JP2013023528A - Polymer composition and manufacturing method therefor - Google Patents

Abstract

An object of the present invention is to provide a polymer composition having a recontamination preventing ability which is further improved as compared with the prior art when used in detergent applications, and a method for producing the same.
[Solution]
A method for producing a polymer composition comprising a step of polymerizing a monomer essentially comprising an amino group-containing (meth) acrylate in the presence of a compound having a polyalkylene glycol structure, wherein the amount of water at the start of polymerization Is 0 to 120 parts by mass with respect to 100 parts by mass of the compound having the polyalkylene glycol structure, and the amount of water in the reaction solution at the end of the addition of the amino group-containing (meth) acrylate is It is a manufacturing method of a polymer composition which is 120-100,000 mass parts with respect to 100 mass parts of usage-amounts of the compound which has a glycol structure.
[Selection figure] None

Description

  The present invention relates to a polymer composition and a method for producing the same. More particularly, the present invention relates to a polymer containing a polyalkylene glycol structure, a polymer composition containing a polymer containing a structure derived from an amino group-containing (meth) acrylate, and a method for producing the same.

  A polyalkylene glycol copolymer and an amino group-containing monomer are useful polymers used in various industrial fields. For example, the copolymer is useful for aqueous applications such as a dispersant and a detergent composition.

  Conventionally, as the polymer, a copolymer of a polyalkylene oxide copolymer and a quaternized nitrogen-containing monomer (Patent Document 1), a polyalkylene oxide copolymer and a quaternized cation group-containing polymer are used. Copolymers with monomers (Patent Document 2) and the like have been proposed.

Further, Patent Document 3 discloses a method for producing a polymer mixture in which a (meth) acrylic acid monomer is polymerized in the presence of a compound having a polyalkylene glycol structure, and the amount of initial charge water is The amount of water is less than 90 parts by mass with respect to 100 parts by mass of the compound having an alkylene glycol structure, and the amount of water at the end of addition of the (meth) acrylic acid monomer is 100 parts by mass of the compound having a polyalkylene glycol structure On the other hand, the manufacturing method of the polymer mixture which is 1-100,000 mass parts is disclosed.
According to the above method, the obtained polymer mixture is excellent in recontamination preventing ability and excellent in storage stability, so that the quality of the manufactured detergent is stabilized. Furthermore, it is disclosed that the degree of freedom in detergent manufacture is improved and the manufacturing cost is reduced by improving storage stability.
However, the polymer mixture produced by the method described in Patent Document 3 is mainly composed of a polymer having an anionic group. For example, in a detergent application, anionic Use of a base polymer (a polymer containing a large amount of anionic groups) may be limited.

Special table 2007-510806 gazette JP 2001-181364 A JP 2004-331839 A

Thus, although various polymers (compositions) have been reported in the past, polymers (compositions) adapted to the above-described current consumer needs have been demanded.
Then, an object of this invention is to provide the polymer (composition) which has a nonion and / or a cationic group mainly, and has the re-contamination prevention ability improved further conventionally, and its manufacturing method.

The present inventors have intensively studied to solve the above problems. As a result, when the present inventors polymerize a monomer component essentially containing an amino group-containing (meth) acrylate in the presence of a compound having a polyalkylene glycol structure (PAG compound) under specific production conditions, it is obtained. The present inventors have found that the ability to prevent recontamination of the polymer composition is improved, and have completed the present invention.

  That is, the present invention provides a method for producing a polymer composition comprising a step of polymerizing a monomer (monomer component) essentially containing an amino group-containing (meth) acrylate in the presence of a compound having a polyalkylene glycol structure. The amount of water at the start of polymerization is 0 to 120 parts by weight with respect to 100 parts by weight of the compound having the polyalkylene glycol structure, and the amount of amino group-containing (meth) acrylate at the start of polymerization is The amount of water contained in the reaction solution at the end of addition of the amino group-containing (meth) acrylate is 30 to 800 parts by mass with respect to 100 parts by mass of the compound having the polyalkylene glycol structure. It is a manufacturing method of a polymer composition which is 120-100,000 mass parts with respect to 100 mass parts of usage-amounts of the compound which has this. .

The polymer composition of the present invention can be designed with a small amount of anionic groups, and has an excellent ability to prevent recontamination. Therefore, if the polymer composition of the present invention is used as a raw material for a detergent composition, the polymer composition of the present invention is preferably used as a detergent additive in order to suppress the reattachment of dirt to fibers during washing. can do

<Water content during polymerization>
The production method of the present invention is a polymer comprising a step (polymerization step) of polymerizing a monomer (monomer component) essentially containing an amino group-containing (meth) acrylate in the presence of a compound having a polyalkylene glycol structure. A method for producing a composition, wherein the amount of water at the start of polymerization is 0 to 120 parts by mass with respect to 100 parts by mass of the compound having a polyalkylene glycol structure, and the addition of an amino group-containing (meth) acrylate In the method for producing a polymer composition, the amount of water contained in the reaction solution at the end is 120 to 100,000 parts by mass with respect to 100 parts by mass of the compound having the polyalkylene glycol structure.

  In the production method of the present invention, by controlling the amount of water added during the production of the polymer composition, the storage stability and the ability to prevent recontamination of the solution containing the produced polymer composition are improved. In the present application, “storage stability” means the degree to which a solution containing a polymer mixture containing a produced polymer is stably present during storage and hardly causes separation or alteration. “Recontamination prevention ability” means a performance that prevents a dirt component in a liquid from reattaching. For example, when the polymer composition of the present invention is incorporated into a detergent, the ability to prevent recontamination is an important factor that greatly affects the quality of the detergent.

  In the present invention, “at the start of polymerization” is the time when the polymerization of the amino group-containing (meth) acrylate starts substantially, specifically, part or all of the amino group-containing (meth) acrylate used for the polymerization. , And a part or all of the polymerization initiator used for the polymerization is added to the reaction vessel (polymerization vessel, polymerization kettle). In the present invention, “when the addition of the amino group-containing (meth) acrylate is completed” means that the entire amount of the amino group-containing (meth) acrylate used for the polymerization is added to the reaction vessel (polymerization vessel, polymerization kettle). is there.

  The “amount of water at the start of polymerization” represents the amount of water present in the reaction vessel (in other words, in the polymerization reaction solution) at the start of polymerization. The amount of water at the start of the polymerization is 120 parts by mass or less with respect to 100 parts by mass of the PAG compound. The lower limit of the amount of water at the start of polymerization is not particularly limited. By reducing the amount of water at the start of polymerization, the ability to prevent recontamination of the resulting polymer composition can be improved. Further, storage stability can be improved by reducing the amount of water at the start of polymerization. The amount of water at the start of the polymerization is preferably 0 to 100 parts by mass, more preferably 0 to 90 parts by mass, and particularly preferably 0 to 80 parts by mass with respect to 100 parts by mass of the PAG compound. When the amount of water at the start of polymerization is about this level, the weight average molecular weight of the polymer contained in the produced polymer composition can be lowered. Polymers used as detergents, scale inhibitors, dispersants, and detergent builders tend to have improved performance as the molecular weight decreases. Therefore, when the amount of water at the start of polymerization is about this level, it is effective in improving the performance. Also, it should be noted that if the amount of water at the start of polymerization is too large, the storage stability and compatibility with the surfactant tend to decrease.

  In the production method of the present invention, the amount of water contained in the reaction solution at the end of the addition of the amino group-containing (meth) acrylate is defined. The amount of water contained in the reaction solution at the end of the addition of the amino group-containing (meth) acrylate is present in the polymerization vessel (in the polymerization reaction solution) at the time when the addition of the amino group-containing (meth) acrylate is completed. Means the amount of water.

  The amount of water contained in the reaction solution at the end of addition of the amino group-containing (meth) acrylate (hereinafter also referred to as “the amount of water at the end of addition”) is 120 to 100, based on 100 parts by mass of the PAG compound. 000 parts by mass. However, since the “amount of water at the end of addition” is increased from the “amount of water at the start of polymerization”, the ability to prevent recontamination when the polymer composition is blended with the detergent composition is improved. preferable. When the amount of water at the end of the addition is within this range, the ability to prevent recontamination of the produced polymer composition can be improved. Further, when the amount of water at the end of the addition is within this range, the storage stability is improved. The amount of water at the end of the addition is preferably 120 to 1,000 parts by mass and more preferably 150 to 500 parts by mass with respect to 100 parts by mass of the PAG compound.

  By controlling the amount of water contained in the reaction solution as described above, graft polymerization of the PAG compound with the monomer (the PAG compound is a trunk and the monomer is a branch) under conditions with little water (for example, at the initial stage of polymerization). The polymerization of the monomers proceeds under the condition of a lot of water (for example, the latter half of the polymerization). Since a polymer having an intermediate structure is also produced, the polymer composition obtained by the presence thereof is prevented from layer separation with time, and storage stability is greatly improved.

<Amino group-containing (meth) acrylate>
The “amino group-containing (meth) acrylate” used in the production method of the present invention means an acrylate having an amino group, a methacrylate having an amino group, and salts thereof. One or more amino group-containing (meth) acrylates are used. Examples of the salt of an acrylate having an amino group and a methacrylate having an amino group include inorganic acid salts such as hydrochloride and organic acid salts such as acetate and methyl sulfate.
The amino group contained in the amino group-containing (meth) acrylate is a primary to quaternary amino group.

  Specific examples of amino group-containing (meth) acrylates include aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, and dimethylaminopropyl (meth). Examples thereof include acrylate, diethylaminopropyl (meth) acrylate, and quaternized products thereof. As the amino group-containing (meth) acrylate, those having 8 to 15 carbon atoms per molecule are preferable, and those having 8 to 14 carbon atoms are particularly preferable. Of these, dimethylaminoethyl acrylate is most preferred. When the amino group-containing (meth) acrylate is as described above, the ability to prevent recontamination of the resulting polymer composition tends to be improved. Moreover, the amount of residual monomers after polymerization can be reduced.

  In the production method of the present invention, the amino group-containing (meth) acrylate is preferably added to the reaction kettle after the start of polymerization, but a part thereof may be added before the start of polymerization.

  The amount of amino group-containing (meth) acrylate used in the production method of the present invention is 100% by mass of the total amount of the PAG compound and monomers (amino group-containing (meth) acrylate and other monomers). On the other hand, it is preferably 4 to 90% by mass because the recontamination preventing ability of the polymer composition tends to be improved, more preferably 5 to 75% by mass, and 20 to 60% by mass. Is more preferable. In addition, when calculating the said usage-amount, when a monomer has an acid group, it calculates by acid type conversion, and when it has an amino group, it calculates by corresponding amine conversion. For example, when the monomer is a hydrochloride of diethylaminoethyl acrylate, the usage amount is calculated as diethylaminoethyl acrylate which is the corresponding amine (amine conversion).

<Compound having polyalkylene glycol structure (PAG compound)>
The polymer composition of the present invention is synthesized by polymerizing an amino group-containing (meth) acrylate as an essential component in the presence of a PAG compound in a polymerization reaction system. Since the separation stability of the polymer composition of the present invention is extremely good, it is considered that the polymer composition contains a polymer that suppresses separation of the polymer of the PAG compound and diethylaminoethyl acrylate. That is, there is a possibility that a part of the polymer formed mainly in the first half of the polymerization in the production method of the present invention incorporates the PAG compound in its structure.

The PAG compound used in the present invention is not particularly limited as long as it has a polyalkylene glycol structure. The polyalkylene glycol structure means a structure represented by the following general formula (1).
-(O-R) _n -General formula (1)
(In the formula, R represents an alkylene group, and n represents the number of repetitions.)
Although it does not specifically limit as an alkylene group, A methylene group, ethylene group, a propylene group, trimethylene group, a cyclohexylene group, etc. are mentioned. Preferably it is a C2-C6 alkylene group. n is usually about 5 to 300, preferably 5 to 100, more preferably 7 to 90, and particularly preferably 10 to 80. However, n is not limited to this range.

  Examples of PAG compounds include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, copolymers of ethylene oxide and propylene oxide, ether compounds of polyalkylene glycols such as polyalkylene glycol monoalkyl ether and polyalkylene glycol monoaryl ether, and the like. It is done. Many components not having a polyalkylene glycol structure may be contained in the PAG compound. For example, what added polyalkylene glycol to the active hydrogen of the compound which has active hydrogen is mentioned. That is, for example, a compound in which active hydrogen of a compound having a plurality of active hydrogens such as polyethyleneimine is substituted with a polyalkylene glycol structure may be used as the PAG compound. In addition, an ester compound of polyalkylene glycol, a polyalkylene glycol adduct of a compound having an unsaturated double bond such as isoprenol or allyl alcohol, and the like can be used as the PAG compound.

  Another example of the preferred PAG compound is a compound represented by the following general formula (2). If the PAG compound is a compound represented by the following general formula (2), the ability to prevent recontamination of the polymer composition tends to be improved.

In the general formula (2), R ₁ and R ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ₂ has 2 to 20 carbon atoms. N represents a number of 5 to 300.
In the above general formula (2), specific examples in the case where R ₁ and R ₃ are alkyl groups having 1 to 20 carbon atoms include methyl group, isopropyl group, n-butyl group, cyclohexyl group, n-octyl group, n -A dodecyl group etc. are illustrated, A phenyl group, a methylphenyl group, a naphthyl group etc. are illustrated as a C6-C20 aryl group.
In the general formula (2), examples of R ₂ include an ethylene group, a propylene group, a butylene group, and a hexylene group, and an ethylene group, an isopropylene group, and an isobutylene group are preferable.

  The PAG compound may be synthesized based on the obtained knowledge, or a commercially available compound may be used. For example, in order to synthesize a compound in which active hydrogen of polyethyleneimine is substituted with a polyalkylene glycol structure, a predetermined amount of alkylene oxide may be polymerized with respect to a predetermined polyethyleneimine. In some cases, two or more types of PAG compounds may be used.

  The molecular weight of the PAG compound is not particularly limited. The PAG compound may be selected according to the structure of the PAG compound and the characteristics required for the polymer mixture. Considering use as a detergent or scale inhibitor, the weight average molecular weight is preferably 500 to 20,000, more preferably 700 to 15,000, still more preferably 800 to 12,000, and particularly preferably 1,000 to 1,000. 10,000 PAG compounds are used.

  In the production method of the present invention, the PAG compound is preferably added to the reaction kettle before the start of polymerization, but a part thereof may be added after the start of polymerization.

  The amount of the PAG compound used in the production method of the present invention is 10 to 96 mass with respect to 100 mass% of the total amount of the PAG compound and the monomer (amino group-containing (meth) acrylate and other monomers). Is preferably from the viewpoint that the recontamination preventing ability of the polymer composition and the compatibility with the surfactant tend to be improved, more preferably 25 to 95% by mass, and 40 to 80% by mass. More preferably. In addition, when calculating the said usage-amount, when a monomer has an acid group, it calculates by acid type conversion, and when it has an amino group, it calculates by corresponding amine conversion.

<Other monomers>
As a monomer used in the production method of the present invention, in addition to the amino group-containing (meth) acrylate, other monomers polymerizable with these may be used as desired. Other monomers include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, maleic acid, itaconic acid 2-methyleneglutaric acid, and salts thereof; 2-acrylamido-2-methylpropanesulfonic acid , (Meth) allylsulfonic acid, vinylsulfonic acid, monomers having a sulfonic acid group such as 2-hydroxy-3-allyloxy-1-propanesulfonic acid, 2-hydroxy-3-butenesulfonic acid; vinylphosphonic acid, Monomers having a phosphonic acid group such as (meth) allylphosphonic acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meta ) Acrylate, 4-hydroxybutyl (meth) acrylate, α-hydride Hydroxyl-containing alkyl (meth) acrylates such as xymethylethyl (meth) acrylate; (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate Alkyl (meth) acrylates obtained by esterification of acrylic acid and alcohols having 1 to 18 carbon atoms; Amide group-containing monomers such as (meth) acrylamide, dimethylacrylamide and isopropylacrylamide; Vinyl esters such as vinyl acetate Alkenes such as ethylene and propylene, aromatic vinyl monomers such as styrene and styrene sulfonic acid, maleimide derivatives such as maleimide, phenylmaleimide and cyclohexylmaleimide, and nitrile group-containing vinyl monomers such as (meth) acrylonitrile Mers; ( Aldehyde group-containing vinyl monomers such as (meth) acrolein; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; monomers having a structure in which an alkylene oxide is added to an unsaturated alcohol such as allyl alcohol or isoprenol; Vinyl chloride, vinylidene chloride, allyl alcohol, vinyl pyrrolidone, etc .; vinyl aromatic amino group-containing monomers having a heterocyclic aromatic hydrocarbon group and a polymerizable group, such as vinyl pyridine and vinyl imidazole, and quaternized products thereof And allylamines such as diallylamine and diallyldimethylamine and quaternized products and salts thereof; (i) (ii) dimethyl on the epoxy ring of (meth) allyl glycidyl ether, isoprenyl glycidyl ether, vinyl glycidyl ether; Reaction with amines such as dialkylamines such as amine, diethylamine, diisopropylamine and di-n-butylamine, alkanolamines such as diethanolamine and diisopropanolamine, aminocarboxylic acids such as iminodiacetic acid and glycine, and cyclic amines such as morpholine and pyrrole. Monomers obtained by this, quaternized products and salts thereof, and the like. Also about these other monomers, only 1 type may be used independently and 2 or more types may be used together.

The amount of the other monomer that is an optional component in the production method of the present invention is 100% by mass of the total amount of the PAG compound and the monomer (amino group-containing (meth) acrylate, other monomer). On the other hand, the content is preferably 0 to 30% by mass because the ability to prevent recontamination of the polymer composition tends to be improved.
In addition, when calculating the said usage-amount, when a monomer has an acid group, it calculates by acid type conversion, and when it has an amino group, it calculates by corresponding amine conversion. For example, when the monomer is sodium acrylate, the amount used is calculated as the corresponding acid, acrylic acid (acid type conversion).

<Polymerization initiator>
The production method of the present invention preferably includes a step of polymerizing a monomer component containing an amino group-containing (meth) acrylate as an essential component in the presence of a compound having a polyalkylene glycol structure and a polymerization initiator.
Examples of the polymerization initiator that can be used in the production method of the present invention include hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; dimethyl 2,2′-azobis (2-methylpropionate). ), 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 ′ -Azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyric acid) dimethyl, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2 -Methylpropionamidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] n hydrate, 2,2'-azobis [2- (2-imidazoline- 2- Yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 1,1′-azobis (cyclohexane-1-carbonitrile) And azo compounds such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydroperoxide and the like. Among these polymerization initiators, it is preferable to use an azo compound because the polymerization of the amino group-containing (meth) acrylate is good and the residual monomer can be reduced.

  The amount of the initiator used is not particularly limited, but is 0.1 g or more and 20 g or less with respect to 1 mol of the total amount of monomers used (also referred to as all monomers), unless otherwise specified below. Preferably it is 1-15g.

In the production method of the present invention, a chain transfer agent may be used as a molecular weight regulator of the polymer within a range that does not adversely affect the polymerization, if necessary. Specific examples of the chain transfer agent include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropion, 3-mercaptopropion, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2- Thiol chain transfer agents such as mercaptoethanesulfonic acid, n-dodecyl mercaptan, octyl mercaptan, butylthioglycolate; halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane; Secondary alcohol; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, bisulfite, dithionite, metabisulfite, and salts thereof ( Sodium bisulfite, potassium bisulfite, sub Sodium dithionite, potassium dithionite, sodium metabisulfite, bisulfite (salt) such potassium metabisulfite and the like) and the like, lower oxides and salts thereof, and the like and the like. The chain transfer agent may be used alone or in the form of a mixture of two or more.
When a chain transfer agent is used, there is an advantage that the polymer to be produced can be prevented from having a higher molecular weight than necessary, and a low molecular weight polymer can be produced efficiently.

  In the production method of the present invention, the addition amount of the chain transfer agent is not particularly limited, but is preferably 1 to 20 g, more preferably 2 to 1 mol with respect to 1 mol of all monomers, unless otherwise specified below. 15 g.

  In the production method of the present invention, heavy metal ions may be blended in the polymerization reaction system. By blending heavy metal ions in the polymerization reaction system, the blending amount of the initiator and the chain transfer agent can be reduced. Initiators and chain transfer agents cause impurities and can cause performance degradation, so the amount is preferably reduced.

A heavy metal means a metal having a specific gravity of 4 g / cm ³ or more. Specific heavy metals include iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium and the like. Two or more heavy metals may be used. The polymerization reaction system contains these ions. Preferably, the polymerization reaction system contains iron ions. There is no particular limitation on the ionic value of the heavy metal ion. For example, when iron is used as the heavy metal, the iron ion dissolved in the polymerization reaction system may be Fe 2+ or Fe ³⁺ . These may be combined.
Heavy metal ions can be added using a solution in which a heavy metal compound is dissolved. The heavy metal compound used in that case is determined according to the heavy metal ion desired to be contained in the polymerization reaction system. When water is used as the solvent, a water-soluble heavy metal salt is preferable. Examples of water-soluble heavy metal salts include molle salt (Fe (NH ₄ ) ₂ (SO ₄ ) ₂ .6H ₂ O), ferrous sulfate heptahydrate, ferrous chloride, ferric chloride, manganese chloride Etc. As a method for adding heavy metal ions, initial addition or sequential addition, preferably initial addition is used. However, the method of adding heavy metal ions is not limited to these. The initial addition refers to a method in which the entire amount of heavy metal ions is added to the polymerization reaction system in advance, and the sequential addition refers to a method in which heavy metal ions are gradually added as the polymerization reaction proceeds.

  The content of heavy metal ions is not particularly limited, but is preferably 0.1 to 20 ppm, more preferably 0.2 to 10 ppm, still more preferably 0.3 to the total mass of the polymerization reaction system when the polymerization reaction is completed. 7 ppm, particularly preferably 0.4 to 6 ppm, most preferably 0.5 to 5 ppm. Since the amount of heavy metal ions added to obtain the effect of the present invention may be such an amount, impurities derived from heavy metal ions are hardly generated. When two or more kinds of heavy metal ions are included, the total amount of heavy metal ions may be in the above range. The time when the polymerization reaction is completed means the time when the polymerization reaction is substantially completed in the polymerization reaction system.

  If the content of heavy metal ions is less than 0.1 ppm, the effect of heavy metal ions may not be sufficiently exhibited. On the other hand, when the content of heavy metal ions exceeds 20 ppm, the color tone may be deteriorated. Moreover, when a polymer mixture is used as a detergent builder or a scale inhibitor, there is a risk of increasing dirt and scale.

<Other additives>
In the production method of the present invention, the amount of water used is controlled as described above. In order to improve the solubility of the monomer, an organic solvent may be used. Usable organic solvents include lower alcohols such as methanol and ethanol; amides such as dimethylformaldehyde; ethers such as diethyl ether and dioxane.

<Other polymerization conditions>
The dropping time of each component dropped during the polymerization is usually 40 minutes to 420 minutes, preferably 60 minutes to 360 minutes. Depending on each component, the dropping time may be different.

  The dropping speed of each component is not particularly limited. For example, the dropping speed may be constant from the start to the end of dropping, and the dropping speed may be changed as necessary. In order to increase the production efficiency of the polymer mixture, the concentration of the solid component in the polymerization reaction system after the completion of the dropping, that is, the concentration of the solid content generated by the polymerization of the monomer is 40% by mass or more. It is preferable to make it drop.

  The polymerization temperature is preferably 25 to 200 ° C, more preferably 50 to 150 ° C, and still more preferably 80 to 120 ° C. If the polymerization temperature is too low, the weight average molecular weight of the polymer contained in the resulting polymer mixture may increase, and the amount of impurities generated may increase. Moreover, since polymerization time becomes long, productivity of a polymer composition falls. If the polymerization temperature is too high, the amount of impurities produced may increase.

  The pressure at the time of polymerization is not particularly limited, and may be any pressure under normal pressure, reduced pressure, or increased pressure.

  In addition to the above polymerization step, the production method of the present invention includes a neutralization step as necessary when the polymer contained in the polymer composition produced in the polymerization step is an acid type or a partially neutralized type. You can leave. In addition, if necessary, the mixing step of adding other components to the polymer composition produced in the polymerization step, the purification step of removing or reducing a part of the components, and increasing or decreasing the amount of solvent in the polymer composition A dilution step and a concentration / drying step may be included.

<Polymer composition of the present invention>
The polymer composition of the present invention is preferably produced by the production method described above.

The polymer composition of the present invention comprises a compound (compound A) having a structural unit derived from an amino group-containing (meth) acrylate and a compound (compound B) having a structural unit derived from a compound having a polyalkylene glycol structure. It is characterized by including.
Compounds A and B may overlap. That is, for example, Compound A may have a structural unit derived from a compound having a polyalkylene glycol structure in addition to a structural unit derived from an amino group-containing (meth) acrylate.

The “structural unit derived from an amino group-containing (meth) acrylate” and the “structural unit derived from a compound having a polyalkylene glycol structure” are as described above.
Compounds A and B are optional, but may have structural units derived from other monomers.

The polymer composition of the present invention includes a structural unit derived from an amino group-containing (meth) acrylate, a structural unit derived from a PAG compound and a structural unit derived from a monomer (derived from an amino group-containing (meth) acrylate). It is preferably 4 to 90% by mass, more preferably 5 to 75% by mass, and more preferably 20 to 60% by mass with respect to 100% by mass in total of the structural unit and the structural unit derived from the other monomer). More preferably.
The structural unit derived from amino group-containing (meth) acrylate is a structure produced by polymerization of amino group-containing (meth) acrylate. For example, if it is a structural unit derived from diethylaminoethyl acrylate, -CH ₂ CH (—C (═O) OCH ₂ CH ₂ N (CH ₃ ) ₂ ) —. Amino group-containing (meth) acrylate structural unit itself, i.e., for example, in the case of diethylaminoethyl _{acrylate, CH 2 = CH (-C (} = O) OCH 2 CH 2 N (CH 3) 2) represented by the structural unit As such, it is not included in the structural unit derived from amino group-containing (meth) acrylate.

The polymer composition of the present invention preferably has 10 to 96% by mass of the structural unit derived from the PAG compound with respect to 100% by mass in total of the structural unit derived from the PAG compound and the structural unit derived from the monomer. It is more preferable to set it as -95 mass%, and it is still more preferable to set it as 40-80 mass%.
The structural unit derived from a compound having a polyalkylene glycol structure is derived from a compound having a polyalkylene glycol structure itself or a monomer of a compound in which a monomer or the like is added to a compound having a polyalkylene glycol structure. The structural unit of the part except the structure to represent is represented.
That is, the structural unit derived from the compound having a polyalkylene glycol structure includes the structural unit of the compound itself having a polyalkylene glycol structure, and also includes a structural portion contained in a polymer or by-product.

  The polymer composition of the present invention is optional, but the structural unit derived from another monomer is 0 to 30% with respect to a total of 100% by mass of the structural unit derived from the PAG compound and the structural unit derived from the monomer. You may have mass%.

If the range of the mass of each structural unit contained in the polymer composition of this invention is the said range, it is preferable from the remarkable effect which the recontamination prevention capability improves.
When calculating the mass% of the structural unit, in the case of a structural unit derived from a monomer containing an acid group, in the case of a structural unit derived from a monomer containing an amino group, in terms of acid type It shall be calculated in terms of amine.

  Content of the said structural unit contained in the polymer composition of this invention can be measured by NMR method etc. (converted from molar ratio).

As described above, the polymer composition of the present invention may be in the form of an aqueous solution (sometimes referred to as the aqueous polymer solution of the present invention).
When the polymer composition of the present invention contains water, the preferred water content of the polymer composition of the present invention is 20 to 80% by mass. Preferably it is 30-70 mass%, More preferably, it is 35-60 mass%. When the polymer composition of the present invention contains water, the preferred solid content concentration of the polymer composition of the present invention is 20 to 80% by mass, preferably 30 to 70% by mass, and more preferably 40 to 65%. % By mass.

  By producing the polymer composition of the present invention by the production method of the present invention, the content of the amino group-containing (meth) acrylate can be set low. In the polymer composition of the present invention, the content of the amino group-containing (meth) acrylate is preferably 0 to 15000 ppm and is 0 to 12000 ppm with respect to 100% by mass of the solid content of the polymer composition of the present invention. More preferably, it is more preferably 0 to 10,000 ppm.

  The weight-average molecular weight of the polymer contained in the polymer composition of the present invention is preferably 1,000 to 100,000, since the ability to prevent recontamination tends to improve, and preferably 1,500 to 50, Is more preferably 2,000, particularly preferably 2,000 to 30,000, still more preferably 2,000 to 20,000, and most preferably 4,000 to 15,000. .

The polymer (composition) of the present invention has a good ability to prevent recontamination. Preferably, it is 49% or more in the evaluation method of the recontamination preventing ability described later.
The polymer composition of the present invention has good storage stability.

<Uses of polymer composition>
The 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.
The polymer composition of the present invention contains the above-described polymer, but from the viewpoint that excellent builder performance can be exhibited, the content of the polymer is preferably 0 with respect to the total amount of the detergent composition. 0.1 to 15% by mass, more preferably 0.3 to 10% by mass, and still more preferably 0.5 to 5% by mass.
Detergent compositions used in detergent applications usually include surfactants and additives used in detergents. Specific forms of these surfactants and additives are not particularly limited, and conventionally known knowledge can be appropriately referred to in the detergent field. The detergent composition may be a powder detergent composition or a liquid detergent composition.
The surfactant is one or more selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant. When two or more kinds are used in combination, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 60% by mass with respect to the total amount of the surfactant. It is above, More preferably, it is 70 mass% or more, Most preferably, it is 80 mass% or more.
Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonate. , Saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, alkenyl phosphate ester or Its salts are preferred. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these anionic surfactants.

  Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters. Esters, alkylamine oxides and the like are preferred. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these nonionic surfactants.

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

  The blending ratio of the surfactant is usually 10 to 80% by mass, preferably 15 to 70% by mass, more preferably 20 to 60% by mass, and particularly preferably based on the total amount of the detergent composition. Is 25-40 mass%. If the surfactant content is too small, sufficient detergency may not be achieved, and if the surfactant content is too high, the economy may be reduced.

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

  The detergent composition may 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, bicarbonates and silicates, tripolyphosphates, pyrophosphates, bow nitrate, nitrilotriacetate, ethylenediaminetetraacetate, Examples thereof include acid salts, copolymer salts of (meth) acrylic acid, acrylic acid-maleic acid copolymers, chelate builders such as fumarate and zeolite, and carboxyl derivatives of polysaccharides such as carboxymethylcellulose. Examples of the counter salt used in the builder include alkali metals such as sodium and potassium, ammonium and amine.

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

  In addition, the concept of the above-mentioned detergent composition includes specific detergents such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance one of the components. Detergents that are only used are also included.

  When the detergent composition is a liquid detergent composition, the amount of water contained in the liquid detergent composition is usually preferably 0.1 to 75% by mass, more preferably based on the total amount of the liquid detergent composition. Is 0.2 to 70% by mass, more preferably 0.5 to 65% by mass, even more preferably 0.7 to 60% by mass, particularly preferably 1 to 55% by mass, Preferably it is 1.5-50 mass%.

  When the detergent composition is a liquid detergent composition, the detergent composition preferably has a kaolin turbidity of 200 mg / L or less, more preferably 150 mg / L or less, and even more preferably 120 mg / L or less. Especially preferably, it is 100 mg / L or less, Most preferably, it is 50 mg / L or less.

  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, a NDU2000 manufactured by Nippon Denshoku Co., Ltd. Kaolin turbidity: mg / L) is measured.

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

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

  Even when the detergent composition of the present invention 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, the salt composition hardly precipitates 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, monomer analysis, anti-recontamination ability, compatibility with surfactants, solid content of the polymer composition and the like of the polymer of the present invention are measured according to the following method. ·evaluated.
<Measurement of molecular weight of polymer>
The weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured values by GPC (gel permeation chromatography).
Measuring device: "L-7000 series" manufactured by Hitachi
Detector: RI
Column: “TOSOH guard column α”, “TSK gel α-3000”, “TSK gel α-2500” manufactured by Showa Denko KK in this order Temperature: 40 ° C.
Flow rate: 0.4 mL / min calibration curve: prepared using a polyethylene oxide standard sample (manufactured by GL Sciences Inc.) Eluent: 100 mM sodium borate aqueous solution (pH 9.2) / acetonitrile: 80/20 (wt%).
<Measurement of monomer in polymer composition>
The monomer was measured using liquid chromatography under the following conditions.
Measuring device: "L-7000 series" manufactured by Hitachi
Detector: UV (detection wavelength 254 nm)
Column: “TOSOH guard column α”, “TSK gel α-3000”, “TSK gel α-2500” manufactured by Showa Denko KK in this order Temperature: 40 ° C.
Flow rate: 0.4 mL / min Eluent: 100 mM sodium borate aqueous solution (pH 9.2) / acetonitrile: 80/20 (wt%).
<Evaluation of ability to prevent recontamination>
The test for preventing recontamination of polyester fabric using carbon black was performed according to the following procedure.
(I) A polyester cloth obtained from Test fabric was cut into 5 cm × 5 cm to prepare a white cloth. The whiteness of the white cloth was measured by reflectance using a colorimetric color difference meter SE2000 type manufactured by Nippon Denshoku Industries Co., Ltd. in advance. (This is called the whiteness of the test cloth before washing.)
(Ii) Water was added to 4.41 g of calcium chloride dihydrate and 2.41 g of magnesium chloride hexahydrate to make 20 L.
(Iii) Emar 270J (70%) diluted to 5% 64 g, Emulgen 108 (100%) 0.4 g, sodium borate decahydrate 0.76 g, citric acid 1.0 g Pure water was added to make 90 g, adjusted to pH 8.5 with 10% NaOH, and further water was added to make 100 g.
(Iv) 0.125 g of carbon black was weighed on the required number of medicine wrappers.
(V) About 20 g of a 1 wt% sample aqueous solution was prepared.
(Vi) Set the targot meter at 40 ° C., put 500 mL of the above (ii), 2.5 g of the above (iii), 0.125 g of the above (iv), and 3.5 g of the above (v) into the pot. And stir at 100 rpm for 1 minute. Then, 5 white cloths were put and stirred at 100 rpm for 30 minutes.
(Vii) Water of the white cloth is drained by hand, and the above (ii) is put into a 500 mL pot and stirred at 100 rpm for 2 minutes. This was done twice.
(Viii) A white cloth was applied and dried while stretching the wrinkles with an iron, and then the whiteness of the white cloth was measured again with the colorimetric color difference meter (i). (This is called the whiteness of the test cloth after washing.)
(Ix) From the above measurement results, the dye transfer prevention ability is determined by the following equation.
(X) Prevention of recontamination dyeing (%) = [(whiteness of test cloth after washing) / (whiteness of test cloth before test)] × 100.
<Compatibility with surfactant>
A polymer composition 0.2 g (solid content) was mixed with 4 g of 25% aqueous solution of polyoxyethylene dodecyl ether (added 8 mol of ethylene oxide on average to dodecanol), and allowed to stand for 1 hour. The case where there was no turbidity was rated as “◯”, the case where it was slightly turbid, “△”, and the case where it was cloudy as “X”. The absence of turbidity indicates that the detergent to which the polymer composition is added can be kept uniform over a long period of time.

<Method for measuring solid content of polymer composition>
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.

<Example 1>
110. A glass separable flask having a capacity of 500 mL equipped with a thermometer, a reflux condenser, and a stirrer was added to methoxypolyethylene glycol 25 (a compound obtained by adding an average of 25 moles of ethylene oxide to methanol; hereinafter referred to as PGM25). 0 g was charged and the temperature was raised to 70 ° C. with stirring, and then 27.5 g of 2- (dimethylamino) ethyl acrylate (hereinafter also referred to as DAA) and 15% by weight 2,2′-azobis (2-methyl) Propionamidine) dihydrochloride (34.6 g) and pure water (35.6 g) were added dropwise from separate dropping ports. Each dropping time was 27.5 g of 2- (dimethylamino) ethyl acrylate for 120 minutes, 34.6 g of 15 wt% 2,2′-azobis (2-methylpropionamidine) dihydrochloride, and 35 pure water .6 g was 130 minutes. The start of dropping was all simultaneous. The temperature was maintained at 70 ° C. until the end of dropping. Furthermore, the same temperature was maintained for 30 minutes after completion of the dropping, and ripening was performed to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then diluted by adding 83.1 g of pure water. Thus, a copolymer composition (1) having a solid concentration of 46% by weight was obtained. The amount of residual DAA in the copolymer composition (1) was 0.9% by mass. The polymerization recipe is summarized in Table 1.

<Example 2>
Methoxypolyethylene glycol 75 (compound obtained by adding an average of 75 moles of ethylene oxide to methanol; hereinafter referred to as PGM75) in a 500 mL glass separable flask equipped with a thermometer, reflux condenser, and stirrer 120. After charging 0 g and heating to 70 ° C. with stirring, 13.3 g of 2- (dimethylamino) ethyl acrylate and 15 wt% 2,2′-azobis (2-methylpropionamidine) dihydrochloride (hereinafter referred to as “hydrochloric acid”) , Also referred to as V-50.) 12.2 g and 49.4 g of pure water were added dropwise from separate dropping ports. Each dropping time was 13.3 g of 2- (dimethylamino) ethyl acrylate for 120 minutes, 12.2 g of 15 wt% 2,2′-azobis (2-methylpropionamidine) dihydrochloride, and 49% pure water. .4g was 130 minutes. The start of dropping was all simultaneous. The temperature was maintained at 70 ° C. until the end of dropping. Furthermore, the same temperature was maintained for 30 minutes after completion of the dropping, and ripening was performed to complete the polymerization. After the completion of the polymerization, the reaction solution was allowed to cool and then diluted by adding 78.0 g of pure water. In this way, a copolymer composition (2) having a solid content concentration of 49% by weight was obtained. The residual DAA content in the copolymer composition (2) was 1.2% by mass. The polymerization recipe is summarized in Table 1.

<Comparative Example 1>
A 500 mL glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 180.0 g of pure water, heated to 70 ° C. with stirring, and then 25.1 g of 2- (dimethylamino) ethyl acrylate. 19.0 g of 15% by weight 2,2′-azobis (2-methylpropionamidine) dihydrochloride and 79.5 g of pure water were added dropwise from separate dropping ports. Each dropping time was 25.1 g of 2- (dimethylamino) ethyl acrylate for 120 minutes, 15 wt% 2,2′-azobis (2-methylpropionamidine) dihydrochloride 19.0 g, and pure water 79 .5 g was 130 minutes. The start of dropping was all simultaneous. The temperature was maintained at 70 ° C. until the end of dropping. Furthermore, the same temperature was maintained for 30 minutes after completion of the dropping, and ripening was performed to complete the polymerization. In this way, a comparative polymer composition (1) having a solid content concentration of 6.9% by weight was obtained. The residual DAA content in the comparative polymer composition (1) was 1.8% by mass. The polymerization recipe is summarized in Table 1.

<Comparative example 2>
Into a 50 mL screw tube, 14.5 g of the polymer aqueous solution obtained in Comparative Example 1 and 10.0 of PGM25 were charged and stirred. In this way, a polymer mixture (comparative polymer composition (3)) having a solid content concentration of 45% by weight was obtained.

<Comparative Example 3>
Into a 50 mL screw tube, 14.5 g of the polymer aqueous solution obtained in Comparative Example 1 and 10.0 of PGM25 were charged and stirred. In this way, a polymer mixture (comparative polymer composition (3)) having a solid content concentration of 45% by weight was obtained.

<Example 3>
Table 2 shows the analysis results of the polymer compositions obtained in Example 1 and Comparative Polymers 1 to 3, and the evaluation results of the recontamination prevention ability of the polymers.

<Example 4>
The results of evaluating the compatibility of the polymers obtained in Example 1 and Comparative Polymers 1 to 3 with the surfactant are shown in Table 3.

From the results shown in Table 2, it was clarified that the polymer of the present invention has an excellent ability to prevent recontamination as compared with conventional polymers. Further, from the results shown in Table 3, it was confirmed that the polymer of the present invention has good compatibility with the surfactant.
Therefore, the polymer of the present invention is suitably used as a detergent builder.

Claims (3)

A method for producing a polymer composition comprising a step of polymerizing a monomer essentially comprising an amino group-containing (meth) acrylate in the presence of a compound having a polyalkylene glycol structure,
The amount of water at the start of polymerization is 0 to 120 parts by mass with respect to 100 parts by mass of the compound having the polyalkylene glycol structure,
The polymer whose amount of water contained in the reaction solution at the end of the addition of the amino group-containing (meth) acrylate is 120 to 100,000 parts by mass with respect to 100 parts by mass of the compound having the polyalkylene glycol structure. A method for producing the composition. A polymer composition obtained by the method according to claim 1. A detergent composition comprising a polymer contained in the polymer composition according to claim 2.