Composition

Abstract

The purpose of the present disclosure is to provide a composition that has excellent detergency and that can be suitably used for detergents and the like. The present disclosure pertains to a composition comprising an enzyme, and an amino group-containing copolymer having: a structural unit (a) derived from an amino group-containing monomer represented by general formula (1) (in general formula (1), R1, R2, and R3 each independently represent a hydrogen atom or an alkyl group having 1-5 carbon atoms, R4 and R5 each independently represent a hydrogen atom or an organic group having 1-12 carbon atoms, X represents a divalent linkage group, and an asterisk represents an atom that is bound to the structural unit represented by general formula (1) and that is included in another structural unit of the same type or of a different type); and a structural unit (b) derived from a monomer having a polyalkylene glycol chain.

Description

composition

[0001] The present disclosure relates to compositions.

[0002] Conventionally, detergent builders (detergent auxiliaries) such as zeolite, carboxymethyl cellulose, polyethylene glycol, etc. have been blended into detergents used for clothing in order to improve the cleaning effect of the detergent. In addition to the above-mentioned various detergent builders, polymers have recently been blended into detergent compositions as detergent builders.

[0003] Regarding such polymers, polymers having a polyalkyleneimine as the main chain and ethylene oxide or the like added to a nitrogen atom in the polyalkyleneimine are also called polyethyleneimine ethoxylate modified products, and can act as polymer builders.

[0004] Enzymes are also commonly used as detergent ingredients. It is known that enzymes incorporated into detergents act on proteinaceous and starch-based stains, providing excellent cleaning effects. Furthermore, it is known that the detergency of enzymes can be improved by combining them with polymer builders. For example, Patent Document 1 discloses the use of a polymer that improves the detergency of protease in a detergent, characterized in that the polymer is ethoxylated polyethyleneimine.

[0005] Chinese Patent Application Publication No. 109135960

[0006] As described above, polymers that improve the detergency of enzymes in detergents have been developed, but there is still room for improvement in the detergency of enzymes.

[0007] The present disclosure has been made in consideration of the above-mentioned current situation, and aims to provide a composition having excellent detergency.

[0008] The present inventors have conducted extensive research into compositions and have found that a composition containing an enzyme and an amino group-containing copolymer having a structure derived from an amino group-containing monomer and a polyalkylene glycol chain has excellent detergency. This has led to the realization that the above-mentioned problems can be solved in an excellent manner, and has led to the present disclosure.

[0009] The present disclosure encompasses the following compositions: [1] A composition comprising an amino group-containing copolymer having a structural unit (a) derived from an amino group-containing monomer represented by the following general formula (1) and a structural unit (b) derived from a monomer having a polyalkylene glycol chain, and an enzyme:

[0010] (In general formula (1), R １ , R ２ , R ３ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R ４ , R ５each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms, and X represents a divalent linking group. Here, an asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit represented by general formula (1) is bonded.) [2] The composition according to [1], further comprising a surfactant. [3] The composition according to [1] or [2], wherein the amino group-containing copolymer further has a structural unit (c) derived from a hydrophobic group-containing monomer. [4] The composition according to any one of [1] to [3], wherein the amino acid-containing copolymer further has a structural unit (d) derived from an unsaturated carboxylic acid. [5] The composition according to any one of [1] to [4], wherein the amino group-containing copolymer has a content of the structural unit (a) in the amino group-containing copolymer of 2% by mass or more and 50% by mass or less, based on 100% by mass of all structural units. [6] The composition according to any one of [1] to [5] above, wherein the content of the structural unit (b) in the amino group-containing copolymer is 5% by mass or more and 98% by mass or less, based on 100% by mass of all structural units. [7] The composition according to any one of [1] to [6] above, wherein the content of the structural unit (c) in the amino group-containing copolymer is 0% by mass or more and 50% by mass or less, based on 100% by mass of all structural units. [8] The composition according to any one of [1] to [7] above, wherein the content of the structural unit (d) in the amino group-containing copolymer is 0% by mass or more and 20% by mass or less, based on 100% by mass of all structural units. [9] The composition according to any one of [1] to [8] above, wherein the amino group-containing copolymer has a weight-average molecular weight of 4,000 or more and 500,000 or less.

[10] The composition according to any one of [1] to [9] above, wherein the content of the enzyme in the composition is 0.01 to 10% by mass, based on 100% by mass of the composition.

[11] The composition according to any one of [2] to

[10] above, wherein the surfactant includes an anionic surfactant and / or a nonionic surfactant.

[0011] The composition of the present disclosure has the above-described configuration and has excellent detergency, and therefore can be suitably used as a detergent or the like.

[0012] Preferred embodiments of the present disclosure will be specifically described below, but the present disclosure is not limited to the following description and can be appropriately modified and applied within the scope that does not change the gist of the present disclosure. Note that a combination of two or more of the individual preferred embodiments of the present disclosure described below also falls under the preferred embodiments of the present disclosure.

[0013] The composition of the present disclosure includes an amino group-containing copolymer (hereinafter also referred to as the copolymer of the present disclosure) and an enzyme. By including the copolymer, the composition of the present disclosure also has excellent detergency against proteinaceous stains.

[0014] The content of the copolymer in the composition of the present disclosure is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and even more preferably 0.5 to 3.5% by mass, relative to 100% by mass of the composition.

[0015] The content of the enzyme in the composition of the present disclosure is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.02 to 1.0% by mass, even more preferably 0.05 to 0.75% by mass, and particularly preferably 0.1 to 0.55% by mass, relative to 100% by mass of the composition.

[0016] In the composition of the present disclosure, the content of the copolymer relative to 100% by mass of the enzyme is preferably 100 to 10,000% by mass, more preferably 100 to 5,000% by mass, and even more preferably 500 to 3,500% by mass.

[0017] The composition may contain a surfactant in addition to the amino group-containing copolymer and enzyme. The content of the surfactant is not particularly limited, but is preferably 5 to 80% by mass, more preferably 25 to 55% by mass, and even more preferably 25 to 40% by mass, relative to 100% by mass of the composition.

[0018] The composition may contain other components in addition to the amino group-containing copolymer, enzyme, and surfactant. The other components are not particularly limited, but examples include water, detergent builders; stain inhibitors such as benzotriazole and ethylene-thiourea; soil release agents; color transfer inhibitors; softeners; alkaline substances for pH adjustment; fragrances; solubilizers; fluorescent agents; colorants; foaming agents; foam stabilizers; polishing agents; disinfectants; bleaching agents; bleaching aids; dyes; and solvents. The content of the other components is not particularly limited, but is preferably 25 to 75% by mass, and more preferably 30 to 65% by mass, relative to 100% by mass of the composition.

[0019] The essential components and optional components contained in the composition of the present disclosure will be further described below. [Amino Group-Containing Copolymer of the Present Disclosure] The amino group-containing copolymer contained in the composition of the present disclosure (hereinafter also referred to as the copolymer of the present disclosure) is a copolymer having a structural unit (a) derived from an amino group-containing monomer described below and a structural unit (b) derived from a monomer having a polyalkylene glycol chain. The composition of the present disclosure can be obtained by including the copolymer of the present disclosure and an enzyme. Furthermore, by including a surfactant in the detergent composition, the detergent composition can exhibit better detergency.

[0020] <Structural Unit (a) Derived from Amino Group-Containing Monomer> The structural unit (a) derived from an amino group-containing monomer of the present disclosure is a structural unit represented by the following general formula (1).

[0021] In general formula (1), R １ , R ２ , R ３ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R ４ , R ５each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms, and X represents a divalent linking group. However, an asterisk represents an atom contained in another structural unit of the same type or a different type to which the structural unit represented by general formula (1) is bonded. In the present disclosure, "an atom contained in another structural unit of the same type" represents, for example, in the case of a structural unit represented by general formula (1), an atom contained in a structural unit represented by another general formula (1), and "an atom contained in another structural unit of a different type" represents, for example, in the case of a structural unit represented by general formula (1), an atom contained in a structural unit other than the structural unit represented by general formula (1). The structural unit derived from the amino group-containing monomer is represented by general formula (1), where -X- is a direct bond, or -C(=O)-O-, -C(=O)-, or -C(=O)-O-(CH ２ )n-(n is 1 to 5) or -C(=O)-N(-H)-(CH ２ )n- (n is 1 to 5). In particular, -X- is preferably a structural unit represented by -C(=O)-O-(CH ２ ) n-, more preferably n=1 to 3, and particularly preferably n=2.

[0022] The above R １ , R ２ , R ３ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group (amyl group), an i-propyl group, a sec-butyl group, an i-butyl group, a t-butyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a 2-methylbutyl group, an i-amyl group, and a neopentyl group. Preferred are alkyl groups having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R １ , R ２ , R ３ is preferably a hydrogen atom or a methyl group. １ and R ２ is a hydrogen atom, and R ３ is a methyl group is one of the preferred embodiments of the present invention.

[0023] The above R ４ , R ５ are each independently a hydrogen atom or an organic group having 1 to 12 carbon atoms. The organic group is not particularly limited, and examples thereof include hydrocarbon groups which may have a substituent. The number of carbon atoms in the organic group is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 to 2.

[0024] Examples of the hydrocarbon group in the organic group include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and aralkyl groups, with alkyl groups being preferred.

[0025] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group (amyl group), an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an i-propyl group, a sec-butyl group, an i-butyl group, a t-butyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a 2-methylbutyl group, an i-amyl group, a neopentyl group, a 1,2-dimethylpropyl group, a 1,1-dimethylpropyl group, a t-amyl group, a 1,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a 2-methylbutyl group, an i-amyl group, a aliphatic alkyl groups such as 2-ethyl-2-methylpropyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, decyl group, undecyl group, and dodecyl group; and alicyclic alkyl groups such as cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group (C7), adamantyl group (C10), and cyclopentylethyl group.

[0026] Examples of the alkenyl group include vinyl, allyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and dodecenyl groups. Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, and dodecynyl groups.

[0027] Examples of the aryl group include a phenyl group, an o-, m-, or p-tolyl group, a 2,3-, or 2,4-xylyl group, a mesityl group, a naphthyl group, etc. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, etc.

[0028] The structure derived from the amino group-containing monomer can be formed, for example, by radical polymerization of a monomer having an ethylenically unsaturated group and a primary to tertiary amino group represented by the following general formula (2), or a neutralized product of a primary to tertiary amino group with an acid, but is not limited thereto.

[0029] R in the above general formula (2) ４ , R ５ is R in the above general formula (1). ４ , R ５ is the same as

[0030] The structural unit (a) derived from the amino group-containing monomer is formed, for example, by radical polymerization of the amino group-containing monomer. Specific examples of the amino group-containing monomer include N,N-dialkylamino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate, and their neutralization products with acids such as hydrochloric acid and acetic acid; N,N-dialkylamino group-containing (meth)acrylamides such as N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl (meth)acrylamide, and their neutralization products with acids such as hydrochloric acid and acetic acid; monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, monomethylaminopropyl (meth)acrylate, monoethylaminopropyl (meth)acrylate, 2-(tert-butylamino)ethyl ... monoalkylamino group-containing (meth)acrylates such as monomethylaminoethyl (meth)acrylamide, monoethylaminoethyl (meth)acrylamide, monomethylaminopropyl (meth)acrylamide, monoethylaminopropyl (meth)acrylamide and the like, and their neutralization products with acids such as hydrochloric acid and acetic acid; monoalkylamino group-containing (meth)acrylamides such as monomethylaminoethyl (meth)acrylamide, monoethylaminoethyl (meth)acrylamide, monomethylaminopropyl (meth)acrylamide and the like, and their neutralization products with acids such as hydrochloric acid and acetic acid; (meth)acrylic acid and an alkali such as 2-aminoethyl (meth)acrylate; esters of N,N-diallylamine and their neutralization with acids such as hydrochloric acid and acetic acid; N,N-diallylmethylamine and their neutralization with acids such as hydrochloric acid and acetic acid; allylamine and their neutralization with acids such as hydrochloric acid and acetic acid; addition reaction products of unsaturated monomers having a cyclic ether-containing group having 2 to 8 carbon atoms, such as 1-allyloxy-3-dibutylamino-2-ol and 1-allyloxy-3-diethanolamino-2-ol, with amine compounds having 1 to 24 carbon atoms, and their neutralization with acids such as hydrochloric acid and acetic acid.

[0031] The structural unit (a) derived from the amino group-containing monomer is preferably a structural unit derived from N,N-dimethylaminoethyl (meth)acrylate, represented by the following general formula (3), or a product thereof neutralized with an acid.

[0032] R in the above general formula (3) ６ represents a hydrogen atom or a methyl group. However, the asterisk represents an atom contained in another structural unit of the same type or a different type to which the structural unit represented by general formula (3) is bonded. Most preferred is a structural unit derived from N,N-dimethylaminoethyl methacrylate or a product thereof neutralized with an acid.

[0033] In the copolymer of the present disclosure, the content of the structural unit (a) derived from the amino group-containing monomer is 2% by mass or more and 50% by mass or less, preferably 3% by mass or more and 45% by mass or less, more preferably 4% by mass or more and 40% by mass or less, and particularly preferably 5% by mass or more and 30% by mass or less, based on 100% by mass of the structural units derived from all monomers constituting the copolymer of the present disclosure (hereinafter also referred to as all structural units). In one aspect, the content of the structural unit (a) may be 5% by mass or more and 50% by mass or less, 7% by mass or more and 45% by mass or less, 8% by mass or more and 40% by mass or less, particularly preferably 10% by mass or more and 30% by mass or less. In one aspect, an embodiment in which the content of the structural unit (a) is 15% by mass or more and 25% by mass or less is also one of the preferred embodiments of the present invention. By being in the above range, the proportion of cationic moieties becomes appropriate, and when the composition of the present disclosure is used as a detergent composition, the detergency tends to be improved.

[0034] <Structural Unit (b) Derived from Monomer Having Polyalkylene Glycol Chain> The structural unit (b) derived from a monomer having a polyalkylene glycol chain of the present disclosure is characterized by containing a polyalkylene glycol chain in its structure. The structural unit (b) is represented, for example, by the following general formula (4):

[0035] In the formula, R ７ , R ８ , R ９each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent, Z represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphate group, an amino group, or a salt thereof. A represents an alkylene group having 1 to 10 carbon atoms which may have a substituent. q represents the average number of moles of (AO) added and is a number from 1 to 200. n represents a number from 0 to 4. m represents 0 or 1.

[0036] The above R ７ , R ８ , R ９ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent, and the substituent is preferably at least one hydrophilic group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphate group, an amino group, and salts thereof.

[0037] The alkyl group is preferably a methyl group, an ethyl group, or a propyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. ７ , R ８ , R ９ are each independently preferably a hydrogen atom or a methyl group. ７ , R ９ is a hydrogen atom, and R ８ is a hydrogen atom or a methyl group. More preferably, R ７ , R ９ is a hydrogen atom, and R ８ is a methyl group.

[0038] Z represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydroxyl group, carboxyl group, sulfonic acid group, phosphate group, amino group, or a salt thereof. The hydrocarbon group is not particularly limited, and examples thereof include linear hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, and cyclic hydrocarbon groups such as aryl groups, aralkyl groups, cycloalkyl groups, and cycloalkenyl groups. The hydrocarbon group may be branched, and when the hydrocarbon group is branched, the number of carbon atoms in the hydrocarbon group refers to the total number of carbon atoms in the main chain and branched chains.

[0039] Examples of the alkyl group include an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a stearyl group, and an icosyl group.

[0040] Examples of the alkenyl group include vinyl, allyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, octadecenyl, and icosenyl groups. Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, dodecynyl, octadecenyl, and icosenyl groups.

[0041] Examples of the aryl group include a phenyl 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, a diethylphenyl group, a dibutylphenyl group, a biphenyl group, a naphthyl group, etc. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a benzhydryl group, a biphenylmethyl group, a biphenylethyl group, a naphthylmethyl group, a naphthylethyl group, etc.

[0042] Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, etc.

[0043] 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 2 to 20, more preferably 2 to 15, even more preferably 2 to 10, and particularly preferably 2 to 5. Z is preferably a hydrogen atom or a methyl group.

[0044] The above A represents an alkylene group having 1 to 10 carbon atoms which may have a substituent. The substituent is preferably at least one hydrophilic group selected from the group consisting of a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphate group, a secondary or tertiary amino group, and salts thereof. The q oxyalkylene groups of AO present in the polyalkylene glycol represented by (AO)q may all be the same or different. The alkylene group represented by A preferably has 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms.

[0045] Examples of oxyalkylene groups represented by AO include oxyethylene, oxypropylene, oxybutylene, oxyisobutylene, oxy-2,3-butylene, oxystyrene, and oxyalkylenes having 2 to 10 carbon atoms. Oxyalkylene groups having 2 to 4 carbon atoms, such as oxyethylene, oxypropylene, and oxybutylene, are more preferred, and oxyethylene and oxypropylene are even more preferred. The oxyalkylene group represented by AO is not limited to groups formed by an addition reaction of oxyalkylene groups. Furthermore, when the polyalkylene glycol is an adduct of two or more types of oxyalkylene groups, the adduct may be in any form, such as random addition, block addition, or alternating addition. It is preferable that the oxyalkylene groups in the polyalkylene glycol contain oxyethylene groups as an essential component, more preferably 50 mol % or more of oxyethylene groups, and even more preferably 90 mol % or more of oxyethylene groups.

[0046] The above q represents the average number of moles of AO added and is a number from 1 to 200. It is preferably from 1 to 180, more preferably from 2 to 150, more preferably from 2 to 100, even more preferably from 2 to 80, particularly preferably from 2 to 50, and most preferably from 20 to 30. In one embodiment, q is preferably from 2 to 180, more preferably from 3 to 150, more preferably from 4 to 100, even more preferably from 5 to 80, and particularly preferably from 9 to 50.

[0047] The above-mentioned n represents a number of 0 to 4, and m represents 0 or 1. n is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0. m is more preferably 1.

[0048] The structural unit (b) having the polyalkylene glycol chain is formed, for example, by radical polymerization of a monomer having a polyalkylene glycol chain. Specific examples of the monomer having the polyalkylene glycol chain include polyalkylene glycol mono(meth)acrylates such as (poly)ethylene glycol mono(meth)acrylate and (poly)propylene glycol mono(meth)acrylate; alkoxypolyalkylene glycol mono(meth)acrylates such as methoxy(poly)ethylene glycol mono(meth)acrylate and methoxy(poly)propylene glycol mono(meth)acrylate; and (poly)alkylene glycol monomers such as compounds in which 10 to 100 moles of oxyalkylene groups are added to any of vinyl alcohol, (meth)allyl alcohol, 3-methyl-3-buten-1-ol (isoprenol), 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-2-buten-1-ol, and 2-methyl-3-buten-1-ol. In particular, (poly)ethylene glycol mono(meth)acrylate and methoxy(poly)ethylene glycol mono(meth)acrylate are preferred.

[0049] The content of the structural unit (b) having a polyalkylene glycol chain in the copolymer of the present disclosure is preferably 5% by mass or more and 98% by mass or less, more preferably 20% by mass or more and 95% by mass or less, even more preferably 30% by mass or more and 90% by mass or less, particularly preferably 40% by mass or more and 85% by mass or less, and most preferably 45% by mass or more and 80% by mass or less, relative to 100% by mass of the structural units derived from all monomers constituting the copolymer of the present disclosure. The content within the above range ensures an appropriate proportion of hydrophilic moieties, which tends to improve detergency when the composition of the present disclosure is used as a detergent composition. In one embodiment, the content of the structural unit (b) may be 5% by mass or more and 95% by mass or less, 20% by mass or more and 80% by mass or less, 30% by mass or more and 70% by mass or less, 40% by mass or more and 65% by mass or less, or 45% by mass or more and 60% by mass or less. In one embodiment, the content of the structural unit (b) may be 50% by mass or more.

[0050] <Structural unit (c) derived from hydrophobic monomer> The copolymer of the present disclosure may have a structural unit (c) derived from a hydrophobic monomer as a structural unit other than the structural unit (a) derived from the amino group-containing monomer and the structural unit (b) derived from the monomer having a polyalkylene glycol chain. The hydrophobic monomer of the present disclosure constituting the structural unit (c) derived from the hydrophobic monomer of the present disclosure is not particularly limited as long as it has a solubility parameter of 13 or less in a homopolymer obtained by homopolymerization. Here, the solubility parameter is a value calculated by the method described on pages 147-154 of "POLYMER ENGINEERING AND SCIENCE" (1974, Vol. 14, No. 2). The method is outlined below. Solubility parameter (δ) (cal / cm) of a homopolymer ３ ) １／２ is calculated by the following calculation method based on the evaporation energy (Δei) and molar volume (Δvi) of the structural units forming the polymer: δ=(Δei / Δvi) １／２ (cal / cm ３ ) １／２

[0051] If the solubility parameter of the homopolymer obtained by polymerizing the hydrophobic monomer of the present disclosure alone is 13 or less, the hydrophobicity of the copolymer of the present disclosure is sufficient and the copolymer has excellent adsorption properties to hydrophobic fibers. The solubility parameter is preferably 12 or less, more preferably 11 or less. The solubility parameter is usually 5 or more.

[0052] The hydrophobic monomer of the present disclosure is not particularly limited as long as the solubility parameter of the homopolymer is 13 or less, but is preferably a monomer having an ethylenically unsaturated group and an alkyl group having 1 to 30 carbon atoms. Examples of the hydrophobic monomer include esters of unsaturated carboxylic acids such as (meth)acrylic acid and alcohols having 1 to 30 carbon atoms which may have a substituent; aromatic vinyl monomers such as styrene; olefin monomers such as ethylene and propylene; esters of unsaturated alcohols such as vinyl acetate and carboxylic acids having 3 to 8 carbon atoms; vinyl halides such as vinyl chloride; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; cyclic vinyl monomers such as N-vinylpyrrolidone; and acrylonitrile.

[0053] The substituent that the alcohol may have may be any substituent other than a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, or a salt thereof, and examples thereof include a halogen atom. The number of carbon atoms in the alcohol is preferably 2 to 22, more preferably 2 to 16, and even more preferably 4 to 8. Preferred examples of the alcohol having 1 to 30 carbon atoms include alkyl alcohols having 1 to 30 carbon atoms and aromatic alcohols having 6 to 30 carbon atoms.

[0054] Examples of the alkyl alcohol having 1 to 30 carbon atoms include methanol, ethanol, propanol, butanol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, and icosyl alcohol.

[0055] Preferred examples of the aromatic alcohol having 6 to 30 carbon atoms include phenol, benzyl alcohol, methylphenyl alcohol (o-cresol, m-cresol, p-cresol), creosol, ethylphenyl alcohol, propylphenyl alcohol, butylphenyl alcohol, butylmethylphenyl alcohol, dimethylphenyl alcohol, diethylphenyl alcohol, dibutylphenyl alcohol, hydroxybiphenyl, 4-hydroxymethylbiphenyl, 3-hydroxymethylbiphenyl, 4-hydroxyethylbiphenyl, 3-hydroxyethylbiphenyl, naphthol, 1-hydroxymethylnaphthalene, 1-hydroxyethylnaphthalene, 2-hydroxymethylnaphthalene, and 2-hydroxyethylnaphthalene.

[0056] The hydrophobic monomer is preferably a monomer represented by the following general formula (5):

[0057]

[0058] (General, R １０ , R １１ , R １２ , are the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. １３ represents a hydrocarbon group having 1 to 30 carbon atoms. That is, the structural unit (c) derived from the hydrophobic monomer of the present disclosure is a compound represented by the following general formula (6):

[0059] (In the formula, R １０ ~R １３is the same as general formula (5). However, the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit represented by general formula (6) is bonded. ) is preferred. When the amino group-containing copolymer of the present disclosure has a structural unit represented by general formula (6), the structural unit may be obtained by polymerization using a compound represented by general formula (5) above, or may be obtained by other methods.

[0060] The above R １０ , R １１ , R １２ The alkyl group in R is preferably a methyl group, an ethyl group, or a propyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. １０ , R １１ and R １２ are preferably the same or different and each is a hydrogen atom or a methyl group. More preferably, R １０ , R １１ is a hydrogen atom, and R １２ is a hydrogen atom or a methyl group.

[0061] The above R １３ The number of carbon atoms in the hydrocarbon group is preferably 1 to 22, more preferably 2 to 16, even more preferably 2 to 12, particularly preferably 4 to 12, and most preferably 4 to 8.

[0062] The above R １３ The hydrocarbon group in is not particularly limited, and examples thereof include chain hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, and cyclic hydrocarbon groups such as aromatic groups, cycloalkyl groups, and cycloalkenyl groups. The hydrocarbon group may have a branch, and when 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 chains. In one embodiment, １３ The hydrocarbon group in R may or may not have an aromatic group. １３ is a hydrocarbon group that does not contain an aromatic group is also one of the preferred embodiments of the present disclosure.

[0063] The above R １３The number of carbon atoms in the alkyl group in the above R is preferably 2 to 22, more preferably 2 to 16, and particularly preferably 2 to 12. The most preferred is 4 to 8. １３ The aromatic group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably 6 to 8 carbon atoms.

[0064] The above R １３ Examples of the alkyl group in the above R include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a stearyl group, and an icosyl group. １３ Examples of the alkenyl group in the above R 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. １３ Examples of the alkynyl group in the formula (I) include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, a dodecynyl group, an octadecynyl group, and an icosynyl group.

[0065] The above R １３ Examples of the aromatic group in the formula (I) include aryl groups such as a phenyl group, benzyl group, methylphenyl group, 1-methoxy-4-methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, butylmethylphenyl group, dimethylphenyl group, diethylphenyl group, dibutylphenyl group, biphenyl group, and naphthyl group; and aralkyl groups such as a benzyl group, 4-methylbenzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, 2-(2-methylphenyl)ethyl group, 2-(3-methylphenyl)ethyl group, 2-(4-methylphenyl)ethyl group, 2-(4-propylphenyl)ethyl group, biphenylmethyl group, biphenylethyl group, naphthylmethyl group, and naphthylethyl group.

[0066] The above R １３Examples of the cycloalkyl group in the formula (I) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. Examples of the cycloalkenyl group in the formula (I) include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, etc.

[0067] The above R １３ The hydrocarbon group in is preferably an alkyl group, an aryl group, or an aralkyl group, more preferably an alkyl group. The hydrophobic monomer is preferably an alkyl (meth)acrylate, an aryl (meth)acrylate, or an aralkyl (meth)acrylate, more preferably an alkyl (meth)acrylate.

[0068] Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and icosyl (meth)acrylate. Of these, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, and dodecyl (meth)acrylate are preferred, and ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, and dodecyl (meth)acrylate are more preferred.

[0069] Examples of the aryl(meth)acrylate include phenyl(meth)acrylate, 2-ethylphenyl(meth)acrylate, propylphenyl(meth)acrylate, butylphenyl(meth)acrylate, pentylphenyl(meth)acrylate, hexylphenyl(meth)acrylate, butylmethylphenyl(meth)acrylate, dimethylphenyl(meth)acrylate, diethylphenyl(meth)acrylate, dibutylphenyl(meth)acrylate, 4-methylphenyl(meth)acrylate, 1-methoxy-4-methylphenyl(meth)acrylate, naphthyl(meth)acrylate, etc. Of these, phenyl(meth)acrylate is preferred.

[0070] Examples of the aralkyl (meth)acrylate include benzyl (meth)acrylate, 2-phenylethyl (meth)acrylate, 3-phenylpropyl (meth)acrylate, 4-phenylbutyl (meth)acrylate, 4-methylbenzyl (meth)acrylate, 2-(2-methylphenyl)ethyl (meth)acrylate, 2-(3-methylphenyl)ethyl (meth)acrylate, 2-(4-methylphenyl)ethyl (meth)acrylate, 2-(4-propylphenyl)ethyl (meth)acrylate, biphenylmethyl (meth)acrylate, biphenylethyl (meth)acrylate, naphthylmethyl (meth)acrylate, and naphthylethyl (meth)acrylate. Of these, benzyl (meth)acrylate is preferred.

[0071] In the copolymer of the present disclosure, the content of the structural unit (c) derived from a hydrophobic monomer is preferably 0% by mass or more and 50% by mass or less, more preferably 0% by mass or more and 40% by mass or less, even more preferably 0% by mass or more and 35% by mass or less, even more preferably 0% by mass or more and 30% by mass or less, particularly preferably 0% by mass or more and 25% by mass or less, and most preferably 0% by mass or more and 20% by mass or less, relative to 100% by mass of the structural units derived from all monomers constituting the copolymer of the present disclosure. By being in the above range, the proportion of hydrophobic moieties becomes appropriate, and when the composition of the present disclosure is used as a detergent composition, the detergency tends to be improved. In one embodiment, the content of the structural unit (c) may be 5% by mass or more and 70% by mass or less, 10% by mass or more and 60% by mass or less, 15% by mass or more and 50% by mass or less, or 20% by mass or more and 45% by mass or less.

[0072] <Structural unit (d) derived from unsaturated carboxylic acid monomer> The copolymer of the present disclosure may have a structural unit (d) derived from an unsaturated carboxylic acid monomer as a structural unit other than the structural unit (a) derived from the amino group-containing monomer and the structural unit (b) derived from the monomer having a polyalkylene glycol chain. An embodiment in which the copolymer of the present disclosure has structural units (a), (b), and (d) is one of the preferred embodiments of the present invention. The structural unit (d) derived from the unsaturated carboxylic acid monomer of the present disclosure is not particularly limited as long as it is a structural unit derived from a monomer having a carboxyl group or a salt thereof and an ethylenically unsaturated hydrocarbon group (unsaturated group), but is preferably a structural unit represented by the following general formula (7) or a salt thereof:

[0073] In general formula (7), R １４ represents a hydrogen atom, a methyl group, or -CH ２ COOH group, and R １５ , R １６ are the same or different and are a hydrogen atom, a methyl group, an ethyl group, a carboxyl group, -CH ２ COOH groups.

[0074] A preferred embodiment of the general formula (7) is R １４is at least one selected from a hydrogen atom and a methyl group, and R １５ , R １６ are the same or different and are at least one selected from a hydrogen atom and a carboxyl group. １４ is at least one selected from a hydrogen atom and a methyl group, and R １５ , R １６ is a hydrogen atom.

[0075] Examples of unsaturated carboxylic acid monomers as precursors of the structural unit (d) derived from an unsaturated carboxylic acid monomer prior to polymerization reaction include unsaturated carboxylic acid monomers such as (meth)acrylic acid, crotonic acid, tiglic acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, etc., and their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts; and unsaturated dicarboxylic acid monomers such as maleic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid, etc., and their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts, anhydrides, and half esters. Among these, (meth)acrylic acid, maleic acid, and salts thereof are preferred, and (meth)acrylic acid is more preferred.

[0076] In the copolymer of the present disclosure, the content of the structural unit (d) derived from the unsaturated carboxylic acid monomer is preferably 0% by mass or more and 20% by mass or less, more preferably 0% by mass or more and 15% by mass or less, even more preferably 0% by mass or more and 10% by mass or less, and particularly preferably 0% by mass or more and 5% by mass or less, relative to 100% by mass of the structural units derived from all monomers constituting the copolymer of the present disclosure. By being in the above range, the ratio of hydrophobic moieties to hydrophilic moieties becomes appropriate, and when the composition of the present disclosure is used as a detergent composition, the detergency tends to be improved. In one embodiment, the content of the structural unit (d) may be 1% by mass or more and 20% by mass or less, 1% by mass or more and 10% by mass or less, or 1% by mass or more and 5% by mass or less.

[0077] <Structural Unit (e) Derived from Other Monomer> The amino group-containing copolymer of the present disclosure may have a structural unit (a) derived from an amino group-containing monomer, a structural unit (b) derived from a monomer having a polyalkylene glycol chain, a structural unit (c) derived from a hydrophobic monomer, and a structural unit (e) derived from a monomer other than the structural unit (d) derived from an unsaturated carboxylic acid monomer.

[0078] The other monomers are not particularly limited, and examples thereof include sulfonic acid group-containing monomers and salts thereof such as styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 3-allyloxy-2-hydroxy-1-propanesulfonic acid, and phosphoric acid group-containing monomers such as 2-methacryloyloxyethyl acid phosphate.

[0079] In the copolymer of the present disclosure, the content of structural units derived from other monomers is preferably 10% by mass or less, more preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably 1% by mass or less, relative to 100% by mass of structural units derived from all monomers constituting the copolymer of the present disclosure. An embodiment in which the content of structural units derived from other monomers is 0% by mass is also one of the preferred embodiments of the present invention.

[0080] <Physical properties of the copolymer of the present disclosure> The amino group-containing copolymer of the present disclosure preferably has a weight average molecular weight (Mw) of 4,000 or more and 500,000 or less, more preferably 6,000 or more and 400,000 or less, and even more preferably 10,000 or more and 300,000 or less. Furthermore, it is preferably 10,000 or more and 200,000 or less, more preferably 10,000 or more and 100,000 or less, even more preferably 12,000 or more and 50,000 or less, particularly preferably 15,000 or more and 40,000 or less, and most preferably 16,000 or more and 30,000 or less. When the weight average molecular weight is within the above range, the detergency tends to be improved when the composition of the present disclosure is used as a detergent composition. The weight average molecular weight of the amino group-containing copolymer can be measured by the method described in the examples.

[0081] <Method for producing the amino group-containing copolymer of the present disclosure> The method for producing the amino group-containing copolymer of the present disclosure is not particularly limited, but the copolymer can be produced by polymerizing monomer components, and specific examples and preferred examples of the monomer components and preferred ratios of each monomer are as described above.

[0082] The method for producing the amino group-containing copolymer includes, for example, a step of polymerizing an amino group-containing monomer or a precursor thereof, a monomer having a polyalkylene glycol chain or a precursor thereof, a hydrophobic group monomer or a precursor thereof, and an unsaturated carboxylic acid monomer (hereinafter referred to as the polymerization step). Methods for initiating the polymerization of the monomer components in the polymerization step include, for example, adding a polymerization initiator, irradiating with UV light, applying heat, and irradiating with light in the presence of a photopolymerization initiator. The use of a polymerization initiator is particularly preferred.

[0083] Examples of the polymerization initiator include persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; azo compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(isobutyronitrile), and 2,2'-azobis(2-methylpropionamidine) dihydrochloride; organic peroxides such as benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, and cumene hydroperoxide; and redox initiators that generate radicals by combining an oxidizing agent and a reducing agent, such as ascorbic acid and hydrogen peroxide, or persulfates and metal salts. Among these, persulfates and azo compounds are preferred, and azo compounds are more preferred, as they tend to reduce residual monomers. These polymerization initiators may be used alone or in the form of a mixture of two or more.

[0084] The amount of the polymerization initiator used is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 8% by mass or less, even more preferably 0.03% by mass or more and 7% by mass or less, and most preferably 0.04% by mass or more and 4% by mass or less, based on the total amount of the monomers constituting the structural units used.

[0085] In the polymerization step, a chain transfer agent may be used as a molecular weight modifier for the polymer, if necessary. Examples of chain transfer agents include mercaptocarboxylic acids such as thioglycolic acid (mercaptoacetic acid), 3-mercaptopropionic acid, 2-mercaptopropionic acid (thiolactic acid), 4-mercaptobutanoic acid, thiomalic acid, and salts thereof; mercaptoethanol, thioglycerol, 2-mercaptoethanesulfonic acid; halides such as carbon tetrachloride, methylene chloride, bromoform, and bromotrichloroethane; secondary alcohols such as isopropanol and glycerin; phosphorous acid, hypophosphorous acid, hypophosphites, and hydrates thereof; hydrogen sulfite (salt); and compounds capable of generating hydrogen sulfite (salt), such as bisulfite (salt), pyrosulfite (salt), dithionous acid (salt), and sulfurous acid (salt). Among these, compounds having a mercapto group are preferred, and mercapto group-containing compounds having a carboxyl group are more preferred.

[0086] The amount of the chain transfer agent used in producing the copolymer of the present disclosure is preferably 0.1 mol% or more and 20 mol% or less, more preferably 0.2 mol% or more and 15 mol% or less, still more preferably 0.3 mol% or more and 10 mol% or less, and most preferably 0.5 mol% or more and 5 mol% or less, relative to 100 mol% of the total amount of monomers constituting the structural units used.

[0087] The solvent used during polymerization can be selected as needed from those capable of dissolving the monomer components, polymerization initiator, chain transfer agent, and copolymer after production. While not particularly limited, preferred solvents include water, alcohols having 1 to 8 carbon atoms such as ethanol, 1-propanol, 2-propanol, 1-butanol, and phenoxyethanol; glycols such as ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol; and glycol ethers such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and propylene glycol monomethyl ether. Of these, water, ethanol, ethylene glycol, propylene glycol, diethylene glycol monobutyl ether, and propylene glycol monomethyl ether are preferred, and a mixture of two or more of these solvents may also be used.

[0088] In the polymerization step, the polymerization temperature is preferably 40° C. or higher and 150° C. or lower, more preferably 45° C. or higher, and even more preferably 50° C. or higher. Also, the polymerization temperature is more preferably 100° C. or lower, and even more preferably 90° C. or lower.

[0089] In the polymerization step, the method for charging the monomer components, polymerization initiator, and chain transfer agent into a reaction vessel is not particularly limited, and examples thereof include a method in which the entire amount is charged into the reaction vessel all at once at the beginning, a method in which the entire amount is charged into the reaction vessel in portions or continuously, a method in which a portion is charged into the reaction vessel at the beginning and the remainder is charged into the reaction vessel in portions or continuously, etc. A preferred method is a method in which a solvent described below is charged at the beginning and the monomer components, polymerization initiator, and chain transfer agent are continuously charged.

[0090] The monomer components may be neutralized with an organic acid such as acetic acid or propionic acid, or a mineral acid such as hydrochloric acid, sulfuric acid or nitric acid before polymerization.

[0091] The copolymer obtained by polymerization can be used as it is as a detergent additive, such as an additive for liquid detergents, but if necessary, it may be further neutralized with an alkaline substance. Examples of alkaline substances that can be used include inorganic salts such as hydroxides and carbonates of monovalent or divalent metals, ammonia, and organic amines. Furthermore, the concentration of the copolymer can be adjusted as necessary after the reaction is complete.

[0092] [Enzymes] The enzymes contained in the composition of the present disclosure are not particularly limited as long as they exhibit cleaning performance, and examples include protease, lipase, phospholipase, hemicellulase, peroxidase, cellulase, xylanase, esterase, cutinase, pectinase, keratanase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, amylase, or a combination thereof. Protease and amylase are preferred, and protease is more preferred.

[0093] [Surfactant] The surfactant contained in the composition of the present disclosure is not particularly limited, and examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. These surfactants can be used alone or in combination of two or more. Preferably, the composition contains an anionic surfactant and / or a nonionic surfactant. When two or more surfactants are used, the combined amount of the anionic surfactant and the nonionic surfactant is preferably 5 to 100% by mass relative to 100% by mass of all surfactants. More preferably, it is 50 to 100% by mass, even more preferably 75 to 100% by mass, and particularly preferably 80 to 100% by mass.

[0094] The composition of the present disclosure preferably contains an anionic surfactant as a surfactant. Among surfactants, anionic surfactants have the greatest effect on enzyme activity, so stabilizing enzymes using the copolymer of the present invention in a composition containing an anionic surfactant is of great technical significance. The content of the anionic surfactant is preferably 10 to 100% by mass relative to 100% by mass of the total surfactants. More preferably, it is 10 to 50% by mass, even more preferably 10 to 45% by mass, and particularly preferably 10 to 40% by mass.

[0095] Suitable anionic surfactants include alkylbenzenesulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, α-olefin sulfonates, α-sulfofatty acid or ester salts, alkanesulfonates, saturated fatty acid salts, unsaturated fatty acid salts, alkyl ether carboxylates, alkenyl ether carboxylates, amino acid surfactants, N-acylamino acid surfactants, alkyl phosphates or salts thereof, alkenyl phosphates or salts thereof, etc. In the alkyl and alkenyl groups in the anionic surfactants, the alkyl group, such as a methyl group, may be branched.

[0096] Suitable nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or their alkylene oxide adducts, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters, alkylamine oxides, etc. The alkyl and alkenyl groups in the nonionic surfactants may have branched alkyl groups such as methyl groups.

[0097] The cationic surfactant is preferably a quaternary ammonium salt, etc. The amphoteric surfactant is preferably a carboxyl-type amphoteric surfactant, a sulfobetaine-type amphoteric surfactant, etc. The alkyl group and alkenyl group in the cationic surfactant and amphoteric surfactant may be a branched alkyl group such as a methyl group.

[0098] [Other Components] The composition of the present disclosure may contain other components in addition to the copolymer, enzyme, and surfactant. The other components are not particularly limited, but examples thereof include detergent builders; stain inhibitors such as benzotriazole and ethylene-thiourea; soil release agents; color transfer inhibitors; fabric softeners; alkaline substances for adjusting pH; fragrances; solubilizers; fluorescent agents; colorants; foaming agents; foam stabilizers; polishing agents; disinfectants; bleaching agents; bleaching aids; dyes; solvents, etc.

[0099] The detergent builder is not particularly limited, but examples thereof include alkali builders such as carbonates, bicarbonates, and silicates; chelating builders such as tripolyphosphates, pyrophosphates, Glauber's salt, nitrilotriacetates, ethylenediaminetetraacetates, citrates, (meth)acrylic acid copolymer salts, acrylic acid-maleic acid copolymers, fumarates, and zeolites; and carboxyl derivatives of polysaccharides such as carboxymethylcellulose. Counter salts used in the detergent builders include alkali metals such as sodium and potassium, and alkaline agents such as sodium hydroxide, ammonium, and amines. One or more of these can be used as other components.

[0100] The solvent is not particularly limited, and examples thereof include water; alcohols having 1 to 8 carbon atoms such as ethanol, 1-propanol, 2-propanol, 1-butanol, and phenoxyethanol; glycols such as propylene glycol, butylene glycol, and hexylene glycol; polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol; diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and diethylene glycol monobutyl ether; Preferred hydrophilic solvents include alkyl ethers such as alkyl ethers; sulfoxides (e.g., dimethyl sulfoxide) such as sulfone, diethyl sulfone, and bis(2-hydroxyethyl) sulfone; cyclic ethers (e.g., tetrahydrofuran and tetrahydropyran); nitriles (e.g., acetonitrile, propionitrile, butyronitrile, acrylonitrile, and methacrylonitrile); carbonates (e.g., ethylene carbonate and propione carbonate); and ketones (e.g., acetone, diethyl ketone, acetophenone, methyl ethyl ketone, cyclohexanone, cyclopentanone, and diacetone alcohol).

[0101] When the composition contains a detergent builder, the blending ratio thereof is usually preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, more preferably 0.3 to 10% by mass, even more preferably 0.4 to 8% by mass, and particularly preferably 0.5 to 5% by mass, relative to 100% by mass of the cleaning composition.

[0102] When the composition is a liquid detergent, the amount of water contained in the liquid detergent is usually preferably 0.1 to 75% by mass, more preferably 0.5 to 65% by mass, and particularly preferably 1 to 55% by mass, relative to 100% by mass of the liquid detergent.

[0103] [Uses of the Composition] The composition of the present disclosure has excellent detergency and can therefore be suitably used in detergents and the like. For example, the composition of the present disclosure can be used in detergents for fibers and hard surfaces. Detergents as used herein include detergents for household clothing, kitchens, homes, the textile industry, and other industrial applications. The composition of the present disclosure is also a detergent composition. A method for producing a detergent composition comprising mixing the composition of the present disclosure with a surfactant also constitutes one aspect of the present invention. A soil release agent comprising the composition of the present disclosure also constitutes one aspect of the present invention. A soil release agent is an agent that is previously treated with a compound that adsorbs to fibers, thereby imparting the effect of making sebum stains and the like that adhere thereto easier to remove during washing. A method for using the composition of the present disclosure as a soil release agent also constitutes one aspect of the present invention.

[0104] 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, "%" means "% by mass."

[0105] <Measurement of Weight-Average Molecular Weight of Copolymer> The weight-average molecular weight (Mw) of the copolymer was measured by GPC (gel permeation chromatography) under the following conditions and using the following apparatus. Apparatus: EcoSEC HLC-8320GPC manufactured by Tosoh Corporation Detector: Differential refractometer (RI) detector Column: TSKgel α-M, α-2500 manufactured by Tosoh Corporation Column temperature: 40°C Flow rate: 0.8 mL / min Injection volume: 20 μL (eluent preparation solution with sample concentration of 0.5 wt%) Calibration curve: Polyethylene glycol manufactured by GL Sciences, Mw = 194, 410, 615, 1020, 1450, 3860, 8160, 16100, 21160, 49930, 67600, 96100, 205500, 542500, 942000 Calibration curve order: 3 GPC software: EcoSEC-WS manufactured by Tosoh Corporation Eluent: 0.5 M acetic acid + 0.2 M Na nitrate / acetonitrile = 50 / 50 (v / v)

[0106] <Test 1 for evaluating detergency for protein stains> (1) The reflectance (Z value) of protein-stained fabric EMPA-117 (manufactured by Swissatest) was measured using a reflectometer (spectrophotometer, manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000). (2) 29.5 g of calcium chloride dihydrate and 13.6 g of magnesium chloride hexahydrate were added to pure water to prepare 500 g of hard water mother liquor (i). (3) 15.5 g of sodium bicarbonate, 884.5 g of pure water, and 100 g of 0.1 M HCl aqueous solution were mixed to prepare 1,000 g of base solution (ii). (4) 4 g of hard water mother liquor (i) and 8 g of base solution (ii) were added to 3,987 g of pure water and stirred to prepare cleaning solution (iii). (5) For rinsing, 4 g of hard water mother liquor (i) was added to 3,996 g of pure water and stirred to prepare rinse solution (iv). (6) 240 g of propylene glycol and 60 g of ethanol were mixed to prepare compatibilizer (v). (7) 500 g of compatibilizer (v) and 1,808 g of pure water were added to 2,692 g of linear alkylbenzenesulfonate sodium (Neopelex G-65 manufactured by Kao Corporation, hereinafter also referred to as LAS) and stirred to prepare LAS aqueous solution (vi). (8) 56.3 g of polyoxyethylene lauryl ether (Emulgen 108 manufactured by Kao Corporation, hereinafter also referred to as PAE), 19.6 g of compatibilizer (v), and 113 g of pure water were added to 53.6 g of LAS aqueous solution (vi) and stirred to prepare 30% surfactant solution (vii). (9) 8.9 g of copolymer (1) with a solid content of 33.6% and 0.3 g of protease ProgressUno101L (Novozymes) were added to 90.8 g of 30% surfactant solution (vii) and stirred to prepare detergent solution (viii). (10) 6.3 g of copolymer (2) with a solid content of 47.1% and 0.3 g of protease ProgressUno101L (Novozymes) were added to 93.4 g of 30% surfactant solution (vii) and stirred to prepare detergent solution (ix). (11) 9 g of pure water was added to 1 g of detergent solution (viii) or (ix), respectively, to prepare detergent solutions (x) and (ix). (12) 994.2 g of the cleaning solution (iii) was added to each pot in a Tergot-o-meter (manufactured by Daiei Scientific Co., Ltd., product name: TM-4) and the temperature was adjusted to 15°C. Further, 5.8 g of each of the detergent solutions (x) and (ix) was added to each pot and stirred for 1 minute.(13) Seven pieces of EMPA-117 were placed in each pot and stirred at 120 ppm for 15 minutes. (14) The soiled cloths were removed from each pot and the water was drained by hand. After removing the liquid from the pots, 1000 g of rinsing solution (iv) was placed in each pot, the temperature was adjusted to 15°C, and the mixture was stirred at 120 rpm for 5 minutes. (15) The operation of (14) was repeated once more. (16) After drying at room temperature, the reflectance (Z value) of the soiled cloths was measured again using the above spectrophotometer (spectrophotometer, manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000), and the cleaning rate was calculated using the following formula. The higher the value of the cleaning rate, the better the cleaning power.

[0107] <Test 2 for evaluating detergency of protein stains> (1) The reflectance (Z value) of protein-stained fabric EMPA-117 (manufactured by Swissatest) was measured using a reflectometer (spectrophotometer, manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000). (2) 29.5 g of calcium chloride dihydrate and 13.6 g of magnesium chloride hexahydrate were added to pure water to prepare 500 g of hard water mother liquor (i). (3) 15.5 g of sodium bicarbonate, 884.5 g of pure water, and 100 g of 0.1 M HCl aqueous solution were mixed to prepare 1,000 g of base solution (ii). (4) 4 g of hard water mother liquor (i) and 8 g of base solution (ii) were added to 3,987 g of pure water and stirred to prepare cleaning solution (iii). (5) For rinsing, 4 g of hard water mother liquor (i) was added to 3,996 g of pure water and stirred to prepare rinse solution (iv). (6) 0.1 g of protease ProgressUno 101L (Novozymes) was weighed out and ion-exchanged water was added to make 10 g to prepare a 1% enzyme solution (v). (7) 0.308 g of copolymer 3 with a solids content of 33.6% was weighed out and ion-exchanged water was added to make 1 g to prepare a 10% copolymer solution (vi). (8) 90 g of pure water was added to 10 g of polyoxyethylene (6) lauryl ether (Kao Emulgen 108, hereinafter also referred to as PAE) and stirred to prepare a 10% surfactant solution (vii). (9) 0.25 g of 1% enzyme solution (v), 6.8 g of ion-exchanged water, 0.30 g of 10% copolymer solution (vi), and 3.0 g of 10% surfactant solution (vii) were weighed and homogenized to prepare a 10-fold diluted detergent solution (viii). (10) 994.2 g of cleaning solution (iii) was added to each pot in a Tergot-o-meter (manufactured by Daiei Scientific Co., Ltd., product name: TM-4) and the temperature was adjusted to 15 ° C., and 5.8 g of detergent solution (viii) was added to each pot and stirred for 1 minute. (11) Seven sheets of EMPA-117 were placed in each pot and stirred at 120 ppm for 15 minutes. (12) The soiled cloth was removed from each pot and the water was drained by hand. After removing the liquid from the pots, 1000 g of the rinse solution (iv) was added to each pot and adjusted to 15°C. The soiled cloths were returned to the pots and stirred at 120 rpm for 5 minutes. (13) The steps of (12) were repeated once more.(14) After drying at room temperature, the reflectance (Z value) of the soiled cloth was measured again using the above-mentioned spectrophotometer (spectrophotometer, manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000), and the cleaning rate was calculated using the following formula. The higher the value of the cleaning rate, the better the cleaning power.

[0108] <Test 3 for evaluating the cleaning power of protein stains> (1) The reflectance (Z value) of protein-stained fabric EMPA-117 (manufactured by Swissatest) was measured using a reflectometer (spectrophotometer, manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000). (2) 0.1 g of protease ProgressUno101L (manufactured by Novozymes) was weighed out and ion-exchanged water was added to make 10 g, thereby preparing a 1% enzyme solution (i). (3) 0.627 g of copolymer 4 having a solids content of 31.9% was weighed out and ion-exchanged water was added to make 1 g, thereby preparing a 10% copolymer solution (ii). (4) 0.633 g of copolymer 5 having a solids content of 31.6% was weighed out and ion-exchanged water was added to make 1 g, thereby preparing a 10% copolymer solution (iii). (5) 0.629 g of copolymer 6 with a solids content of 31.8% was weighed out and ion-exchanged water was added to make 1 g to prepare a 10% copolymer solution (iv). (6) 90 g of pure water was added to 10 g of polyoxyethylene (6) lauryl ether (Kao Emulgen 108, hereinafter also referred to as PAE) and stirred to prepare a 10% surfactant solution (v). (7) 0.25 g of 1% enzyme solution (i), 6.8 g of ion-exchanged water, 0.30 g of 10% copolymer solution (ii), (iii), or (iv), and 3.0 g of 10% surfactant solution (v) were weighed out and homogenized to prepare 10-fold diluted detergent solutions (vi), (vii), and (viii), respectively. (8) 994.2 g of tap water was added to each pot in a Tergot-o-meter (manufactured by Daiei Scientific Co., Ltd., product name: TM-4) and the temperature was adjusted to 15°C. 5.8 g of 10-fold diluted detergent solutions (vi), (vii), and (viii) were added to each pot and stirred for 1 minute. (9) Seven sheets of EMPA-117 were placed in each pot and stirred at 120 ppm for 15 minutes. (10) The soiled cloth was removed from each pot and the water was drained by hand. After removing the liquid from the pot, 1000 g of tap water was added to each pot and the temperature was adjusted to 15°C. The soiled cloth was returned to the pot and stirred at 120 rpm for 5 minutes. (11) The procedure in (10) was repeated once more. (12) After drying at room temperature, the reflectance (Z value) of the soiled cloth was measured again using the above-mentioned spectrophotometer (spectrophotometer, manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000), and the cleaning rate was calculated using the following formula. The higher the value of the cleaning rate, the better the cleaning power.

[0109] <Detergency Evaluation Test 4 Including Soil Release Effect> (Fabric Pretreatment) 55 g of an aqueous solution was prepared using tap water, adjusted to 1000 ppm of Emulgen 108 (Kao Corporation), 100 ppm of the copolymer obtained in the example (based on non-volatile content), and 8.3 ppm of protease Progress Uno 101L (Novozymes). 2.7 g of polyester crepe cut into 5 x 5 cm pieces was added to this aqueous solution and stirred for 10 minutes using a roller shaker. After stirring, the solution was dehydrated and air-dried for 1 day. (Preparation of Soiled Fabric) 61.5 g of olive oil, 37 g of oleic acid, 1 g of iron (III) oxide, and 0.5 g of oil red were mixed to prepare an oil-stained solution. 15 μL of this contaminated solution was dropped onto the polymer-treated fabric obtained by the above pretreatment and left at 40 °C for 1 hour to prepare a soiled fabric. (Detergency Evaluation) (1) Preparation of Surfactant Aqueous Solution 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. (2) Detergency Test A Tergot-o-meter was set to 25 ° C., and 497.5 g of tap water and 0.875 g of the surfactant aqueous solution (1) were added to a pot. The copolymer aqueous solution was adjusted to 1% so that the copolymer concentration in the pot was 17.5 ppm in terms of nonvolatile content, and mixed. Then, 0.73 g of protease Progress Uno 101L adjusted to 0.1% with ion-exchanged water was added and mixed. Five soiled cloths whose Z values ​​had been measured in advance using a spectrophotometer (Nippon Denshoku Industries Co., Ltd., product name: SE7700) and a liquor ratio adjustment cloth were added to a 16.7 g pot and washed by stirring at 120 rpm for 10 minutes. The water in the pot was discarded, and after rinsing once for 3 minutes, the cloth was dehydrated and air-dried for 1 day. After air-drying, the Z value of the soiled cloth after washing was measured again using a color difference meter, and the cleaning rate was calculated using the following formula. Based on the obtained cleaning rate, the detergency was evaluated according to the following criteria: +++: The cleaning rate differs by 40% or more from the evaluation result of a product to which no polymer was added. ++: The cleaning rate differs by 20% or more but less than 40% from the evaluation result of a product to which no polymer was added. +: The cleaning rate differs by 5% or more but less than 20% from the evaluation result of a product to which no polymer was added. -: The cleaning rate differs by less than 5% from the evaluation result of a product to which no polymer was added.

[0110] <Production Example 1> 84.8 g of pure water was placed in a separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer, and after flowing nitrogen at 200 ml / min for 60 minutes while stirring, the temperature was raised to 70°C. After the nitrogen flow was increased to 50 ml / min, into the polymerization reaction system kept at a constant temperature of 70°C under stirring, a monomer solution consisting of 48 g of methoxypolyethylene glycol monoacrylate (average number of moles of ethylene oxide added: 23, trade name "AM-230G" manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as PGA23E), 12 g of dimethylaminoethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter referred to as DAM), 25.9 g of pure water, 4.36 g of acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.5 g of 3-mercaptopropionic acid (manufactured by SC Organic Chemical Industries, Ltd.); and an initiator aqueous solution consisting of 24.4 g of an 8% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (trade name "V-50" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were dropped from separate dropping nozzles. The monomer solution and the initiator aqueous solution were added dropwise simultaneously for 180 minutes and 240 minutes, respectively. After the completion of all the additions, the reaction solution was maintained at 70°C for another 60 minutes to mature the solution, thereby completing the polymerization and obtaining Copolymer 1.

[0111] <Production Example 2> 50 g of ethanol was placed in a separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer, and after flowing nitrogen at 100 ml / min for 60 minutes while stirring, the temperature was raised to 70°C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 68.4 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 23, trade name "M-230G" manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as PGM23E), 5.36 g of methacrylic acid, 40.5 g of DAM, 37.9 g of ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 14.7 g of acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 20.3 g of benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter referred to as BnMA); and an initiator aqueous solution consisting of 43.2 g of a 6% ethanol solution of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were each added dropwise from separate dropping nozzles into the polymerization reaction system under stirring and kept at a constant temperature of 70°C. The monomer solution and the initiator aqueous solution were added dropwise simultaneously for 180 minutes and 240 minutes, respectively. After the completion of all the additions, the reaction solution was maintained at 70°C for another 60 minutes to mature the solution, thereby completing the polymerization and obtaining Copolymer 2.

[0112] <Production Example 3> 37.8 g of ion-exchanged water was placed in a separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer, and after flowing nitrogen at 200 ml / min for 60 minutes while stirring, the temperature was raised to 70°C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 33.3 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 25, hereinafter also referred to as PGM25E), 2.7 g of methacrylic acid, 9.0 g of DAM, 21.0 g of ion-exchanged water, 3.3 g of acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.74 g of mercaptopropionic acid; and an initiator aqueous solution consisting of 42.2 g of a 1.5 wt % aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (trade name "V-50" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were each added dropwise from separate dropping nozzles into the polymerization reaction system, which was kept at a constant temperature of 70°C under stirring. The monomer solution and the initiator aqueous solution were added dropwise simultaneously, with the monomer solution added over 180 minutes and the initiator aqueous solution added over 240 minutes. After the completion of all the dropwise addition, the reaction solution was kept at 70° C. for an additional 60 minutes to mature, thereby completing the polymerization and obtaining Copolymer 3.

[0113] Production Example 4 60.6 g of pure water was placed in a separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer, and after flowing nitrogen at 200 ml / min for 60 minutes while stirring, the temperature was raised to 70°C. After the nitrogen flow was increased to 50 ml / min, into the polymerization reaction system kept at a constant temperature of 70°C under stirring, a monomer solution consisting of 48 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 23, trade name "M-230G" manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as PGM23E), 12 g of dimethylaminoethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter referred to as DAM), 25.9 g of pure water, 4.35 g of acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.5 g of 3-mercaptopropionic acid (manufactured by SC Organic Chemical Industries, Ltd.); and an initiator aqueous solution consisting of 46.6 g of a 4% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (trade name "V-50" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were dropped from separate dropping nozzles. The monomer solution and the aqueous initiator solution were added dropwise simultaneously for 180 minutes and 240 minutes, respectively. After the completion of all the additions, the reaction solution was maintained at 70°C for another 60 minutes to mature the solution, thereby completing the polymerization and obtaining Copolymer 4.

[0114] Production Example 5 76.3 g of pure water was placed in a separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer, and after flowing nitrogen at 200 ml / min for 60 minutes while stirring, the temperature was raised to 70°C. After the nitrogen flow was increased to 50 ml / min, into the polymerization reaction system kept at a constant temperature of 70°C under stirring, a monomer solution consisting of 54 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 23, trade name "M-230G" manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as PGM23E), 6 g of dimethylaminoethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter referred to as DAM), 25.9 g of pure water, 2.18 g of acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.4 g of 3-mercaptopropionic acid (manufactured by SC Organic Chemical Industries, Ltd.); and an initiator aqueous solution consisting of 35.3 g of a 4% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (trade name "V-50" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were each dropped from separate dropping nozzles. The monomer solution and the aqueous initiator solution were added dropwise simultaneously for 180 minutes and 240 minutes, respectively. After the completion of all the additions, the reaction solution was maintained at 70°C for another 60 minutes to mature the solution and complete the polymerization, thereby obtaining Copolymer 5.

[0115] Production Example 6 84.2 g of pure water was placed in a separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer, and after flowing nitrogen at 200 ml / min for 60 minutes while stirring, the temperature was raised to 70°C. After the nitrogen flow was increased to 50 ml / min, into the polymerization reaction system kept at a constant temperature of 70°C under stirring, a monomer solution consisting of 57 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 23, trade name "M-230G" manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as PGM23E), 3.0 g of dimethylaminoethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter referred to as DAM), 25.8 g of pure water, 1.09 g of acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.3 g of 3-mercaptopropionic acid (manufactured by SC Organic Chemical Industries, Ltd.); and an initiator aqueous solution consisting of 28.6 g of a 4% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (trade name "V-50" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were dropped from separate dropping nozzles. The monomer solution and the aqueous initiator solution were added dropwise simultaneously for 180 minutes and 240 minutes, respectively. After the completion of all the additions, the reaction solution was maintained at 70°C for another 60 minutes to mature the solution and complete the polymerization, thereby obtaining Copolymer 6.

[0116] <Production Example 7> A separable glass flask equipped with a thermometer, reflux condenser, and stirrer was charged with 53.1 g of ethanol, and after stirring, nitrogen was flowed at 200 ml / min for 60 minutes, and the temperature was raised to 70 ° C. After the nitrogen flow was reduced to 50 ml / min, a monomer solution consisting of 56.0 g of PGM25E, 4.7 g of methacrylic acid, 27.0 g of DAM, 36.6 g of ethanol, 9.8 g of acetic acid, and 47.3 g of BnMA was added dropwise to the polymerization reaction system under stirring at a constant temperature of 70 ° C.; and an aqueous initiator solution consisting of 50.4 g of a 4% ethanol solution of V-65 were each added dropwise from separate dropping nozzles. With regard to the dropping time, the monomer solution and the aqueous initiator solution were added dropwise simultaneously, the monomer solution was added dropwise for 180 minutes, and the aqueous initiator solution was added dropwise for 240 minutes. After the completion of all dropping, the reaction solution was maintained at 70 ° C. for an additional 60 minutes to mature, and the polymerization was completed, yielding Copolymer 7.

[0117] <Production Example 8> A separable glass flask equipped with a thermometer, reflux condenser, and stirrer was charged with 58.5 g of ethanol, and after stirring, nitrogen was flowed at 200 ml / min for 60 minutes, and the temperature was raised to 70 ° C. After the nitrogen flow was reduced to 50 ml / min, a monomer solution consisting of 93.0 g of PGM23E, 7.8 g of methacrylic acid, 28.8 g of DAM, 66.2 g of ethanol, 10.5 g of acetic acid, and 14.4 g of BnMA was added dropwise to the polymerization reaction system under stirring at a constant temperature of 70 ° C.; and an aqueous initiator solution consisting of 40.9 g of a 4% ethanol solution of V-65 were each added dropwise from separate dropping nozzles. With regard to the dropping time, the monomer solution and the aqueous initiator solution were added dropwise simultaneously, the monomer solution was added dropwise for 180 minutes, and the aqueous initiator solution was added dropwise for 240 minutes. After the completion of all the dropping, the reaction solution was maintained at 70 ° C. for an additional 60 minutes to mature, and the polymerization was completed, and copolymer 8 was obtained.

[0118] <Production Example 9> A separable glass flask equipped with a thermometer, reflux condenser, and stirrer was charged with 60.7 g of ethanol, and after stirring, nitrogen was flowed at 200 ml / min for 60 minutes, and the temperature was raised to 70 ° C. After the nitrogen flow was reduced to 50 ml / min, a monomer solution consisting of 47.3 g of PGM25E, 4.0 g of methacrylic acid, 50.0 g of DAM, 38.6 g of ethanol, 18.1 g of acetic acid, and 33.8 g of BnMA was added dropwise to the polymerization reaction system under stirring at a constant temperature of 70 ° C.; and an aqueous initiator solution consisting of 34.5 g of a 6-ethanol solution of V-65 were each added dropwise from separate dropping nozzles. With regard to the dropping time, the monomer solution and the aqueous initiator solution were added dropwise simultaneously, the monomer solution was added dropwise for 180 minutes, and the aqueous initiator solution was added dropwise for 240 minutes. After the completion of all dropping, the reaction solution was maintained at 70 ° C. for an additional 60 minutes to mature, and the polymerization was completed, and Copolymer 9 was obtained.

[0119] The mass % of the monomers used in Production Examples 1 to 9 and the weight average molecular weights of Copolymers 1 to 9 are shown in Table 1.

[0120]

[0121] Table 2 shows the results of protein stain detergency test 1 for Examples 1 and 2 using copolymers 1 and 2, and Comparative Example 1, a system not using any copolymer.

[0122]

[0123] Table 3 shows the results of protein stain detergency test 2 for Example 3, which used copolymer 3, and Comparative Example 2, which did not use any copolymer.

[0124]

[0125] Table 4 shows the results of protein stain detergency test 3 for Examples 4, 5 and 6, which used copolymers 4, 5 and 6, and Comparative Example 3, which did not use any copolymer.

[0126]

[0127] Table 5 shows the results of protein stain detergency test 3 for Examples 7 and 8, in which copolymers 7 and 8 were used instead of copolymers 4, 5 and 6, and for Comparative Example 4, in which no copolymer was used.

[0128]

[0129] Table 6 shows the results of Test 4 for Detergency Evaluation, including Soil Release Effect, conducted on Examples 9, 10, and 11, which used Copolymers 3, 4, and 9, and Comparative Example 5, which did not use any copolymer.

[0130]

Claims

1. A composition comprising an amino group-containing copolymer having a structural unit (a) derived from an amino group-containing monomer represented by the following general formula (1) or its acid-neutralized product, a structural unit (b) derived from a monomer having a polyalkylene glycol chain, and a structural unit (d) derived from an unsaturated carboxylic acid monomer, and an enzyme. 【Chemistry 1】 (In general formula (1), R １ , R ２ , R ３ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ４ , R ５ Each of these independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms, and X represents a divalent linking group. However, an asterisk represents an atom included in another structural unit of the same or different type to which the structural unit represented by general formula (1) is bonded.

2. Furthermore, the composition according to claim 1, further comprising a surfactant.

3. The composition according to claim 1 or 2, wherein the amino group-containing copolymer further comprises a structural unit (c) derived from a hydrophobic group-containing monomer.

4. The composition according to claim 1 or 2, wherein the amino group-containing copolymer has a content of structural unit (a) of 2% by mass or more and 50% by mass or less based on 100% by mass of all structural units.

5. The composition according to claim 1 or 2, wherein the amino group-containing copolymer has a content of structural unit (b) of 5% by mass or more and 98% by mass or less based on 100% by mass of all structural units.

6. The composition according to claim 1 or 2, wherein the amino group-containing copolymer has a content of structural unit (c) of 0% by mass or more and 50% by mass or less based on 100% by mass of all structural units.

7. The composition according to claim 1 or 2, wherein the amino group-containing copolymer has a content of structural unit (d) of 0% by mass or more and 20% by mass or less based on 100% by mass of all structural units.

8. The composition according to claim 1 or 2, wherein the amino group-containing copolymer has a weight-average molecular weight of 4,000 or more and 500,000 or less.

9. The composition according to claim 1 or 2, wherein the content of the enzyme is 0.01 to 10% by mass based on 100% by mass of the composition.

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