JP2020122054A - Copolymer, re-pollution control agent for clothing cleaner, and manufacturing method for copolymer - Google Patents

Abstract

To provide a copolymer exerting excellent re-pollution control performance when using as a re-pollution control agent for clothing cleaner.SOLUTION: A copolymer in this invention includes: a structural unit (A) derived from a monomer including an ethylenic unsaturated group and carboxyl group; the structural unit (B) derived from methylenemalonic acid diester; and a structural unit (C) derived from an optional hydrophilic monomer. The copolymer includes 50 mass% or more in total of the structural units (A) and (C) based on total mass except the structural unit (B) in the copolymer and includes 0.1 to 100 mol% of the structural unit (B) based on 100 mol% of the structural unit (A).SELECTED DRAWING: None

Description

The present disclosure relates to a copolymer, an anti-soil redeposition agent for clothes detergents, and a method for producing the copolymer.

Conventionally, polyacrylic acid, acrylic acid-maleic acid copolymers or salts thereof (Patent Document 1), (meth)acrylic acid, and the like have been used as agents exhibiting excellent detergency and anti-soil redeposition ability for detergents for clothing. An oxyalkylene group-containing monomer-containing copolymer (Patent Document 2) and the like are known.

Patent Document 3 describes a grafted polymer containing a first component obtained by polymerizing a monomer containing a 1,1-disubstituted-1-alkene compound and a second component which is a water-soluble component. Although a detergent is described as an application of the grafted polymer, the cleaning performance has not been evaluated, and an acrylic (co)polymer is modified with a 1,1-disubstituted-1-alkene compound. No such grafted polymer is disclosed.

JP, 2016-88981, A JP, 2008-50561, A International Publication No. 2017/210084

However, there is still room for improvement in the recontamination preventing ability, and development of a recontamination preventing agent having a better recontamination preventing ability is desired.

The present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide a copolymer having an excellent anti-soil redeposition ability when used as an anti-soil redeposition agent for a clothing detergent. The present disclosure also relates to a composition containing the polymer, an anti-soil redeposition agent for a clothing detergent, and a method for producing the copolymer.

The copolymer of the present disclosure includes a structural unit (A) derived from a monomer containing an ethylenically unsaturated group and a carboxyl group, a structural unit (B) derived from a methylenemalonic acid diester or a derivative thereof, and optionally A copolymer containing a structural unit (C) derived from a hydrophilic monomer, wherein the structural unit (A) and the structural unit (C) are included with respect to the total mass of the copolymer excluding the structural unit (B). 50% by mass or more in total, and 0.1 to 100 mol% of the structural unit (B) relative to 100 mol% of the structural unit (A).

Further, the copolymer of the present disclosure includes a structural unit (A) derived from a monomer containing an ethylenically unsaturated group and a carboxyl group, and a structural unit (B) derived from a methylenemalonic acid diester or a derivative thereof. Optionally containing a structural unit (C) derived from a hydrophilic monomer, the content of the structural unit (B) is 0.1 to 100 mol% with respect to 100 mol% of the structural unit (A), It may be a copolymer, which is a water-soluble copolymer.

The copolymer of the present disclosure has a main chain containing the structural unit (A), and preferably contains the structural unit (B) bonded to the carboxyl group of the structural unit (A) in the main chain.

The hydrophilic monomer is an ethylenically unsaturated group, a sulfonic acid group and a salt thereof, a phosphoric acid group and a salt thereof, an alkylene glycol group, a polyalkylene glycol group, a hydroxyl group, an amino group, an acyclic amide group, and a cyclic It is preferable to have at least one group selected from an amide group.

The composition of the present disclosure contains a (co)polymer (X) and a copolymer (Y), the copolymer (Y) is the above copolymer, and the (co)polymer (X) is A methylenemalonic acid diester and its derivative containing a structural unit (A) derived from a monomer containing an ethylenically unsaturated group and a carboxyl group and optionally a structural unit (C) derived from a hydrophilic monomer The (co)polymer (X) which does not contain the structural unit (B) derived from any of the above satisfies at least one of the following conditions (a) and (b).
The total amount of the structural unit (A) and the structural unit (C) is 80% by mass or more based on the total mass of the (a) (co)polymer (X).
(B) The (co)polymer (X) is a water-soluble copolymer.

The anti-soil redeposition agent for clothing detergents of the present disclosure includes the above copolymer or the above composition.

The method for producing a copolymer of the present disclosure includes a step of adding a methylenemalonic acid diester or a derivative thereof to the (co)polymer (X), wherein the (co)polymer (X) contains an ethylenically unsaturated group and Structural unit (A) derived from a monomer containing a carboxyl group, structural unit (B) optionally derived from a methylenemalonic acid diester or a derivative thereof, and structural unit (C) optionally derived from a hydrophilic monomer. And the (co)polymer (X) satisfies at least one of the following conditions (a) and (b).
The total amount of the structural unit (A) and the structural unit (C) in the (a) (co)polymer (X) excluding the structural unit (B) is 50% by mass or more.
The (b) (co)polymer (X) is a water-soluble copolymer.

According to the present disclosure, it is possible to provide a copolymer having an excellent anti-soil redeposition ability when used as an anti-soil redeposition agent for a clothing detergent. Moreover, according to this indication, the composition containing such a polymer, the anti-soil redeposition agent for clothing detergents, and the manufacturing method of the said copolymer can be provided.

The copolymer of the present disclosure (hereinafter, also referred to as a copolymer (Y)) includes a structural unit (A) derived from a monomer containing an ethylenically unsaturated group and a carboxyl group, and a methylenemalonic acid diester. A structural unit (B), and optionally a structural unit (C) derived from a hydrophilic monomer, wherein the structural unit (B) is 100 mol% relative to the structural unit (A). 0.1 to 100 mol% is included. In addition, the copolymer (Y) of the present disclosure contains the structural unit (A) and the structural unit (C) in a total amount of 50% by mass or more based on the total mass of the copolymer excluding the structural unit (B). Or a water-soluble copolymer. The copolymers of the present disclosure exhibit excellent anti-soil redeposition ability.

The copolymer (Y) of the present disclosure preferably contains the structural unit (A) and the structural unit (C) in a total amount of 70% by mass or more based on the total mass of the copolymer excluding the structural unit (B). , 80% by mass or more is more preferable, 90% by mass or more is further preferable, and substantially 100% by mass is particularly preferable.

The content of the structural unit (A) in the copolymer (Y) is preferably 10 to 100% by mass relative to the total mass of the copolymer (Y) excluding the structural unit (B), and preferably 20 to 100%. More preferably, it is mass %.

The copolymer (Y) preferably contains the structural unit (B) in an amount of 0.1 to 20 mol% and more preferably 0.1 to 10 mol% with respect to 100 mol% of the structural unit (A). It is preferably 0.1 to 5 mol% and particularly preferably.

In addition, in the present specification, “water-soluble” preferably means that 10 g or more is dissolved in 1 L of water at 25°C. When the copolymer (Y) of the present disclosure is a water-soluble copolymer, it is preferably one that dissolves in 1 L of water at 25° C. in an amount of 50 g or more, more preferably 100 g or more.

The structural unit (A) is a structural unit derived from a monomer containing an ethylenically unsaturated group and a carboxyl group (hereinafter, also referred to as monomer (A)). "Structural unit (A)" means a structural unit formed by polymerizing a monomer (A) mainly with an ethylenically unsaturated group, or a methylenemalonic acid diester or a derivative thereof (hereinafter, referred to as a structural unit having a carboxyl group). The same as the structural unit formed by combining with the structural unit derived from the monomer (B) (however, the structural unit part derived from the monomer (B) is not included in the structural unit (A)). Refers to the structural unit of structure. The structural unit (A) is a structural unit formed by actually polymerizing the monomer (A), or a structural unit formed by actually bonding the structural unit with the monomer (B). It is not limited, and includes a structural unit formed by another manufacturing method as long as it has the same structure as those structural units. As the structural unit formed by polymerizing the monomer (A), for example, when the monomer (A) is acrylic acid, CH ₂ ═CH(COOH), —CH ₂ —CH(COOH)— Can be represented by. The structural unit formed by polymerizing the monomer (A) and the structural unit derived from the monomer (B) is, for example, a carboxyl group-containing monomer is acrylic acid, When the monomer (B) is dimethyl methylenemalonate and CH ₂ ═C(COOCH ₃ ) ₂ , for example, a structural unit in which one molecule of dimethyl methylenemalonate is added is —CH ₂ —CH(COO—CH _{2 -CH (COOCH 3) 2) -} , a structural unit (a) except the structural unit part derived from malonic acid _{diester, -CH 2 -CH (COO -)} -, is.

Examples of the monomer (A) include monocarboxylic acids, dicarboxylic acids, dicarboxylic acid monoesters and the like. More specifically, (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, cinnamic acid, itaconic acid, citraconic acid, maleic anhydride, monomethyl maleate, monobutyl maleate, itaconic anhydride, monomethyl itaconate. , Monobutyl itaconate, vinyl benzoic acid, monohydroxyethyl (meth)acrylate oxalate, carboxyl group-terminated caprolactone modified acrylate (for example, "Plaxel FA" series; manufactured by Daicel Industries), carboxyl group-terminated caprolactone modified methacrylate (for example, "Plaxel FMA") Series; manufactured by Daicel Industries, Ltd.); cyclopolymerizable unsaturated carboxylic acids such as allyloxymethylacrylic acid, and the like. Among these, (meth)acrylic acid, itaconic acid, and maleic anhydride are preferable. These can be used by appropriately selecting one kind or two or more kinds.

The carboxyl group contained in the structural unit (A) may be neutralized. When the carboxyl group is neutralized, the neutralized carboxyl group may be one introduced by polymerizing a monomer having a neutralized carboxyl group, and an unneutralized carboxyl group. It may be obtained by polymerizing a monomer having a group and then neutralizing it. The counter cation of the neutralized carboxyl group is not particularly limited, but examples thereof include monovalent cations such as alkali metal ions and ammonium ions. The degree of neutralization of the copolymer (Y) (ratio of the number of moles of neutralized carboxyl groups to the total number of moles of neutralized and unneutralized carboxyl groups) is preferably 80% or more, and 90% or more. Is more preferable. In the present specification, the term carboxyl group includes both a carboxyl group in an acid state (that is, —COOH group) and a neutralized carboxyl group.

The structural unit (B) is a structural unit derived from the monomer (B). The “structural unit (B)” is the same as the structural unit formed by the addition of the monomer (B) to the carboxyl group or the structural unit formed by the polymerization of the monomer (B) with a methylene group. Refers to the structural unit of structure. The structural unit (B) is limited to a structural unit formed by actually reacting the monomer (B) with a carboxyl group or a structural unit formed by actually polymerizing the monomer (B). However, structural units formed by another manufacturing method are also included as long as they have the same structure as those structural units. For example, if the monomer (B) is dimethyl _{malonate, CH 2 = C (COOCH 3} ) 2,, structural unit _{(B), -CH 2 -CH (COOCH 3)} 2, -CH 2 - C(COOCH ₃ ) ₂ — and the like.

Examples of the methylenemalonic acid diester or its derivative include a diester compound of the formula (I) and a polyfunctional methylenemalonic acid diester in which a plurality of methylenemalonic acid diesters are bonded. The polyfunctional methylenemalonic acid diester may be a reaction product obtained by reacting a diester compound of the formula (I) and a polyhydric alcohol under conditions in which a transesterification reaction takes place between the two, for example, a compound represented by the formula (II ) And the compound represented by Formula (III) are illustrated. In the present disclosure, when a compound in which n methylenemalonic acid diesters are bonded is used, it is treated as using n monomers (B). Therefore, when a compound in which n methylenemalonic acid diesters are bonded is incorporated into the copolymer of the present disclosure as a monomer, it is treated as having formed n structural units (B).

（式（Ｉ）において、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、１〜１５個の炭素原子を有する炭化水素基、又はＲ^１及びＲ^２が一緒になって３〜１５個の炭素原子を有する２価の炭化水素基を形成しており、Ｒ^３及びＲ^４は、それぞれ独立に１〜３０個の炭素原子を有する１価の有機基を表す。）

（式（ＩＩ）において、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、１〜１５個の炭素原子を有する炭化水素基、又はＲ^１及びＲ^２が一緒になって３〜１５個の炭素原子を有する２価の炭化水素基を形成しており、Ｒ^３は、それぞれ独立に１〜３０個の炭素原子を有する１価の有機基を表し、ｎは、式（ＩＩ）の化合物に含まれる括弧内の構造単位の個数を表し、２以上の数を表し、Ｒ^５はｎ価の有機基を表し、複数あるＲ^１は互いに同一であっても、異なっていてもよく、複数あるＲ^２は互いに同一であっても、異なっていてもよく、複数あるＲ^３は互いに同一であっても、異なっていてもよい。）

（式（ＩＩＩ）において、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、１〜１５個の炭素原子を有する炭化水素基、又はＲ^１及びＲ^２が一緒になって３〜１５個の炭素原子を有する２価の炭化水素基を形成しており、Ｒ^３は１〜３０個の炭素原子を有する１価の有機基を表し、ｎは、式（ＩＩ）の化合物に含まれる括弧内の構造単位の個数を表し、２以上の数を表し、Ｒ^６は２価の有機基を表し、Ｒ^７は、一価の有機基であり、好ましくは水酸基、又は下記式（Ｖ）で表される基であり、複数あるＲ^１は互いに同一であっても、異なっていてもよく、複数あるＲ^２は互いに同一であっても、異なっていてもよく、複数あるＲ^６は互いに同一であっても、異なっていてもよい。）

（式（Ｖ）において、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、１〜１５個の炭素原子を有する炭化水素基、又はＲ^１及びＲ^２が一緒になって３〜１５個の炭素原子を有する２価の炭化水素基を形成しており、Ｒ^４は、それぞれ独立に１〜３０個の炭素原子を有する１価の有機基を表す。Ｒ^７は、式（Ｉ）で表される化合物からＲ^３を除いた残基であってよい。）

(In the formula (I), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, or R ¹ and R ² together form 3 to 15 carbon atoms. Forming a divalent hydrocarbon group having an atom, and R ³ and R ⁴ each independently represent a monovalent organic group having 1 to 30 carbon atoms.)

(In the formula (II), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, or R ¹ and R ² together form 3 to 15 carbon atoms. Forming a divalent hydrocarbon group having an atom, each R ³ independently represents a monovalent organic group having 1 to 30 carbon atoms, and n is included in the compound of the formula (II). Represents the number of structural units in parentheses, represents a number of 2 or more, R ⁵ represents an n-valent organic group, plural R ^{1 s} may be the same or different from each other, and plural R ^{1 s} are present. ² may be the same or different from each other, and a plurality of R ³ may be the same or different from each other.)

(In the formula (III), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, or 3 to 15 carbon atoms when R ¹ and R ² are taken together. Forming a divalent hydrocarbon group having an atom, R ³ represents a monovalent organic group having 1 to 30 carbon atoms, and n is in the parentheses contained in the compound of the formula (II). It represents the number of structural units, represents a number of 2 or more, R ⁶ represents a divalent organic group, R ⁷ represents a monovalent organic group, preferably a hydroxyl group or represented by the following formula (V): Plural R ^{1 s} may be the same or different from each other, plural R ^{2 s} may be the same or different from each other, and plural R ^{6 s} are the same as each other. Or they may be different.)

(In the formula (V), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, or R ¹ and R ² together form 3 to 15 carbon atoms. Forming a divalent hydrocarbon group having an atom, each R ⁴ independently represents a monovalent organic group having 1 to 30 carbon atoms, and R ⁷ is represented by the formula (I). The compound may be a residue obtained by removing R ³ from the compound.)

In formulas (I) to (III), the number of carbon atoms of the hydrocarbon group of R ¹ and R ² is preferably 1 to 10, and preferably 1 to 5. Specific examples of R ¹ and R ² include methyl group, ethyl group, n-butyl group, n-pentyl group (amyl group), n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group. , N-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, isopropyl group, 2-methylbutyl group, isoamyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, isoheptyl group, isooctyl group, 2-ethylhexyl group, 2-propylpentyl group, neononyl group, 2-ethylheptyl group, 2-propylhexyl group, 2-butyl Pentyl group, isodecyl group, neodecyl group, 2-ethyloctyl group, 2-propylheptyl group, 2-butylhexyl group, isoundecyl group, neoundecyl group, 2-ethylnonyl group, 2-propyloctyl group, 2-butylheptyl group, 2-pentylhexyl group, isododecyl group, neododecyl group, 2-ethyldecyl group, 2-propylnonyl group, 2-butyloctyl group, 2-pentylheptyl group, isotridecyl group, neotridecyl group, 2-ethylundecyl group, 2- Propyldecyl group, 2-butyloctyl group, 2-pentyloctyl group, 2-hexylheptyl group, isotetradecyl group, neotetradecyl group, 2-ethyldodecyl group, 2-propylundecyl group, 2-butyldecyl group, Examples thereof include a 2-pentylnonyl group, a 2-hexyloctyl group, an isopentadecyl group, a neopentadecyl group, a cyclohexylmethyl group and a benzyl group.

In the compound of formula (I) or the structural unit in parentheses of formula (II) or formula (III), at least one of R ¹ and R ² may be a hydrogen atom, or both may be hydrogen atoms. .. Both R ¹ and R ² are preferably hydrogen atoms.

When R ¹ and R ² together form a divalent hydrocarbon group having 3 to 15 carbon atoms, the divalent hydrocarbon group preferably has 4 to 12 carbon atoms. , 5 to 9 are more preferable. Specific examples of the divalent hydrocarbon group include 1,3-propylene group, 1,4-butylene group, 1,5-pentylene group, 1,6-hexylene group and 1,5-hexylene group. Can be mentioned.

In formulas (I) to (III), R ³ and R ⁴ are monovalent organic groups, and examples of such an organic group include monovalent hydrocarbon groups and monovalent hetero atom-containing groups. , And these may have one or more substituents. Examples of the substituent include an alkoxy group, a hydroxyl group, a nitro group, an azido group, a cyano group, an acyl group, an acyloxy group, a carboxyl group, a heterocyclic group, an ester group, a residue of another monomer (B), and the like. However, these may be further substituted with a substituent. R ³ and R ⁴ each have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, even more preferably 1 to 10 carbon atoms, and 1 to 6 carbon atoms. It is particularly preferable that When R ³ and R ⁴ have 1 or 2 or more substituents, the number of carbon atoms including the substituents is preferably within the above range. The number of substituents that R ³ and R ⁴ have is not limited, but is preferably 5 or less, and more preferably 3 or less. Examples of the monovalent hetero atom-containing group include a polyalkylene oxide group and a polyester group.

The hydrocarbon group may be any of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, the aliphatic hydrocarbon group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, And an alicyclic hydrocarbon group. Moreover, the aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aromatic hydrocarbon group is a group having an aromatic ring and may have an aliphatic portion, and the alicyclic hydrocarbon group is a group having a cyclic aliphatic hydrocarbon portion. It may have a linear or branched aliphatic hydrocarbon moiety.

As the linear saturated hydrocarbon group, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group (amyl group), an n-hexyl group, an n-heptyl group, an n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, Examples thereof include n-nonadecyl group, n-icosyl group, n-henicosyl group, and n-docosyl group.

Examples of the branched saturated hydrocarbon group include isopropyl group, sec-butyl group, isobutyl group, tert-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, isoamyl group, 1,2-dimethyl group. Propyl group, 1,1-dimethylpropyl group, tert-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-methylpentyl group, 1-methylbutyl group, 1-ethylbutyl group, 2- Ethylbutyl group, 2-ethyl-2-methylpropyl group, sec-heptyl group, tert-heptyl group, isoheptyl group, sec-octyl group, tert-octyl group, isooctyl group, 1-ethylhexyl group, 1-propylpentyl group, 2-ethylhexyl group, 2-propylpentyl group, sec-nonyl group, tert-nonyl group, neononyl group, 1-ethylheptyl group, 1-propylhexyl group, 1-butylpentyl group, 2-ethylheptyl group, 2- Propylhexyl group, 2-butylpentyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, 1-ethyloctyl group, 1-propylheptyl group, 1-butylhexyl group, 2-ethyloctyl group, 2-propylheptyl group, 2-butylhexyl group, isoundecyl group, sec-undecyl group, tert-undecyl group, neoundecyl group, 1-ethylnonyl group, 1-propyloctyl group, 1-butylheptyl group, 1-pentylhexyl group , 2-ethylnonyl group, 2-propyloctyl group, 2-butylheptyl group, 2-pentylhexyl group, isododecyl group, sec-dodecyl group, tert-dodecyl group, neododecyl group, 1-ethyldecyl group, 1-propylnonyl group , 1-butyloctyl group, 1-pentylheptyl group, 2-ethyldecyl group, 2-propylnonyl group, 2-butyloctyl group, 2-pentylheptyl group, isotridecyl group, sec-tridecyl group, tert-tridecyl group, neotridecyl group Group, 1-ethylundecyl group, 1-propyldecyl group, 1-butylnonyl group, 1-pentyloctyl group, 1-hexylheptyl group, 2-ethylundecyl group, 2-propyldecyl group, 2-butyloctyl group , 2-pentyloctyl group, 2-hexylheptyl group, isotetradecyl group, sec-tetradecyl group, tert-tetradecyl group, neotetradecyl group, 1-ethyldodecyl group, 1-propylundecyl group, 1-butyldecyl group , 1-pentylnonyl group, 1-hexyloctyl group, 2-ethyldodecyl group, 2-propylundecyl group, 2-butyldecyl group, 2-pentylnonyl group, 2-hexyloctyl group, isopentadecyl group, sec-pentadecyl group Group, tert-pentadecyl group, neopentadecyl group, isohexadecyl group, sec-hexadecyl group, tert-hexadecyl group, neohexadecyl group, isoheptadecyl group, sec-heptadecyl group, tert-heptadecyl group, neoheptadecyl group, isooctadecyl group (Isostearyl) group, sec-octadecyl group, tert-octadecyl group, neooctadecyl group, isononadecyl group, sec-nonadecyl group, tert-nonadecyl group, neononadecyl group, isoicosyl group, sec-icosyl group, tert-icosyl group, neoicosyl group Group, isohenicosyl group, sec-henicosyl group, tert-henicosyl group, neohenicosyl group, isodocosyl group, sec-docosyl group, tert-docosyl group, neodocosyl group, isotricosyl group, sec-tricosyl group, tert-tricosyl group, neotricosyl group, Isotetracosyl group, sec-tetracosyl group, tert-tetracosyl group, neotetracosyl group, isopentacosyl group, sec-pentacosyl group, tert-pentacosyl group, neopentacosyl group, isohexacosyl group, sec-hexacosyl group, tert-hexacosyl group, neohexacosyl group, isoheptacosyl group , Sec-heptacosyl group, tert-heptacosyl group, neoheptacosyl group, isooctacosyl group, sec-octacosyl group, tert-octacosyl group, neooctacosyl group, isononacosyl group, sec-nonacosyl group, tert-nonacosyl group, neononacosyl group, isotriacontyl group Group, sec-triacontyl group, tert-triacontyl group and the like.

Examples of the alicyclic hydrocarbon group include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, methylcyclohexyl group, cyclohexylmethyl group, adamantyl group and norbornyl group.

Examples of the unsaturated hydrocarbon group include a linear alkenyl group and a branched chain alkenyl group, and specific examples of the linear alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, Examples thereof include a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, an octadecenyl group and an icosenyl group.
Examples of the branched alkenyl group include an isopropenyl group, an isobutenyl group, an isopentenyl) group, an isohexenyl group, an isoheptenyl group, an isooctenyl group, an isononenyl group, an isodecenyl group, an isododecenyl group, an isooctadecenyl group, an isoicosenyl group.

Examples of the aromatic hydrocarbon group include phenyl group; naphthyl group; aralkyl group such as benzyl group, 1-phenylethyl group, 2-phenylethyl group, 3-phenylpropyl group, 4-phenylbutyl group; styryl group. (Ph-CH = C- group); a cinnamyl group (Ph-CH = CHCH ₂ - group); 1-benzocyclobutenyl group; 1,2,3,4-tetrahydronaphthyl group, etc. distyrenated phenyl group can be mentioned To be

When R ³ and R ⁴ together form a divalent organic group having 3 to 30 carbon atoms, the carbon number of the divalent organic group is preferably 3 to 10 and 3 ~6 is more preferable. Moreover, a bivalent hydrocarbon group is mentioned as a bivalent organic group, and a specific example of a bivalent hydrocarbon group is a 2,2-propylene group, a 1,3-propylene group, 1,4- Examples thereof include a butylene group, a 1,5-pentylene group, a 1,6-hexylene group and a 1,5-hexylene group. The divalent organic group may be a group in which one or more hydrogen atoms of a divalent hydrocarbon group having 3 to 15 carbon atoms are substituted with a substituent. Examples of the substituent include the substituents exemplified when R ³ and R ⁴ are monovalent organic groups. The divalent organic group preferably has 1 to 5 or less, and more preferably 1 to 3 substituents.
The divalent organic group may be a divalent hetero atom-containing group, and examples of the divalent hetero atom-containing group include a polyalkylene oxide group and a polyester group.
In the formula (II), R ⁵ is an n-valent organic group, which is a divalent or higher valent organic group, and is, for example, a residue obtained by removing two or more hydroxyl groups from a polyol. Examples of the polyol include glycerin, polyglycerin, a compound obtained by adding alkylene glycol to glycerin, erythritol, xylitol, sorbitol, trimethylolpropane, pentaerythritol, dipentaerythritol and the like. The upper limit of n is not particularly limited, but is preferably 100 or less, more preferably 12 or less, and further preferably 6 or less. The carbon number of each R5 is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 15, and particularly preferably 1 to 10.
In the formula (III), R ⁶ is a divalent organic group and is not particularly limited, but is preferably an organic group having 1 to 30 carbon atoms. Preferred examples include a residue obtained by removing two hydroxyl groups from diol and a residue obtained by removing two hydroxyl groups from polyalkylene glycol. Examples of the diol or polyalkylene glycol include ethylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol and the like. The carbon number of each R ⁶ is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 15, and particularly preferably 1 to 10.

Examples of the compound represented by the formula (I) include methylpropyl methylene malonate, dihexyl methylene malonate, dicyclohexyl methylene malonate, diisopropyl methylene malonate, butylmethyl methylene malonate, ethoxyethyl ethyl methylene malonate and methoxyethyl methylene malonate. Methyl, hexyl ethyl methylene malonate, dipentyl methylene malonate, ethyl pentyl methylene malonate, methyl pentyl methylene malonate, ethyl ethyl methylene malonate methoxyl, ethoxyethyl methyl methylene malonate, butyl ethyl methylene malonate, dibutyl methylene malonate, methylene Diethyl malonate (DEMM), diethoxyethyl methylene malonate, dimethyl methylene malonate, di-n-propyl methylene malonate, ethylhexyl methylene malonate, phenethyl methyl methylene malonate, menthyl methyl methylene malonate, methylene malonate 2 -Phenylpropylethyl, 3-phenylpropyl methylenemalonate, dimethoxyethyl methylenemalonate and the like.

The content of the structural unit derived from the compound of formula (II) or formula (III) is not particularly limited, but is preferably 0 to 5 mol% with respect to 100 mol% of the structural unit (B). , 0 to 3 mol% is more preferable, 0 to 1 mol% is particularly preferable, and it may be substantially 0 mol%.

In the copolymer of the present disclosure, the following monomers (B-1) to (B-9) are exemplified as preferred forms of the monomer (B).
(B-1) At least one of the monomers represented by the formulas (I) to (III).
(B-2) In formulas (I) to (III), R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, and preferably each independently a hydrogen atom. Or a hydrocarbon group having 1 to 10 carbon atoms, and more preferably, a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms each independently, (B-1) body.
(B-3) In formulas (I) to (III), at least one of R ¹ and R ² is a hydrogen atom, and preferably both are hydrogen atoms (B-1) or (B-2). The monomer described in.
(B-4) In formulas (I) to (III), R ³ and R ⁴ each represent an organic group, and preferably each independently has a hydrocarbon group which may have a substituent or a substituent. Is a group selected from a hetero atom-containing group that may be, more preferably, each independently, an aliphatic hydrocarbon group which may have a substituent, an aromatic which may have a substituent. Group (B-1) to (B-3), which is a group hydrocarbon group, a polyoxyalkylene group which may have a substituent, or a polyester group which may have a substituent. Monomer.
(B-5) In formulas (I) to (III), the substituents are each independently an alkoxy group, a hydroxyl group, a nitro group, an azido group, a cyano group, an acyl group, an acyloxy group, a carboxyl group, a heterocyclic group, an ester. The monomer according to (B-4) above, which is a group selected from the groups.
(B-6) Each of R ^{3 to} R ⁶ has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and further preferably 1 to 10 carbon atoms. -1) to the monomer according to any one of (B-5).
(B-7) In the formula (II), R ⁵ is a residue obtained by removing two or more hydroxyl groups from the polyol, and in the formula (III), R ⁶ is obtained by removing two hydroxyl groups from the diol or polyalkylene glycol. The monomer according to any one of (B-1) to (B-6), which is a residue.
(B-8) When R ³ and R ⁴ are hydrocarbon groups and R ³ and R ⁴ have 1 or 2 or more substituents, the number of carbon atoms including the substituents is 1 to 30 respectively. Yes, preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10, the monomer according to any of (B-1) to (B-7).
(B-9) The monomer according to any one of (B-1) to (B-8), which is a compound represented by the formula (I).

The “structural unit (C) derived from a hydrophilic monomer” refers to a structural unit having the same structure as a structural unit formed by polymerizing a hydrophilic monomer. The structural unit (C) is not limited to a structural unit formed by actually polymerizing a hydrophilic monomer, and as long as it has the same structure as those structural units, a structural unit formed by another manufacturing method. Units are also included.

The hydrophilic monomer means a monomer having a solubility in water at 25° C. of more than 6 g/100 ml. In this specification, the monomer (A) and methylenemalonic acid diester or its derivative are not included in the hydrophilic monomer.

The hydrophilic monomer is selected from an ethylenically unsaturated group, a sulfonic acid group and its salt, a phosphoric acid group and its salt, a polyalkylene glycol group, a hydroxyl group, an amino group, an acyclic amide group, and a cyclic amide group. And a compound having at least one group represented by the formula: The hydrophilic monomers may be used alone or in combination of two or more.

Examples of the compound having an ethylenically unsaturated group, a sulfonic acid group and a salt include 3-allyloxy-2-hydroxypropanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, methacrylsulfonic acid, styrenesulfonic acid and 2-acrylamido-2. -Methylpropanesulfonic acid, sulfoethyl (meth)acrylate, 2-hydroxy-3-butenesulfonic acid, and other monomers, and salts thereof.
Examples of the compound having an ethylenically unsaturated group, a phosphoric acid group and a salt include monomers such as 2-hydroxyethyl(meth)acryloyl phosphate and 2-acryloyloxyethyl phosphate and salts thereof.
Examples of the compound having an ethylenically unsaturated group and a hydroxyl group include 3-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol, 2-methyl-3-buten-2-ol and the like. Hydroxyl-substituted alkenes, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, Examples thereof include hydroxyl group-containing (meth)acrylic acid esters such as caprolactone-modified hydroxy(meth)acrylate (for example, "Plaxel F" series manufactured by Daicel Chemical Industries, Ltd.).

Examples of the compound having an ethylenically unsaturated group and an acyclic amide group include (meth)acrylamide, N-vinylformamide, N-vinylacetamide and the like.

Examples of the compound having an ethylenically unsaturated group and a cyclic amide group include N-vinylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam and 1-(2-propenyl)-2. -Piperidone and the like.

Examples of the compound having an ethylenically unsaturated group and an alkylene glycol group or a polyalkylene glycol group include compounds represented by the following formula (IV).

The formula (IV), A represents an organic group having a hydrogen atom or a substituent having 1 to 20 carbon atoms which may have, X is _{-C (= O) -, -} CH 2 -, - CH 2 CH _{2 -, - CH 2 CH 2} CH 2 - or a single bond, Q represents an alkylene group having 2 to 20 carbon atoms, n represents a number from 1 to 200 with a repeating unit of alkylene oxide groups, a _k represents a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent.

Each of A and A _k is preferably a hydrogen atom or an organic group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an organic group having 1 to 8 carbon atoms, and when it has a substituent, More preferably, the number of carbon atoms including the substituents is in the above range. More preferably, each of A and A _k is a hydrogen atom or a methyl group.

The Q is preferably an alkylene group having 2 to 5 carbon atoms, and more preferably an ethylene group, an n-propylene group or an isopropylene group. Note that Q may contain only one kind of alkylene group, but may contain two or more kinds of alkylene groups. When Q contains an ethylene group, 50 to 100 mol% of the total alkylene glycol units in the polyalkylene glycol group is preferably an ethylene group, more preferably 80 to 100 mol% is an ethylene group, and 90 It is preferable that -100 mol% is an ethylene group.

m may be the average number of added moles of the entire compound represented by formula (IV). m is preferably 1 to 100, more preferably 5 to 80, and further preferably 10 to 60.
When X is represented by -C(=O)-, an alkylene oxide adduct having 1 to 100 carbon atoms to (meth)acrylic acid: a carbon atom such as methanol, ethanol, 2-propanol or 1-butanol. Examples thereof include esterified products of (meth)acrylic acid with alkoxypolyalkylene glycols obtained by adding an alkylene oxide having 1 to 100 carbon atoms to an alkyl alcohol having 1 to 30 carbon atoms.
X is _{-CH 2 -, - CH 2 CH} 2 -, - CH 2 CH 2 CH 2 - when represented by the allyl alcohol, methallyl alcohol, 2-buten-1-ol, 2-methyl-2- For unsaturated alcohols such as buten-1-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, vinyl alcohol, etc. The compound of the structure which added 1-100 mol of alkylene oxides can be mentioned, and these 1 type(s) or 2 or more types can be used.
Further, as the compound represented by the formula (IV), a polyalkylene oxide chain-containing (meth)acrylic acid ester such as 2-ethylhexylcarbitol (meth)acrylate, methoxybutyl (meth)acrylate, methoxyethyl (meth)acrylate And alkoxyalkyl (meth)acrylic acid esters such as ethoxybutyl (meth)acrylate.

When the copolymer (Y) contains the structural unit (C), the content of the structural unit (C) is 1 to 95 with respect to the total mass of the copolymer (Y) excluding the structural unit (B). It is preferably mass%, and more preferably 1 to 80 mass%. The copolymer (Y) may not include the structural unit (C).

The copolymer (Y) may contain a structural unit (hereinafter referred to as a structural unit (D)) other than the structural units (A), (B) and (C). That is, the structural unit (D) includes the above-mentioned monomer (A), methylenemalonic acid diester or its derivative, and other monomer that is not a hydrophilic monomer (hereinafter, referred to as the monomer (D)). It is a structural unit derived from. The “structural unit (D)” refers to a structural unit having the same structure as the structural unit formed by polymerizing the monomer (D). The structural unit (D) is not limited to a structural unit formed by actually polymerizing another monomer, and if it has the same structure as those structural units, a structure formed by another manufacturing method Units are also included.

Examples of the monomer (D) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl. (Meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth) Alkyl (meth)acrylic acid ester such as acrylate, t-butylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, polyfunctional alkoxyalkyl (meth)acrylic acid ester such as trimethylolpropane tripropoxy (meth)acrylate, styrene , Aromatic unsaturated hydrocarbon compounds such as α-methylstyrene, p-methylstyrene and vinyltoluene, vinyl esters of monocarboxylic acids having 1 to 5 carbon atoms such as vinyl acetate and vinyl propionate, dimethyl (meth)acrylamide, Examples thereof include vinyl compounds such as diethyl (meth)acrylamide, isopropyl (meth)acrylamide, (meth)acryloylmorpholine, and (meth)acrylonitrile.

When calculating the total of the structural unit (A), the structural unit (C), and the structural unit (D) for the copolymer (Y), the structural unit Has a salt of an acid group such as a carboxylate, a sulfonate, or a phosphate, the salt of the acid group is calculated by converting the mass of the corresponding acid group (acid conversion). For example, when the structural unit (A) is a structural unit derived from sodium acrylate, —CH ₂ —CH(COONa)—, a structural unit derived from acrylic acid having a corresponding acid group, —CH ₂ —CH(COOH). )-, calculated in terms of mass.
Similarly, when the structural unit has a salt of an amino group, the salt of the amino group is calculated by converting the mass into the corresponding amino group (amine conversion).

The copolymer (Y) may have a main chain containing the structural unit (A) and a structural unit (B) bonded to the carboxyl group of the structural unit (A). The structural unit (B) may form a graft chain in which two or more structural units (B) are bonded. In this case, the structural unit (C) may be contained in either the main chain or the graft chain, but is preferably contained in the main chain. The structural unit (B) may also be included in the main chain. The main chain refers to a polymer chain having a structure formed by addition polymerization of an ethylenically unsaturated group, and the graft chain refers to a polymer chain bonded to a carboxyl group of the main chain.

The graft chain may contain the structural unit (B) in an amount of 80% by mass or more, or 90% by mass or more, based on the total amount of the graft chains contained in the copolymer (Y). The graft chain may include, for example, a structural unit (C) or a structural unit (D) in addition to the structural unit (B).

Further, the copolymer (Y) may have a structure in which the structural units (A) and (B) are contained in the main chain without having a graft chain.

The lower limit of the weight average molecular weight of the copolymer (Y) is preferably 2,000 or more, more preferably 3,000 or more, and particularly preferably 5,000 or more, from the viewpoint of exhibiting excellent anti-soil redeposition ability. .. The upper limit of the weight average molecular weight of the copolymer (Y) is preferably 500,000 or less, more preferably 200,000 or less, and particularly preferably 100,000 or less.

In addition, in this specification, a weight average molecular weight says the weight average molecular weight measured by gel permeation chromatography (GPC). As the weight average molecular weight, more specifically, Tosoh Corporation, product number: HLC-8220GPC is used as a measuring device, Tosoh Corporation product number: TSKgel Super HZM-M is used as a separation column, and a standard It can be a value converted with polystyrene [manufactured by Tosoh Corporation].
Examples of preferable forms of the copolymer of the present disclosure include the following (I) to (X).
(I) Structural unit (A) derived from a monomer containing an ethylenically unsaturated group and a carboxyl group, structural unit (B) derived from a methylenemalonic acid diester or its derivative, and optionally a hydrophilic monomer And a structural unit (C) derived from the copolymer, wherein the structural unit (A) and the structural unit (C) are based on the total mass of the copolymer excluding the structural unit (B). Of 50% by mass or more in total, and 0.1 to 100 mol% of the structural unit (B) with respect to 100 mol% of the structural unit (A).
(II) Copolymer according to (I) above, wherein the structural unit (B) derived from methylenemalonic acid diester or a derivative thereof is any of the above monomers (B-1) to (B-9). Coalescing.
(III) The hydrophilic monomer is an ethylenically unsaturated group, a sulfonic acid group and its salt, a phosphoric acid group and its salt, an alkylene glycol group, a polyalkylene glycol group, a hydroxyl group, an amino group, an acyclic amide group. , And at least one group selected from cyclic amide groups, the copolymer according to (I) or (II) above.
(IV) The hydrophilic monomer has an ethylenically unsaturated group and at least one group selected from a sulfonic acid group and a salt thereof, an alkylene glycol group, and a polyalkylene glycol group, (I) ~ The copolymer according to any one of (III).
(V) The copolymer according to (III) or (IV) above, wherein the compound having an ethylenically unsaturated group and an alkylene glycol group or a polyalkylene glycol group is a compound represented by formula (III).
(VI) The total amount of the structural unit (A) and the structural unit (C) based on the total mass of the copolymer excluding the structural unit (B) is 50% by mass or more, preferably 70% or more, more preferably 90% by mass. %, more preferably substantially 100% by mass, the copolymer according to any one of the above (I) to (V).
(VII) The content of the structural unit (A) is 10% by mass or more and 100% by mass or less, preferably 20% by mass or more and 100% by mass with respect to the total mass excluding the structural unit (B) in the copolymer. The following is the copolymer according to any one of (I) to (VI) above.
(VIII) Containing 0.1 to 20 mol%, preferably 0.1 to 10 mol%, and more preferably 0.1 to 5 mol% of the structural unit (B) based on 100 mol% of the structural unit (A). The copolymer according to any one of (I) to (VII) above.
(IX) The weight average molecular weight is 2000 or more, preferably 3000 or more, more preferably 5000 or more, and 500,000 or less, preferably 200,000 or less, more preferably 100,000 or less, (I) to (VIII) The copolymer according to any one of (1) to (4).
(X) The copolymer according to any one of (I) to (IX) above, which is water-soluble.

The method for producing the copolymer (Y) in the present disclosure is not particularly limited, but first, the (co)polymer (X) containing the structural unit (A) is synthesized and converted into the (co)polymer (X). Examples thereof include a method of adding methylenemalonic acid diester or its derivative.

The (co)polymer (X) contains the structural unit (A) and optionally the structural unit (C). Further, at least one of the condition that the structural unit (A) and the structural unit (C) are contained in a total amount of 80% by mass or more and that the compound is a water-soluble (co)polymer is satisfied. That is, the (co)polymer (X) may be a polymer having the same structure as the copolymer (Y) except that it does not include the graft chain having the structural unit (B). The (co)polymer (X) may or may not contain the structural unit (B). When the (co)polymer (X) contains the structural unit (B), the (co)polymer (X) itself can be used as the copolymer (Y). The (co)polymer means a polymer obtained by polymerizing only one type of monomer (a polymer containing only one type of structural unit) and a copolymer obtained by copolymerizing two or more types of monomers. Both are included.

The (co)polymer (X) can be obtained by polymerizing a monomer composition containing the monomer (A) by a known method. The monomer composition may contain any of a methylenemalonic acid diester or a derivative thereof, a hydrophilic monomer, and another monomer (D) in addition to the monomer (A). When polymerizing the monomer composition, a chain transfer agent or a polymerization initiator can be used. The molecular weight of the (co)polymer (X) can be easily adjusted by adjusting the amount of the chain transfer agent.

Examples of the chain transfer agent include 2-mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionic acid, and 2-mercapto. Thiol compounds such as ethanesulfonic acid, n-dodecyl mercaptan, octyl mercaptan and butyl thioglycolate; halides such as carbon tetrachloride, methylene chloride, bromoform and bromotrichloroethane; secondary alcohols such as isopropanol; phosphorous acid and the like. Examples thereof include salts, hypophosphorous acid and its salts, sulfurous acid and its salts, hydrogen sulfite and its salts, dithionous acid and its salts, metabisulfite and its salts, and the like.

The amount of the chain transfer agent cannot be unconditionally determined because it depends on the molecular weight of the target (co)polymer (X). Therefore, depending on the molecular weight of the target (co)polymer (X). It is preferable to adjust appropriately.

As the polymerization initiator, for example, persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, which are substances that decompose by heat to generate molecules having radicals, 2,2′- Azobis(2-amidinopropane) dihydrochloride, water-soluble azo compounds such as 4,4′-azobis(4-cyanopentanoic acid), thermal decomposition initiators such as hydrogen peroxide, oxidizer and reducing agent Hydrogen peroxide and L-ascorbic acid, t-butylhydroperoxide and Rongalit, sodium perfluate and metal salts, ammonium perfluate and sodium bisulfite, etc. are combined to generate molecules having radicals through redox reactions. Examples thereof include redox polymerization initiators, which may be used alone or in combination of two or more kinds.

The amount of the polymerization initiator is not particularly limited, but is usually preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the raw material monomer of the (co)polymer (X). Is.

A solvent may be used when polymerizing the monomer composition. The solvent is preferably an aqueous solvent such as water, alcohol, glycol, glycerin or polyethylene glycol, and particularly preferably water. These may be used alone or in combination of two or more. Further, in order to improve the solubility of the above-mentioned monomer composition in a solvent, an organic solvent may be appropriately added within a range that does not adversely affect the polymerization of each monomer.

By adding methylenemalonic acid diester or its derivative to the obtained (co)polymer (X), the carboxyl group contained in the (co)polymer (X) is reacted with methylenemalonic acid diester or its derivative. be able to.

The (co)polymer (X) may be neutralized before adding the methylenemalonic acid diester or its derivative. The reaction can be promoted by forming a salt of a carboxyl group by neutralization. The base used for neutralization is not particularly limited, but a strong base such as an alkali metal or alkaline earth metal hydroxide is preferable, and sodium hydroxide may be used. The degree of neutralization (the ratio of neutralized carboxyl groups to the total number of moles of carboxyl groups in the (co)polymer (X)) is preferably 1 to 10%, more preferably 2 to 7%. After the reaction, the carboxyl group of the obtained copolymer (Y) and the carboxyl group of the unreacted (co)polymer (X), if present, may be further neutralized. The neutralization degree is preferably 80% or more, and more preferably 90% or more with respect to the total of the carboxyl groups of the polymer (Y) and the unreacted (co)polymer (X).

The step of adding the methylenemalonic acid diester or its derivative to the (co)polymer (X) may be performed in an aqueous solution. In this case, an aqueous solution of the (co)polymer (X) may be prepared and the methylenemalonic acid diester or its derivative may be added to the aqueous solution. After completion of the reaction between the (co)polymer (X) and the methylenemalonic acid diester or its derivative, the aqueous solution is added to a poor solvent to precipitate the copolymer (Y), which can be recovered.

The composition of the present disclosure contains a (co)polymer (X) and a copolymer (Y). As the copolymer (Y), those mentioned above can be used without limitation.

The (co)polymer (X) contained in the composition contains the structural unit (A) and optionally the structural unit (C), but does not contain the structural unit (B). Further, the (co)polymer (X) contained in the composition is the (co)polymer (X) based on the total mass of the (co)polymer (X). The total amount of C) is 80% by mass or more, or the (co)polymer (X) is a water-soluble copolymer. Examples of the structural unit (A), structural unit (C) and structural unit (D) contained in the (co)polymer (X) include the same as those contained in the copolymer (Y), The suitable content may be the same as that exemplified for the copolymer (Y).

The (co)polymer (X) may be one that has not reacted with the monomer (B) among those used as a raw material when the above-mentioned copolymer (Y) is produced, It may be added to the polymer (Y). The copolymer (Y) and the (co)polymer (X) may have different compositions, in addition to not containing the structural unit (B).

The content of the (co)polymer (X) in the composition may be 5 to 95% by mass, 10 to 80% by mass, or 20 to 50% by mass based on the total amount of the composition. You can The content of the copolymer (Y) in the composition may be 5 to 95% by mass, 10 to 80% by mass, or 20 to 50% by mass with respect to the total amount of the composition. Good.

The degree of neutralization of the (co)polymer (X) and the copolymer (Y) in the composition is based on the total amount of the carboxyl groups of the (co)polymer (X) and the carboxyl groups of the copolymer (Y). Therefore, it is preferably 80% or more, and more preferably 90% or more.

Since the copolymer (Y) of the present disclosure and the above composition have excellent anti-soil redeposition ability, they can be used as an anti-soil redeposition agent for clothes detergents. That is, the anti-redeposition agent for clothing detergents of the present disclosure contains the above-mentioned copolymer (Y) or composition.

The anti-soil redeposition agent for clothes detergents can be used by adding it to a detergent composition. The form of the detergent composition is not particularly limited and may be liquid, solid, powder or the like.

The detergent composition of the present disclosure may include various components used in the detergent composition, in addition to the anti-soil redeposition agent for clothing detergents. As components contained in the detergent composition, a surfactant and an additive for detergent which is usually used in detergent compositions can be used.

The above-mentioned surfactant may be any of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant, and one kind or two or more kinds can be used.

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 its ester salt, alkane sulfonic acid. Salt, 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 the salt etc. are suitable. The alkyl group and alkenyl group in these anionic surfactants may be branched with an alkyl group such as a methyl group.

As the nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide or alkylene oxide adduct thereof, sucrose fatty acid ester, alkylglycoxide, fatty acid glycerin monoester Examples thereof include esters and alkylamine oxides. The alkyl group or alkenyl group in these nonionic surfactants may be branched with an alkyl group such as a methyl group.

Examples of the cationic surfactant include quaternary ammonium salts and the like. Examples of the amphoteric surfactant include carboxyl-type amphoteric surfactant and sulfobetaine-type amphoteric surfactant. The alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may have a branched alkyl group such as a methyl group.

The content of the surfactant is preferably 10 to 60 mass% with respect to the total amount of the detergent composition, more preferably 15 to 50 mass%, still more preferably 20 to 45 mass%, and 25 It is particularly preferable that the content is ˜40% by mass. When the content of the surfactant is 10 to 60% by mass with respect to the total amount of the detergent composition, the detergency and the economical efficiency tend to be compatible with each other.

<Synthesis example 1>
255.4 parts by mass of water was charged into a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introducing tube and a reflux cooling device, and the inside of the reactor was heated to 100° C. with stirring.
In the above reaction apparatus, 72.2 parts by mass of 80% by mass aqueous acrylic acid solution was added dropwise over 3 hours, and 49.1 parts by mass of water was added dropwise over 2 hours and 50 minutes to prepare a 15% sodium persulfate aqueous solution (hereinafter , NaPS) was added dropwise over 3 hours and 5 minutes.
After the dropping was completed, the temperature was maintained at 100° C. for 30 minutes to complete the polymerization reaction, and an unneutralized polyacrylic acid aqueous solution (solid content: 45.0% by mass) having a weight average molecular weight of 10,000 was obtained.

<Example 1>
50.0 parts by mass of the unneutralized polyacrylic acid aqueous solution obtained in Synthesis Example 1 and 1.21 parts by mass of a 50% by mass aqueous sodium hydroxide solution were added to a polypropylene reaction vessel containing a stir bar while cooling. The degree of neutralization was adjusted to 5%. Further, 0.53 parts by mass of diethyl methylenemalonate (hereinafter referred to as DEMM) was added, and the mixture was stirred at room temperature for 6 hours to obtain a reaction liquid. After the reaction, 50% by mass aqueous sodium hydroxide solution was added while cooling 23.09 parts by mass to adjust the degree of neutralization to 100%.
Next, 75.0 parts by mass of deionized water was added to the reaction solution and stirred to form a uniform dropping solution. 3000.0 parts by mass of methanol was added to a reaction container different from the above, and the dropping solution was added dropwise over 5 minutes while stirring. After the dropping, the mixture was stirred at room temperature for 5 minutes, and then the stirring was stopped to precipitate a precipitate. The supernatant was removed by decantation, 1000.0 parts by mass of methanol was further added, and the same operation was repeated twice. The precipitate was collected by vacuum filtration and dried under vacuum to obtain a copolymer containing the DEMM-derived structural unit of Example 1.

<Synthesis example 2>
105.88 parts by mass of water was charged into a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introducing tube and a reflux cooling device, and the inside of the reactor was replaced with nitrogen under stirring to 90°C under a nitrogen atmosphere. Heated. Methoxy polyethylene glycol monomethacrylic acid ester (average number of moles of ethylene oxide added: 25 moles) 148.9 parts by mass, methacrylic acid 46.8 parts by mass, water 50.4 parts by mass, and 3-mercaptopropionic acid as a chain transfer agent 4. An aqueous monomer solution mixed with 55 parts by mass was added dropwise over 4 hours, and 42.5 parts by mass of a 6.9% by mass NaPS aqueous solution was added over 7 hours.
After completion of the dropping, the temperature was maintained at 90° C. for 2 hours to complete the polymerization reaction, and after cooling, the mixture was adjusted with 50% by mass aqueous sodium hydroxide solution and deionized water to obtain a neutralization degree of weight average molecular weight of 10,500. 8.0% methoxy polyethylene glycol monomethacrylic acid ester/methacrylic acid copolymer aqueous solution (solid content 40.0% by mass) was obtained.

<Example 2>
In a polypropylene reaction vessel containing a stir bar, 0.95 parts by mass of DEMM was added to 50.0 parts by mass of the aqueous copolymer solution obtained in Synthesis Example 2, and the reaction solution was obtained by stirring at room temperature for 6 hours. It was After the reaction, 50% by mass sodium hydroxide aqueous solution was added while cooling 4.15 parts by mass to adjust the degree of neutralization to 100%.
Next, 110.2 parts by mass of methanol was added to the reaction solution and stirred to form a uniform dropping solution. 3300.0 parts by mass of tert-butyl methyl ether was added to a reaction vessel different from the above, and the dropping solution was added dropwise over 5 minutes while stirring. After the dropping, the mixture was stirred for 5 minutes at room temperature, and then the stirring was stopped to precipitate a precipitate. The supernatant was removed by decantation, 1100.0 parts by mass of tert-butyl methyl ether was further added, and the same operation was repeated twice. The precipitate was collected by vacuum filtration and dried under vacuum to obtain a copolymer containing the DEMM-derived structural unit of Example 2.

[Method for measuring carboxylic acid value in copolymers obtained in Examples 1 and 2]
Carboxylic acid value: It means the number of mg of potassium hydroxide equivalent to the carboxylic acid group contained in 1 g of copolymer (carboxylic acid is converted to sodium carboxylate). About 1 g of the obtained copolymer is weighed, and 0.1N HCl is added to adjust the pH to 2.0 or less. Next, potentiometric titration was carried out using an aqueous potassium hydroxide solution, and the carboxylic acid value (C1) was determined from the titration value obtained. The number of moles per unit mass of the structural unit (A) derived from the monomer containing an ethylenically unsaturated group and a carboxyl group in the obtained copolymer is the calculated carboxylic acid value (C1) and water. It can be calculated from the formula weight 56.11 of potassium oxide.
[Mole% of the structural unit (B) derived from DEMM to 100 mol% of the structural unit (A) derived from the monomer containing an ethylenically unsaturated group and a carboxyl group in the copolymers obtained in Examples 1 and 2] Evaluation of content rate (hereinafter, content rate of structural unit derived from DEMM)]
Using a nuclear magnetic resonance apparatus (600 MHz Varian NMR system, manufactured by Varian), dimethyl sulfoxide (internal standard agent) was added to the copolymer containing the structural unit derived from DEMM obtained in Example 1 or 2, and heavy water was added. The ¹ H-NMR spectrum was measured using a sample diluted with (NMR solvent, 99.8 atom% D) as a measurement sample. A chemical shift signal (around 6.48 to 6.52 ppm based on tetramethylsilane) derived from the methylene proton on the double bond of the raw material DEMM was not observed. A mass (W1) of the added dimethyl sulfoxide and an area value (H1) of a chemical shift signal (around 2.69 to 2.73 ppm based on tetramethylsilane) derived from the proton thereof, and a compound containing a structural unit derived from DEMM Area value (H2) of the chemical shift signal (around 4.00 to 4.35 ppm based on tetramethylsilane) derived from the methylene protons of the ethyl ester group of DEMM bonded to the polymer mass (W2) and its copolymer ) And the carboxylic acid value (C1) were used to calculate the DEMM-derived structural unit content by the following formula. The results are shown in Table 1.
Number of moles per weight of structural unit (A) derived from a monomer containing an ethylenically unsaturated group and a carboxyl group in the obtained copolymer=(C1)/(56.11×1000)
Number of moles of added dimethyl sulfoxide=(W1)/(78.13)
Number of moles per unit weight of the structural unit derived from DEMM in the obtained copolymer=(number of moles of added dimethyl sulfoxide)/((H1)/6)×((H2)/4)/(W2)
DEMM-derived structural unit content=(number of moles per weight of DEMM-derived structural unit (B) in the obtained copolymer)/(including ethylenically unsaturated group and carboxyl group in the obtained copolymer) Number of moles of structural unit (A) derived from monomer per weight)×100

[Evaluation of recontamination prevention effect]
Using the copolymers of Examples 1 and 2 and the (co)polymers of Synthesis Examples 1 and 2 as Comparative Examples 1 and 2, respectively, the following washing step, rinsing step, and drying step were performed twice in this order. Repeated washing process was performed.

Washing process:
The following two types of cotton cloth were used as the articles to be washed.
Cotton cloth (1): 5 pieces of cotton knitted cloth (manufactured by Tanigami Shoten Co., Ltd.) 5 cm×5 cm as a redeposition determination cloth.
Cotton cloth (2): 30 g of cotton cloth obtained from Testfabrics, including cotton cloth (1)
As a surfactant, an aqueous solution in which linear alkylbenzene sulfonate sodium (manufactured by Kao Corporation, product name: Neoperex 65 (solid content 65%)) is adjusted to 3% by mass, and polyoxyethylene alkyl ether (manufactured by Kao Corporation) An aqueous solution in which the product name: Emulgen 108) was adjusted to 3% by mass, and a 1% by mass aqueous solution of the (co)polymer of Examples 1-2 and Comparative Examples 1-2 were prepared.
900 mL of 3.5° DH hard water (prepared with calcium chloride and magnesium chloride. Ca/Mg=3 (mass ratio)) at 20° C. in a Tergot-o-meter (manufactured by Daiei Kagaku Co., Ltd., product name: TM-4) , 3.75 g of the above-mentioned aqueous solution of sodium linear alkylbenzene sulfonate and polyoxyethylene alkyl ether, and 0.75 g of the aqueous solution of (co)polymer of Examples 1-2 and Comparative Examples 1-2, respectively. 1.35 g of strained red soil and cotton cloths (1) and (2) were added. Then, it was washed at a stirring speed of 120 rpm and 20° C. for 10 minutes.
Rinsing process:
The article to be washed after the washing step was dehydrated for 1.5 minutes, 900 mL of hard water at 20° C. was added, and rinsed at 120 rpm and 20° C. for 3 minutes. This operation (dehydration and rinsing) was repeated twice.
Drying process:
After the rinsed article was dehydrated for 1.5 minutes, only the cotton cloth (1) was taken out, sandwiched with cotton cloth, and dried with an iron.

Using a reflectance meter (spectroscopic color difference meter, manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000), the reflectance (Z value) of the recontamination judging cloth before and after the washing process is measured, and the recontamination is prevented from the following formula. I asked for the rate. The results are shown in Table 2.
Redeposition prevention rate=(Z value after washing treatment)/(Z value before washing treatment)×100

Claims (7)

A structural unit (A) derived from a monomer containing an ethylenically unsaturated group and a carboxyl group,
A structural unit (B) derived from methylenemalonic acid diester or a derivative thereof,
A copolymer which optionally comprises a structural unit (C) derived from a hydrophilic monomer,
Including 50% by mass or more of the structural unit (A) and the structural unit (C) in total with respect to the total mass excluding the structural unit (B) in the copolymer,
A copolymer containing 0.1 to 100 mol% of the structural unit (B) with respect to 100 mol% of the structural unit (A). A structural unit (A) derived from a monomer containing an ethylenically unsaturated group and a carboxyl group,
A structural unit (B) derived from methylenemalonic acid diester or a derivative thereof,
Optionally including a structural unit (C) derived from a hydrophilic monomer,
The content of the structural unit (B) is 0.1 to 100 mol% with respect to 100 mol% of the structural unit (A),
A copolymer that is a water-soluble copolymer. The copolymer according to claim 1 or 2, which has a main chain containing the structural unit (A) and contains a structural unit (B) bonded to a carboxyl group of the structural unit (A) in the main chain. The hydrophilic monomer is an ethylenically unsaturated group, a sulfonic acid group and a salt thereof, a phosphoric acid group and a salt thereof, an alkylene glycol group, a polyalkylene glycol group, a hydroxyl group, an amino group, an acyclic amide group, and a cyclic The copolymer according to any one of claims 1 to 3, which has at least one group selected from amide groups. Containing a (co)polymer (X) and a copolymer (Y),
The copolymer (Y) is the copolymer according to any one of claims 1 to 4,
The (co)polymer (X) contains a structural unit (A) derived from a monomer containing an ethylenically unsaturated group and a carboxyl group, and optionally a structural unit (C) derived from a hydrophilic monomer. However, the (co)polymer (X) does not include a structural unit (B) derived from any one of methylenemalonic acid diester and its derivative, and the (co)polymer (X) has at least one of the following conditions (a) and (b): Fill the composition.
(A) The structural unit (A) and the structural unit (C) are contained in a total amount of 50% by mass or more based on the total mass of the (co)polymer (X).
(B) The (co)polymer (X) is a water-soluble copolymer. A redeposition preventive agent for a clothing detergent, comprising the copolymer according to any one of claims 1 to 4 or the composition according to claim 5. A method for producing a copolymer, comprising:
A step of adding a methylenemalonic acid diester or a derivative thereof to the (co)polymer (X),
The (co)polymer (X) is a structural unit (A) derived from a monomer containing an ethylenically unsaturated group and a carboxyl group, and a structural unit (B) optionally derived from a methylenemalonic acid diester or a derivative thereof. ) And optionally a structural unit (C) derived from a hydrophilic monomer, and the (co)polymer (X) satisfies at least one of the following conditions (a) and (b): Method for producing copolymer.
(A) Containing 50% by mass or more of the structural unit (A) and the structural unit (C) in total with respect to the total mass excluding the structural unit (B) in the (co)polymer (X).
(B) The (co)polymer (X) is a water-soluble copolymer.