Copolymer, composition, and additive for detergent

Abstract

Disclosed is a copolymer which has a structural unit (A) represented by formula (1) and / or a structural unit (A02) represented by formula (7), and a structural unit (B) represented by formula (2) and / or a structural unit (C) represented by formula (3). (In the formulae, R1 represents a hydrogen atom or -C(=O)-X; R2 represents a hydrogen atom or a methyl group; X represents an optionally substituted aryl group or an optionally substituted alkyl group having 1 to 4 carbon atoms; R3 represents an alkyl group having 1 to 4 carbon atoms; m represents an integer of 0 to 30; R4 represents an alkyl group having 1 to 4 carbon atoms; and n represents an integer of 0 to 30.)

Description

Copolymer, composition and detergent additive 【0001】 The present disclosure relates to copolymers, compositions and detergent additives. 【0002】 BACKGROUND ART Detergents used for clothing and the like have conventionally been blended with detergent additives such as zeolite, carboxymethyl cellulose, polyethylene glycol, and (meth)acrylic acid polymers in order to improve the cleaning effect of the detergent. 【0003】 For example, Patent Document 1 proposes a (meth)acrylic acid-based copolymer containing structural units derived from a monoethylenically unsaturated carboxylic acid, an alkyl (meth)acrylate ester, and an alkoxylated (meth)acrylate monomer as a laundry detergent formulation. 【0004】 Japanese Patent Application Laid-Open No. 2002-3551 【0005】 However, conventional detergent additives such as the (meth)acrylic acid-based polymer described in Patent Document 1 have room for improvement in terms of cleaning oily stains and the like. 【0006】 Therefore, an object of the present disclosure is to provide a copolymer that has excellent cleaning performance for oily stains when used, for example, as a detergent additive, as well as a composition and a detergent additive containing the copolymer. 【0007】 The present disclosure provides copolymers described in the following [1] to [8], compositions described in [9], detergent additives described in

[10] , uses described in

[11] , and cleaning methods described in

[12] . [1] A structural unit (A) represented by the following formula (1) and / or a structural unit (A) represented by the following formula (7): ０２ ) and a structural unit (B) represented by the following formula (2) and / or a structural unit (C) represented by the following formula (3): [In formula (1), R １ represents a hydrogen atom or —C(═O)—X, and R ２ represents a hydrogen atom or a methyl group, and X represents an optionally substituted aryl group or an optionally substituted alkyl group having 1 to 4 carbon atoms. [In formula (7), R ２ represents a hydrogen atom or a methyl group. [In formula (2), R ３ represents an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 30. [In formula (3), R ４ represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 30.] [2] The copolymer according to [1], having a structural unit (A), a structural unit (B), and a structural unit (C). [3] A copolymer according to [1], having a structural unit (A) represented by the following formula (5): ０ ) and a structural unit (B) represented by the above formula (2) and / or a structural unit (C) represented by the above formula (3). [In formula (5), R ２ represents a hydrogen atom or a methyl group, and R ９ represents a group having a structure formed by ring-opening of an oxazoline ring by the action of water and / or a carboxylic acid as a raw material compound.] [4] Structural unit (A ０ ) is a structural unit (A ０１ ) and / or a structural unit represented by the following formula (7) (A ０２ The copolymer according to [3], comprising: [In formula (6), R １ represents a hydrogen atom or —C(═O)—X, and R ２ represents a hydrogen atom or a methyl group, and X represents an optionally substituted aryl group or an optionally substituted alkyl group having 1 to 4 carbon atoms. [In formula (7), R ２ represents a hydrogen atom or a methyl group.] [5] The copolymer according to [1] or [2], wherein the content of the structural unit (A) in the copolymer is 5% by mass or more and 98% by mass or less, the content of the structural unit (B) in the copolymer is 1% by mass or more and 50% by mass or less, and the content of the structural unit (C) in the copolymer is 1% by mass or more and 60% by mass or less. [6] R １ is at least one selected from a hydrogen atom and —C(═O)—X, where X is an o-hydroxyphenyl group. [7] The copolymer according to [1], [2], or [4], wherein m is 0 and R ３ [8] The copolymer according to any one of [1] to [6], wherein n is 0 and R ４is an ethyl group, or n is 5 to 30 and R ４ is a methyl group. [9] The copolymer according to any one of [1] to [8], wherein the content of structural units (structural units (X)) formed using 2-vinyl-2-oxazoline and / or 2-isopropenyl-2-oxazoline as monomers in the copolymer is 0% by mass or more and 49% by mass or less.

[10] A composition comprising the copolymer according to any one of [1] to [9] and water.

[11] A detergent additive comprising the copolymer according to any one of [1] to [9] or the composition according to [9].

[12] Use of the copolymer according to any one of [1] to [9] as a detergent additive.

[13] A cleaning method using the copolymer according to any one of [1] to [9]. 【0008】 According to the present disclosure, it is possible to provide a copolymer that has excellent cleaning performance for oily stains when used as a detergent additive, as well as a composition and a detergent additive containing the copolymer. 【0009】 Hereinafter, embodiments of the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following description, "(meth)acrylic" is used as a term that encompasses both methacrylic and acrylic. Furthermore, when a numerical range is indicated as X to Y, it means X or more and Y or less. For example, "5 to 100 nm" means 5 nm or more and 100 nm or less. Unless otherwise specified, the materials or components exemplified in this specification can be used alone or in combination of two or more. 【0010】 [Copolymer] The copolymer according to one embodiment of the present disclosure comprises a structural unit (A) and / or a structural unit (A ０２ ) and structural unit (B) and / or structural unit (C). Such a copolymer has excellent cleaning performance for oily stains when used as a detergent additive. Each structural unit in the copolymer may be of one type alone or a combination of two or more types. For example, the copolymer may have, as structural unit (A), R １ may have only one structural unit in which R is a hydrogen atom, １ is a hydrogen atom and R１ or may have two types of structural units, i.e., -C(=O)-X. 【0011】 A copolymer according to another embodiment of the present disclosure has a structural unit (A), a structural unit (B), and a structural unit (C). When used as a detergent additive, such a copolymer exhibits excellent cleaning performance for oily stains. Each structural unit in the copolymer may be a single type or a combination of two or more types. For example, the copolymer may contain, as the structural unit (A), R １ may have only one structural unit in which R is a hydrogen atom, １ is a hydrogen atom and R １ or may have two types of structural units, i.e., -C(=O)-X. 【0012】 The copolymer according to another embodiment of the present disclosure may comprise a structural unit (A ０ ) and the structural unit (B) and / or the structural unit (C). When used as a detergent additive, such a copolymer exhibits excellent cleaning performance for oily stains. The structural units in the copolymer may be of one type alone or a combination of two or more types. 【0013】 Each structural unit will be explained below. 【0014】 <Structural unit (A), structural unit (A ０２ The structural unit (A) is a structural unit represented by the following formula (1): ０２ ) is a structural unit represented by the following formula (7): 【0015】 【0016】 In formula (1), R １ represents a hydrogen atom or -C(=O)-X. X represents an optionally substituted aryl group or an optionally substituted alkyl group having 1 to 4 carbon atoms. The optionally substituted aryl group and the optionally substituted alkyl group having 1 to 4 carbon atoms may have one or more substituents. Examples of the substituent include a hydroxy group, an alkoxy group, an acyl group, an alkoxycarbonyl group, and a carbamoyl group. 【0017】 R １ is preferably at least one selected from a hydrogen atom and —C(═O)—X where X is an aryl group optionally substituted with a hydroxy group, more preferably at least one selected from a hydrogen atom and —C(═O)—X where X is an o-hydroxyphenyl group, and even more preferably only a hydrogen atom, or a hydrogen atom and —C(═O)—X where X is an o-hydroxyphenyl group. 【0018】 R １ However, when the hydrogen atom and X are -C(═O)-X, where X is an o-hydroxyphenyl group, the ratio is preferably 99 parts by mass:1 part by mass to 30 parts by mass:70 parts by mass, more preferably 95 parts by mass:5 parts by mass to 40 parts by mass:60 parts by mass, and even more preferably 90 parts by mass:10 parts by mass to 50 parts by mass:50 parts by mass. 【0019】 In formula (1) and / or (7), R ２ represents a hydrogen atom or a methyl group, and is preferably a methyl group. 【0020】 Structural unit (A) and / or structural unit (A ０２ ) can be formed by further opening the oxazoline ring of a structural unit formed using, for example, 2-vinyl-2-oxazoline or 2-isopropenyl-2-oxazoline as a monomer. When 2-vinyl-2-oxazoline is used as a monomer, R ２ is a hydrogen atom and / or a structural unit (A ０２ ) is obtained, and when 2-isopropenyl-2-oxazoline is used as a monomer, R ２ is a methyl group and / or a structural unit (A ０２ During the ring-opening of the oxazoline rings, some of the oxazoline rings may not be opened, and structural units formed using 2-vinyl-2-oxazoline and / or 2-isopropenyl-2-oxazoline as monomers may remain in the copolymer. 【0021】 The structural unit (A) and the structural unit (A ０２The ratio of the total content of structural units formed using 2-vinyl-2-oxazoline and / or 2-isopropenyl-2-oxazoline as a monomer to the total content of structural units formed using 2-vinyl-2-oxazoline and / or 2-isopropenyl-2-oxazoline as a monomer is preferably 100:0 to 20:80, more preferably 100:0 to 30:70, even more preferably 100:0 to 40:60, still more preferably 100:0 to 50:50, and particularly preferably 100:0 to 70:30, in molar ratio. 【0022】 The ratio of the content of the structural unit (A) in the copolymer to the total content of structural units formed using 2-vinyl-2-oxazoline and / or 2-isopropenyl-2-oxazoline as monomers (hereinafter also referred to as structural units (X)) is preferably 100:0 to 20:80, more preferably 100:0 to 30:70, even more preferably 100:0 to 40:60, still more preferably 100:0 to 50:50, and particularly preferably 100:0 to 70:30, in molar ratio. 【0023】 The oxazoline ring can be opened, for example, by hydrolysis under commonly applied acidic conditions, whereby R １ is a hydrogen atom, and / or a structural unit (A) represented by formula (1) ０２ In this case, the degree of ring-opening of the oxazoline ring may be adjusted by, for example, sampling the reaction mixture during the reaction to check the degree of ring-opening of the oxazoline ring. If a carboxylic acid is present during the ring-opening of the oxazoline ring, the group derived from the carboxylic acid may be converted to R １ For example, when benzoic acid is used as the carboxylic acid, R １ When salicylic acid is used as the carboxylic acid, -C(=O)-X, where X is a phenyl group, can be introduced as １ As a result, it is possible to introduce -C(=O)-X, where X is an o-hydroxyphenyl group. 【0024】 The structural unit (A) and the structural unit (A ０２) is preferably 5% by mass or more and 98% by mass or less, more preferably 10% by mass or more and 98% by mass or less, more preferably 15% by mass or more and 98% by mass or less, still more preferably 25% by mass or more and 98% by mass or less, even more preferably 30% by mass or more and 96% by mass or less, and still more preferably 40% by mass or more and 90% by mass or less. 【0025】 The content of the structural unit (A) in the copolymer is preferably 5% by mass or more and 98% by mass or less, more preferably 10% by mass or more and 98% by mass or less, still more preferably 15% by mass or more and 98% by mass or less, still more preferably 25% by mass or more and 98% by mass or less, even more preferably 30% by mass or more and 96% by mass or less, and particularly preferably 40% by mass or more and 90% by mass or less. 【0026】 The structural unit in the copolymer (A ０２ The content of (I) may be 0% by mass, but is preferably 1% by mass or more and 98% by mass or less, more preferably 3% by mass or more and 98% by mass or less, even more preferably 5% by mass or more and 96% by mass or less, and particularly preferably 10% by mass or more and 90% by mass or less. 【0027】 The content of the structural unit (structural unit (X)) formed using 2-vinyl-2-oxazoline and / or 2-isopropenyl-2-oxazoline as a monomer in the copolymer may be 0% by mass, but is preferably 0% by mass or more and 49% by mass or less, more preferably 0% by mass or more and 48% by mass or less, and even more preferably 0% by mass or more and 45% by mass or less. 【0028】 <Structural unit (A ０ ), structural unit (A ０１ ) > structural unit (A ０ ) is a structural unit represented by the following formula (5). 【0029】 In formula (5), R ２ represents a hydrogen atom or a methyl group, and R ９ represents a group having a structure formed by ring-opening of an oxazoline ring by the action of water and / or a carboxylic acid as a raw material compound. 【0030】 R ９ Examples include -C(=O)-NHCH ２ CH ２ OR １ , -C(=O)-OCH ２ CH ２ NR １ (R １ ) etc. (R １ is R in formula (1) １ (which is the same as 【0031】 The term "structural unit having a structure formed by ring-opening of an oxazoline ring by the action of water and / or carboxylic acid as a raw material compound" is not limited to a structure formed by ring-opening of an oxazoline ring by the action of water and / or carboxylic acid as a raw material compound, but is sufficient as long as the structure has a structure formed by ring-opening of an oxazoline ring by the action of water and / or carboxylic acid as a raw material compound. 【0032】 The structural unit (A) represented by formula (5) ０ ) can be a structural unit formed by further opening the oxazoline ring of a structural unit formed using, for example, 2-vinyl-2-oxazoline or 2-isopropenyl-2-oxazoline as a monomer. 【0033】 The oxazoline ring can be opened by hydrolysis under commonly applied acidic conditions. In this case, the oxazoline ring is opened by the action of water as a raw material compound. On the other hand, if a carboxylic acid is present during the ring-opening of the oxazoline ring, a group derived from the carboxylic acid can be introduced. In this case, the oxazoline ring is opened by the action of water and a carboxylic acid as raw materials. 【0034】 The structural unit in the copolymer (A ０The ratio of the content of the structural units formed by using 2-vinyl-2-oxazoline and / or 2-isopropenyl-2-oxazoline as a monomer to the total content of structural units formed by using 2-vinyl-2-oxazoline and / or 2-isopropenyl-2-oxazoline as a monomer is preferably 100:0 to 20:80, more preferably 100:0 to 30:70, even more preferably 100:0 to 40:60, still more preferably 100:0 to 50:50, and particularly preferably 100:0 to 70:30, in terms of molar ratio. 【0035】 Structural unit (A ０ ) may be the above-mentioned structural unit (A ０２ ) and the following structural unit (A ０１ ) is a preferred example. 【0036】 The structural unit in the copolymer (A ０ The content of ) is more preferably 10% by mass or more and 98% by mass or less, more preferably 15% by mass or more and 98% by mass or less, more preferably 25% by mass or more and 98% by mass or less, even more preferably 30% by mass or more and 96% by mass or less, and even more preferably 40% by mass or more and 90% by mass or less. 【0037】 Structural unit (A ０１ ) is a structural unit represented by the following formula (6). 【0038】 R in formula (6) １ and R ２ The embodiments and preferred embodiments are the same as those of formula (1). 【0039】 The structural unit in the copolymer (A ０１ ) and structural unit (A ０２ The ratio of the total content of structural units formed using 2-vinyl-2-oxazoline and / or 2-isopropenyl-2-oxazoline as a monomer to the total content of structural units formed using 2-vinyl-2-oxazoline and / or 2-isopropenyl-2-oxazoline as a monomer is preferably 100:0 to 20:80, more preferably 100:0 to 30:70, even more preferably 100:0 to 40:60, still more preferably 100:0 to 50:50, and particularly preferably 100:0 to 70:30, in molar ratio. 【0040】 The structural unit in the copolymer (A０1 The content of ) is preferably 5% by mass or more and 98% by mass or less, more preferably 10% by mass or more and 98% by mass or less, still more preferably 15% by mass or more and 98% by mass or less, still more preferably 25% by mass or more and 98% by mass or less, still more preferably 30% by mass or more and 96% by mass or less, and particularly preferably 40% by mass or more and 90% by mass or less. 【0041】 <Structural Unit (B)> The structural unit (B) is a structural unit represented by the following formula (2). 【0042】 In formula (2), R ３ represents an alkyl group having 1 to 4 carbon atoms. ３ is preferably an alkyl group having 1 to 2 carbon atoms, and more preferably a methyl group. 【0043】 In formula (2), m represents an integer of 0 to 30. It is preferable that m is 0. 【0044】 In formula (2), when m is 0, R ３ is preferably a methyl group. When m is 1 to 30, particularly 5 to 30, R ３ is preferably a methyl group or an ethyl group, and more preferably a methyl group. 【0045】 The structural unit (B) in which m is 0 can be formed, for example, by using alkyl methacrylate as a monomer. For example, when methyl methacrylate is used as a monomer, R ３ is a methyl group. 【0046】 The structural unit (B) in which m is 1 to 30 can be formed by using, for example, methoxy(poly)ethylene glycol methacrylate, ethoxy(poly)ethylene glycol methacrylate, propoxy(poly)ethylene glycol methacrylate, or butoxy(poly)ethylene glycol methacrylate as a monomer. For example, when methoxypolyethylene glycol methacrylate (average number of moles of polyethylene glycol moieties (number of moles of ethylene oxide (EO) added): 9) is used as a monomer, a structural unit (B) in which m is 9 and R ３ is a methyl group. 【0047】 Specific examples of methoxypolyethylene glycol methacrylate include NK Ester M-90G (number of moles of EO added: 9), NK Ester M-130G (number of moles of EO added: 13), and NK Ester AM-230G (number of moles of EO added: 23), all manufactured by Shin-Nakamura Chemical Co., Ltd. 【0048】 The content of the structural unit (B) in the copolymer may be 0% by mass, or may be from 0% by mass to 95% by mass, but is preferably from 1% by mass to 50% by mass, more preferably from 2% by mass to 40% by mass, and even more preferably from 5% by mass to 30% by mass. 【0049】 <Structural Unit (C)> The structural unit (C) is a structural unit represented by the following formula (3). 【0050】 In formula (3), R ４ represents an alkyl group having 1 to 4 carbon atoms. ４ is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. 【0051】 In formula (3), n represents an integer of 0 to 30. 【0052】 In formula (3), when n is 0, R ４ is preferably an ethyl group. When n is 1 to 30, particularly 5 to 30, R ４ is preferably a methyl group or an ethyl group, and more preferably a methyl group. 【0053】 The structural unit (C) in which n is 0 can be formed by using, for example, alkyl acrylate as a monomer. For example, when ethyl acrylate is used as a monomer, n is 0 and R ４ is an ethyl group. 【0054】The structural unit (C) in which n is 1 to 30 can be formed by using, for example, methoxy(poly)ethylene glycol acrylate, ethoxy(poly)ethylene glycol acrylate, propoxy(poly)ethylene glycol acrylate, or butoxy(poly)ethylene glycol acrylate as a monomer. For example, when methoxypolyethylene glycol acrylate (average number of moles of polyethylene glycol moieties (number of moles of ethylene oxide (EO) added): 9) is used as a monomer, a structural unit (C) in which n is 9 and R ４ is a methyl group. 【0055】 Specific examples of methoxypolyethylene glycol acrylate include NK Ester AM-90G (number of moles of EO added: 9), NK Ester AM-130G (number of moles of EO added: 13), and NK Ester AM-230G (number of moles of EO added: 23), all manufactured by Shin-Nakamura Chemical Co., Ltd. 【0056】 The content of the structural unit (C) in the copolymer may be 0% by mass, or may be from 0% by mass to 85% by mass, but is preferably from 1% by mass to 60% by mass, more preferably from 1% by mass to 50% by mass, even more preferably from 2% by mass to 40% by mass, and particularly preferably from 5% by mass to 30% by mass. 【0057】 The total content of the structural unit (B) and the structural unit (C) in the copolymer is preferably 2% by mass or more and 85% by mass or less, more preferably 3% by mass or more and 80% by mass or less, even more preferably 4% by mass or more and 70% by mass or less, and particularly preferably 10% by mass or more and 60% by mass or less. 【0058】 The copolymer preferably contains structural units formed by using alkyl (meth)acrylate as a monomer as the structural unit (B) and / or the structural unit (C) (i.e., one or more types selected from the structural unit in which m is 0 in formula (2) and the structural unit in which n is 0 in formula (3)), and more preferably contains the structural units in such a way that the total content of the structural units is 1% by mass or more and 85% by mass or less. 【0059】<Other Structural Units> The above-described copolymer may have structural units other than the above-described structural units. Examples of the other structural units include structural units derived from monomers such as benzyl (meth)acrylate, chloromethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, styrene, vinyl toluene, α-methyl styrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, and vinyl acetate, as well as a structural unit represented by the following formula (4): 【0060】 In formula (4), R ５ represents a hydrogen atom or a methyl group, and R ６ is a direct bond, -CH ２ - or CH ２ CH ２ - indicates R ７ represents an alkylene group having 2 to 20 carbon atoms, R ８ represents an alkyl group having 1 to 4 carbon atoms, and s represents an integer of 1 to 300. In formula (4), R ７ Of the alkylene groups represented by the formula (I), 50 mol % to 100 mol % are ethylene groups (—CH ２ CH ２ -) is preferred. 【0061】 The above-mentioned copolymer contains, as other structural units, structural units (A) and (A) formed upon hydrolysis of the structural unit (X). ０１ ), (A ０２ The copolymer may contain a structural unit other than (A), (B), and (C) (hereinafter also referred to as structural unit (Y)). 【0062】 The content of other structural units in the copolymer is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 0% by mass. 【0063】 The weight average molecular weight (Mw) of the copolymer of this embodiment is not particularly limited, but is usually preferably 1,000 to 1,000,000, more preferably 3,000 to 500,000, and even more preferably 5,000 to 100,000. 【0064】The weight average molecular weight (Mw) of the copolymer can be determined in terms of polyethylene glycol using gel permeation chromatography (GPC). 【0065】 (Method for Producing Copolymer) The copolymer of one embodiment of the present disclosure can be produced by a conventionally known method, for example, by solution polymerizing monomer components corresponding to the structural units described above in an aqueous solvent, followed by necessary post-treatment such as hydrolysis. Note that the aqueous solvent referred to in this specification means a solvent having a water content of 50% by mass or more. 【0066】 The aqueous solvent may be water or a mixed solvent of water and an organic solvent compatible with water. Examples of organic solvents compatible with water include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol, acetone, and methyl ethyl ketone. 【0067】 The monomer component may be mixed with the aqueous solvent all at once, or may be mixed with the aqueous solvent gradually by means of dropwise addition, etc. The amount of the monomer component per 100 parts by mass of the aqueous solvent is, for example, 5 to 1,000 parts by mass, or 10 to 500 parts by mass. 【0068】A polymerization initiator can be used when polymerizing the monomer components. Examples of polymerization initiators include azo compounds such as azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-amidinopropane) dihydrochloride, 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2-methylpropionamidine); persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; and peroxides such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide. These polymerization initiators may be used alone or in combination of two or more. The amount of polymerization initiator varies depending on the type of polymerization initiator and cannot be determined in general. Therefore, it is preferable to adjust the amount to be appropriate for the type of polymerization initiator. 【0069】 The method for adding the polymerization initiator is not particularly limited. Examples of the method for adding the polymerization initiator include batch charging, divided charging, continuous dropwise addition, etc. In order to hasten the completion of the polymerization reaction of the monomer components, a portion of the polymerization initiator may be added before or after the completion of the addition of the monomer components to the reaction system. 【0070】 In order to promote the decomposition of the polymerization initiator, a suitable amount of a decomposer for the polymerization initiator, such as a reducing agent such as sodium hydrogen sulfite or a transition metal salt such as ferrous sulfate, may be added to the reaction system. 【0071】 If necessary, additives such as a chain transfer agent, such as a compound having a thiol group, e.g., tert-dodecyl mercaptan, a pH buffer, a chelating agent, etc., may be added to the reaction system. The amount of the additive varies depending on the type of additive and cannot be determined in general, so it is preferable to adjust the amount to be appropriate for the type of additive. 【0072】 The atmosphere in which the monomer components are polymerized is not particularly limited, but from the viewpoint of increasing the efficiency of the polymerization initiator, an inert gas such as nitrogen gas or argon gas is preferred. 【0073】 The polymerization temperature of the monomer components is not particularly limited, but is usually preferably 20 to 150° C., more preferably 50 to 95° C. The polymerization temperature may be constant while the monomer components are polymerized, or may be changed during the polymerization reaction. 【0074】 The polymerization time of the monomer components is not particularly limited and may be appropriately set depending on the progress of the polymerization reaction of the monomer components, but is usually about 1 to 24 hours. 【0075】 The copolymer obtained as above can be obtained by ring-opening the oxazoline ring. 【0076】 The copolymer described above can also be produced by another method. Specifically, for example, the copolymer of the present disclosure can be produced by opening the oxazoline ring of 2-vinyl-2-oxazoline or 2-isopropenyl-2-oxazoline, followed by polymerization. 【0077】 When opening the oxazoline ring, water and / or a compound having a carboxy group (carboxylic acid) can be used as a raw material compound. The compound having a carboxy group is a carboxylic acid having an optionally substituted aryl group or an optionally substituted alkyl group having 1 to 4 carbon atoms, and examples of the substituents in the optionally substituted aryl group and the optionally substituted alkyl group having 1 to 4 carbon atoms include a hydroxy group, an alkoxy group, an acyl group, an alkoxycarbonyl group, and a carbamoyl group. 【0078】 As the compound having a carboxy group, a monocarboxylic acid containing only one carboxy group per molecule is preferred, since there is a risk of gelation during the reaction. 【0079】Among the raw material compounds, from the viewpoint of increasing reactivity, water and a carboxylic acid having an optionally substituted aryl group, which can be used in large excess as a reaction solvent, are preferred, water and a carboxylic acid having an aryl group substituted with a hydroxy group are preferred, water and a carboxylic acid having a 2-hydroxybenzoyl group in which the hydroxyl group and the carboxy group are adjacent are more preferred, and water alone or water and a carboxylic acid having a 2-hydroxybenzoyl group are even more preferred. 【0080】 The reaction solvent, temperature and time for opening the oxazoline ring are not particularly limited, but the conditions for the copolymer described above may be used. 【0081】 A catalyst such as an acid may be used to promote the ring-opening reaction of the oxazoline ring. 【0082】 (Composition Comprising Copolymer and Water) A composition according to one embodiment of the present disclosure comprises the above-described copolymer and water. 【0083】 The content of the copolymer in the composition is preferably 0.01% by mass or more and 95% by mass or less, more preferably 1% by mass or more and 90% by mass or less, and even more preferably 5% by mass or more and 30% by mass or less, based on the total amount of the composition. 【0084】 The water content in the composition is preferably 5% by mass or more and 99.99% by mass or less, more preferably 10% by mass or more and 99% by mass or less, and even more preferably 50% by mass or more and 95% by mass or less, based on the total amount of the composition. 【0085】The composition may contain other additives, such as surfactants such as anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, anti-redeposition agents for preventing redeposition of contaminants such as sodium carboxymethylcellulose, stain inhibitors such as benzotriazole and ethylene-thiourea, soil release agents, color transfer inhibitors, fabric softeners, alkaline substances such as carbonates, bicarbonates, and silicates, tripolyphosphates, pyrophosphates, Glauber's salt, nitrilotriacetates, ethylenediaminetetraacetates, citrates, copolymer salts of (meth)acrylic acid, acrylic acid-maleic acid copolymers, fumarates, fragrances, and solubilizers. , fluorescent agents, colorants, foaming agents, foam stabilizers, glossing agents, disinfectants, bleaching agents, bleaching aids, enzymes such as proteases, lipases, cellulases, and amylases, dyes, solvents, chelating agents, pH adjusters, highly hydrophilic polymers having ionic properties such as hydroxyl groups, carboxyl groups, and amino groups, among which hydrophilic water-soluble resins such as polyvinyl alcohol and polyvinyl alcohol / polyethylene glycol; acrylic resins, polyester resins, epoxy resins, urethane resins, pigments, dispersants, drying agents, antioxidants, antifoaming agents, dehydrating agents, leveling agents, anti-settling agents, anti-sagging agents, anti-algae agents, anti-mold agents, preservatives, UV absorbers, and light stabilizers. Countersalts used in the other additives mentioned above include alkali metals such as sodium and potassium, and alkali agents such as sodium hydroxide, ammonium, and amines. One or more of these can be used. 【0086】 When other additives are contained, the content thereof is preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.01% by mass or more and 1% by mass or less, based on the total amount of the composition. 【0087】 The pH of the composition can be, for example, 1 or more and 6 or less, preferably 2 or more and 5 or less. 【0088】The composition contains the copolymer and can be suitably used as a detergent additive, for example, as an additive to be added to powder detergents for laundry, liquid detergents for laundry, detergents for hard surfaces such as glass, metal, tableware, kitchens, toilets, automobiles, and industrial machinery, detergents for tires and wood, and detergents for plastic films and plastic containers. 【0089】 (Detergent Additive) A detergent additive according to one embodiment of the present disclosure includes the above-described copolymer or the above-described composition. 【0090】 The detergent additive contains the copolymer or the composition described above, and therefore has excellent cleaning performance for oily stains. 【0091】 (Use of copolymer as detergent additive) The copolymer of one embodiment of the present disclosure can be used as a detergent additive. Preferably, the copolymer of one embodiment of the present disclosure can be used as the above-mentioned detergent additive. Preferred forms of the copolymer are as described above. 【0092】 (Cleaning method using copolymer) A cleaning method according to an embodiment of the present disclosure is characterized by using the copolymer described above. Preferably, the cleaning method according to an embodiment of the present disclosure can be used to clean, for example, clothing; hard surfaces such as glass, metal, tableware, kitchens, toilets, automobiles, and industrial machinery; tires, wood; plastic films, plastic containers, and the like. 【0093】 The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass." 【0094】Production Example 1 A flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer was charged with 578 parts of ion-exchanged water and 262 parts of isopropyl alcohol, and the mixture was heated to 80° C. while gently flowing nitrogen gas. A monomer mixture consisting of 105 parts of methyl methacrylate, 210 parts of 2-isopropenyl-2-oxazoline, and 105 parts of methoxypolyethylene glycol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., EO addition mole number 9, trade name: NK Ester AM-90G), which had been prepared in advance, and a polymerization initiator solution consisting of 21 parts of 2,2′-azobis(2-methylpropionamidine) dihydrochloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product number: V-50) as a polymerization initiator and 189 parts of ion-exchanged water were each added dropwise from the dropping funnel into the flask over 2 hours. During the polymerization reaction, nitrogen gas was continuously flowed into the flask, and the temperature inside the flask was maintained at 80° C.±1° C. After the dropwise addition was completed, the contents of the flask were maintained at the same temperature for 5 hours and then cooled to obtain an oxazoline group-containing polymer with a solid content (non-volatile content) of 30.4%. 【0095】 Production Example 2 A flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with 179 parts of deionized water and 1 part of V-50 (polymerization initiator: 2,2'-azobis(2-methylpropionamidine) dihydrochloride, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and heated to 60°C while gently flowing nitrogen gas. A monomer mixture prepared in advance and consisting of 1 part of ethyl acrylate, 1 part of methyl methacrylate, and 18 parts of 2-isopropenyl-2-oxazoline was added dropwise from the dropping funnel over 1 hour. Nitrogen gas was continued to flow during the reaction, and the temperature inside the flask was maintained at 60±1°C. After completion of the dropwise addition, the temperature was maintained for 9 hours and then cooled, yielding an aqueous solution of an oxazoline group-containing polymer with a nonvolatile content of 10.5% and a pH of 7.4. 【0096】[Production Example 3] An oxazoline group-containing polymer having a solid content (non-volatile content) of 30.4% was obtained in the same manner as in Production Example 1, except that the amount of 2-isopropenyl-2-oxazoline used was changed from 210 parts to 105 parts, and the amount of methoxypolyethylene glycol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., number of moles of EO added: 9, trade name: NK Ester AM-90G) used was changed from 105 parts to 210 parts. 【0097】 [Example 1] 30.4 parts of the oxazoline group-containing polymer solution obtained in Production Example 1 was added to a reaction vessel, and then 156.4 parts of water and 13.0 parts of a 1 mol% aqueous hydrochloric acid solution were added dropwise and mixed while stirring. Next, the mixture was heated in an oil bath until the internal temperature reached 90°C, and then stirred for 5 hours to allow the ring-opening reaction of the oxazoline group-containing polymer to proceed. After that, the mixture was dried in a vacuum dryer at 25°C under 0.01 MPa for 5 hours to obtain polymer (1). The obtained polymer (1) was dissolved in 189.8 parts of water to obtain an aqueous solution containing polymer (1) with a non-volatile content of 5%. The pH of this aqueous solution was 4.0. １ H-NMR measurement and colloid titration revealed that R １ The structural unit (A) is a hydrogen atom at 21% by mass, and the structural unit (A ０２ ) was 6% by mass, the structural unit (X) was 25% by mass, the structural unit (B) was 24% by mass, and the structural unit (C) was 24% by mass. 【0098】 [Example 2] 29.0 parts by mass of the oxazoline group-containing polymer solution obtained in Production Example 1 was added to a reaction vessel, and then 157.6 parts of water, 0.55 parts of salicylic acid, and 13.0 parts of a 1 mol% aqueous hydrochloric acid solution were added dropwise and mixed while stirring. The mixture was then heated in an oil bath until the internal temperature reached 60°C, and stirred for 4 hours. The mixture was further heated in an oil bath until the internal temperature reached 90°C, and stirred for 1 hour to allow the ring-opening reaction of the oxazoline group-containing polymer to proceed. The mixture was then dried in a vacuum dryer at 25°C under 0.01 MPa for 5 hours to obtain polymer (2). The obtained polymer (2) was dissolved in 189.8 parts of water to obtain an aqueous solution containing polymer (2). The pH of this aqueous solution was 3.2. １H-NMR measurement and colloid titration confirmed the peaks derived from aromatic rings, and the reaction rate of the raw material salicylic acid was 98%. １ The structural unit (A) in which R is a hydrogen atom accounts for 34% by mass, １ The structural unit (A) is a 2-hydroxybenzoyl group, and the structural unit (A ０２ A polymer (2) containing 8% by mass of structural unit (A), 22% by mass of structural unit (B), and 21% by mass of structural unit (C) was confirmed. 【0099】 [Example 3] 83.0 parts of the aqueous solution of the oxazoline group-containing polymer obtained in Production Example 2 was added to a reaction vessel, and then 105.0 parts of water and 12.0 parts of a 1 mol% aqueous hydrochloric acid solution were added dropwise and mixed while stirring. Next, the mixture was heated in an oil bath until the internal temperature reached 90°C, and then stirred for 5 hours to promote the ring-opening reaction of the oxazoline group-containing polymer, thereby obtaining an aqueous solution containing polymer (3) with a non-volatile content of 5%. The pH of this aqueous solution was 4.3. １ H-NMR measurement and colloid titration revealed that R １ The structural unit (A) is a hydrogen atom at 47% by mass, and the structural unit (A ０２ A polymer (3) was confirmed to contain 13% by mass of the structural unit (X), 31% by mass of the structural unit (B), and 5% by mass of the structural unit (C). 【0100】 [Example 4] 66.0 parts of the aqueous solution of the oxazoline group-containing polymer obtained in Production Example 2 was added to a reaction vessel, and then 119.6 parts of water, 2.35 parts of salicylic acid, and 12.0 parts of a 1 mol% aqueous hydrochloric acid solution were added dropwise and mixed while stirring. Next, the mixture was heated in an oil bath until the internal temperature reached 60°C, and then stirred for 4 hours. It was further heated in an oil bath until the internal temperature reached 90°C, and then stirred for 1 hour to allow the ring-opening reaction of the oxazoline group-containing polymer to proceed, thereby obtaining an aqueous solution containing polymer (4) with a non-volatile content of 5%. The pH of this aqueous solution was 3.9. The pH of this polymer (4) １ H-NMR measurement and colloid titration confirmed the peaks derived from aromatic rings, and the reaction rate of the raw material salicylic acid was 98%. １ The structural unit (A) is 25% by mass, and R １The structural unit (A) is a 2-hydroxybenzoyl group, and the structural unit (A ０２ A polymer (4) containing 11% by mass of structural unit (A), 3% by mass of structural unit (B), and 3% by mass of structural unit (C) was confirmed. 【0101】 [Example 5] An aqueous solution containing polymer (5) with a nonvolatile content of 5% was obtained in the same manner as in Example 1, except that 30.4 parts of the oxazoline group-containing polymer solution obtained in Production Example 3 was used instead of 30.4 parts of the oxazoline group-containing polymer solution obtained in Production Example 1. The pH of this aqueous solution was 4.0. １ H-NMR measurement and colloid titration revealed that R １ The structural unit (A) is a hydrogen atom at 11% by mass, and the structural unit (A ０２ ) was 3% by mass, the structural unit (X) was 13% by mass, the structural unit (B) was 24% by mass, and the structural unit (C) was 49% by mass. 【0102】 <Conditions for measuring weight-average molecular weight (GPC)> Apparatus: HLC8320 manufactured by Tosoh Corporation Column: TSKgel α-M, TSKgel α-2500 manufactured by Tosoh Corporation Column temperature: 40°C Flow rate: 0.8 ml / min Calibration curve: polyethylene glycol (manufactured by GL Sciences, Mw = 194, 410, 615, 1020, 1450, 3860, 8160, 16100, 21160, 49930, 67600, 96100, 205500, 542500, 942000) Eluent: 200 mM sodium nitrate + 500 mM acetic acid aqueous solution / acetonitrile = 50:50 vol% 【0103】 <Measurement of Reaction Rate of Raw Material Compound> The reaction rate of the raw material compound (salicylic acid) was determined by measuring the amount of unreacted raw material compound in the resulting reaction aqueous solution under the following LC measurement conditions: Measurement device: Prominence UFLC manufactured by Shimadzu Corporation Column: CAPCELL PAK ADME manufactured by Shiseido Co., Ltd. Temperature: 40.0°C Eluent: 10 mmol / L aqueous phosphoric acid solution / acetonitrile = 50 / 50 (volume ratio) Flow rate: 1.0 ml / min Detector: UV (detection wavelength 254 nm) 【0104】<NMR measurement> To confirm the synthesis of the polymer, the following measurement equipment and measurement conditions were used: １ H-NMR measurement was carried out. Specifically, 50 mg of a polymer that had been previously vacuum dried at 0.01 MPa and 25°C for 5 hours was placed in a 5 mm diameter NMR tube, and heavy water was added to dissolve it. The prepared solution was measured under the following conditions. Measurement device: Varian VNMRS 600 MHz, Scan number: 16, Measurement temperature: 20°C 【0105】 <Colloid titration> To confirm the synthesis of the polymer, the amount of amine was quantified by the following method. 0.7 g of the polymer was added to a 100 ml beaker, and after dissolving it in 70 g of pure water, toluidine blue was added as an indicator to prepare a measurement sample. Colloid titration was performed on the measurement sample using a 1 / 400 N solution of potassium polyvinyl sulfate, and the amount of amine was quantified. 【0106】<Measurement of Carbon Black Dispersibility> The carbon black dispersibility of the polymers obtained in Examples 1 to 4 was measured using the following method. The results are shown in Table 1. Carbon black is a model for oily stains that are difficult to clean, and carbon black dispersibility serves as an indicator of the cleanability of oily stains. To measure carbon black dispersibility, a buffer solution and a 0.1% polymer aqueous solution were first prepared. The buffer solution was prepared by adding pure water to 6.76 g of glycine, 5.26 g of sodium chloride, and 0.50 g of 48% sodium hydroxide to a total volume of 60.0 g, followed by the addition of 0.123 g of calcium chloride dihydrate and 0.056 g of magnesium chloride hexahydrate, and further adding pure water to a total volume of 1000.0 g. The 0.1% polymer aqueous solution was prepared by diluting the polymers obtained in Examples 1 to 4 with an appropriate amount of water to a solids concentration of 0.1% by mass. Next, each of the solutions and carbon black powder was placed in a 30 ml test tube in a predetermined order and in a predetermined amount. The predetermined order and amounts were as follows: 0.03 g of carbon black powder was charged first, 27.0 g of buffer solution was charged second, and 3.0 g of 0.1% polymer aqueous solution was charged last. After charging each solution and carbon black powder in this order, the test tube was capped and slowly inverted up and down 60 times to agitate the contents. The tube was then left to stand at room temperature for 4 hours. Immediately after 4 hours, the supernatant was placed in a 1 cm quartz cell, and the absorbance at a UV wavelength of 380 nm was measured using a spectrophotometer (measuring device: Shimadzu UV-1800). Note that a higher absorbance indicates better dispersion of the carbon black powder. A comparative example was prepared without using the 0.1% polymer aqueous solution. 【0107】<Foaming and Foam Retention Evaluation Test> A 50 ppm aqueous solution (0.8 mL) of the polymer obtained in Examples 1 to 4 above, or pure water (0.8 mL) as a comparative example, and a 312.5 ppm aqueous solution (3.2 mL) of LAS were added to a 15 mL sample tube (diameter 2.4 cm x height 5 cm) to prepare an evaluation sample. The evaluation sample was manually shaken for 10 seconds (30 times) to foam. Neopelex G-25 (manufactured by Kao Corporation) was used as the LAS. The foam height immediately after shaking and after leaving to stand for 30 minutes were evaluated as foaming and foam retention, respectively, according to the following criteria. The results are shown in Table 1. A higher foam height immediately after shaking indicates better foaming performance. A higher foam height after leaving to stand for 30 minutes indicates better foam retention performance. ◯: 2 cm or more and 3 cm or less △: 1 cm or more and less than 2 cm ×: 0 cm or more and less than 1 cm 【0108】 【0109】<Detergency Test> The copolymers (polymer (1) and polymer (3)) obtained in Examples 1 and 3 were subjected to a detergency test by the following method. A detergency test was conducted in the same manner except that no copolymer was added, and a blank was used for comparison. (i) 200 g of the buffer solution prepared in the carbon black dispersibility measurement described above was diluted to 400 g to obtain a diluted buffer solution. (ii) 0.1 g of a copolymer with a nonvolatile content of 5% was diluted to 50 g with the diluted buffer solution of (i) to obtain a copolymer solution. (iii) Two pieces of cloth (0.38 g) were added to 50 g of the copolymer solution of (ii), stirred with a stirrer for 30 minutes, and air-dried for one day to obtain a treated cloth. (iv) 61.5 g of olive oil, 38 g of oleic acid, and 0.5 g of oil red were mixed to prepare an oil-stained solution. 15 μL of the oil-stained solution was dropped onto the treated cloth of (iii) and left at 40° C. for 1 hour to obtain a stained cloth. (v) 10 g of Emulgen 108 (Kao Corporation) was weighed into a beaker and ion-exchanged water was added to make 100 g to prepare a 10% surfactant solution. (vi) A 100 mL beaker was charged with a stirrer, 50 g of the diluted buffer solution (i), and 0.085 g of the surfactant solution (v), and the resulting mixture was mixed. One piece of the soiled cloth (iv), whose Z value had previously been measured using a color difference analyzer (SE6000, Nippon Denshoku Industries Co., Ltd.), was then added and stirred for 10 minutes. The water in the beaker was discarded, and the cloth was rinsed once for 3 minutes using the diluted buffer solution (i). The cloth was then dehydrated and air-dried for 1 day. After air-drying, the Z value of the soiled cloth after washing was measured again using the color difference analyzer, and the cleaning ratio was calculated using the following formula: Cleaning ratio (Δ) = Zw - Zs, where Zs represents the Z value of the soiled cloth before washing, and Zw represents the Z value of the soiled cloth after washing. 【0110】 The results of the detergency test for the copolymers were as follows. The larger the value of the detergency, the higher the detergency (effect of cleaning soiled cloth). Polymer (1): Detergency (Δ) = 1.40 Polymer (3): Detergency (Δ) = 1.58 Blank: Detergency (Δ) = 0.27

Claims

[Claim 1] A structural unit (A) represented by the following formula (1), The structural unit (A) is represented by the following formula (7). ０２ )and, A copolymer having a structural unit (B) represented by the following formula (2) and / or a structural unit (C) represented by the following formula (3). 【Chemistry 1】 [In formula (1), R １ R represents a hydrogen atom or -C(=O)-X, ２ X represents a hydrogen atom or a methyl group. X represents an optionally substituted aryl group or an optionally substituted C1-C4 alkyl group. 【Chemistry 2】 [In formula (7), R ２ [This represents a hydrogen atom or a methyl group.] 【Transformation 3】 [In formula (2), R ３ [where m represents an alkyl group having 1 to 4 carbon atoms, and m represents an integer from 0 to 30.] 【Chemistry 4】 [In formula (3), R ４ [where n represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer from 0 to 30.] [Claim 2] The copolymer according to claim 1, having structural unit (A), structural unit (A02), structural unit (B), and structural unit (C). [Claim 3] The content of structural unit (A) in the copolymer is 5% by mass or more and 98% by mass or less. The content of structural unit (B) in the copolymer is 1% by mass or more and 50% by mass or less. The copolymer according to claim 1 or 2, wherein the content of structural units (C) in the copolymer is 1% by mass or more and 60% by mass or less. [Claim 4] R １ The copolymer according to claim 1 or 2, wherein the hydrogen atom and X are at least one selected from -C(=O)-X, where X is an o-hydroxyphenyl group. [Claim 5] m is 0 and R ３ The copolymer according to claim 1 or 2, wherein is a methyl group. [Claim 6] where n is 0 and R ４ is an ethyl group, or where n is from 5 to 30 and R ４ is a methyl group, the copolymer according to claim 1 or 2. [Claim 7] The copolymer according to claim 1 or 2, wherein the content of structural unit (A02) in the copolymer is 1% by mass or more and 98% by mass or less. [Claim 8] A composition comprising the copolymer according to claim 1 or 2 and water. [Claim 9] A detergent additive comprising the copolymer described in claim 1 or 2.

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