general formula (p-1),
A lactam ring-containing copolymer having
The composition of the structure derived from the lactam ring-containing monomer (R1) with respect to 100% by mass of the structure derived from all monomers of the copolymer is 30 to 90% by mass,
The composition of the structure derived from the polyoxyalkylene monomer (P1) with respect to 100% by mass of the structure derived from all monomers of the copolymer is 10 to 70% by mass,
The total composition of the structure derived from a lactam ring-containing monomer (R1) and the structure derived from a polyoxyalkylene monomer (P1) with respect to 100% by mass of the structure derived from all monomers of the copolymer is 50 to 50%. 100% by weight,
A lactam ring-containing copolymer.

In the general formula (r-1), R ₁ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6.

In the general formula (p-1), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 20 carbon atoms, n is a number from 1 to 200, and R ₃ is A hydrogen atom or a C1-C20 organic group is represented. A lactam ring-containing monomer represented by the following general formula (r-1):
A polyoxyalkylene monomer represented by the following general formula (p-1):
Is copolymerized,
2. A method for producing a lactam ring-containing copolymer according to claim 1.

In the general formula (r-1), R ₁ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6.

In the general formula (p-1), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 20 carbon atoms, n is a number from 1 to 200, and R ₃ is A hydrogen atom or a C1-C20 organic group is represented. A detergent composition comprising the lactam ring-containing copolymer according to claim 1.