JP2023181590A - Multiester-type polyalkylene oxide-containing monomer, and polymer including the same - Google Patents

Abstract

To provide a novel biodegradable compound and a method for producing the same, and further provide a polymer that includes the compound and is superior at preventing recontamination.SOLUTION: The present invention provides a compound represented by the general formula (1) and a polymer thereof. (In the general formula (1), X represents a C1-10 organic group. m represents 0 or 1. n represents an integer of 1-200. R1 represents a hydrogen atom and/or a methyl group. With m=0, R2 represents a direct bond or at least one selected from C1-10 organic groups, or with m=1, R2 represents at least one selected from C1-10 organic groups. R3 represents at least one selected from C2-6 organic groups. R4 represents a hydrogen atom or at least one selected from C1-30 organic groups).SELECTED DRAWING: None

Description

The present disclosure relates to a novel biodegradable compound, a polymer containing the same, and uses thereof. More specifically, multiester type polyalkylene oxide-containing (meth)acrylates suitable as various industrial raw materials, multiesters that can be used for various purposes such as detergent compositions, fiber treatment agents, water treatment agents, pigment dispersants, etc. The present invention relates to (meth)acrylate polymers containing type polyalkylene oxide.

Conventionally, various types of polymers having polyalkylene oxide chains in side chains have been proposed. Polymers with polyalkylene oxide chains in their side chains are known to exhibit excellent cleaning power when used in detergent compositions for liquid detergents because they have excellent compatibility with surfactants. .

For example, Patent Documents 1 and 2 disclose copolymers having methylpolyethylene glycol methacrylate in their side chains.

Special table 2007-511652 Special table 2007-511654

By the way, the inventors of the present application have been studying the use of a polymer having a polyethylene glycol chain (hydrophilic group) and a chain hydrocarbon group having 10 or more carbon atoms in the side chain as an additive for detergents.
In recent years, detergent additives used in detergent compositions are required to be biodegradable.
However, it has been confirmed that polymers having polyalkylene oxide chains in their side chains, including the polymers described in Patent Documents 1 and 2, have poor biodegradability. Therefore, when the detergent composition is discharged into a river or the like after washing, there is a problem in that the environmental load is high.
In conventional polymers with polyalkylene glycol in the side chain, the ester bond, which is the starting point for biodegradability, is directly connected to the polymer main chain, and due to the steric hindrance, hydrolytic enzymes act on the ester bond. It was preventing me from doing that. Therefore, the ester bond is not hydrolyzed and the polyethylene glycol chain is not detached from the polymer chain, making it difficult to exhibit biodegradability.
Therefore, the inventors of the present application have developed a multi-ester polyester polyester having multiple ester groups that makes it easier for hydrolytic enzymes to act by suppressing the effects of steric hindrance by introducing an ester bond in a portion away from the main chain. This led us to propose an alkylene oxide-containing (meth)acrylate.

The present disclosure has been made in view of the deception and provides novel biodegradable compounds, polymers containing the same, and uses thereof.

That is, the compounds of the present disclosure:
It is a compound represented by the following general formula (1).

（一般式（１）中、
Ｘは、炭素数１～１０の有機基である。
ｍは、０または１である。ｎは、１～２００の整数である。
Ｒ^１は、水素原子、及び／又は、メチル基である。
Ｒ^２は、ｍ＝０の場合は直接結合、もしくは、炭素数１～１０の有機基から選ばれる１種以上であり、ｍ＝１の場合は炭素数１～１０の有機基から選ばれる１種以上である。
Ｒ^３は、炭素数２～６の有機基から選ばれる１種以上である。
Ｒ^４は、水素原子、炭素数１～３０の有機基から選ばれる１種以上である。）

(In general formula (1),
X is an organic group having 1 to 10 carbon atoms.
m is 0 or 1. n is an integer from 1 to 200.
R ¹ is a hydrogen atom and/or a methyl group.
R ² is a direct bond or one or more selected from organic groups having 1 to 10 carbon atoms when m=0, and 1 selected from organic groups having 1 to 10 carbon atoms when m=1. More than a species.
R ³ is one or more selected from organic groups having 2 to 6 carbon atoms.
R ⁴ is one or more selected from a hydrogen atom and an organic group having 1 to 30 carbon atoms. )

That is, the polymer of the present disclosure is
It is a polymer having a structural unit (A) represented by the following general formula (2).

（一般式（２）中、
Ｘは、炭素数１～１０の有機基である。
ｍは、０または１である。ｎは、１～２００の整数である。
Ｒ^１は、水素原子、及び／又は、メチル基である。
Ｒ^２は、ｍ＝０の場合は直接結合、もしくは、炭素数１～１０の有機基から選ばれる１種以上であり、ｍ＝１の場合は炭素数１～１０の有機基から選ばれる１種以上である。
Ｒ^３は、炭素数２～６の有機基から選ばれる１種以上である。
Ｒ^４は、水素原子、炭素数１～３０の有機基から選ばれる１種以上である。
但し、アスタリスクは、一般式（１）で表される構造単位（Ａ）が結合している同種もしくは異種の他の構造単位に含まれる原子を表す。）

(In general formula (2),
X is an organic group having 1 to 10 carbon atoms.
m is 0 or 1. n is an integer from 1 to 200.
R ¹ is a hydrogen atom and/or a methyl group.
R ² is a direct bond or one or more selected from organic groups having 1 to 10 carbon atoms when m=0, and 1 selected from organic groups having 1 to 10 carbon atoms when m=1. More than a species.
R ³ is one or more selected from organic groups having 2 to 6 carbon atoms.
R ⁴ is one or more selected from a hydrogen atom and an organic group having 1 to 30 carbon atoms.
However, the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit (A) represented by general formula (1) is bonded. )

Furthermore, the copolymer of the present disclosure
It is a copolymer having a structural unit (A) represented by the following general formula (2) and a structural unit (B) represented by the following general formula (3).

（一般式（２）中、
Ｘは、炭素数１～１０の有機基である。
ｍは、０または１である。ｎは、１～２００の整数である。
Ｒ^１は、水素原子、及び／又は、メチル基である。
Ｒ^２は、ｍ＝０の場合は直接結合、もしくは、炭素数１～１０の有機基から選ばれる１種以上であり、ｍ＝１の場合は炭素数１～１０の有機基から選ばれる１種以上である。
Ｒ^３は、炭素数２～６の有機基から選ばれる１種以上である。
Ｒ^４は、水素原子、炭素数１～３０の有機基から選ばれる１種以上である。
但し、アスタリスクは、一般式（１）で表される構造単位（Ａ）が結合している同種もしくは異種の他の構造単位に含まれる原子を表す。）

(In general formula (2),
X is an organic group having 1 to 10 carbon atoms.
m is 0 or 1. n is an integer from 1 to 200.
R ¹ is a hydrogen atom and/or a methyl group.
R ² is a direct bond or one or more selected from organic groups having 1 to 10 carbon atoms when m=0, and 1 selected from organic groups having 1 to 10 carbon atoms when m=1. More than a species.
R ³ is one or more selected from organic groups having 2 to 6 carbon atoms.
R ⁴ is one or more selected from a hydrogen atom and an organic group having 1 to 30 carbon atoms.
However, the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit (A) represented by general formula (1) is bonded. )

（一般式（３）中、
Ｒ^５は、水素原子、及び／又は、メチル基である。
Ｒ^６は、炭素数１～６の有機基から選ばれる１種以上である。
Ｒ^７、Ｒ^８は、同一、もしくは異なって、水素原子、炭素数１～６の有機基から選ばれる１種以上である。
但し、アスタリスクは、一般式（１）で表される構造単位（Ａ）が結合している同種もしくは異種の他の構造単位に含まれる原子を表す。）

(In general formula (3),
R ⁵ is a hydrogen atom and/or a methyl group.
R ⁶ is one or more selected from organic groups having 1 to 6 carbon atoms.
R ⁷ and R ⁸ are the same or different and are one or more selected from a hydrogen atom and an organic group having 1 to 6 carbon atoms.
However, the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit (A) represented by general formula (1) is bonded. )

According to the present disclosure, it is possible to provide a novel biodegradable compound, a polymer containing the same, and uses thereof.

Embodiments of the present disclosure will be described in detail below. The following description of preferred embodiments is merely exemplary in nature and is in no way intended to limit the present disclosure, its applications, or its uses.

In the following explanation, unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass," and "A to B" indicating a range means A to B. Indicates that: Further, in the present disclosure, "(meth)acrylate" means "acrylate" or "methacrylate", and "(meth)acrylic" means "acrylic" or "methacrylic".

〔Compound〕
Compounds of the present disclosure include:
There is no particular limitation as long as it is a compound represented by the following general formula (1).

（一般式（１）中、
Ｘは、炭素数１～１０の有機基である。
ｍは、０または１である。ｎは、１～２００の整数である。
Ｒ^１は、水素原子、及び／又は、メチル基である。
Ｒ^２は、ｍ＝０の場合は直接結合、もしくは、炭素数１～１０の有機基から選ばれる１種以上であり、ｍ＝１の場合は炭素数１～１０の有機基から選ばれる１種以上である。
Ｒ^３は、炭素数２～６の有機基から選ばれる１種以上である。
Ｒ^４は、水素原子、炭素数１～３０の有機基から選ばれる１種以上である。）
また、本開示の化合物は、二つ以上のエステル基を有していて、ポリアルキレンオキシド構造を有し、且つ、重合可能な不飽和二重結合を有していれば、マルチエステル型ポリアルキレンオキシド含有単量体と称することもできる。

(In general formula (1),
X is an organic group having 1 to 10 carbon atoms.
m is 0 or 1. n is an integer from 1 to 200.
R ¹ is a hydrogen atom and/or a methyl group.
R ² is a direct bond or one or more selected from organic groups having 1 to 10 carbon atoms when m=0, and 1 selected from organic groups having 1 to 10 carbon atoms when m=1. More than a species.
R ³ is one or more selected from organic groups having 2 to 6 carbon atoms.
R ⁴ is one or more selected from a hydrogen atom and an organic group having 1 to 30 carbon atoms. )
Moreover, the compound of the present disclosure has two or more ester groups, has a polyalkylene oxide structure, and has a polymerizable unsaturated double bond, so that it can be considered as a multiester type polyalkylene. It can also be referred to as an oxide-containing monomer.

X in the general formula (1) is not particularly limited as long as it is an organic group having 1 to 10 carbon atoms. The organic group may be a saturated or unsaturated chain hydrocarbon, and may be linear or branched. Further, aromatic groups and heteroatoms may be included. Preferably, it is a linear or branched hydrocarbon group.
When the organic group having 1 to 10 carbon atoms is a hydrocarbon group having 1 to 10 carbon atoms, specifically,
-CH ₂ -CH ₂ - group, -CH ₂ -CH ₂ -CH ₂ - group, -CH ₂ -CH ₂ -CH ₂ -CH ₂ - group, -CH ₂ -CH(OH)-CH ₂ - group, -CH ₂ -CH(CH ₂ OH)- and the like.
Among these, it is generally one or more selected from -CH ₂ -CH(OH)-CH ₂ - group, -CH ₂ -CH(CH ₂ OH)- group, and -CH ₂ -CH ₂ - group. It is preferable in terms of ease of obtaining intermediates for synthesizing the compound of formula (1), ease of subsequent synthesis, and ease of biodegradation.

m in the general formula (1) is not particularly limited as long as it is 0 or 1. When m is 0, it is a direct bond, and when m is 1, it is an ester bond. In the compounds of the present disclosure, m may have only 0 or 1 bond, or may have both bonds. If m=1, it is preferable from the viewpoint that more ester bonds, which serve as starting points for biodegradability, can be introduced.

n in the general formula (1) is not particularly limited as long as it is an integer of 1 to 200. The n is more preferably 1 to 150, still more preferably 5 to 100, particularly preferably 10 to 50.
It is preferable that n in the general formula (1) of the present disclosure is within the above range because the polyalkylene oxide chain improves the dispersion effect of particle dirt such as mud.

R ¹ in the general formula (1) is not particularly limited as long as it is a hydrogen atom and/or a methyl group.

R ² in the general formula (1) is a direct bond or one or more selected from organic groups having 1 to 10 carbon atoms when m=0, and R 2 is a group having 1 to 10 carbon atoms when m=1. There is no particular limitation as long as it is one or more selected from 10 organic groups.
When R ² is one or more selected from organic groups having 1 to 10 carbon atoms, it may be linear or branched. Further, aromatic groups and heteroatoms may be included. Specific examples include methylene group, ethylene group, propylene group, butylene group, O-phenylene group, -CH=CH- group, and the like.
Preferred are methylene group, ethylene group, propylene group, butylene group, and -CH=CH- group, and more preferred are ethylene group and -CH=CH- group.
When the compound of the present disclosure is synthesized, it is preferable that R ² is the above-mentioned substituent because raw materials are easily available and synthesis is easy.

R ³ in the general formula (1) is not particularly limited as long as it is one or more selected from organic groups having 2 to 6 carbon atoms.
The above R ³ is not particularly limited as long as it is an organic group having 2 to 6 carbon atoms. The R ³ may be a hydrocarbon group having 1 to 6 carbon atoms. Preferably, it is a hydrocarbon group having 2 to 4 carbon atoms. The R ³ may have the same number of carbon atoms, or may be a combination of different carbon numbers, and the R ³ may be one or more selected from 2 to 6 carbon atoms. As mentioned above, the preferable number of carbon atoms in R ³ is 2 to 4 carbon atoms. Furthermore, if R ³ is one or more selected from ethylene, propylene, and butylene groups, it can improve the water solubility of the compound of the present disclosure. Further, from the viewpoint of improving the dispersibility of dirt components such as mud particles, the polymer obtained using the compound of the present disclosure preferably has the above-mentioned substituents.

R ⁴ in the general formula (1) is not particularly limited as long as it is one or more selected from a hydrogen atom and an organic group having 1 to 30 carbon atoms.
When R ⁴ is an organic group having 1 to 30 carbon atoms, it may be a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group is not particularly limited, and examples include chain hydrocarbon groups such as an alkyl group, alkenyl group, and alkynyl group, and cyclic hydrocarbon groups such as an aryl group, a cycloalkyl group, and a cycloalkenyl group. The hydrocarbon group may have a branch, and in the case where the hydrocarbon group has a branch, the number of carbon atoms in the hydrocarbon group means the total number of carbon atoms in the main chain and the branched chain. Moreover, it may have an oxygen atom or a hetero atom other than a carbon atom or a hydrogen atom.

Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, and dodecyl group. , stearyl group, icosyl group, etc.
Examples of the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, 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. etc. Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, dodecynyl group, octadecynyl group, and icosynyl group. etc.
Examples of the aryl group include a phenyl group, a benzyl group, a methylphenyl group, a 1-methoxy-4-methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a butylmethylphenyl group, a dimethylphenyl group, and a diethyl group. Examples include phenyl group, dibutylphenyl group, biphenyl group, biphenylmethyl group, biphenylethyl group, naphthyl group, naphthylmethyl group, naphthylethyl group, and the like.
Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.

The hydrocarbon group is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and even more preferably 1. When the number of carbon atoms in the hydrocarbon group is within the above range, the water solubility of the compound represented by the general formula (1) of the present disclosure improves, and the compound represented by the general formula (1) of the present disclosure improves. This is preferred because the monomers contained therein can be polymerized in an aqueous medium.

Further, R ⁴ in the general formula (1) may be a hydrogen atom depending on the intended use. For example, when it is desired to increase hydrophilicity, a hydrogen atom is preferable.
Further, R ⁴ may be one or more selected from a hydrogen atom and an organic group having 1 to 30 carbon atoms, and may include only one type, or one or more types as necessary.

[Polymer]
Using the compound of the present disclosure as a monomer, a polymerization reaction can be performed to form a polymer. There is no particular limitation as long as it is a polymer having a structural unit (A) represented by the following general formula (2).
Even if the compound of the present disclosure is a homopolymer obtained by carrying out a polymerization reaction alone, a copolymer can be obtained by carrying out a polymerization reaction using one or more monomers other than the compound of the present disclosure. You can also do this.
When the polymer of the present disclosure is simply referred to as a "polymer", it represents a homopolymer (homopolymer) and/or a copolymer.

（一般式（２）中、
Ｘは、炭素数１～１０の有機基である。
ｍは、０または１である。ｎは、１～２００の整数である。
Ｒ^１は、水素原子、及び／又はメチル基であれば特に限定はない。
Ｒ^２は、ｍ＝０の場合は直接結合、もしくは、炭素数１～１０の有機基から選ばれる１種以上であり、ｍ＝１の場合は炭素数１～１０の有機基から選ばれる１種以上である。
Ｒ^３は、炭素数２～６の有機基から選ばれる１種以上である。
Ｒ^４は、水素原子、炭素数１～３０の有機基から選ばれる１種以上である。
但し、アスタリスクは、一般式（１）で表される構造単位（Ａ）が結合している同種もしくは異種の他の構造単位に含まれる原子を表す。）
前記一般式（２）中のＸ、ｍ、ｎ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は、前記一般式（１）と同じであり、好ましい形態についても同じである。

(In general formula (2),
X is an organic group having 1 to 10 carbon atoms.
m is 0 or 1. n is an integer from 1 to 200.
R ¹ is not particularly limited as long as it is a hydrogen atom and/or a methyl group.
R ² is a direct bond or one or more selected from organic groups having 1 to 10 carbon atoms when m=0, and 1 selected from organic groups having 1 to 10 carbon atoms when m=1. More than a species.
R ³ is one or more selected from organic groups having 2 to 6 carbon atoms.
R ⁴ is one or more selected from a hydrogen atom and an organic group having 1 to 30 carbon atoms.
However, the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit (A) represented by general formula (1) is bonded. )
X, m, n, R ¹ , R ² , R ³ and R ⁴ in the general formula (2) are the same as in the general formula (1), and their preferred forms are also the same.

A copolymer containing structural units derived from other monomers may be obtained by performing a polymerization reaction with other monomers using the compound of the present disclosure as a monomer.
The structural unit derived from other monomers is a structure obtained by copolymerizing other monomers. For example, when the other monomer is methyl acrylate, *-CH ₂ -CH (COOCH ₃ )-*. (However, the asterisk represents an atom contained in another structural unit of the same or different type to which a structural unit derived from another monomer is bonded.)
Other monomers can be represented by the following general formula (4).

（一般式（４）中、
Ｒ^５は、水素原子、及び／又は、メチル基である。
Ｒ^６は、炭素数１～６の有機基から選ばれる１種以上である。
Ｒ^７、Ｒ^８は、同一、もしくは異なって、水素原子、炭素数１～６の有機基から選ばれる１種以上である。）
なお、一般式（４）中のＲ^５～Ｒ^８は、後述する一般式（３）中のＲ^５～Ｒ^８と同じである。

(In general formula (4),
R ⁵ is a hydrogen atom and/or a methyl group.
R ⁶ is one or more selected from organic groups having 1 to 6 carbon atoms.
R ⁷ and R ⁸ are the same or different and are one or more selected from a hydrogen atom and an organic group having 1 to 6 carbon atoms. )
Note that R ⁵ to R ⁸ in general formula (4) are the same as R ⁵ to R ⁸ in general formula (3), which will be described later.

In addition, monomers other than the other monomers that can be represented by the general formula (4) can be represented as other monomers (E), and are derived from other monomers (E). The structural unit can be represented as a structural unit (E).
Other monomers (E) include carboxyl group-containing monomers (also referred to as carboxyl group-containing unsaturated monomers). A carboxyl group-containing monomer is a monomer having a carboxyl group and a carbon-carbon double bond. The carboxyl group includes carboxylic acids and salts thereof. Examples of the carboxylic acid salt include, but are not particularly limited to, metal salts, ammonium salts, and organic amine salts of carboxylic acids. Preferred metal atoms in the metal salt include alkali metals such as sodium and potassium; alkaline earth metals such as magnesium, calcium, strontium, and barium; aluminum and iron; and as the organic amine group in the organic amine salt, Preferred are alkanolamine groups such as monoethanolamine, diethanolamine, and triethanolamine; alkylamine groups such as monoethylamine, diethylamine, and triethylamine; and polyamine groups such as ethylenediamine and triethylenediamine. The salts of the carboxylic acids include lithium salts, potassium salts, sodium salts, ammonium salts, and quaternary amine salts.

Examples of the carboxyl group-containing monomer include (meth)acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, 2-methyleneglutaric acid, and salts thereof. Among these, (meth)acrylic acid, maleic acid, maleic anhydride, or salts thereof are more preferable from the viewpoint of high re-staining prevention ability of the copolymer obtained with high polymerizability. Acid, maleic anhydride or a salt thereof is more preferred, and acrylic acid or an acrylate salt is particularly preferred. In the case of a compound that forms an acid anhydride such as maleic acid, these acid anhydrides may be used. These carboxyl group-containing monomers may be used alone or in combination of two or more.

Further, examples of the other monomer (E) include sulfonic acid group-containing monomers. Specifically, 2-acrylamido-2-methylpropanesulfonic acid, 3-(meth)allyloxy-2-hydroxypropanesulfonic acid (salt), 3-(meth)allyloxy-1-hydroxypropanesulfonic acid (salt) Can be mentioned.

Furthermore, other monomers (E) include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate. , 4-hydroxybutyl (meth)acrylate, α-hydroxymethylethyl (meth)acrylate, and other hydroxyl group-containing alkyl (meth)acrylates; methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate , cyclohexyl (meth)acrylate, lauryl (meth)acrylate, and other alkyl (meth)acrylates obtained by esterification of (meth)acrylic acid with an alcohol having 1 to 18 carbon atoms; dimethylaminoethyl (meth)acrylate Amino group-containing acrylates such as or quaternized products thereof; Amide group-containing monomers such as (meth)acrylamide, dimethylacrylamide, and isopropylacrylamide; Vinyl esters such as vinyl acetate; Alkenes such as ethylene and propylene; styrene, etc. Aromatic vinyl monomers; maleimide derivatives such as maleimide, phenylmaleimide, and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as (meth)acrylonitrile;

Monomers having a phosphonic acid (salt) group such as vinylphosphonic acid, (meth)allylphosphonic acid and their salts; vinyl monomers containing an aldehyde group such as (meth)acrolein; methyl vinyl ether, ethyl vinyl ether , alkyl vinyl ethers such as butyl vinyl ether; other functional group-containing monomers such as vinyl chloride, vinylidene chloride, allyl alcohol: vinyl pyrrolidone, and the like. Regarding these other monomers, only one type may be used alone, or two or more types may be used in combination.

[Copolymer]
The copolymer of the present disclosure is not particularly limited as long as it contains a structural unit (A) represented by the following general formula (2), but the copolymer has a structure represented by the following general formula (2). One preferred form is a copolymer having a unit (A) and a structural unit (B) represented by the following general formula (3).

（一般式（２）中、
Ｘは、炭素数１～１０の有機基である。
ｍは、０または１である。ｎは、１～２００の整数である。
Ｒ^１は、水素原子、及び／又は、メチル基であれば特に限定はない。Ｒ^２は、ｍ＝０の場合は直接結合、もしくは、炭素数１～１０の有機基から選ばれる１種以上であり、ｍ＝１の場合は炭素数１～１０の有機基から選ばれる１種以上である。
Ｒ^３は、炭素数２～６の有機基から選ばれる１種以上である。
Ｒ^４は、水素原子、炭素数１～３０の有機基から選ばれる１種以上である。
但し、アスタリスクは、一般式（１）で表される構造単位（Ａ）が結合している同種もしくは異種の他の構造単位に含まれる原子を表す。）

(In general formula (2),
X is an organic group having 1 to 10 carbon atoms.
m is 0 or 1. n is an integer from 1 to 200.
R ¹ is not particularly limited as long as it is a hydrogen atom and/or a methyl group. R ² is a direct bond or one or more selected from organic groups having 1 to 10 carbon atoms when m=0, and 1 selected from organic groups having 1 to 10 carbon atoms when m=1. More than a species.
R ³ is one or more selected from organic groups having 2 to 6 carbon atoms.
R ⁴ is one or more selected from a hydrogen atom and an organic group having 1 to 30 carbon atoms.
However, the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit (A) represented by general formula (1) is bonded. )

（一般式（３）中、
Ｒ^５は、水素原子、及び／又は、メチル基である。
Ｒ^６は、炭素数１～６の有機基から選ばれる１種以上である。
Ｒ^７、Ｒ^８は、同一、もしくは異なって、水素原子、炭素数１～６の有機基から選ばれる１種以上である。
但し、アスタリスクは、一般式（１）で表される構造単位（Ａ）が結合している同種もしくは異種の他の構造単位に含まれる原子を表す。）

(In general formula (3),
R ⁵ is a hydrogen atom and/or a methyl group.
R ⁶ is one or more selected from organic groups having 1 to 6 carbon atoms.
R ⁷ and R ⁸ are the same or different and are one or more selected from a hydrogen atom and an organic group having 1 to 6 carbon atoms.
However, the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit (A) represented by general formula (1) is bonded. )

R ⁵ in the general formula (3) is not particularly limited as long as it is a hydrogen atom and/or a methyl group. It may be selected appropriately as necessary.

The above R ⁶ is not particularly limited as long as it is one or more types selected from organic groups having 1 to 6 carbon atoms. The R ⁶ may be a hydrocarbon group having 1 to 6 carbon atoms. The hydrocarbon group is not particularly limited, and examples include chain hydrocarbon groups such as an alkyl group, alkenyl group, and alkynyl group, and cyclic hydrocarbon groups such as an aryl group, a cycloalkyl group, and a cycloalkenyl group. The hydrocarbon group may have a branch, and in the case where the hydrocarbon group has a branch, the number of carbon atoms in the hydrocarbon group means the total number of carbon atoms in the main chain and the branched chain. Moreover, it may have an oxygen atom or a hetero atom other than a carbon atom or a hydrogen atom.
From the viewpoint of polymerizability of the monomer giving the structure of the general formula (3) (the monomer represented by the general formula (4)), the R ⁷ (R ⁸ ) N- group and the polymer main chain are The bonding is preferably an ester bond, an ether bond, or an amide bond, and particularly preferably a -C(O)O-CH ₂ CH ₂ - group or a -C(O)NH-CH ₂ CH ₂ - group.

The R ⁷ and R ⁸ are not particularly limited as long as they are the same or different and are one or more selected from a hydrogen atom and an organic group having 1 to 6 carbon atoms. The R ⁷ and R ⁸ may be a hydrocarbon group having 1 to 6 carbon atoms. The hydrocarbon group is not particularly limited, and examples include chain hydrocarbon groups such as an alkyl group, alkenyl group, and alkynyl group, and cyclic hydrocarbon groups such as an aryl group, a cycloalkyl group, and a cycloalkenyl group. The hydrocarbon group may have a branch, and in the case where the hydrocarbon group has a branch, the number of carbon atoms in the hydrocarbon group means the total number of carbon atoms in the main chain and the branched chain. Moreover, it may have an oxygen atom or a hetero atom other than a carbon atom or a hydrogen atom. Preferably, it is a linear and/or branched alkyl group.
Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and hexyl group.
The R ⁷ and R ⁸ are preferably at least one selected from a hydrogen atom, a methyl group, an ethyl group, and a propyl group.
When R ⁷ and R ⁸ are the above-mentioned substituents, the water solubility of the polymer can be improved, and the interaction with fatty acids such as oleic acid, which is a component of sebum stains, can be improved. It is preferable.

The weight average molecular weight Mw of the copolymer of the present disclosure is not particularly limited as long as it is from 1,000 to 500,000, and is preferably from 10,000 to 100,000.
It is preferable that the weight average molecular weight of the copolymer of the present disclosure is within the above-mentioned range because when the copolymer of the present disclosure is used in detergent applications, the ability to prevent re-staining is improved.

When the total amount of the structural unit (A) represented by the general formula (2) and the structural unit (B) represented by the general formula (3) contained in the copolymer of the present disclosure is 100% by mass, The mass ratio of the structural unit (A)/the structural unit (B) is not particularly limited as long as it is 1 to 99/1 to 99. Preferably it is 30-99/1-70, more preferably 40-95/5-60.
It is preferable that the mass ratio of the structural unit (A) and the structural unit (B) contained in the copolymer of the present disclosure is within the above-mentioned range, since redeposition prevention ability and biodegradability are improved.

The copolymer of the present disclosure may also include a structural unit (E) derived from another monomer (E). The content of the structural unit (E) is preferably 0 to 30% by mass based on 100% by mass of the total amount of structural units derived from all monomers forming the copolymer of the present disclosure. It is more preferably 0 to 20% by weight, and even more preferably 0 to 10% by weight.

[Method for producing the compound of the present disclosure]
The method for producing the compound of the present disclosure is not particularly limited as long as it has the structure of the compound represented by the general formula (1), but the following synthesis methods A to D will be explained as specific examples.
Synthesis method A: Reaction using glycidyl (meth)acrylate and dicarboxylic acid derivative Synthesis method B: Reaction and synthesis method using hydroxyalkyl (meth)acrylate and dicarboxylic acid derivative C: Hydroxyalkyl (meth)acrylate and carboxylic acid derivative Reaction synthesis method using D: Reaction using unsaturated alcohol and dicarboxylic acid derivative

As the synthesis method A, a synthesis scheme for a reaction using glycidyl (meth)acrylate is shown below.
The synthesis method A is comprised of two steps, step A-1 and step A-2, as described below.
Step A-1 involves reacting a dicarboxylic acid anhydride such as succinic anhydride represented by the following general formula (5) and an alkoxypolyalkylene glycol such as methoxypolyethylene glycol represented by the following general formula (6). This is a step of synthesizing a dicarboxylic acid derivative intermediate represented by the following general formula (7) in which a polyalkylene glycol and a carboxyl group are bonded via an ester bond.

なお、前記一般式（６）、及び、前記一般式（７）中のＲ^３、Ｒ^４、ｎは、前記一般式（１）と同じであり、好ましい形態についても同じである。
工程Ａ－２は、前記工程Ａ－１で合成し得られた下記一般式（７）で表されるジカルボン酸誘導体中間体のカルボキシル基に対して、下記一般式（８）で表される（メタ）アクリル酸グリシジルのエポキシ基を開環エステル化させることによる、本開示の化合物を得る工程である。

Note that R ³ , R ⁴ , and n in the general formula (6) and the general formula (7) are the same as in the general formula (1), and their preferred forms are also the same.
In step A-2, the carboxyl group of the dicarboxylic acid derivative intermediate represented by the following general formula (7) synthesized in the step A-1 is converted to the carboxyl group represented by the following general formula (8). This is a step of obtaining a compound of the present disclosure by ring-opening and esterifying the epoxy group of glycidyl meth)acrylate.

なお、前記一般式（７）、及び、前記一般式（９）中のＲ^３、Ｒ^４、ｎは、前記一般式（１）と同じであり、好ましい形態についても同じである。

Note that R ³ , R ⁴ , and n in the general formula (7) and the general formula (9) are the same as in the general formula (1), and their preferred forms are also the same.

As the synthesis method B, a synthesis scheme for a reaction using hydroxyalkyl (meth)acrylate is shown below.
The synthesis method B consists of two steps, step B-1 and step B-2, as described below.
Step B-1 involves reacting a dicarboxylic acid anhydride such as succinic anhydride represented by the following general formula (5) and an alkoxypolyalkylene glycol such as methoxypolyethylene glycol represented by the following general formula (6). This is a step of synthesizing a dicarboxylic acid derivative intermediate represented by the following general formula (7) in which a polyalkylene glycol and a carboxyl group are bonded via an ester bond.

なお、前記一般式（６）、及び、前記一般式（７）中のＲ^３、Ｒ^４、ｎは、前記一般式（１）と同じであり、好ましい形態についても同じである。

Note that R ³ , R ⁴ , and n in the general formula (6) and the general formula (7) are the same as in the general formula (1), and their preferred forms are also the same.

In step B-2, the carboxyl group of the dicarboxylic acid derivative intermediate represented by the following general formula (7) synthesized in the above step A-1 is converted to the carboxyl group represented by the following general formula (10) ( A process for obtaining compounds of the present disclosure by esterifying hydroxyalkyl meth)acrylates.
The esterification reaction can be carried out by dehydration esterification using an acid catalyst or by using a dehydration condensation agent such as dicyclohexylcarbodiimide. From the viewpoint of preventing decomposition of ester bonds, it is preferable to use a dehydration condensation agent such as dicyclohexylcarbodiimide.

なお、前記一般式（７）、及び、前記一般式（１１）中のＲ^３、Ｒ^４、ｎは、前記一般式（１）と同じであり、好ましい形態についても同じである。

Note that R ³ , R ⁴ , and n in the general formula (7) and the general formula (11) are the same as in the general formula (1), and their preferred forms are also the same.

In the synthesis method C, an alkoxypolyalkylene glycol carboxylic acid such as methoxypolyethylene glycol acetic acid represented by the following general formula (12) and a hydroxyalkyl (meth)acrylate represented by the following general formula (10) are esterified. The compound of the present disclosure can be obtained by
The esterification reaction can be carried out by dehydration esterification using an acid catalyst or by using a dehydration condensation agent such as dicyclohexylcarbodiimide. From the viewpoint of preventing decomposition of ester bonds, it is preferable to use a dehydration condensation agent such as dicyclohexylcarbodiimide.

なお、前記一般式（１２）、及び、前記一般式（１３）中のＲ^３、Ｒ^４、ｎは、前記一般式（１）と同じであり、好ましい形態についても同じである。

Note that R ³ , R ⁴ , and n in the general formula (12) and the general formula (13) are the same as in the general formula (1), and the preferred forms are also the same.

The synthesis method D uses an unsaturated alcohol such as (meth)allyl alcohol or isoprenyl alcohol represented by the following general formula (15), and a dicarbonate represented by A-1 represented by the following general formula (7). Compounds of the present disclosure can be obtained by esterifying acid intermediates.
The esterification reaction can be carried out by dehydration esterification using an acid catalyst or by using a dehydration condensation agent such as dicyclohexylcarbodiimide. From the viewpoint of preventing decomposition of ester bonds, it is preferable to use a dehydration condensation agent such as dicyclohexylcarbodiimide.

なお、前記一般式（７）、及び、前記一般式（１６）中のＲ^３、Ｒ^４、ｎは、前記一般式（１）と同じであり、好ましい形態についても同じである。

Note that R ³ , R ⁴ , and n in the general formula (7) and the general formula (16) are the same as in the general formula (1), and their preferred forms are also the same.

[Polymerization method]
The method for producing the polymer of the present disclosure is not particularly limited, but known polymerization methods or methods modified from known methods can be used.

When conducting a polymerization reaction using the compound of the present disclosure as a monomer, the compound of the present disclosure may be polymerized alone using a polymerization initiator, and the compound of the present disclosure may be copolymerized with other monomers. There is.
As the initiator, known initiators can be used, such as hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; 2,2'-azobis(2-amidinopropane) hydrochloride, 4,4'-azobis-4-cyanovaleric acid, azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2, Preferred are azo compounds such as 4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, and cumene hydroperoxide. Among these polymerization initiators, hydrogen peroxide and persulfates are preferred, and persulfates are most preferred. These polymerization initiators may be used alone or in the form of a mixture of two or more.
The amount of the polymerization initiator used in the polymerization reaction may be appropriately adjusted depending on the amount of the monomer component used, and is not particularly limited. The content is 0.001 parts by mass or more and 20 parts by mass or less, more preferably 0.005 parts by mass or more and 15 parts by mass or less, and even more preferably 0.01 parts by mass or more and 10 parts by mass or less.

In the method for producing a polymer of the present disclosure, it is preferable to use a chain transfer agent in addition to a polymerization initiator. The chain transfer agent that can be used in this case is not particularly limited as long as it is a compound that can control the molecular weight, and any known chain transfer agent can be used. Specifically, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, n - Thiol chain transfer agents such as dodecyl mercaptan, octyl mercaptan, and butyl thioglycolate; halides such as carbon tetrachloride, methylene chloride, bromoform, and bromotrichloroethane; secondary alcohols such as isopropanol and glycerin; phosphorus Acids, hypophosphorous acid, and its salts (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, and its salts (sodium hydrogen sulfite, hydrogen sulfite, etc.) Examples include lower oxides and their salts, such as potassium, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc. The above chain transfer agents may be used alone or in the form of a mixture of two or more.

The amount of the chain transfer agent used in the method for producing the polymer of the present disclosure is 0.1 to 10 mol % based on 1 mol of the total monomer components, and by using it in such a ratio, a desirable molecular weight co-existence can be achieved. It becomes easier to produce polymers. The amount of chain transfer agent used is preferably 1 to 10 mol % based on 1 mol of all monomer components, and more preferably 2 to 5 mol % based on 1 mol of all monomer components. .

In the method for producing a polymer of the present disclosure, a reaction accelerator may be added for the purpose of reducing the amount of an initiator or the like used. Examples of reaction accelerators include heavy metal ions. In the present disclosure, heavy metal ions refer to metals with a specific gravity of 4 g/cm ³ or more. The metal ions are preferably iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium, or the like. These heavy metals can be used alone or in combination of two or more. Among these, iron is more preferred. The ionic valence of the heavy metal ion is not particularly limited. For example, when iron is used as the heavy metal, the iron ion in the initiator may be Fe ²⁺ or Fe ³⁺ , and a combination of these may be used. may have been done.

The heavy metal ion is not particularly limited as long as it is contained in the form of an ion, but a method using a solution prepared by dissolving a heavy metal compound is preferable because it is easy to handle. The heavy metal compound used in this case may be any compound containing the heavy metal ion desired to be contained in the initiator, and can be determined depending on the initiator used. When iron is used as the heavy metal ion, Mohr's salt (Fe(NH ₄ ) ₂ (SO ₄ ) _{2.6H 2} O), ferrous sulfate heptahydrate, ferrous chloride, ferric chloride, etc. It is preferable to use a heavy metal compound or the like.
Furthermore, when manganese is used as the heavy metal ion, manganese chloride or the like can be suitably used. When these heavy metal compounds are used, since they are all water-soluble compounds, they can be used in the form of an aqueous solution, resulting in excellent handling properties. Note that the solvent for the solution formed by dissolving the heavy metal compound is not limited to water, and any solvent that does not interfere with the polymerization reaction and dissolves the heavy metal compound in the production of the polymer of the present disclosure may be used. That's fine.

The content of the heavy metal ions is preferably 0.1 to 10 ppm based on the total mass of the polymerization reaction solution upon completion of the polymerization reaction. If the content of heavy metal ions is 0.1 ppm or more, the effects of heavy metal ions can be more fully expressed. Moreover, if the content of heavy metal ions is 10 ppm or less, the color tone of the obtained polymer can be further improved. Furthermore, if the content of heavy metal ions is high, it may cause staining of the detergent builder when the product polymer of the present disclosure is used as a detergent builder. Within this range, such problems can be more fully suppressed.
In addition, the time when the polymerization reaction is completed means the time point when the polymerization reaction in the polymerization reaction liquid is substantially completed and the desired polymer is obtained. For example, when a polymer polymerized in a polymerization reaction solution is neutralized with an alkali component, the content of heavy metal ions is calculated based on the total mass of the polymerization reaction solution after neutralization. When two or more types of heavy metal ions are included, the total amount of heavy metal ions may be within the above range.

As the combination of the initiator and chain transfer agent, it is most preferable to use one or more of each of persulfates and sulfites. In this case, the mixing ratio of persulfate and sulfite is not particularly limited, but it is preferable to use 0.3 to 8 parts by mass of sulfite per 1 part by mass of persulfate. More preferably, the lower limit of sulfite is 0.5 parts by mass, most preferably 0.7 parts by mass, per 1 part by mass of persulfate. Further, the upper limit of the sulfite is more preferably 7 parts by mass, and most preferably 6 parts by mass per 1 part by mass of the persulfate. Here, if the sulfite is 0.3 parts by mass or more, the total amount of initiator when lowering the molecular weight can be kept lower, and if it is 8 parts by mass or less, side reactions can be suppressed more fully. However, impurities caused by this can be more sufficiently reduced.

The combination of the chain transfer agent, initiator, and reaction promoter is not particularly limited, and can be appropriately selected from the above examples. For example, combinations of chain transfer agents, initiators, and reaction promoters include sodium bisulfite (SBS)/hydrogen peroxide (H ₂ O ₂ ), sodium bisulfite (SBS)/sodium persulfate (NaPS), and hydrogen sulfite. Sodium (SBS)/Fe, Sodium Bisulfite (SBS)/ _H2O2 /Fe, Sodium Bisulfite (SBS)/Sodium Persulfate ( _NaPS )/Fe, Sodium Bisulfite (SBS)/H2O2 Preferred forms include sodium sulfate (NaPS)/hydrogen peroxide (H ₂ O ₂ ), sodium bisulfite (SBS)/oxygen/Fe, and the like. More preferably, sodium bisulfite (SBS)/sodium persulfate (NaPS), sodium bisulfite (SBS)/sodium persulfate (NaPS)/Fe, and most preferably sodium bisulfite (SBS)/sodium persulfate ( NaPS)/Fe.

In the method for producing a polymer of the present disclosure, in addition to the above-mentioned polymerization initiator, a decomposition catalyst and a reducing compound for the polymerization initiator may be added to the reaction system during polymerization. Examples of decomposition catalysts for polymerization initiators include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid, nitric acid, etc. Metal salts of inorganic acids; carboxylic acids such as formic acid, acetic acid, propionic acid, lactic acid, isolactic acid, benzoic acid, their esters and their metal salts; heterocyclic amines such as pyridine, indole, imidazole, carbazole and their derivatives, etc. Can be mentioned. These decomposition catalysts may be used alone or in combination of two or more.

Examples of the reducing compound include organometallic compounds such as ferrocene; naphthenic acid metal salts such as iron naphthenate, copper naphthenate, nickel naphthenate, cobalt naphthenate, and manganese naphthenate; iron, copper, nickel, cobalt, Inorganic compounds that can generate metal ions such as manganese; Inorganic compounds such as boron trifluoride ether adduct, potassium permanganate, perchloric acid; Sulfur dioxide, sulfites, sulfuric esters, bisulfites, thiosulfates, sulfoxy Sulfur-containing compounds such as acid salts, benzenesulfinic acid and its substituted products, and analogs of cyclic sulfinic acids such as para-toluenesulfinic acid; octyl mercaptan, dodecyl mercaptan, mercaptoethanol, α-mercaptopropionic acid, thioglycolic acid, thiopropion acids, mercapto compounds such as α-thiopropionate sodium sulfopropyl ester, α-thiopropionate sodium sulfoethyl ester; nitrogen-containing compounds such as hydrazine, β-hydroxyethylhydrazine, hydroxylamine; formaldehyde, acetaldehyde, propionaldehyde, n - Aldehydes such as butyraldehyde, isobutyraldehyde, isovalerian aldehyde; ascorbic acid, etc. These reducing compounds may also be used alone or in combination of two or more. A reducing compound such as a mercapto compound may be added as a chain transfer agent.

The total amount of the chain transfer agent, initiator, and reaction promoter used is the compound of the present disclosure, if necessary, the monomer represented by the general formula (4), and, if necessary, others. The amount is preferably 2 to 20 g per mole of the total monomer component consisting of the monomers. By setting it as such a range, the polymer of this indication can be efficiently produced, and the molecular weight distribution of the polymer of this indication can be made into a desired one. More preferably, it is 2 to 15 g, and still more preferably 3 to 10 g.

As a method for adding the polymerization initiator and chain transfer agent to the reaction vessel, a continuous addition method such as dropwise addition or divided addition can be applied. Further, the chain transfer agent may be introduced alone into the reaction vessel, or may be mixed in advance with each monomer, solvent, etc. constituting the monomer component.

In the above polymerization method, the method for adding monomer components, polymerization initiator, etc. to the reaction container is to charge all the monomer components into the reaction container, and then add the polymerization initiator into the reaction container to start the polymerization reaction. A method of carrying out; by charging a part of the monomer components into a reaction vessel, and adding a polymerization initiator and the remaining monomer components into the reaction vessel continuously or in stages (preferably continuously). A method of conducting a polymerization reaction; a method of charging a polymerization solvent into a reaction vessel and adding the entire amount of monomer components and a polymerization initiator; a method of adding a portion of one of the monomers (for example, a compound of the present disclosure) to a reaction vessel; Preferred is a method in which the polymerization reaction is carried out by adding the polymerization initiator and the remaining monomer components into the reaction vessel (preferably continuously). Among these methods, the molecular weight distribution of the obtained polymer can be narrowed (sharp) and the dispersibility when used as a detergent builder can be improved. Preferably, the copolymerization is carried out by sequentially dropping the components into a reaction vessel.

The polymerization method may be, for example, a commonly used method such as solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization, and is not particularly limited, but solution polymerization is preferred. As mentioned above, the solvent that can be used in this case is preferably water or a mixed solvent in which water accounts for 50% by mass based on the total solvent. When only water is used, it is preferable that the solvent removal step can be omitted.

The polymerization method can be carried out either batchwise or continuously. In addition, known solvents can be used as needed in the polymerization reaction, including water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; glycerin; polyethylene glycol; benzene, toluene, and xylene. Aromatic or aliphatic hydrocarbons such as , cyclohexane and n-heptane; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide; ethers such as diethyl ether and dioxane, etc. are suitable. It is. These may be used alone or in combination of two or more. Among these, it is preferable to use one or more solvents selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms, in view of the solubility of the monomer components and the resulting polymer. .
In the method for producing a polymer of the present disclosure, any chain transfer agent, pH adjuster, buffer, etc. can be used as necessary.

The temperature during the polymerization reaction is preferably 40°C or higher, more preferably 50 to 110°C, and still more preferably 60 to 100°C. If the temperature during polymerization is within the above range, the amount of residual monomer components will decrease, and the ability of the polymer to prevent redeposition tends to improve. Note that the temperature during polymerization does not need to be kept constant during the progress of the polymerization reaction; for example, starting the polymerization from room temperature and increasing the temperature to a set temperature at an appropriate temperature increase time or rate, Thereafter, the set temperature may be maintained, or the polymerization temperature may be varied (increased or decreased) over time during the progress of the polymerization reaction, depending on the method of dropping monomer components, initiators, etc. Good too.

The polymerization time is not particularly limited, but is preferably 30 to 420 minutes, more preferably 45 to 390 minutes, still more preferably 60 to 360 minutes, and most preferably 90 to 240 minutes. In the present invention, "polymerization time" refers to the time during which the monomer is added.

The pressure in the reaction system may be normal pressure (atmospheric pressure), reduced pressure, or increased pressure; however, in terms of the molecular weight of the resulting polymer, it is recommended to use normal pressure or seal the reaction system. However, it is preferable to carry out under pressure. Furthermore, in terms of equipment such as a pressurizing device, a pressure reducing device, a pressure-resistant reaction vessel, and piping, it is preferable to carry out the reaction under normal pressure (atmospheric pressure). The atmosphere in the reaction system may be an air atmosphere, but it is preferably an inert atmosphere. For example, it is preferable to replace the inside of the system with an inert gas such as nitrogen before starting the polymerization.

The solid content concentration in the aqueous solution (i.e., the polymerized solid content concentration of the monomer) at the time when the polymerization reaction in the polymerization reaction system is completed is preferably 20% by mass or more, and more preferably 30 to 70% by mass. . If the solid content concentration at the end of the polymerization reaction is as high as 35% by mass or more, polymerization can be carried out at high concentration and in one step. Therefore, the polymer of the present disclosure can be efficiently obtained, such as by omitting the concentration step that is sometimes necessary in conventional production methods. Therefore, the manufacturing efficiency can be significantly increased, and as a result, it is possible to significantly improve the productivity of the polymer of the present disclosure and suppress the increase in manufacturing costs.

[Applications of the polymer of the present disclosure]
The polymer of the present disclosure can be used for various purposes, such as detergent compositions, fiber treatment agents, dispersants, flocculants, scale inhibitors, chelating agents, bleaching aids, pH adjusters, water treatment agents, It can be suitably used in various applications such as peroxide stabilizers, cement additives, cement admixtures, and cement compositions.

<Water treatment agent>
The polymer of the present disclosure can be used in water treatment agents. The water treatment agent may contain other additives such as polymerized phosphates, phosphonates, anticorrosive agents, slime control agents, and chelating agents, as required. The water treatment agent is useful for preventing scale in cooling water circulation systems, boiler water circulation systems, seawater desalination equipment, pulp digesters, black liquor concentrators, and the like. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance or effect.

<Fiber treatment agent>
The polymer of the present disclosure can be used in a fiber treatment agent. The fiber treatment agent includes at least one selected from the group consisting of a dye, a peroxide, and a surfactant, and the polymer of the present disclosure. The content of the polymer of the present disclosure in the fiber treatment agent is preferably 1 to 100% by mass, more preferably 5 to 100% by mass, based on the entire fiber treatment agent. In addition, any appropriate water-soluble polymer may be contained within a range that does not affect performance or effects. Below, a blending example of a fiber treatment agent that is closer to the embodiment is shown. This fiber treatment agent can be used in the steps of scouring, dyeing, bleaching, and soaping in fiber treatment. The dyes, peroxides and surfactants include those commonly used in fiber treatment agents.

The blending ratio of the polymer of the present disclosure and at least one selected from the group consisting of dyeing agents, peroxides, and surfactants is, for example, in order to improve the whiteness, color unevenness, and dyeing consistency of fibers. In terms of pure fiber treatment agent, 0.1 to 100 parts by mass of at least one selected from the group consisting of dyes, peroxides, and surfactants is added to 1 part by mass of the polymer of the present invention. It is preferable to use a composition blended in this ratio as a fiber treatment agent. Any suitable fiber can be used as the fiber that can be used with the fiber treatment agent. Examples include cellulose fibers such as cotton and hemp, chemical fibers such as nylon and polyester, animal fibers such as wool and silk, semi-synthetic fibers such as human silk, and woven and blended products thereof. When applying the fiber treatment agent to a refining process, it is preferable to blend the polymer of the present disclosure, an alkali agent, and a surfactant. When applied to a bleaching process, it is preferable to blend the polymer of the present disclosure, a peroxide, and a silicic acid-based agent such as sodium silicate as a decomposition inhibitor for alkaline bleaching agents.

<Inorganic pigment dispersant>
The polymers of the present disclosure can be used in inorganic pigment dispersants. If necessary, condensed phosphoric acid and its salts, phosphonic acid and its salts, and polyvinyl alcohol may be used as other compounding agents in the inorganic pigment dispersant. The content of the polymer of the present disclosure in the inorganic pigment dispersant is preferably 5 to 100% by mass based on the entire inorganic pigment dispersant. Further, any appropriate soluble polymer may be included as long as it does not affect the performance or effect. The inorganic pigment dispersant can exhibit good performance as a dispersant for inorganic pigments such as heavy or light calcium carbonate and clay used in paper coating. For example, by adding a small amount of an inorganic pigment dispersant to an inorganic pigment and dispersing it in water, we can create a highly concentrated calcium carbonate that has low viscosity, high fluidity, and good stability over time. A highly concentrated inorganic pigment slurry such as a slurry can be produced. When the inorganic pigment dispersant is used as a dispersant for inorganic pigments, the amount of the inorganic pigment dispersant used is preferably 0.05 to 2.0 parts by weight per 100 parts by weight of the inorganic pigment. When the amount of the inorganic pigment dispersant used is within the above range, it becomes possible to obtain a sufficient dispersion effect, and it becomes possible to obtain an effect commensurate with the amount added, which may be economically advantageous.

[Detergent composition containing the polymer of the present disclosure]
The detergent composition of the present disclosure includes the polymer of the present disclosure as an essential component. The content of the polymer of the present disclosure contained in the detergent composition of the present disclosure is not particularly limited, but from the viewpoint of exhibiting excellent recontamination prevention ability, the content of the polymer of the present disclosure is It is preferably contained in an amount of 0.1 to 15% by mass based on the total amount of the detergent composition. The amount is more preferably 0.3 to 10% by weight, and even more preferably 0.5 to 5% by weight.

Detergent compositions used in detergent applications usually contain surfactants and additives used in detergents. The specific forms of these surfactants and additives are not particularly limited, and conventionally known knowledge in the field of detergents can be appropriately referred to. Further, the detergent composition may be a powder detergent composition or a liquid detergent composition.

The surfactant is one or more selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. When two or more types are used in combination, the total amount of anionic surfactant and nonionic surfactant is preferably 50% by mass or more, more preferably 60% by mass based on the total amount of surfactant. The content is more preferably 70% by mass or more, particularly preferably 80% by mass or more.

Examples of anionic surfactants include alkylbenzene sulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, α-olefin sulfonates, α-sulfo fatty acids or ester salts, and alkanesulfonates. , saturated fatty acid salts, unsaturated fatty acid salts, alkyl ether carboxylates, alkenyl ether carboxylates, amino acid type surfactants, N-acylamino acid type surfactants, alkyl phosphate esters or salts thereof, alkenyl phosphate esters, Salts thereof are suitable. The alkyl group or alkenyl group in these anionic surfactants may have a branched alkyl group such as a methyl group.

Examples of nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, alkyl glycoxide, fatty acid glycerin monomer. Ester, alkylamine oxide, etc. are suitable. The alkyl group and alkenyl group in these nonionic surfactants may have a branched alkyl group such as a methyl group.

As the cationic surfactant, quaternary ammonium salts and the like are suitable. Further, as the amphoteric surfactant, carboxyl-type amphoteric surfactants, sulfobetaine-type amphoteric surfactants, etc. are suitable. 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 blending ratio of the surfactant is generally not particularly limited as long as it is 10 to 60% by mass based on the total amount of the detergent composition of the present disclosure, preferably 15 to 50% by mass, and more preferably 20 to 60% by mass. The amount is 45% by weight, particularly preferably 25-40% by weight. If the blending ratio of the surfactant is too low, there is a risk that sufficient cleaning power cannot be exhibited, and if the blending ratio of the surfactant is too high, there is a risk that the economical efficiency will decrease.

Additives include alkali builders, chelate builders, anti-redeposition agents to prevent redeposition of pollutants such as sodium carboxymethyl cellulose, stain inhibitors such as benzotriazole and ethylene-thiourea, soil release agents, and color transfer agents. Inhibitors, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishing agents, disinfectants, bleaching agents, bleaching aids, enzymes, dyes , a solvent, etc. are suitable. Moreover, in the case of a powder detergent composition, it is preferable to incorporate zeolite.

Detergent compositions of the present disclosure may include other detergent builders in addition to the polymers of the present disclosure. Examples of other detergent builders include, but are not limited to, alkali builders such as carbonates, hydrogen carbonates, and silicates; Examples include acid salts, (meth)acrylic acid copolymer salts, acrylic acid-maleic acid copolymers, fumarates, chelate builders such as zeolites, and carboxyl derivatives of polysaccharides such as carboxymethyl cellulose. Examples of the counter salt used in the builder include alkali metals such as sodium and potassium, ammonium, and amines.

The total blending ratio of the additives and other detergent builders is usually preferably 0.1 to 50% by mass based on 100% by mass of the detergent composition. More preferably 0.2 to 40% by mass, still more preferably 0.3 to 35% by mass, particularly preferably 0.4 to 30% by mass, and most preferably 0.5 to 20% by mass. be. If the blending ratio of additives/other detergent builders is less than 0.1% by mass, there is a risk that sufficient detergent performance will not be exhibited, and if it exceeds 50% by mass, there is a risk that economic efficiency will decrease.

The concept of detergent compositions includes synthetic detergents for household detergents, detergents for the textile industry and other industries, hard surface cleaners, as well as bleaching detergents with enhanced functionality of one of their components, and other specific uses. Also includes detergents that are only used.

When the detergent composition of the present disclosure is a liquid detergent composition, the amount of water contained in the liquid detergent composition is usually preferably 0.1 to 75% by mass based on the total amount of the liquid detergent composition, More preferably 0.2 to 70% by mass, still more preferably 0.5 to 65% by mass, even more preferably 0.7 to 60% by mass, particularly preferably 1 to 55% by mass. , most preferably from 1.5 to 50% by weight.

When the detergent composition of the present disclosure is a liquid detergent composition, the detergent composition preferably has a kaolin turbidity of 200 mg/L or less, more preferably 150 mg/L or less, and even more preferably 120 mg/L. L or less, particularly preferably 100 mg/L or less, and most preferably 50 mg/L or less.

Further, the change (difference) in kaolin turbidity between when the polymer of the present invention is added to a liquid detergent composition as a detergent builder and when it is not is preferably 500 mg/L or less, more preferably 400 mg/L or less. L or less, more preferably 300 mg/L or less, particularly preferably 200 mg/L or less, and most preferably 100 mg/L or less. As the value of kaolin turbidity, the value measured by the following method shall be adopted.

<How to measure kaolin turbidity>
A uniformly stirred sample (liquid detergent) was placed in a 50 mm square cell with a thickness of 10 mm, and after removing air bubbles, Tubidity was measured at 25 °C using NDH2000 (trade name, turbidity meter) manufactured by Nippon Denshoku Industries Co., Ltd. (Kaolin turbidity: mg/L) is measured.

Proteases, lipases, cellulases, and the like are suitable as enzymes that can be incorporated into the cleaning composition of the present disclosure. Among these, proteases, alkaline lipases, and alkaline cellulases, which have high activity in alkaline cleaning solutions, are preferred.

The amount of the enzyme added is preferably 5% by mass or less based on 100% by mass of the cleaning composition. If it exceeds 5% by mass, no improvement in detergency will be seen and there is a risk that economic efficiency will decrease.

Even when the detergent composition of the present disclosure is used in areas with hard water having a high concentration of calcium ions and magnesium ions (for example, 100 mg/L or more), it has little salt precipitation and has excellent cleaning effects. This effect is particularly pronounced when the detergent composition contains an anionic surfactant such as LAS.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.

<Manufacture example 1>
183.77 g of methoxypolyethylene glycol (25 moles of ethylene oxide, manufactured by Nippon Shokubai) was weighed into a glass reaction vessel equipped with a thermometer and a stirrer, and the temperature was raised to 80°C. Thereafter, while stirring, 16.23 g of succinic anhydride (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added in 5 portions of 3.25 g each. After continuing the reaction for 6 hours, it was confirmed by ¹ H NMR measurement that the entire amount of succinic anhydride was consumed, and terminally carboxylated methoxypolyethylene glycol (1) was obtained.

<Manufacture example 2>
In a glass reaction vessel equipped with a thermometer, a reflux condenser, and a stirrer, 131.25 g of terminally carboxylated methoxypolyethylene glycol (1), 16.02 g of glycidyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0 4-methoxyphenol were added. .47 g (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 7.60 g of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged, and the temperature was raised to 100° C. while stirring. After 18 hours, the reaction solution was taken out to obtain glycidyl methacrylate adduct (2) to (1).

<Manufacture example 3>
A glass reaction vessel equipped with a thermometer, a nitrogen inlet tube, a reflux condenser, and a stirrer was charged with 33.92 g of pure water, and after purging the inside of the reaction vessel with nitrogen, the temperature was raised to 50° C. while stirring. Next, under stirring, a monomer solution (A) consisting of 27 g of (2) and 27 g of pure water; 3.00 g of 2-(dimethylamino)ethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a polymerization reaction system kept at a constant temperature of 50°C. ), a monomer solution (B) consisting of 1.09 g of acetic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and 3.00 g of pure water; a chain transfer agent consisting of 1.23 g of a 10% aqueous solution of 3-mercaptopropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) Aqueous solution; an initiator aqueous solution consisting of 3.75 g of a 10% aqueous solution of 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (manufactured by Wako Pure Chemical Industries, hereinafter referred to as VA-044) A total of four types were dropped from separate dropping nozzles.
Regarding the dropping start time, monomer solution (A), monomer solution (B), chain transfer agent aqueous solution, and initiator aqueous solution started dropping at the same time, and the monomer solution and chain transfer agent aqueous solution were dropped for 180 minutes, and the initiator aqueous solution was dropped for 240 minutes. did.
After all the dropwise additions were completed, the reaction solution was further aged at 50° C. for 60 minutes to complete the polymerization and obtain a polymer (1). The obtained polymer had a solid content of 32.0% and a weight average molecular weight of 50,800.

<Manufacture example 4>
A glass reaction vessel equipped with a thermometer, a nitrogen inlet tube, a reflux condenser, and a stirrer was charged with 30.66 g of pure water, and after the inside of the reaction vessel was purged with nitrogen, the temperature was raised to 50° C. while stirring. Next, under stirring, a monomer solution (A) consisting of 24 g of (2) and 24 g of pure water; 6.00 g of 2-(dimethylamino)ethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a polymerization reaction system kept at a constant 50°C. ), a monomer solution (B) consisting of 2.18 g of acetic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and 6.00 g of pure water; a chain transfer agent consisting of 1.77 g of a 10% aqueous solution of 3-mercaptopropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) Aqueous solution: A total of four types of initiator aqueous solutions each consisting of 5.39 g of a 10% aqueous solution of VA-044 were dropped from separate dropping nozzles.
Regarding the dropping start time, monomer solution (A), monomer solution (B), chain transfer agent aqueous solution, and initiator aqueous solution started dropping at the same time, and the monomer solution and chain transfer agent aqueous solution were dropped for 180 minutes, and the initiator aqueous solution was dropped for 240 minutes. did.
After all the dropwise additions were completed, the reaction solution was further maintained at 50° C. for 60 minutes to mature, thereby completing the polymerization and obtaining a polymer (2). The obtained polymer had a solid content of 32.9% and a weight average molecular weight of 59,700.

<Solid content measurement>
The solid content of the obtained aqueous polymer solution was measured by the following method.
Approximately 1 g of the aqueous polymer solution was weighed into an aluminum cup, placed in an oven heated to 130°C, and dried for 2 hours. The aluminum cup after drying was weighed, and the solid content was calculated as the weight after drying.

[Formula]
Solid content (%) = (weight after drying - weight of empty aluminum cup) / weighed value of polymer aqueous solution × 100

<Measurement of recontamination prevention ability>
The following washing step, rinsing step, and drying step were performed in this order, and the ability to prevent recontamination of cloth was measured.
Cleaning process:
The following two types of cotton cloths were used as items to be washed.
Cotton cloth (1): Five pieces of cotton knitted fabric (manufactured by Tanigashira Shoten) 5 cm x 5 cm were prepared as recontamination determination cloth.
Cotton fabric (2): Cotton fabric obtained from Testfabrics was prepared in a total weight of 30 g together with cotton fabric (1).
As a surfactant, a 3% LAS aqueous solution and a 0.1% by mass aqueous solution of the copolymer obtained in the production example were prepared.
In a Tergot-o-meter (manufactured by Daiei Kagakusha, product name: TM-4), 900 mL of 15° DH hard water at 25°C (prepared with calcium chloride and magnesium chloride. Ca/Mg = 3 (mass ratio)), and the above 7.5 g of a 3% LAS aqueous solution, 7.5 g of a 0.1% aqueous solution of the above polymers (1) to (5), 0.9 g of finely sanded red clay, and cotton cloths (1) and (2) were added. Thereafter, washing was performed at a stirring speed of 120 rpm and 25° C. for 10 minutes.
Rinsing process:
After the washing step, the object to be washed was dehydrated for 1.5 minutes, and then 900 mL of 15° DH hard water at 25° C. was added thereto and rinsed at 120 rpm and 25° C. for 3 minutes. This operation (dehydration and rinsing) was repeated twice.
Drying process:
After the rinsing process, the items to be washed and the mud-stained cloth were dehydrated for 1.5 minutes, and then only the cotton cloth (1) was taken out, sandwiched between cotton cloths, and dried with an iron.
The reflectance (Z value) was measured, and the recontamination prevention rate was determined from the following formula.
Recontamination prevention rate = (Z value of cotton fabric (1) after washing process) / (Z value of cotton fabric (1) before washing process) x 100
Table 1 shows the re-staining prevention rate of the cotton fabric (1) after the above washing treatment.

By repeating this procedure, it is also possible to measure recontamination prevention performance in repeated washing.

<Biodegradability test>
A biodegradability test of the obtained polymer was conducted in accordance with OECD301F.
Preparation of medium:
Culture medium stock solutions A to D were prepared by the following method.
Solution A: 0.850 g of potassium dihydrogen phosphate (KH ₂ PO ₄ ), 2.175 g of dipotassium hydrogen phosphate (K ₂ HPO ₄ ), disodium hydrogen phosphate dodecahydrate (Na ₂ HPO ₄ 12H _6.7217 g of ammonium chloride (NH 4 Cl) and 0.050 g of ammonium chloride (NH ₄ Cl) were weighed into a 50 ml sample bottle, dissolved in an appropriate amount of water, transferred to a 100 ml volumetric flask, and water was added up to the marked line.
Solution B: 3.640 g of calcium chloride dihydrate (CaCl ₂ .2H ₂ O) was dissolved in an appropriate amount of water and transferred to a 100 ml volumetric flask, and then water was added up to the marked line.
Solution C: 2.250 g of magnesium sulfate heptahydrate (MgSO ₄ .7H ₂ O) was dissolved in an appropriate amount of water, transferred to a 100 ml volumetric flask, and water was added up to the marked line.
Solution D: 0.025 g of iron (III) chloride hexahydrate (FeCl ₃ .6H ₂ O) was dissolved in an appropriate amount of water and transferred to a 100 ml volumetric flask, and then water was added up to the marked line.
The temperature of the above culture medium stock solutions A to D was adjusted to 25°C, and 10 ml of A was put into a 1 L volumetric flask using a whole pipette, and diluted with approximately 800 ml of water. Thereafter, 1 ml each of B, C, and D was added using a whole pipette, and the mixture was diluted to the marked line with water adjusted to 25°C. Multiple volumes of the above medium were prepared according to the amount required for the test. The prepared medium was transferred to a 5L beaker, mixed, and bubbled for over 1 hour while stirring.
Preparation of sludge solution:
The sludge used for the biodegradability test was obtained from Minami Suita Sewage Treatment Plant. First, the concentration of the sludge obtained was measured using the method described below. Bubbling was performed while stirring the obtained sludge, 5 ml was taken using a whole pipette, and suction filtration was performed using filter paper. Five sheets of filter paper from which sludge was collected in this manner were prepared, and after drying in a drier at 105° C. for 1 hour, the concentration of the sludge was calculated from the average weight loss of the five sheets. This sludge was diluted with the medium prepared above to prepare a 1000 ppm sludge solution.
Preparation of polymer aqueous solution:
Polymer (1) obtained in Production Example (1) was diluted with pure water to obtain a 2% by mass aqueous polymer solution. Further, as a standard substance, sodium benzoate was diluted with pure water to obtain a 2% by mass aqueous sodium benzoate solution.
BOD test:
A pressure sensor type BOD meter was used to measure BOD. After weighing 144.75 g of the medium prepared above into a flan bottle, 0.75 g of a 2% aqueous polymer solution was added. In addition, 0.75 g of pure water was added for blank measurement, and 0.75 g of 2% sodium benzoate aqueous solution was added for standard substance measurement. Thereafter, the pH of the solution was measured, and the pH was adjusted with a 0.1M hydrochloric acid aqueous solution so that the pH value of the solution was 7.4±0.2. Thereafter, 4.5 ml of 1000 ppm sludge solution was added to prepare a test solution. After putting a stirrer into the flan bottle, 1.8 g of CO ₂ absorbent (Yabashi Lime) was placed in the CO ₂ absorbent holder, and the BOD sensor was attached. A flan bottle equipped with a BOD sensor was stirred in a constant temperature bath at 24° C., and the BOD value was calculated from the pressure sensor.
Calculation of decomposition rate:
The theoretical oxygen demand (ppm) of the polymer was calculated, and the decomposition rate was calculated from the difference between the BOD value of the blank measurement and the BOD value measured using the polyalkylene oxide-containing compound. The decomposition rate 28 days after the start of the test was defined as the biodegradation rate.
The decomposition rate of the copolymer is shown in Table 1.

[Formula]
Degradation rate (%) = (biochemical oxygen consumption derived from polymer) / (theoretical oxygen demand of polymer) x 100

Claims (3)

A compound represented by the following general formula (1).

(In general formula (1),
X is an organic group having 1 to 10 carbon atoms.
m is 0 or 1. n is an integer from 1 to 200.
R ¹ is a hydrogen atom and/or a methyl group.
R ² is a direct bond or one or more selected from organic groups having 1 to 10 carbon atoms when m=0, and 1 selected from organic groups having 1 to 10 carbon atoms when m=1. More than a species.
R ³ is one or more selected from organic groups having 2 to 6 carbon atoms.
R ⁴ is one or more selected from a hydrogen atom and an organic group having 1 to 30 carbon atoms. ) A polymer having a structural unit (A) represented by the following general formula (2).

(In general formula (2),
X is an organic group having 1 to 10 carbon atoms.
m is 0 or 1. n is an integer from 1 to 200.
R ¹ is a hydrogen atom and/or a methyl group.
R ² is a direct bond or one or more selected from organic groups having 1 to 10 carbon atoms when m=0, and 1 selected from organic groups having 1 to 10 carbon atoms when m=1. More than a species.
R ³ is one or more selected from organic groups having 2 to 6 carbon atoms.
R ⁴ is one or more selected from a hydrogen atom and an organic group having 1 to 30 carbon atoms.
However, the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit (A) represented by general formula (1) is bonded. ) A copolymer having a structural unit (A) represented by the following general formula (2) and a structural unit (B) represented by the following general formula (3).

(In general formula (2),
X is an organic group having 1 to 10 carbon atoms.
m is 0 or 1. n is an integer from 1 to 200.
R ¹ is a hydrogen atom and/or a methyl group.
R ² is a direct bond or one or more selected from organic groups having 1 to 10 carbon atoms when m=0, and 1 selected from organic groups having 1 to 10 carbon atoms when m=1. More than a species.
R ³ is one or more selected from organic groups having 2 to 6 carbon atoms.
R ⁴ is one or more selected from a hydrogen atom and an organic group having 1 to 30 carbon atoms.
However, the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit (A) represented by general formula (1) is bonded. )

(In general formula (3),
R ⁵ is a hydrogen atom and/or a methyl group.
R ⁶ is one or more selected from organic groups having 1 to 6 carbon atoms.
R ⁷ and R ⁸ are the same or different and are one or more selected from a hydrogen atom and an organic group having 1 to 6 carbon atoms.
However, the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit (B) represented by general formula (3) is bonded. )