JP2014193954A - Polymer composition production method thereof and detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer composition which is excellent in storage stability, compatibility with liquid detergents and dispersibility of hydrophobic dirt, its production method and a detergent composition.SOLUTION: A polymer composition contains a polymer containing a structural unit originated from a (meth)acrylic acid-based monomer and a structural unit originated from a dicarboxylic acid type monomer, in a content of the polymer of 20-70 mass% to 100 mass% of the polymer composition, and also includes 0.01-30 mass% of a compound having a polyalkylene glycol structure and 10-70 mass% of water. The compound having a polyalkylene glycol structure has, at the terminal, a phenoxy group optionally having a substituent group.

Description

The present invention relates to a polymer composition, a method for producing the same, and a detergent composition. More specifically, including a polymer having a structural unit derived from a (meth) acrylic acid monomer and a structural unit derived from a dicarboxylic acid monomer, and a compound having a polyalkylene glycol structure, The present invention relates to a polymer composition that is excellent in compatibility with a liquid detergent and can be blended in a liquid detergent, and a method for producing the same, and a detergent composition containing the polymer composition.

Polymer compositions are used, for example, in detergent composition applications. Among them, a polymer composition containing a compound having a polyalkylene glycol structure has attracted attention and has been developed. For example, the addition of a compound having a polyalkylene glycol structure to a detergent together with a polymer formed from a (meth) acrylic acid monomer has been actively studied. However, the polymer formed from the (meth) acrylic acid monomer and the compound having a polyalkylene glycol structure are not mixed uniformly. There has been a strong demand to improve the storage stability by uniformly mixing them. In addition, there has been a strong demand for improving compatibility with surfactants to improve compatibility with liquid detergents and improving dispersibility of hydrophobic soils.

As a solution to the demand for storage stability, for example, 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, the initial charge The amount of water is less than 90 parts by mass with respect to 100 parts by mass of the compound having a polyalkylene glycol structure, and the amount of water at the end of the addition of the (meth) acrylic acid monomer is the polyalkylene glycol structure The manufacturing method of the polymer mixture which is 1-100,000 mass parts with respect to 100 mass parts of compounds which have is disclosed (for example, refer patent document 1).
According to the above method, the obtained polymer mixture is improved in storage stability, so that the degree of freedom in detergent production is improved and the production cost is also reduced.
However, the polymer mixture produced by the method described in Patent Document 1 has room for improving the compatibility with the liquid detergent. In addition, there is room for improving the dispersibility of the hydrophobic soil.

In addition, a method for producing a polymer composition comprising a step of polymerizing a monomer having a (meth) acrylic acid monomer and a dicarboxylic acid monomer 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 the dicarboxylic acid monomer at the start of polymerization is The amount of water contained in the reaction solution at the end of the addition of the (meth) acrylic acid monomer is 30 to 800 parts by mass with respect to 100 parts by mass of the compound having an alkylene glycol structure. The manufacturing method of the polymer composition which is 100-100,000 mass parts with respect to 100 mass parts of usage-amounts of the compound which has a structure is disclosed (for example, patent Document 2 reference.).
According to the above method, the polymer composition obtained is excellent in storage stability and compatibility with a liquid detergent is improved. On the other hand, there is room for improving the dispersibility of the hydrophobic soil.

JP 2004-331839 A JP 2012-177007 A

Therefore, the present invention provides a polymer composition having excellent storage stability, compatibility with a liquid detergent and dispersibility of hydrophobic soil, a method for producing the same, and a detergent composition. Objective.

The present inventors have intensively studied to solve the above problems. As a result, the present inventors focused on the compound having a polyalkylene glycol structure in the polymer composition, limited the substituent introduced into the compound, and adjusted the mass ratio of the compound, the polymer, and water. Thus, it was studied to improve the dispersibility of the hydrophobic soil while improving the storage stability of the polymer composition and the compatibility with the liquid detergent. And when it is set as the polymer composition which has the compound which introduce | transduced the phenoxy group into the terminal of this compound, a polymer, and water in a predetermined ratio, while the obtained polymer composition is excellent in storage stability, it becomes liquid detergent. Thus, the inventors have found that both the compatibility and the dispersibility of hydrophobic soil are remarkably improved, and the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly.

That is, the present invention is a polymer composition comprising a polymer comprising a structural unit derived from a (meth) acrylic acid monomer and a structural unit derived from a dicarboxylic acid monomer, The coalescence composition contains 20 to 70% by mass of the polymer with respect to 100% by mass of the polymer composition, 0.01 to 30% by mass of a compound having a polyalkylene glycol structure, and 10 to 70% by mass of water. %, And the compound having a polyalkylene glycol structure is a polymer composition having a phenoxy group which may have a substituent at the terminal.
Below, the polymer composition of this invention is explained in full detail.

<Polymer composition of the present invention>
The mass ratio of the polymer containing the structural unit derived from the (meth) acrylic acid monomer and the structural unit derived from the dicarboxylic acid monomer contained in the polymer composition of the present invention is the polymer composition. It is 20-70 mass% with respect to 100 mass% of things. Moreover, the mass ratio of the compound which has a polyalkylene glycol structure contained in the polymer composition of this invention is 0.01-30 mass% with respect to 100 mass% of polymer compositions. Furthermore, the mass proportion of water contained in the polymer composition of the present invention is 10 to 70 mass% with respect to 100 mass% of the polymer composition. By being in the said range, the storage stability of a polymer composition becomes favorable. In addition, the compatibility with the liquid detergent and the dispersibility of the hydrophobic soil are both excellent.
The mass of the polymer contained in the polymer composition is the water content, polyalkylene glycol compound, (meth) acrylic acid monomer, and dicarboxylic acid monomer content based on the total mass of the polymer composition. The mass minus the amount.

<Compound having a polyalkylene glycol structure>
The compound having the polyalkylene glycol structure contained in the polymer composition of the present invention may be any compound having a polyalkylene glycol structure and having a phenoxy group which may have a substituent at the terminal.

The polyalkylene glycol structure refers to a structure represented by the following general formula (1).
-(O-R) _n- (1)
(In the formula, R represents an alkylene group, and n represents the number of repetitions.)
The alkylene group is preferably an alkylene group having 2 to 20 carbon atoms. More preferred are ethylene group, propylene group, trimethylene group, cyclohexylene group and the like.
The n is preferably 5 or more. More preferably, it is 7 or more, and particularly preferably 10 or more. The n is preferably 300 or less. More preferably, it is 100 or less, More preferably, it is 90 or less, Especially preferably, it is 80 or less.

Examples of the compound having a polyalkylene glycol structure include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, copolymers of ethylene oxide and propylene oxide, polyalkylene glycols such as polyalkylene glycol monoalkyl ether and polyalkylene glycol monoaryl ether. And those having a phenoxy group added to the terminal. A component not having a polyalkylene glycol structure may be contained in a compound having a polyalkylene glycol structure. For example, a compound in which polyalkylene glycol is added to active hydrogen of a compound having active hydrogen, and the added polyalkylene glycol further has a phenoxy group at the terminal. That is, for example, a compound having a polyalkylene glycol structure in which a compound having a plurality of active hydrogens such as polyethyleneimine is substituted with a polyalkylene glycol structure and a phenoxy group is added to the terminal of the polyalkylene glycol structure. It may be used as In addition, polyalkylene glycol ester compounds, polyalkylene glycol adducts of compounds having an unsaturated double bond such as isoprenol and allyl alcohol, which further have a phenoxy group at the terminal have a polyalkylene glycol structure. It can be used as a compound having.

Another example of the compound having a preferable polyalkylene glycol structure is a compound represented by the following general formula (2). If the compound having a polyalkylene glycol structure 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 O (oxygen atom directly bonded to R ¹ and R ¹ ) represents a phenoxy group which may have a substituent.
The substituent which the said phenoxy group may have is a substituent which substitutes for the hydrogen atom of an aromatic ring couple | bonded with the aromatic ring of a phenoxy group. The substituent may be plural. Examples of the substituent include an alkyl group, an aromatic ring group, and an alkynyl group. Preferably, it is an aromatic ring.
In the general formula (2), ^{R 2} represents an alkylene group having 2 to 20 carbon atoms. More preferred are ethylene group, propylene group, trimethylene group, cyclohexylene group and the like. Particularly preferred are ethylene group and propylene group.
M represents a number of 5 to 300. More preferably, it is 7 or more, and particularly preferably 10 or more. Further, m is more preferably 100 or less, still more preferably 90 or less, still more preferably 80 or less, still more preferably 40 or less, and particularly preferably 30 or less.
R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an isopropyl group, an n-butyl group, a cyclohexyl group, an n-octyl group, and an n-dodecyl group. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a methylphenyl group, and a naphthyl group.

The compound having the polyalkylene glycol structure may be synthesized based on the knowledge obtained so far, or a commercially available compound may be used. Moreover, 1 type of compounds which have the polyalkylene glycol structure which has the phenoxy group which may have a substituent may be used, and 2 or more types may be used. Moreover, as long as the effects of the present invention are exhibited, the compound having a polyalkylene glycol structure having a terminal phenoxy group which may have a substituent and a polyalkylene glycol structure having no terminal phenoxy group A compound may be used.

The weight average molecular weight of the compound having a polyalkylene glycol structure is preferably 300 to 20,000 in consideration of the use as a detergent. More preferably, it is 500-15,000, Most preferably, it is 800-10,000. A compound having a polyalkylene glycol structure may be selected according to the structure of the compound having a polyalkylene glycol structure and the characteristics required of the polymer composition.
The weight average molecular weight of the compound having the polyalkylene glycol structure can be measured by gel permeation chromatography (GPC) in the same manner as in the examples.

The compound having a polyalkylene glycol structure contained in the polymer composition of the present invention may be contained in an amount of 0.01 to 30% by mass with respect to the polymer composition. In the polymer composition of the present invention, the mass ratio of the compound having a polyalkylene glycol structure contained in the polymer composition is preferably 0.1% by mass or more with respect to 100% by mass of the polymer composition, More preferably, it is 0.3 mass% or more. Moreover, Preferably it is 20 mass% or less, More preferably, it is 15 mass% or less. Thereby, the recontamination prevention ability of a polymer composition improves.
The content of the compound having a polyalkylene glycol structure in the polymer composition can be measured by the same method as in the examples using liquid chromatography (HPLC).

<Polymer according to the present invention>
The polymer according to the present invention includes a structural unit derived from a (meth) acrylic acid monomer and a structural unit derived from a dicarboxylic acid monomer, and has a polyalkylene glycol structure described later. The structural unit derived from may be included. Hereinafter, a structural unit derived from a (meth) acrylic acid monomer, a structural unit derived from a dicarboxylic acid monomer, or a structural unit derived from a compound having a polyalkylene glycol structure, contained in the polymer of the present invention. The structural units derived from other monomers will be described in order.

(Structural unit derived from (meth) acrylic acid monomer)
The “structural unit derived from a (meth) acrylic acid monomer” constituting the polymer composition of the present invention is:
The following general formula (3);

(In the formula, R ⁴ represents a hydrogen atom or a methyl group. M ¹ represents a hydrogen atom, a metal atom, an ammonium base or an organic amine base.) To do. The structural unit derived from the (meth) acrylic acid monomer may be only one type or two or more types. Examples of the “structural unit derived from a (meth) acrylic acid monomer” include a structural unit obtained by polymerizing acrylic acid (salt) and methacrylic acid (salt). Salts referred to herein, is a salt of a carboxyl group represented by -COOM ^1, M ¹ is a metal atom, an ammonium base or an organic amine base. Examples of the metal atom include alkali metals such as sodium, lithium and potassium; alkaline earth metals such as magnesium and calcium; aluminum and iron. Moreover, a quaternary ammonium base is mentioned as said ammonium base. Examples of the organic amine base include alkanolamine groups such as monoethanolamine group, diethanolamine group and triethanolamine group; alkylamine groups such as monoethylamine group, diethylamine group and triethylamine group; polyamine groups such as ethylenediamine group and triethylenediamine group. Is mentioned. Of these, ammonium base, sodium, and potassium are preferable, and sodium is more preferable because the resulting polymer has a high effect of improving the ability to prevent recontamination. Further, the R ⁴ represents a hydrogen atom, the M ¹ is also preferred that a hydrogen atom.

The polymer composition is composed of “structural units derived from (meth) acrylic acid monomers”, the total amount of all structural units in the polymer (“structural units derived from dicarboxylic acid monomers”, “ Total amount of “structural unit derived from (meth) acrylic acid monomer” and “structural unit derived from compound having polyalkylene glycol structure”. The same applies to the following. The content is 99% by mass or less. When the content of “structural unit derived from (meth) acrylic acid monomer” is within the above range, the effect of preventing the polymer from recontamination and the compatibility with liquid detergents can be significantly improved. The ratio of the “structural unit derived from the (meth) acrylic acid monomer” to the total amount of 100% by mass of all the structural units is preferably 4% by mass or more and 80% by mass or less, more preferably 5% by mass or more. 75 mass% or less, more preferably 10 mass% or more and 60 mass% or less.

When the polymer according to the present invention is used as a detergent builder, the compatibility of the polymer is excellent by containing the “structural unit derived from the (meth) acrylic acid monomer” at the specific ratio described above. Thus, the effect of dispersing the dirt particles can be exhibited.

(Structural unit derived from dicarboxylic acid monomer)
The “structural unit derived from a dicarboxylic acid monomer” constituting the polymer composition of the present invention has the following general formula (4):

(In the formula, one selected from the group consisting of R ⁵ , R ⁶ and R ⁷ represents (CH ₂ ) _x COOM ³ , and the other represents the same or different and represents a hydrogen atom or a methyl group. . it should be _{noted, - (CH 2) x COOM} 3 is -COOM ² and good .x also form a anhydrides, .M ² and ^{M 3} is an integer of 0 to 2 are the same or different, Represents a hydrogen atom, a metal atom, an ammonium base, or an organic amine base). The structural unit derived from the dicarboxylic acid monomer may be only one type or two or more types.
The “structural unit derived from a dicarboxylic acid monomer” includes, for example, maleic acid (salt), maleic anhydride, fumaric acid (salt), itaconic acid (salt), itaconic anhydride, 2-methyleneglutaric acid ( And a structural unit obtained by polymerizing a salt). Preferably, it is a structural unit obtained by polymerizing maleic acid (salt) and / or maleic anhydride. The salt here is a salt of a carboxyl group represented by —COOM ² or — (CH ₂ ) _x COOM ³ as described above, and M ² or M ³ is a metal atom, an ammonium base, Or it is an organic amine base. Examples of the metal atom include alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and calcium, and iron. Moreover, a quaternary ammonium base is mentioned as said ammonium base. Examples of the organic amine base include alkanolamine groups such as monoethanolamine group, diethanolamine group and triethanolamine group; alkylamine groups such as monoethylamine group, diethylamine group and triethylamine group; polyamine groups such as ethylenediamine group and triethylenediamine group. Is mentioned. Of these, ammonium base, sodium and potassium are preferable, and sodium is more preferable. It is also preferable that M ² or M ³ represents a hydrogen atom.

In the polymer composition, the “structural unit derived from the dicarboxylic acid monomer” is usually 1% by mass to 99% by mass with respect to 100% by mass of the total amount of all structural units in the polymer. Have. If the content of the “structural unit derived from the dicarboxylic acid monomer” is within the above range, the effect of improving the detergency can be obtained. The ratio of the “structural unit derived from the dicarboxylic acid monomer” to the total amount of 100% by mass of all the structural units is preferably 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 70% by mass. % Or less, and more preferably 15% by mass or more and 60% by mass or less.

When the polymer of the present invention is used as a detergent builder, by containing the “structural unit derived from a dicarboxylic acid monomer” at the specific ratio described above, the compatibility of the polymer is improved, and dirt particles It is possible to exert the effect of dispersing the.

(Structural unit derived from a compound having a polyalkylene glycol structure)
The structural unit derived from the compound having a polyalkylene glycol structure represents a portion corresponding to the compound having a polyalkylene glycol structure in the polymer.
The polymer has “a structural unit derived from a compound having a polyalkylene glycol structure” at a ratio of 1% by mass to 99% by mass with respect to 100% by mass of the total amount of all structural units in the polymer. Is preferred. If the content of the “structural unit derived from the compound having a polyalkylene glycol structure” is within the above range, the stability of the polymer composition will be good, and the ability of the polymer to prevent recontamination and to be compatible with liquid detergents. A remarkable improvement effect of solubility is obtained. The ratio of the “structural unit derived from the compound having a polyalkylene glycol structure” to the total amount of 100% by mass of all the structural units is preferably 4% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass. It is not more than mass%, more preferably not less than 7 mass% and not more than 50 mass%.

When the polymer according to the present invention is used as a detergent builder, by containing the “structural unit derived from the compound having a polyalkylene glycol structure” at the above-described specific ratio, the compatibility of the polymer becomes good. An effect of dispersing the dirt particles can be exhibited.

(Structural units derived from other monomers)
As structural units derived from other monomers constituting the polymer composition of the present invention, the compound having the polyalkylene glycol structure, the (meth) acrylic acid monomer, and the dicarboxylic acid monomer In addition, other monomers polymerizable with these may be used.

Examples of other monomers include 2-acrylamido-2-methylpropanesulfonic acid, (meth) allylsulfonic acid, vinylsulfonic acid, 2-hydroxy-3-allyloxy-1-propanesulfonic acid, and 2-hydroxy-3. A monomer having a sulfonic acid group such as butenesulfonic acid; a monomer having a phosphonic acid group such as vinylphosphonic acid or (meth) allylphosphonic acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Hydroxyl group-containing alkyl (meth) acrylates such as (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and α-hydroxymethylethyl (meth) acrylate ; Methyl (meth) acrylate, (meth) a Alkyl (meth) acrylates obtained by esterification of (meth) acrylic acid such as ethyl laurate, butyl (meth) acrylate, cyclohexyl (meth) acrylate and alcohols having 1 to 18 carbon atoms; dimethylaminoethyl ( Amino group-containing acrylate such as (meth) acrylate or quaternized product thereof; 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; nitrile group-containing vinyl monomers such as (meth) acrylonitrile; (meth) acrolein, etc. Aldehyde group of Containing vinyl monomers; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; monomers having a structure in which alkylene oxide is added to unsaturated alcohol such as allyl alcohol or isoprenol; vinyl chloride, vinylidene chloride, allyl Examples include alcohol and vinyl pyrrolidone. Also about these other monomers, only 1 type may be used independently and 2 or more types may be used together. The polymer composition preferably has “structural units derived from other monomers” at a ratio of 0% by mass or more and 10% by mass or less with respect to 100% by mass of the total amount of all structural units.

When calculating the mass% of each structural unit, it is calculated in terms of acid type. Calculating in terms of acid type means converting the amount of carboxyl group salt or carboxyl group dehydrated and condensed into the amount of carboxyl group, for example, dicarboxylic acid monomer as an example When the dicarboxylic acid monomer is disodium maleate or maleic anhydride, the mass is calculated as maleic acid.

The polymer contained in the polymer composition of this invention should just be 20-70 mass% with respect to a polymer composition. Preferably, it is 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 45% by mass or more. Preferably, it is 60 mass% or less, More preferably, it is 55 mass% or less.

<Water contained in polymer composition>
If the water contained in the polymer composition of the present invention is contained in an amount of 10 to 70% by mass with respect to the polymer composition, the addition method is not particularly limited. For example, water may be added before the start of polymerization. The water to be added may be water contained in the above various monomer components, or may be water added separately from the monomer components.
The water contained in the polymer composition is preferably 20% by mass or more, and more preferably 30% by mass or more. Moreover, Preferably it is 70 mass% or less, More preferably, it is 60 mass% or less. Thereby, the storage stability and the compatibility with a liquid detergent can be made more excellent.
The mass of water contained in the polymer composition may be converted from the measured value of the solid content measuring method described in the examples, or may be measured by the Karl Fischer method.

The weight average molecular weight of the polymer composition of the present invention is preferably 1,000 to 100,000 because the recontamination preventing ability tends to be improved. It is more preferably 1,500 to 50,000, particularly preferably 2,000 to 30,000, still more preferably 2,000 to 20,000, and 3,000 to 15,000. Most preferably.
The weight average molecular weight of the polymer of this invention can be measured by the method similar to an Example using a gel permeation chromatography (GPC).

The solid content concentration of the polymer composition of the present invention is preferably 30 to 90% by mass. More preferably, it is 40 mass% or more. More preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less.

The polymer composition of the present invention is preferably produced by the method for producing the polymer composition of the present invention described later.
For example, the polymer composition of the present invention polymerizes a monomer component essentially comprising a (meth) acrylic acid monomer and a dicarboxylic acid monomer in the presence of a compound having a polyalkylene glycol structure. The mass ratio between the amount of the compound having a polyalkylene glycol structure and the total amount of the (meth) acrylic acid monomer and the dicarboxylic acid monomer is 10 / It is preferable that it is 90-70 / 30.
Below, the manufacturing method of the polymer composition of this invention is explained in full detail.

<Method for Producing Polymer Composition of the Present Invention>
The method for producing a polymer composition of the present invention is a method for producing a polymer composition, and the production method described above is a simple method in which a (meth) acrylic acid monomer and a dicarboxylic acid monomer are essential. A step of polymerizing a monomer component in the presence of a compound having a polyalkylene glycol structure, wherein the compound having a polyalkylene glycol structure is a polymer composition having a phenoxy group which may have a substituent as a terminal. It is a manufacturing method of a thing.
The method for producing a polymer composition of the present invention comprises a monomer component essentially comprising a (meth) acrylic acid monomer and a dicarboxylic acid monomer, and a phenoxy optionally having a substituent at the terminal. By polymerizing in the presence of a compound having a polyalkylene glycol structure having a group introduced therein, functions such as detergency inherent to the monomer component can be exhibited, and polymers having various compositions can be obtained. As a result, the polymer composition is excellent in storage stability and sufficiently compatible with liquid detergents. Furthermore, the dispersibility of the hydrophobic soil is remarkably improved based on a structural unit derived from a compound having a polyalkylene glycol structure, such as a compound having a polyalkylene glycol structure.

<Compound having a polyalkylene glycol structure>
The compound having a polyalkylene glycol structure used in the production method of the present invention and preferred one thereof are the same as those described above as the compound having a polyalkylene glycol structure contained in the polymer composition of the present invention. In the production method of the present invention, the total amount of the compound having a polyalkylene glycol structure is preferably added to the reaction kettle before the start of polymerization, but a part of the compound after the start of polymerization or addition of a (meth) acrylic monomer You may add after completion | finish.

The amount of the compound having a polyalkylene glycol structure used in the production method of the present invention is the sum of the compound having a polyalkylene glycol structure and the monomer (dicarboxylic acid monomer, (meth) acrylic acid monomer). 4 to 70% by mass with respect to 100% by mass is preferably used because the ability to prevent recontamination of the polymer composition tends to be improved, and more preferably 5 to 60% by mass. More preferably, it is made into 50 mass%. In addition, when calculating the said usage-amount, when a monomer has an acid group, it calculates by conversion of a corresponding acid type, and when it has an amino group, it calculates by conversion of a corresponding amine. The calculation in terms of the corresponding acid type is as described above. The calculation in terms of corresponding amine means that, for example, when the monomer has an amine hydrochloride, the mass is calculated using the amine hydrochloride as an amine. More specifically, when the monomer is vinylamine hydrochloride, the mass is calculated as vinylamine.

<Water content during polymerization>
The production method of the present invention comprises a step of polymerizing a monomer component essentially comprising a (meth) acrylic acid monomer and a dicarboxylic acid monomer in the presence of a compound having a polyalkylene glycol structure. It is a method, It is preferable to add water before superposition | polymerization start. In the present specification, “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 (of the dicarboxylic acid monomer at the start of polymerization). If an anhydride is present, it reacts stoichiometrically with water, so water in a range not exceeding the number of moles of anhydride of the dicarboxylic acid monomer present is "the amount of water at the start of polymerization" Will be excluded from this). The amount of water at the start of polymerization is preferably 0 to 120 parts by mass with respect to 100 parts by mass of the compound having a polyalkylene glycol structure. By setting the amount of water in the above range, the reaction efficiency can be increased, and the amount of unreacted monomer can be reduced to carry out polymerization suitably. Moreover, it can suppress that the dicarboxylic acid at the time of heating up before superposition | polymerization sublimates and adheres to a reaction container. The amount of water at the start of the polymerization is more preferably 1 part by mass or more and still more preferably 10 parts by mass or more with respect to 100 parts by mass of the compound having a polyalkylene glycol structure. Preferably it is 120 mass parts or less, More preferably, it is 100 mass parts or less, More preferably, it is 90 mass parts or less.

When polymerizing a (meth) acrylic acid monomer or the like in the presence of a compound having the polyalkylene glycol structure, under conditions where water is not substantially present or under conditions where a large amount of water is present It is common to polymerize. On the other hand, 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 of the solution containing the produced polymer composition and the ability to prevent recontamination. Will improve. 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.

In the present invention, “at the start of polymerization” is the time when the polymerization of the (meth) acrylic acid monomer starts substantially, and specifically, the (meth) acrylic acid based monomer used for the polymerization. This is a time when part or all of the body and part or all of the polymerization initiator used for the polymerization are added to the reaction vessel (polymerization vessel, polymerization kettle). In the present invention, “at the end of the addition of the (meth) acrylic acid monomer” means that the entire amount of the (meth) acrylic monomer used for the polymerization is added to the reaction vessel (polymerization vessel, polymerization kettle). It is time when.

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 (meth) acrylic acid-based monomer is the polymerization at the time when the addition of the (meth) acrylic acid-based monomer is completed. It means the amount of water present in the kettle (in the polymerization reaction solution).

The amount of water contained in the reaction solution at the end of the addition of the (meth) acrylic acid monomer (hereinafter also referred to as “the amount of water at the end of addition”) is the unreacted polymer contained in the reaction solution. The total amount of the compound having an alkylene glycol structure and the structural unit derived from the compound having a polyalkylene glycol structure contained in the polymer produced by the reaction is 100 to 100,000 parts by mass. Is preferred. 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 100 parts by mass in total of the compound having an unreacted polyalkylene glycol structure and the structural unit derived from the compound having a polyalkylene glycol structure contained in the polymer produced by the reaction. On the other hand, it is more preferably 100 to 1,000 parts by mass, still more preferably 150 to 500 parts by mass. However, when an anhydride of a dicarboxylic acid monomer is used as a dicarboxylic acid monomer, the dicarboxylic acid anhydride reacts stoichiometrically with water, so the existing dicarboxylic acid Water in a range that does not exceed the number of moles of anhydride of the monomer is excluded from the “amount of water at the end of addition”.

As described above, by controlling the amount of water contained in the reaction solution, graft polymerization (polyalkylene glycol structure) of a compound having a polyalkylene glycol structure and a monomer under conditions with little water (for example, in the initial stage of polymerization) The compound having a main chain and the monomer constitutes a branch) mainly proceeds, and the polymerization of the monomers proceeds under conditions with a lot of water (for example, in the latter half of the polymerization). A polymer having an intermediate structure is also produced, and the polymer composition obtained by the presence of the polymer having an intermediate structure is suppressed from phase separation over time, and the storage stability is greatly improved. Will be. When a predetermined amount of the dicarboxylic acid monomer is contained, the storage stability and the compatibility with the liquid detergent become better.

((Meth) acrylic acid monomer)
The “(meth) acrylic acid monomer” used in the production method of the present invention means a compound represented by the above general formula (3). A (meth) acrylic-acid type monomer may be used only by 1 type, and may be used by 2 or more types. Examples of the “(meth) acrylic acid monomer” include acrylic acid (salt) and methacrylic acid (salt). Salts referred to herein, is a salt of a carboxyl group represented by -COOM ^1, M ¹ is a metal atom, an ammonium base or an organic amine base. Examples of the metal atom include alkali metals such as sodium, lithium and potassium; alkaline earth metals such as magnesium and calcium; aluminum and iron. Moreover, a quaternary ammonium base is mentioned as said ammonium base. Examples of the organic amine base include alkanolamine groups such as monoethanolamine group, diethanolamine group and triethanolamine group; alkylamine groups such as monoethylamine group, diethylamine group and triethylamine group; polyamine groups such as ethylenediamine group and triethylenediamine group. Is mentioned. Of these, ammonium base, sodium, and potassium are preferable, and sodium is more preferable because the resulting polymer has a high effect of improving the ability to prevent recontamination. Further, the R ⁴ represents a hydrogen atom, the M ¹ is also preferred that a hydrogen atom.

In the production method of the present invention, the total amount of the (meth) acrylic acid monomer 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 the (meth) acrylic acid monomer used in the production method of the present invention is that of the compound having a polyalkylene glycol structure and the monomer (dicarboxylic acid monomer, (meth) acrylic acid monomer). It is preferable to set it to 1 mass% or more and 99 mass% or less with respect to 100 mass% of total usage. Especially, it is more preferable to set it as 4 mass% or more and 80 mass% or less from the tendency for the recontamination prevention ability of a polymer composition to improve, and it is still more preferable to set it as 5 mass% or more and 75 mass% or less. It is particularly preferable that the content be 10% by mass or more and 60% by mass or less. In addition, when calculating the said usage-amount, when a monomer has an acid group, it calculates by conversion of a corresponding acid type, and when it has an amino group, it calculates by conversion of a corresponding amine.

(Dicarboxylic acid monomer)
The “dicarboxylic acid monomer” used in the production method of the present invention means a compound represented by the above general formula (4). The dicarboxylic acid monomer may be used alone or in combination of two or more. Examples of the “dicarboxylic acid monomer” include maleic acid (salt), maleic anhydride, fumaric acid (salt), itaconic acid (salt), itaconic anhydride, 2-methyleneglutaric acid (salt), and the like. It is done. Maleic acid (salt) and / or maleic anhydride are preferred. The salt here is a salt of a carboxyl group represented by —COOM ² or — (CH ₂ ) _x COOM ³ as described above, and M ² or M ³ is a metal atom, an ammonium base, Or it is an organic amine base. Examples of the metal atom include alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and calcium, and iron. Moreover, a quaternary ammonium base is mentioned as said ammonium base. Examples of the organic amine base include alkanolamine groups such as monoethanolamine group, diethanolamine group and triethanolamine group; alkylamine groups such as monoethylamine group, diethylamine group and triethylamine group; polyamine groups such as ethylenediamine group and triethylenediamine group. Is mentioned. Of these, ammonium base, sodium and potassium are preferable, and sodium is more preferable. It is also preferable that M ² or M ³ represents a hydrogen atom.

In the production method of the present invention, the amount of the dicarboxylic acid monomer at the start of polymerization is preferably 10 to 800 parts by mass with respect to 100 parts by mass of the compound having the polyalkylene glycol structure. In the present invention, the “amount of dicarboxylic acid monomer at the start of polymerization” represents the amount of dicarboxylic acid monomer present in the reaction vessel (in other words, in the polymerization reaction solution) at the start of polymerization. The amount of the dicarboxylic acid monomer at the start of the polymerization is more preferably 20 parts by mass or more with respect to 100 parts by mass of the compound having a polyalkylene glycol structure. More preferably, it is 25 parts by mass or more. More preferably, it is 30 parts by mass or more. More preferably, it is 40 parts by mass or more. Especially preferably, it is 60 mass parts or more. More preferably, it is 700 parts by mass or less. More preferably, it is 650 parts by mass or less. More preferably, it is 600 parts by mass or less. More preferably, it is 180 parts by mass or less. Particularly preferably, it is 100 parts by mass or less. By being in the said range, the recontamination prevention ability of the polymer composition obtained is improved. In addition, storage stability is improved.
In addition, when calculating the quantity of the dicarboxylic acid type monomer with respect to 100 parts by mass of the compound having a polyalkylene glycol structure, the dicarboxylic acid type monomer is calculated in terms of the corresponding acid type. The calculation in terms of the corresponding acid type is as described above.

In the production method of the present invention, a -COOM ² group or a-(CH ₂ ) _x COOM ³ group (M ² and M ³ are the same or different in the dicarboxylic acid monomer at the start of polymerization, From 0 to 50 mol% of an atom, an ammonium group or an organic amine group) is preferably a salt-type structure from the viewpoint of suppressing the increase in viscosity during polymerization. The group having a salt structure means that M ² or M ³ is a metal atom, an ammonium group or an organic amine group. For example, a sodium salt structure of a carboxyl group represents a structure represented by —COONa. It is. For example, in the case of maleic acid monosodium salt, it can be said that 50 mol% of the above groups of maleic acid have a salt structure (that is, one of the two groups has a salt structure).

In order to make 0-50 mol% of -COOM ² group and-(CH ₂ ) _x COOM ³ group of the dicarboxylic acid monomer at the start of polymerization into a salt structure, (i) acid type dicarboxylic acid A combination of a monomer, a mono-salt (half salt) dicarboxylic acid monomer, or a di-salt dicarboxylic acid monomer so as to achieve a desired degree of neutralization, or a single reaction vessel (Ii) Reacting acid type dicarboxylic acid monomer and / or monosalt type (half salt type) dicarboxylic acid monomer, and carboxyl group and neutralizable alkaline substance separately A method of adding to the container is performed.
Examples of the alkaline substance include hydroxides of alkali metal atoms such as sodium hydroxide, hydroxides of alkaline earth metal atoms such as calcium hydroxide, carbonates such as sodium carbonate and sodium hydrogen carbonate, monoethanolamine, methyl Examples include amines such as amines and ammonia. The alkaline substance may be added to the reaction vessel as an aqueous solution, but possible substances may be added as pellets or powder. According to the above method (ii), water is generated by the neutralization reaction, but for the purpose of reducing the amount of water at the start of polymerization, the water is retained before the start of polymerization under heating and / or reduced pressure conditions. You may leave.

In the production method of the present invention, it is preferable to add the entire amount of the dicarboxylic acid monomer to the reaction kettle before the start of polymerization, but a part or the entire amount may be added after the start of polymerization. The amount of the dicarboxylic acid monomer used in the production method of the present invention is the total use of the compound having a polyalkylene glycol structure and the monomer (dicarboxylic acid monomer, (meth) acrylic acid monomer). The amount is usually 1 to 99% by mass with respect to 100% by mass. Among them, the content of 5% by mass or more and 80% by mass or less is preferable because the recontamination preventing ability of the polymer composition and the compatibility with the liquid detergent tend to be improved. It is more preferable to set it as 15 mass% or more and 60 mass% or less. In addition, when calculating the said usage-amount, when a monomer has an acid group, it calculates by conversion of a corresponding acid type, and when it has an amino group, it calculates by conversion of a corresponding amine. Calculation with the corresponding acid type and calculation with the corresponding amine conversion are as described above.

The method for producing the polymer composition of the present invention comprises a total amount of a compound having a polyalkylene glycol structure, a use amount of a dicarboxylic acid monomer, and a use amount of a (meth) acrylic monomer. Is preferably 10/90 to 70/30. More preferably, it is 30/70 or more. More preferably, it is 60/40 or less.

<Other monomers>
As the monomer used in the production method of the present invention, in addition to the above dicarboxylic acid monomer and (meth) acrylic acid monomer, other monomers polymerizable with these are used. Also good.
Examples of other monomers include 2-acrylamido-2-methylpropanesulfonic acid, (meth) allylsulfonic acid, vinylsulfonic acid, 2-hydroxy-3-allyloxy-1-propanesulfonic acid, and 2-hydroxy-3. A monomer having a sulfonic acid group such as butenesulfonic acid; a monomer having a phosphonic acid group such as vinylphosphonic acid or (meth) allylphosphonic acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Hydroxyl group-containing alkyl (meth) acrylates such as (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and α-hydroxymethylethyl (meth) acrylate ; Methyl (meth) acrylate, (meth) a Alkyl (meth) acrylates obtained by esterification of (meth) acrylic acid such as ethyl laurate, butyl (meth) acrylate, cyclohexyl (meth) acrylate and alcohols having 1 to 18 carbon atoms; dimethylaminoethyl ( Amino group-containing acrylate such as (meth) acrylate or quaternized product thereof; 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; nitrile group-containing vinyl monomers such as (meth) acrylonitrile; (meth) acrolein, etc. Aldehyde group of Containing vinyl monomers; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; monomers having a structure in which alkylene oxide is added to unsaturated alcohol such as allyl alcohol or isoprenol; vinyl chloride, vinylidene chloride, allyl Examples include alcohol and vinyl pyrrolidone. 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, which is an optional component in the production method of the present invention, includes a compound having a polyalkylene glycol structure and a monomer (dicarboxylic acid monomer, (meth) acrylic acid monomer). It is preferable to use 0 to 10% by mass with respect to 100% by mass of the total use amount because the ability to prevent recontamination of the polymer composition tends to be improved.
That is, the polymer contained in the polymer composition of the present invention is a structural unit derived from a compound having a polyalkylene glycol structure and a structural unit derived from a monomer having a structural unit derived from another monomer as an optional component. It is preferable to have 0 to 10% by mass with respect to 100% by mass in total.

<Polymerization initiator>
The production method of the present invention comprises a step of polymerizing a monomer component essentially comprising a (meth) acrylic acid monomer and a dicarboxylic acid monomer in the presence of a compound having a polyalkylene glycol structure and a polymerization initiator. It is preferable to contain.
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 persulfate and hydrogen peroxide because the polymerization of the dicarboxylic acid is good. That is, it is preferable to use persulfate and hydrogen peroxide as polymerization initiators, or use only persulfate or only hydrogen peroxide.

The amount of the polymerization 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. It is preferable that More preferably, it is 1 to 15 g.

When persulfate is used as the polymerization initiator, the amount of persulfate added is preferably 1.0 to 8.0 g, and 2.0 to 6.0 g, based on 1 mol of the monomer. More preferably. When the amount of persulfate added is less than this, the molecular weight of the resulting polymer tends to increase. On the other hand, when the addition amount is too large, the effect of persulfate cannot be obtained as the addition amount increases, and the purity of the resulting polymer tends to decrease.

When hydrogen peroxide is used as the polymerization initiator, the amount of hydrogen peroxide added is preferably 1.0 to 30.0 g, and 2.0 to 25.0 g, based on 1 mol of the monomer. More preferably. When the amount of hydrogen peroxide added is less than 1.0 g, the polymerization average molecular weight of the resulting copolymer tends to increase. On the other hand, when the addition amount exceeds 30.0 g, the effect of hydrogen peroxide cannot be obtained as the addition amount increases, and the amount of remaining hydrogen peroxide tends to increase.

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-mercaptopropionic acid, 3-mercaptopropionic acid, 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 alcohols; lower oxides such as phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), salts thereof, and the like. The said chain transfer agent may be used independently and may be used with the form of 2 or more types of mixtures.
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, when a chain transfer agent is used, the addition amount is not particularly limited, but is preferably 1 to 20 g with respect to 1 mol of all monomers. More preferably, it is 2 to 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 it is preferable to reduce the blending amount to some extent.

The 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 heavy metal ion preferably contains an iron ion. 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.

The heavy metal ions can be added using a solution obtained by dissolving a heavy metal compound. 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. Examples of the method for adding heavy metal ions include initial addition or sequential addition. The initial addition is preferred. 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 system in advance before the start of polymerization, and the sequential addition refers to a method in which heavy metal ions are gradually added as the polymerization reaction proceeds.

When the heavy metal ions are blended, the content of the heavy metal ions is not particularly limited, but is preferably 0.1 to 20 ppm with respect to the total mass of the polymerization reaction system when the polymerization reaction is completed. When the amount is such a level, impurities derived from heavy metal ions are hardly generated. More preferably, it is 0.2-10 ppm, More preferably, it is 0.3-7 ppm, Especially preferably, it is 0.4-6 ppm, Most preferably, it is 0.5-5 ppm. 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.

<Other additives>
In the production method of the present invention, the amount of water used is preferably 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.

As described above, in the production method of the present invention, an alkaline substance may be added before the start of polymerization, but an alkaline substance may be added during the polymerization for the purpose of controlling the degree of neutralization during the polymerization. Of course, an alkaline substance may be added after the polymerization.

<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, it is preferable to add each component dropwise so that the concentration of the solid component in the polymerization reaction system after the completion of dropping is 40% by mass or more.

When using hydrogen peroxide as a polymerization initiator, the addition of hydrogen peroxide may be started at the same time as the addition of monomers (excluding the initial charge monomer) to the reaction vessel (reaction solution), The addition of hydrogen peroxide may be started after the start of monomer addition.
The end of the addition of hydrogen peroxide to the reaction vessel (reaction solution) may be before the end of the monomer addition, at the same time as the end of the monomer addition, or after the end of the monomer addition. But you can.

When using a persulfate as a polymerization initiator, the addition time to the reaction vessel (reaction solution) is not particularly limited, but it is preferable to drop it until after the end of the addition of the (meth) acrylic acid monomer, It is more preferable to finish within 30 minutes from the end of the addition of the (meth) acrylic acid monomer, and it may be completed within 5 to 20 minutes after the end of the addition of the (meth) acrylic monomer. Particularly preferred. Thereby, it exists in the tendency for the residual amount of the monomer in the manufactured polymer (composition) to reduce.

The polymerization temperature is preferably 25 to 200 ° C, more preferably 50 to 150 ° C, and still more preferably 70 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.

The polymerization reaction system may be in an air atmosphere or an inert gas atmosphere.

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 may go out. 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 part of the components, the amount of solvent of the polymer composition A diluting step and a concentrating / drying step that increase or decrease may be included.
Below, the use of the polymer composition of this invention is explained in full detail.

<Uses of polymer composition>
The polymer composition of the present invention can be used as a detergent builder (or detergent composition) or the like. As a detergent builder, it can be used by being added to detergents for various uses such as clothing, tableware, dwelling, hair, body, toothpaste, and automobile.

<Detergent composition>
The polymer composition of the present invention can also be added to a detergent composition. The present invention is also a detergent composition containing the polymerization composition of the present invention.
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. Further, the detergent composition may be a powder detergent composition or a liquid detergent composition, but since the effect of improving the compatibility of the polymer composition of the present invention is particularly exerted, Particularly preferred is 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. Or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. It does not specifically limit regarding an upper limit, It is 100 mass% or less.

Examples of anionic surfactants 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 mono 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 blending ratio of the surfactant is too small, sufficient detergency may not be exhibited, and if the blending ratio of the surfactant is too large, the economy may be lowered.

Examples of the additives include alkali builder, chelate builder, anti-redeposition agent for preventing redeposition of contaminants such as sodium carboxymethyl cellulose, stain inhibitor such as benzotriazole and ethylene-thiourea, soil release agent, color Anti-transfer agent, softener, alkaline substance for pH adjustment, fragrance, solubilizer, fluorescent agent, colorant, foaming agent, foam stabilizer, glossing agent, bactericidal agent, bleaching agent, bleaching aid, enzyme, Dyes, solvents and the like are preferred. 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, silicates, tripolyphosphates, pyrophosphates, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, citric acid. 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 blending ratio is less than 0.1% by mass, sufficient detergent performance may not be exhibited, 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, still 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 still 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.

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 polymer composition of the present invention is excellent in storage stability, as well as compatibility with liquid detergents and dispersibility of hydrophobic soils. The polymer composition of the present invention can be preferably used as a detergent additive.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”. In the present specification, a dicarboxylic acid monomer and a (meth) acrylic acid monomer are also simply referred to as a monomer.

Moreover, the weight average molecular weight of the graft polymer of this invention, storage stability, the solid content of a polymer composition, and the analysis of a raw material were measured in accordance with the following method.
<Method for measuring weight average molecular weight of polymer>
Equipment: High-speed GPC equipment (HLC-8320GPC) manufactured by Tosoh Corporation
Detector: RI
Column: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B manufactured by Showa Denko KK
Column temperature: 40 ° C
Flow rate: 0.5 ml / min
Calibration curve: POLYACRYLIC ACID STANDARD made by Soka Science Co., Ltd.
Eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio)

<Measurement method of residual monomer (PEG)>
Measuring apparatus: 8020 series manufactured by Tosoh Corporation Column: CAPCELL PAK C1 UG120 × 2 columns manufactured by Shiseido Co., Ltd. Column temperature: 40 ° 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 200 nm)

<Measurement method of residual monomer (AA, MA)>
Measuring device: Alliance e-2695 manufactured by Waters System detector: UV detector (200 nm)
Column: SHODEX RSpak DE-413L manufactured by Showa Denko KK
Column temperature: 40 ° C
Eluent: 0.1% phosphoric acid aqueous solution Flow rate: 1.0 ml / min

<Storage stability evaluation method>
(1) 20 g of the obtained polymer was allowed to stand at room temperature for 1 week.
(2) The case where there was no turbidity was marked with ◯, and the case where it was cloudy was marked with ×. The absence of turbidity indicates that the polymer solution can be kept uniform over a long period of time.

<Compatibility evaluation method>
(1) Polyoxyethylene dodecyl ether (added 8 mol of ethylene oxide on average to dodecanol) 25 g of 25% aqueous solution was mixed with 0.2 g of polymer composition (solid content conversion) and allowed to stand at room temperature for 1 hour.
(2) The case where there was no turbidity was indicated as ◯, the case where it was slightly turbid, Δ, and the case where it was turbid 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.

<Carbon black dispersibility evaluation method>
(1) A glycine buffer solution was prepared by adding ion exchange water to 60 ml of glycine 67.6 g, sodium chloride 52.6 g and 1 mol / L NaOH aqueous solution to make 600 g.
(2) 0.0615 g of calcium chloride dihydrate and 60 g of glycine buffer solution prepared in (1) were added with pure water to 1000 g to prepare a dispersion.
(3) A 0.1% polymer composition aqueous solution in terms of solid content was prepared.
(4) To a tester having a capacity of about 30 cc, 0.03 g of carbon black (obtained from the Laundry Science Association), 27 g of the dispersion of (2), and 3 g of the aqueous polymer composition solution of (3) were added. At this time, the calcium concentration of the test solution was 50 ppm in terms of calcium carbonate.
(5) The test tube was sealed with a rubber stopper and then shaken up and down 60 times. The test tube was allowed to stand in a place not exposed to direct sunlight for 25 hours, and then the dispersion was visually observed.
(6) The carbon black dispersibility was evaluated by measuring the absorbance at a wavelength of 380 nm using a Shimadzu UV-visible spectrophotometer UV 1800.

<Example 1>
To a SUS reactor equipped with a thermometer, a stirrer, and a reflux condenser, phenoxypolyethylene glycol (obtained by adding 20 moles of phenol to ethylene oxide on average, hereinafter abbreviated as PH200): 200 g, maleic anhydride: 126. 7 g and pure water: 153.1 g were charged and heated to 100 ° C. Next, 80% acrylic acid aqueous solution (abbreviated as 80% AA): 187.5 g for 180 minutes, 15% sodium persulfate aqueous solution (abbreviated as 15% NaPS): 90.0 g for 190 minutes, 35% aqueous hydrogen peroxide solution (Abbreviated as 35% H ₂ O ₂ ): 96.5 g was added dropwise continuously over 180 minutes. After completion of the 80% AA dropwise addition, the mixture was stirred for 30 minutes to obtain the polymer composition 1 of the present invention. The weight average molecular weight of the polymer contained in the polymer composition 1 was 8,700. In the polymer composition 1, the amount of residual maleic acid was 62200 ppm, the amount of residual acrylic acid was 1400 ppm, and the amount of residual PH200 was 37000 ppm. The solid content was 64%.

<Example 2>
A SUS reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with PH 200: 200 g, maleic anhydride: 169.0 g, and pure water: 263.8 g, and the temperature was raised to 100 ° C. Next, 80% AA: 125.0 g was added dropwise continuously over 180 minutes, 15% NaPS: 83.0 g was added dropwise over 190 minutes, and 35% H ₂ O ₂ : 88.9 g was added separately over 180 minutes. After the completion of 80% AA dropping, the mixture was stirred for 30 minutes to obtain a polymer composition 2 of the present invention. The weight average molecular weight of the polymer contained in the polymer composition 2 was 5,800. In the polymer composition 2, the amount of residual maleic acid was 99500 ppm, the amount of residual acrylic acid was 1500 ppm, and the amount of residual PH200 was 38000 ppm. The solid content was 47%.

<Example 3>
A SUS reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with PH200: 150 g, maleic anhydride: 126.7 g, and pure water: 142.0 g, and the temperature was raised to 100 ° C. Next, 80% AA: 250.0 g was added dropwise continuously for 180 minutes, 15% NaPS: 135.7 g for 190 minutes, and 35% H ₂ O ₂ : 139.6 g separately for 180 minutes. After completion of the 80% AA dropwise addition, the mixture was stirred for 30 minutes to obtain a polymer composition 3 of the present invention. The weight average molecular weight of the polymer contained in the polymer composition 3 was 9,500. In Polymer Composition 3, the amount of residual maleic acid was 76000 ppm, the amount of residual acrylic acid was 4800 ppm, and the amount of residual PH 200 was 7900 ppm. The solid content was 50%.

<Example 4>
A SUS reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with PH 200: 174 g, maleic anhydride: 140 g, and pure water: 30 g, and the temperature was raised to 100.degree. Next, 80% AA: 300 g was dropped dropwise continuously for 120 minutes, and 35% H ₂ O ₂ : 236 g was dropped separately over 90 minutes. After the completion of the 80% AA dropwise addition, the mixture was stirred for 60 minutes and then 310.4 g of pure water was added to obtain a polymer composition 4 of the present invention. The weight average molecular weight of the polymer contained in the polymer composition 4 was 14,200. In the polymer composition 4, the amount of residual maleic acid was 23000 ppm, the amount of residual acrylic acid was 900 ppm, and the amount of residual PH 200 was 5100 ppm. The solid content was 53%.

<Example 5>
A SUS reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with PH200: 232 g, maleic anhydride: 186 g, and pure water: 40 g, and the temperature was raised to 100 ° C. Next, 80% AA: 400 g was added dropwise continuously for 120 minutes and 35% H ₂ O ₂ : 245 g separately for 90 minutes. After the completion of the 80% AA dropwise addition, the mixture was stirred for 60 minutes, and then 165 g of pure water was added to obtain a polymer composition 5 of the present invention. The weight average molecular weight of the polymer contained in the polymer composition 5 was 9,600. In the polymer composition 5, the amount of residual maleic acid was 44400 ppm, the amount of residual acrylic acid was 540 ppm, and the amount of residual PH200 was 4600 ppm. The solid content was 52%.

<Comparative Example 1>
To a SUS reactor equipped with a thermometer, a stirrer, and a reflux condenser, methoxypolyethylene glycol (obtained by adding an average of 25 moles of ethylene oxide to methanol, hereinafter abbreviated as PGM25): 85 g, maleic anhydride: 143 g, Pure water: 26.4 g was charged and heated to 90 ° C. Next, 80% AA: 389.6 g was added dropwise continuously for 180 minutes, 35% H ₂ O ₂ : 236 g for 180 minutes, and 15% NaPS: 309 g for 190 minutes. After completion of the 80% AA dropwise addition, the mixture was stirred for 30 minutes, and then 145 g of pure water was added to obtain a polymer composition 6 of the present invention. The weight average molecular weight of the polymer contained in the polymer composition 6 was 12,000. In polymer composition 6, the amount of residual maleic acid was 19000 ppm, the amount of residual acrylic acid was 720 ppm, and the amount of residual PGM25 was 36000 ppm. The solid content was 47%.

<Comparative example 2>
A SUS reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 341.5 g of maleic anhydride, 439.6 g of 48% NaOH aqueous solution, and 136.7 g of pure water, and the temperature was raised to 100 ° C.
Then, 80% AA: in 313.5g of 120 _{minutes, 35% H 2 O 2:} 75g at 50-100 minutes, 15% NaPS: a 66.3g at 10-130 minutes, respectively separately continuously It was dripped.
After completion of the dropwise addition of 15% NaPS, the mixture was stirred for 10 minutes, and a 48% NaOH aqueous solution: 246.8 g was added to obtain a (meth) acrylic acid (salt) -dicarboxylic acid (salt) -based copolymer.
The amount of residual monomer was 500 ppm for residual acrylic acid and 1500 ppm for residual maleic acid, and the reaction proceeded almost completely. The molecular weight was 11,000 and the solid content was 37%.

<Comparative Example 3>
Comparative Example 3 relates to phenoxypolyethylene glycol (PH200) obtained by adding 20 moles of ethylene oxide on average to phenol.

Table 1 below shows the evaluation results of carbon black dispersibility, compatibility, and storage stability in each Example and Comparative Example.

From the results shown in Table 1, it was shown that the polymer composition of the present invention has excellent storage stability and compatibility with liquid detergents as compared with conventional polymer compositions. Moreover, it was shown that carbon black dispersibility is excellent.
Therefore, when the polymer composition of the present invention is used as a detergent builder, it is expected that good detergency can be obtained.

Claims (4)

A polymer composition comprising a polymer comprising a structural unit derived from a (meth) acrylic acid monomer and a structural unit derived from a dicarboxylic acid monomer,
The polymer composition contains 20 to 70% by mass of the polymer with respect to 100% by mass of the polymer composition, 0.01 to 30% by mass of a compound having a polyalkylene glycol structure, and 10 to 10% of water. Including 70% by mass,
The polymer composition having a polyalkylene glycol structure having a phenoxy group which may have a substituent at the terminal. The polymer composition is obtained through a step of polymerizing a monomer component essentially comprising a (meth) acrylic acid monomer and a dicarboxylic acid monomer in the presence of a compound having a polyalkylene glycol structure. Is,
The mass ratio between the amount of the compound having a polyalkylene glycol structure and the total amount of the (meth) acrylic acid monomer and the dicarboxylic acid monomer used is 10/90 to 70/30. The polymer composition according to claim 1, wherein A method for producing a polymer composition comprising:
The production method includes a step of polymerizing a monomer component essentially comprising a (meth) acrylic acid monomer and a dicarboxylic acid monomer in the presence of a compound having a polyalkylene glycol structure,
The method for producing a polymer composition, wherein the compound having a polyalkylene glycol structure has a terminal phenoxy group which may have a substituent. A detergent composition comprising the polymer composition according to claim 1 or 2.