Detergent composition

Abstract

The purpose of the present disclosure is to provide a detergent composition that is suitable for use in detergents for clothing and the like, and that has excellent sebum stain detergency and excellent prevention of soil redeposition. The present disclosure provides a detergent composition which contains an amino group-containing copolymer that has a structural unit (a) derived from an amino group-containing monomer represented by general formula (1-1) and / or general formula (1-2) (in general formula (1-1) and / or general formula (1-2), each of R1, R2, and R3 independently represents a hydrogen atom or an alkyl group having 1-5 carbon atoms; each of R4 and R5 independently represents a hydrogen atom or an organic group having 1-12 carbon atoms; X represents a direct bond or a divalent linking group; Y - represents an anion; and 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 (1-1) and / or general formula (1-2) is bonded) and a structural unit (b) derived from a monomer having a polyalkylene glycol chain, and a sulfonic acid group-containing anionic surfactant. The ratio of the amount of the sulfonic acid group-containing anionic surfactant to the total amount of surfactants contained in the detergent composition is 0.5-90 mass%.

Description

Detergent composition

[0001] This disclosure relates to a detergent composition.

[0002] In recent years, changes in laundry practices, such as shorter washing times and bulk washing, have led to a demand for detergents used for washing clothes and other items that can effectively remove a variety of stains.

[0003] For example, Patent Document 1 proposes a combination of nonionic and anionic surfactants to achieve both cleaning performance against stains of different properties, but it does not mention re-soiling prevention.

[0004] Incidentally, regarding the ability to remove sebum stains from clothing, pre-treating the fibers with compounds that adsorb to the fibers can be expected to make it easier to remove stains during washing. This function is called soil release, and various compounds have been proposed. Patent document 2 discloses a polymer that exhibits high sebum stain removal performance due to its high soil release effect, but in light of recent changes in washing habits such as washing in batches, there has been a demand for a polymer that also has higher re-soiling prevention properties.

[0005] Japanese Patent Publication No. 2018-24855, International Publication No. 2022 / 215652

[0006] As mentioned above, detergent compositions have been developed to improve the ability to remove sebum stains and prevent re-soiling in detergents. It is generally known that incorporating nonionic surfactants improves sebum stain removal and incorporating anionic surfactants improves re-soiling prevention, but there was still room for improvement in achieving both of these performances simultaneously.

[0007] This disclosure is made in view of the above-mentioned circumstances and aims to provide a detergent composition that is excellent in sebum stain removal and re-soiling prevention.

[0008] The present inventors, after conducting various studies on detergent compositions, discovered that a detergent composition comprising an amino group-containing copolymer having a structure derived from an amino group-containing monomer and a polyalkylene glycol chain, and a predetermined amount of a sulfonic acid group-containing anionic surfactant, excels in both sebum stain removal and re-soiling prevention, and thus conceived that it can successfully solve the above-mentioned problems, leading to this disclosure.

[0009] This disclosure encompasses the following detergent compositions: [1] A detergent 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 (1-1) and / or (1-2) and a structural unit (b) derived from a monomer having a polyalkylene glycol chain, and a sulfonic acid group-containing anionic surfactant, wherein the ratio of the sulfonic acid group-containing anionic surfactant to the total amount of surfactants contained in the detergent composition is 0.5 to 90% by mass.

[0010] (In general formulas (1-1) and / or (1-2), 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 direct bond or a divalent linking group. －(1) represents an anion. However, the asterisk represents an atom included in another structural unit of the same or different type to which the structural unit represented by general formula (1-1) and / or (1-2) is bonded.) [2] The detergent composition according to [1], further comprising a nonionic surfactant. [3] The detergent composition according to [1] or [2], wherein the amino group-containing copolymer further comprises a structural unit (c) derived from a hydrophobic group-containing monomer. [4] The detergent composition according to any one of [1] to [3], wherein the amino acid-containing copolymer further comprises a structural unit (d) derived from an unsaturated carboxylic acid. [5] The detergent composition according to any one of [1] to [4], wherein the weight-average molecular weight of the amino group-containing copolymer is 4,000 or more and 500,000 or less. [6] The detergent composition according to any one of [1] to [5], wherein the content of the sulfonic acid group-containing anionic surfactant is 1 to 60% by mass with respect to 100% by mass of the detergent composition. [7] A detergent composition according to any one of [2] to [6] above, wherein, when the total amount of the sulfonic acid group-containing anionic surfactant and the nonionic surfactant is 100% by mass, the content ratio of the sulfonic acid group-containing anionic surfactant is 0.5 to 90% by mass. [8] A laundry detergent composition comprising the detergent composition according to any one of [1] to [7] above.

[0011] The detergent composition disclosed herein, by combining an amino group-containing copolymer and a sulfonic acid group-containing anionic surfactant in a specific ratio, can exhibit superior re-soiling prevention effects and is suitable for use in detergents and the like due to its excellent sebum stain removal and re-soiling prevention properties.

[0012] The following describes preferred forms of this disclosure, but this disclosure is not limited to the descriptions below and may be modified and applied as appropriate, provided that the gist of this disclosure is not altered. Furthermore, combinations of two or more of the individual preferred forms of this disclosure described below also constitute preferred forms of this disclosure.

[0013] The detergent composition of this disclosure comprises an amino group-containing copolymer (hereinafter also referred to as the copolymer of this disclosure) and a sulfonic acid group-containing anionic surfactant. The detergent composition of this disclosure comprises the copolymer and the sulfonic acid group-containing anionic surfactant, and by setting the ratio of the sulfonic acid group-containing anionic surfactant to the total amount of surfactants to 0.5 to 90% by mass, it exhibits excellent sebum stain removal and re-soiling prevention properties. Furthermore, the detergent composition of this disclosure exhibits excellent soil release properties, i.e., the effect of making dirt easier to remove during washing by pre-treating the fibers (pre-treatment step), and also exhibits excellent primary cleaning properties, which is the ability to effectively remove dirt attached to the target object in a single washing operation without going through a pre-treatment step.

[0014] The content of the copolymer in the detergent composition of this disclosure is not particularly limited, but from the viewpoint of sebum stain removal performance, it is preferably 0.1 to 10% by mass per 100% by mass of the detergent composition. More preferably it is 0.2 to 5% by mass, and even more preferably 0.3 to 3.5% by mass.

[0015] The content of the sulfonic acid group-containing anionic surfactant in the detergent composition of this disclosure may be 0.5 to 90% by mass of the total amount of surfactants, but is preferably 1 to 80% by mass. More preferably 2 to 70% by mass, and particularly preferably 5 to 60% by mass.

[0016] The content of the sulfonic acid group-containing anionic surfactant in the detergent composition of this disclosure is not particularly limited, but from the viewpoint of improving re-soiling prevention, it is preferably 1 to 60% by mass per 100% by mass of the detergent composition. More preferably it is 2 to 50% by mass, even more preferably 3 to 30% by mass, and most preferably 5 to 10% by mass.

[0017] In the detergent composition of this disclosure, the content ratio of the copolymer to 100% by mass of the sulfonic acid group-containing anionic surfactant is preferably 0.01 to 50% by mass, from the viewpoint of improving the ability to clean sebum stains. More preferably it is 0.05 to 30% by mass, and even more preferably 0.1 to 10% by mass.

[0018] The detergent composition of this disclosure may contain a nonionic surfactant in addition to the above-mentioned amino group-containing copolymer and sulfonic acid group-containing anionic surfactant. The ratio of sulfonic acid group-containing anionic surfactant to nonionic surfactant is not particularly limited, but when the total amount of sulfonic acid group-containing anionic surfactant and nonionic surfactant is 100% by mass, the content of sulfonic acid group-containing anionic surfactant is preferably 0.5 to 90% by mass from the viewpoint of improving both sebum stain removal performance and re-soiling prevention performance. More preferably it is 1 to 70% by mass, 3 to 30% by mass, and even more preferably 5 to 15% by mass. In one embodiment, it is also preferable that the content of sulfonic acid group-containing anionic surfactant is 50 to 90% by mass, 55 to 85% by mass, or 60 to 80% by mass relative to the total amount of sulfonic acid group-containing anionic surfactant and nonionic surfactant at 100% by mass.

[0019] In the above-mentioned detergent composition, the mass ratio of surfactant to amino group-containing copolymer (surfactant / amino group-containing copolymer) is preferably 1 to 200. More preferably 1 to 150, even more preferably 1 to 100, even more preferably 5 to 80, and particularly preferably 10 to 50.

[0020] The detergent compositions of this disclosure may contain other components besides the amino group-containing copolymer, sulfonic acid group-containing anionic surfactant, and nonionic surfactant. These other components are not particularly limited, but examples include antibacterial agents, anti-redeposition agents such as sodium carboxymethylcellulose, 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, enzymes, dyes, and solvents. In the case of powder detergent compositions, zeolite is also preferably included. The content of these other components is not particularly limited, but is preferably 0.1 to 75% by mass, based on 100% by mass of the detergent composition. More preferably, it is 0.5 to 65% by mass.

[0021] Hereinafter, the essential components and optional components contained in the detergent composition of the present disclosure will be further described. [Amino group-containing copolymer of the present disclosure] The amino group-containing copolymer contained in the detergent 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 the amino group-containing monomer described below and a structural unit (b) derived from a monomer having a polyalkylene glycol chain. By including the copolymer of the present disclosure and a sulfonic acid group-containing anionic surfactant, the detergent composition of the present disclosure can be obtained. Furthermore, by using a detergent composition containing a nonionic surfactant, excellent sebum stain detergency and re-staining prevention performance can be exhibited.

[0022] In addition, due to the increasing environmental awareness in recent years, laundry detergents with a low environmental impact are in demand. Therefore, it is desirable to reduce the total amount of surfactant used per laundry. Since the detergent composition of the present disclosure is excellent in sebum stain detergency and re-staining prevention performance, it has the characteristic of being excellent in the effect of reducing the amount of surfactant used per laundry.

[0023] <Structural unit (a) derived from amino group-containing monomer> The structural unit (a) derived from the amino group-containing monomer of the present disclosure is a structural unit represented by the following general formula (1-1) and / or (1-2).

[0024] In general formula (1-1) and / or (1-2), R １ , R ２ , R ３ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ４ , R ５ each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms, and X represents a direct bond or a divalent linking group. Y －represents an anion. 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 (1-1) and / or (1-2) is bonded. In this disclosure, "an atom contained in another structural unit of the same type" means, for example, an atom contained in a structural unit represented by another general formula (1-1) if the structural unit is represented by general formula (1-1), and "an atom contained in another structural unit of different type" means, for example, an atom contained in a structural unit other than the structural unit represented by general formula (1-1) if the structural unit is represented by general formula (1-1). In the above-mentioned structural unit derived from the amino basic monomer, in general formula (1-1) and / or (1-2), -X- is directly bonded, or -C(=O)-O- or -C(=O)-O-(CH ２ )n-(n is 1-5) or-C(=O)-N(-H)-(CH ２ It is preferable that the structural unit is represented as n-(n is 1 to 5). In particular, -X- is -C(=O)-O-(CH ２ It is preferable that n is -, more preferably that n = 1 to 3, and particularly preferably that n = 2.

[0025] The above Y － The anions are not particularly limited, but examples include halide ions such as chloride ions, bromide ions, and iodide ions; and organic acid ions such as acetate ions and citrate ions. Halide ions are preferred among these.

[0026] The above R ４ , R ５ The organic group in is not particularly limited, but a hydrocarbon group is preferred. The hydrocarbon group may have a chain structure or a ring structure, but a chain structure is preferred. When the hydrocarbon group has a chain structure, it may be linear or branched. Preferred hydrocarbon groups are alkyl groups, alkenyl groups, aryl groups, and aralkyl groups, with alkyl groups being more preferred. The number of carbon atoms in the organic group is preferably 1 to 10, more preferably 1 to 8, particularly preferably 1 to 5, even more preferably 1 to 2, and most preferably 1.

[0027] Examples of the alkyl groups mentioned above include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, stearyl, and eicosyl groups.

[0028] Examples of the above alkenyl groups include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, octadecenyl group, and ecosenyl group. Examples of the above alkynyl groups include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octinyl group, noninyl group, decinyl group, dodecinyl group, octadecinyl group, and ecosenyl group.

[0029] Examples of the aryl groups mentioned above include phenyl group, methylphenyl group, 1-methoxy-4-methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, butylmethylphenyl group, dimethylphenyl group, diethylphenyl group, dibutylphenyl group, biphenyl group, naphthyl group, etc. Examples of the aralkyl groups mentioned above include benzyl group, biphenylmethyl group, biphenylethyl group, naphthylmethyl group, naphthylethyl group, etc.

[0030] The above-mentioned 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 an acid-neutralized product of a primary to tertiary amino group, but is not limited thereto.

[0031] R in the above general formula (2) ４ , R ５ R is the R in the above general formula (1-1) or (1-2). ４ , R ５ It is the same as this.

[0032] The structural unit (a) derived from the above amino group-containing monomer is formed, for example, by radical polymerization of the amino group-containing monomer. The above amino group-containing monomers specifically include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, and other N,N-dialkylamino group-containing (meth)acrylates, and their neutralization products with acids such as hydrochloric acid and acetic acid; N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, and other N,N-dialkylamino group-containing (meth)acrylamides, 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, and 2-(tert-butylamino) (meth)acrylic acid. Monoalkylamino group-containing (meth)acrylates such as tyl and their neutralized 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, monoethylaminopropyl (meth)acrylamide and their neutralized products with acids such as hydrochloric acid and acetic acid; (meth)acrylic acid and alkali such as (meth)acrylic acid-2-aminoethyl Examples include esters with nolamines and their neutralized products with acids such as hydrochloric acid and acetic acid; N,N-diallylmethylamine and its neutralized products with acids such as hydrochloric acid and acetic acid; allylamine and its neutralized products with acids such as hydrochloric acid and acetic acid; addition reaction products of unsaturated monomers having cyclic ether-containing groups with 2 to 8 carbon atoms, such as 1-allyloxy-3-dibutylamino-2-ol and 1-allyloxy-3-diethanolamino-2-ol, and amine compounds having 1 to 24 carbon atoms, and their neutralized products with acids such as hydrochloric acid and acetic acid.

[0033] The structural unit (a) derived from the above amino group-containing monomer is preferably the following general formula (3), which is a structural unit derived from N,N-dimethylaminoethyl (meth)acrylate.

[0034] R in the above general formula (3) ６ The '' represents a hydrogen atom or a methyl group. 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 (3) is bonded. Most preferably, the structural unit is derived from N,N-dimethylaminoethyl methacrylate.

[0035] In the copolymer of the present disclosure, the content of structural unit (a) derived from the amino group-containing monomer is 5% by mass or more and 80% by mass or less, preferably 7% by mass or more and 70% by mass or less, and more preferably 10% by mass or more and 60% by mass or less, based on 100% by mass of structural units derived from all monomers constituting the copolymer of the present disclosure (hereinafter also referred to as total structural units). In one embodiment, the content of structural unit (a) may be 13% by mass or more and 50% by mass or less, or 15% by mass or more and 45% by mass or less. By being within the above range, the proportion of cationic sites becomes appropriate, and when the detergent composition of the present disclosure is used as a detergent composition, the cleaning power tends to improve.

[0036] <Structural unit (b) derived from a monomer having a polyalkylene glycol chain> The structural unit (b) derived from a monomer having a polyalkylene glycol chain according to 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).

[0037] In the formula, R ７ , R ８ , R ９Each of the following independently represents a hydrogen atom or an optionally substituted C1-C5 alkyl group; Z represents a hydrogen atom, an optionally substituted C1-C30 hydrocarbon group, a hydroxyl group, or a carboxyl group, a sulfonic acid group, a phosphate group, an amino group, or a salt thereof; A represents an optionally substituted C1-C10 alkylene group; q represents the average number of moles added of (AO), and is a number from 1 to 200; n represents a number from 0 to 4; m represents 0 or 1.

[0038] The above R ７ , R ８ , R ９ Each of these is independently a hydrogen atom or a C1-C5 alkyl group which may have substituents, and the substituent is preferably at least one hydrophilic group selected from the group consisting of hydroxyl groups, carboxyl groups, sulfonic acid groups, phosphate groups, amino groups and salts thereof.

[0039] 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 Each is preferably independently a hydrogen atom or a methyl group. More preferably R ７ , R ９ is a hydrogen atom, R ８ is a hydrogen atom or a methyl group. More preferably, R ７ , R ９ is a hydrogen atom, R ８ This is a methyl group.

[0040] The above Z represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms which may have substituents, a hydroxyl group, or a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, or a salt thereof. The above hydrocarbon group is not particularly limited and includes chain 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 above hydrocarbon group may be branched, and in the case of branching, the number of carbon atoms of the hydrocarbon group means the total number of carbon atoms of the main chain and the branched chain. The substituents that the above hydrocarbon group may have are not particularly limited, but at least one hydrophilic group selected from the group consisting of hydroxyl groups, carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups, and salts thereof is preferred.

[0041] Examples of the alkyl groups mentioned above include ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, dodecyl group, stearyl group, and eicosyl group.

[0042] Examples of the above alkenyl groups include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, octadecenyl group, and ecosenyl group. Examples of the above alkynyl groups include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octinyl group, noninyl group, decinyl group, dodecinyl group, octadecinyl group, and ecosenyl group.

[0043] Examples of the aryl groups mentioned above include phenyl group, methylphenyl group, 1-methoxy-4-methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, butylmethylphenyl group, dimethylphenyl group, diethylphenyl group, dibutylphenyl group, biphenyl group, naphthyl group, etc. Examples of the aralkyl groups mentioned above include benzyl group, biphenylmethyl group, biphenylethyl group, naphthylmethyl group, naphthylethyl group, etc.

[0044] Examples of the above-mentioned cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of the above-mentioned cycloalkenyl groups include cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl groups.

[0045] The hydrocarbon group is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. The hydrocarbon group has preferably 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, even more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 5 carbon atoms. The Z is preferably a hydrogen atom or a methyl group.

[0046] The above A represents an alkylene group having 1 to 10 carbon atoms, which may have substituents. 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 phosphoric acid group, a secondary or tertiary amino group, and salts thereof. The q oxyalkylene groups of AO in the polyalkylene glycol represented by (AO)q may all be the same or different. The alkylene group represented by A is preferably having 2 to 10 carbon atoms, and more preferably 2 to 4 carbon atoms.

[0047] Examples of oxyalkylene groups represented by AO include oxyethylene, oxypropylene, oxybutylene, oxyisobutylene, oxy2,3-butylene, oxystyrene, and oxyalkylenes having 2 to 10 carbon atoms. More preferably, oxyalkylene groups having 2 to 4 carbon atoms, such as oxyethylene, oxypropylene, and oxybutylene, are used, and even more preferably, oxyethylene and oxypropylene. Note that the oxyalkylene group represented by AO is not limited to a group formed by an addition reaction of oxyalkylene groups. Furthermore, if the polyalkylene glycol is an adduct of two or more oxyalkylene groups, it may be in any form such as random addition, block addition, or alternating addition. It is preferable that the polyalkylene glycol contains an oxyethylene group as an essential component, more preferably 50 mol% or more being oxyethylene groups, and even more preferably 90 mol% or more being oxyethylene groups.

[0048] The above q represents the average number of moles of AO added, and is a number from 1 to 200. Preferably it is 1 to 180, more preferably 2 to 150, even more preferably 2 to 100, even more preferably 2 to 80, particularly preferably 2 to 50, and most preferably 20 to 30. In one embodiment, q is preferably 2 to 180, more preferably 3 to 150, even more preferably 4 to 100, even more preferably 5 to 80, and particularly preferably 9 to 50.

[0049] In the above, n represents a number from 0 to 4, and m represents 0 or 1. Preferably, n is from 0 to 3, more preferably from 0 to 2, and even more preferably 0. More preferably, m is 1.

[0050] The structural unit (b) having the polyalkylene glycol chain described above is formed, for example, by radical polymerization of a monomer having a polyalkylene glycol chain. Specifically, the monomer having a polyalkylene glycol chain can be, for example, polyalkylene glycol mono(meth)acrylates such as (poly)ethylene glycol mono(meth)acrylate and (poly)propylene glycol mono(meth)acrylate; alkoxy polyalkylene glycol mono(meth)acrylates such as methoxy(poly)ethylene glycol mono(meth)acrylate and methoxy(poly)propylene glycol mono(meth)acrylate; or (poly)alkylene glycol monomers such as 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, or 2-methyl-3-buten-1-ol, to which 10 to 100 moles of oxyalkylene groups are added. (Poly)ethylene glycol mono(meth)acrylate and methoxy(poly)ethylene glycol mono(meth)acrylate are particularly preferred.

[0051] In the copolymer of the present disclosure, the content of structural unit (b) having a polyalkylene glycol chain is preferably 5% by mass or more and 95% by mass or less, more preferably 20% by mass or more and 80% by mass or less, even more preferably 30% by mass or more and 70% by mass or less, and particularly preferably 40% by mass or more and 65% by mass or less, based on 100% by mass of structural units derived from all monomers constituting the copolymer of the present disclosure. In one embodiment, the content of structural unit (b) may be 45% by mass or more and 60% by mass or less. By being within the above range, the proportion of hydrophilic parts becomes appropriate, and when the detergent composition of the present disclosure is used as a laundry detergent composition, the cleaning power tends to improve.

[0052] <Structural unit (c) derived from hydrophobic monomer> The copolymer of this 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 this disclosure that constitutes the structural unit (c) derived from the hydrophobic monomer is not particularly limited as long as its solubility parameter in a homopolymer obtained by homopolymerization is 13 or less. 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) of homopolymer (cal / cm ３ ) １／２ The δ is calculated based on the evaporation energy (Δei) and molar volume (Δvi) of the constituent units forming the polymer, using the following calculation method: δ = (Δei / Δvi) １／２ (cal / cm ３ ) １／２

[0053] If the solubility parameter for the homopolymer obtained when the hydrophobic monomer of this disclosure is polymerized alone is 13 or less, the copolymer of this disclosure will have sufficient hydrophobicity and excellent adsorption to hydrophobic fibers. The solubility parameter is preferably 12 or less, and more preferably 11 or less. The solubility parameter is usually 5 or more.

[0054] The hydrophobic monomers of this disclosure are not particularly limited as long as their solubility parameter in the homopolymer is 13 or less, but they are preferably monomers having an ethylenically unsaturated group and an alkyl group having 1 to 30 carbon atoms. Examples of hydrophobic monomers include esters of unsaturated carboxylic acids such as (meth)acrylic acid and alcohols having 1 to 30 carbon atoms, which may have substituents; 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; acrylonitrile, etc.

[0055] The substituents that may be present in the C1 to C30 alcohol which may have the above substituents are any substituents other than hydroxyl groups, oxyalkylene groups, carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups and salts thereof, but examples include halogen atoms. The number of carbon atoms in the C1 to C30 alcohol which may have the above substituents is preferably 2 to 22, more preferably 2 to 16, and even more preferably 4 to 8. Examples of the C1 to C30 alcohol which may have the above substituents are alkyl alcohols with 1 to 30 carbon atoms, aromatic alcohols such as aryl alcohols and aralkyl alcohols with 6 to 30 carbon atoms, etc.

[0056] Examples of alkyl alcohols having 1 to 30 carbon atoms that may have the above substituents 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 eicosyl alcohol.

[0057] Preferred examples of the above-mentioned aromatic alcohols 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.

[0058] The hydrophobic monomer described above is preferably of the following general formula (5);

[0059]

[0060] (General, R １０ , R １１ , R １２ R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, either identical or different. １３ represents a hydrocarbon group having 1 to 30 carbon atoms. ) is a compound represented by the following general formula (6);

[0061] (In the formula, R １０ ~R １３ This is the same as general formula (5). However, the asterisk represents an atom included in another structural unit of the same or different type to which the structural unit represented by general formula (6) is bonded. Preferably, it is a structural unit represented by ). If the amino group-containing copolymer of this disclosure has a structural unit represented by the above general formula (6), the structural unit may be obtained by polymerization using the compound represented by the above general formula (5), or by other methods.

[0062] The above R １０ , R １１ , R １２The alkyl group in 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 It is preferable that R is the same or different hydrogen atom or methyl group. １０ , R １１ is a hydrogen atom, R １２ This is either a hydrogen atom or a methyl group.

[0063] 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.

[0064] The above R １３ The hydrocarbon group in is not particularly limited and includes 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 in the case of branching, the number of carbon atoms in the hydrocarbon group refers to the total number of carbon atoms in the main chain and the branched chain. In one embodiment, the above R １３ The hydrocarbon group in R may or may not have an aromatic group such as an aryl group or an aralkyl group, １３ A form in which is a hydrocarbon group that does not have an aromatic group is also one of the preferred embodiments of the present disclosure.

[0065] The above R １３ The number of carbon atoms in the alkyl group is preferably 2 to 22, more preferably 2 to 16, and particularly preferably 2 to 12. Most preferably 4 to 8. １３ The number of carbon atoms in the aryl group is preferably 6 to 12, more preferably 6 to 10, and particularly preferably 6 to 8.

[0066] The above R １３Examples of alkyl groups in R include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, dodecyl group, stearyl group, eicosyl group, etc. １３ Examples of alkenyl groups in include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, octadecenyl group, eicosenyl group, etc. ７ Examples of alkynyl groups in this context include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octinyl group, noninyl group, desinyl group, dodecynyl group, octadecynyl group, and icosinyl group.

[0067] The above R １３ Examples of aryl groups in this context include phenyl group, methylphenyl group, 1-methoxy-4-methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, butylmethylphenyl group, dimethylphenyl group, diethylphenyl group, dibutylphenyl group, biphenyl group, naphthyl group, etc. Examples of aralkyl groups include benzyl 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, naphthylethyl group, etc.

[0068] The above R １３ Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of cycloalkenyl groups include cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl groups.

[0069] The above R １３The hydrocarbon group in is preferably an aromatic group such as an alkyl group, aryl group, or aralkyl group, and more preferably an alkyl group. The hydrophobic monomer is preferably an alkyl (meth)acrylate or an aromatic (meth)acrylate, and more preferably an alkyl (meth)acrylate.

[0070] Examples of the alkyl (meth)acrylates mentioned above 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 eicosyl (meth)acrylate. Preferably, these are 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. More preferably, these are 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.

[0071] Examples of the above aromatic (meth)acrylates include phenyl (meth)acrylate, benzyl (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, 2-phenylethyl (meth)acrylate, and 4-methylphenyl (meth)acrylate. Examples include acrylates, 4-methylbenzyl (meth)acrylate, 1-methoxy-4-methylphenyl (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, naphthyl (meth)acrylate, naphthylmethyl (meth)acrylate, naphthylethyl (meth)acrylate, etc. Among these, phenyl (meth)acrylate and benzyl (meth)acrylate are preferred.

[0072] In the copolymer of the present disclosure, the content of structural units (c) derived from hydrophobic monomers is preferably 0% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, even more preferably 5% by mass or more and 50% by mass or less, and most preferably 5% by mass or more and 45% by mass or less, based on 100% by mass of structural units derived from all monomers constituting the copolymer of the present disclosure. This range results in an appropriate proportion of hydrophobic sites, and when the detergent composition of the present disclosure is used as a detergent composition, the cleaning power tends to improve. In one embodiment, the content of structural units (c) may be 10% by mass or more, 15% by mass or more, or 20% by mass or more.

[0073] <Structural unit (d) derived from an 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. The structural unit (d) derived from an 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 and an ethylenically unsaturated hydrocarbon group (unsaturated group), but it is preferably a structural unit represented by the following general formula (7).

[0074] In general formula (7), R １４ is a hydrogen atom, a methyl group, or -CH ２ It is a COOH group, R １５ , R １６ These are identical or different hydrogen atoms, methyl groups, ethyl groups, carboxyl groups, or -CH ２ It is a COOH group.

[0075] A preferred form of the above general formula (7) is R １４ However, it is a hydrogen atom or a methyl group, R １５ , R １６ R is the same or different hydrogen atom or carboxyl group. A more preferred form is R １４ However, it is a hydrogen atom or a methyl group, R １５ , R １６ This is a hydrogen atom.

[0076] Examples of unsaturated carboxylic acid monomers used as precursors before the polymerization reaction of structural unit (d) derived from unsaturated carboxylic acid monomers include (meth)acrylic acid, crotonic acid, tigric acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, 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, and their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts, their anhydrides, or half-esters. Among these, (meth)acrylic acid, maleic acid, and their salts are preferred, and (meth)acrylic acid is more preferred.

[0077] The content of structural units (d) derived from unsaturated carboxylic acid monomers in the copolymer of this disclosure is preferably 1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 10% by mass or less, and even more preferably 1% by mass or more and 5% by mass or less, based on 100% by mass of structural units derived from all monomers constituting the copolymer of this disclosure. Being within this range results in an appropriate ratio of hydrophobic to hydrophilic parts, and tends to improve cleaning power when the detergent composition of this disclosure is used as a laundry detergent composition.

[0078] <Structural unit (f) derived from a quaternary ammonium group-containing monomer> The structural unit (f) derived from a quaternary ammonium group-containing monomer is characterized by having a quaternary ammonium group in its structure. The above structural unit (f) is represented by the following general formula (8); (In the formula, R １７ , R １８ , R １９ R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, either identical or different. ２０ , R ２１ , R ２２ represents an organic group having 1 to 12 carbon atoms, either identical or different. X represents a direct bond or a divalent linking group. W － represents an anion. 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 (8) is bonded. Preferably, it is a structural unit represented by ).

[0079] In the above formula (8), R １７ , R １８ , R １９ represents, independently or differently, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 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 still more preferably a methyl group. In the above R １７ , R １８ , R １９ , it is preferable that they are, independently or differently, a hydrogen atom or a methyl group. More preferably, R １７ , R １９ is a hydrogen atom and R １８ is a hydrogen atom or a methyl group. Still more preferably, R １７ , R １９ are hydrogen atoms and R １８ is a methyl group.

[0080] The organic groups in the above R ２０ , R ２１ , R ２２ are not particularly limited, but hydrocarbon groups are preferred. The hydrocarbon group may have a chain structure or a ring structure, but a chain structure is preferred. When the hydrocarbon group has a chain structure, it may be linear or branched. As the hydrocarbon group, an alkyl group, an alkenyl group, an aryl group, or an aralkyl group is preferred. Specific examples thereof are as described for R ４ , R ５ . More preferably, the hydrocarbon group is an alkyl group. Also, the number of carbon atoms of the organic group is preferably 1 to 10, more preferably 1 to 8, particularly preferably 1 to 5, still more preferably 1 to 2, and most preferably 1. In the above formula (8), the divalent linking group represented by -X- is not particularly limited, but a direct bond or a structure represented by -C(=O)-O-, -C(=O)-, -C(=O)-O-(CH ２ )p- (p is 1 to 5), or -C(=O)-N(-H)-(CH ２ )p- (p is 1 to 5) is preferably included. More preferably, -X- is -C(=O)-O-(CH ２) p-. In this case, it is preferable that p = 1 to 3, and more preferably that p = 2.

[0081] The above W － The ions are not particularly limited, but examples include halide ions such as chloride ions, bromide ions, and iodide ions; alkyl sulfate ions such as methyl sulfate ions; and organic acid ions such as acetate ions and citrate ions. Halide ions and alkyl sulfate ions are preferred among these.

[0082] Examples of the above-mentioned quaternary ammonium group-containing monomers include (meth)acrylate-based quaternary ammonium salts such as (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, (meth)acryloyloxyethyldimethylbenzylammonium chloride, and (meth)acryloyloxyethylmethylmorpholinoammonium chloride; (meth)acryloylamide-based quaternary ammonium salts such as (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloylaminoethyltriethylammonium chloride, and (meth)acryloylaminoethyldimethylbenzylammonium chloride; dimethyldiallylammonium methyl sulfate; and trimethylvinylphenylammonium chloride. Among these, (meth)acrylate-based quaternary ammonium salts are preferred, more preferably (meth)acryloyloxyethyltrimethylammonium salts, and even more preferably (meth)acryloyloxyethyltrimethylammonium chloride.

[0083] In the copolymer of the present disclosure, the content of structural units (f) derived from quaternary ammonium group-containing monomers is preferably 0% by mass or more and 50% by mass or less, based on 100% by mass of structural units derived from all monomers constituting the copolymer of the present disclosure. In one embodiment, the content of structural units (f) is preferably 5% by mass or more and 45% by mass or less, more preferably 10% by mass or more and 40% by mass or less, even more preferably 15% by mass or more and 35% by mass or less, and particularly preferably 15% by mass or more and 30% by mass or less.

[0084] <Other monomer-derived structural units (e)> The amino group-containing copolymer of this disclosure may have structural units (a) derived from an amino group-containing monomer, structural units (b) derived from a monomer having a polyalkylene glycol chain, structural units (c) derived from a hydrophobic monomer, and structural units (d) derived from an unsaturated carboxylic acid monomer, as well as structural units (e) derived from other monomers.

[0085] Other monomers are not particularly limited, but examples include sulfonic acid group-containing monomers and their salts such as styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 3-allyloxy-2-hydroxy-1-propanesulfonic acid, and phosphate group-containing monomers such as 2-methachlorooxyethyl acid phosphate.

[0086] In the copolymer of the present disclosure, the content of structural units (e) derived from other monomers is preferably 40% by mass or less, more preferably 30% by mass or less, particularly preferably 20% by mass or less, and most preferably 10% by mass or less, based on 100% by mass of structural units derived from all monomers constituting the copolymer of the present disclosure. A form in which the content of structural units (e) is 0% by mass is also one of the preferred embodiments of the present invention.

[0087] <Physical Properties of the Copolymers of the Disclosure> The amino group-containing copolymers of the Disclosure preferably have 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, 10,000 or more and 200,000 or less is preferred, 10,000 or more and 100,000 or less is more preferred, 12,000 or more and 50,000 or less is even more preferred, 15,000 or more and 40,000 or less is particularly preferred, and 16,000 or more and 30,000 or less is most preferred. When the molecular weight is within the above range, the cleaning power tends to improve when the detergent composition of the Disclosure is used as a laundry detergent composition.

[0088] <Method for producing the amino group-containing copolymer of this disclosure> The method for producing the amino group-containing copolymer of this disclosure is not particularly limited, but it can be produced by polymerizing monomer components. Specific examples and preferred examples of monomer components, as well as preferred proportions of each monomer, are as described above.

[0089] The above-mentioned method for producing the amino group-containing copolymer includes, for example, a step of polymerizing an amino group-containing monomer or its precursor, a monomer having a polyalkylene glycol chain or its precursor, a hydrophobic group monomer or its precursor, and an unsaturated carboxylic acid monomer (hereinafter referred to as the polymerization step). Methods for initiating the polymerization of monomer components in the polymerization step include, for example, adding a polymerization initiator, irradiating with UV light, applying heat, or irradiating with light in the presence of a photopolymerization initiator. In particular, the use of a polymerization initiator is preferred.

[0090] Examples of polymerization initiators 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 the amount of residual monomers. These polymerization initiators may be used alone or in the form of a mixture of two or more.

[0091] The amount of 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, relative to the total amount of monomers constituting the structural units.

[0092] In the polymerization step described above, a chain transfer agent may be used as a molecular weight modifier of the polymer as needed. 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 their salts, as well as mercaptoethanol, thioglycerol, 2-mercaptoethanesulfonic acid, halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, secondary alcohols such as isopropanol and glycerin, phosphorous acid, hypophosphorous acid, hypophosphite and their hydrates, etc., as well as bisulfite (salt) and compounds that can generate bisulfite (salt) (bisulfite (salt), pyrosulfite (salt), dithionic acid (salt), sulfite (salt), etc.). Among these, compounds having a mercapto group are preferred, and mercapto group-containing compounds having a carboxyl group are more preferred.

[0093] The amount of chain transfer agent used in the production of the copolymer of this disclosure is preferably 0.1 mol% to 20 mol%, more preferably 0.2 mol% to 15 mol%, even more preferably 0.3 mol% to 10 mol%, and most preferably 0.5 mol% to 5 mol%, based on 100 mol% of the total amount of monomers constituting the structural unit.

[0094] The solvent used during the polymerization described above can be selected as needed from among those that can dissolve the monomer components, polymerization initiator, chain transfer agent, and the copolymer after production. There are no particular restrictions, but water, ethanol, C1-C8 alcohols such as 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 are preferably used. In particular, water, ethanol, ethylene glycol, propylene glycol, diethylene glycol monobutyl ether, and propylene glycol monomethyl ether are preferred, and mixtures of two or more of these may also be used.

[0095] The polymerization temperature in the above polymerization step is preferably 40°C or higher, and preferably 150°C or lower. More preferably 45°C or higher, and even more preferably 50°C or higher. Even more preferably 100°C or lower, and even more preferably 90°C or lower.

[0096] In the polymerization process described above, the method of adding the monomer components, polymerization initiator, and chain transfer agent to the reaction vessel is not particularly limited. Examples include adding the entire amount to the reaction vessel all at once at the beginning, adding the entire amount to the reaction vessel in installments or continuously, adding a portion to the reaction vessel initially and then adding the remainder in installments or continuously. Preferably, the solvent described later is charged at the beginning, and the monomer components, polymerization initiator, and chain transfer agent are added continuously.

[0097] Alternatively, the monomer components may be neutralized with organic acids such as acetic acid and propionic acid, or mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid, before polymerization.

[0098] The copolymer obtained by polymerization can be used as is as a detergent additive, such as an additive for liquid detergents, but it may also be neutralized with an alkaline substance if necessary. Suitable alkaline substances include inorganic salts such as hydroxides and carbonates of monovalent or divalent metals, ammonia, and organic amines. The concentration of the copolymer can also be adjusted after the reaction is complete if necessary.

[0099] [Enzymes] The enzymes included in the detergent composition of this disclosure are not particularly limited as long as they exhibit detergent performance, but examples include proteases, lipases, phospholipases, hemicellulases, peroxidases, cellulases, xylanases, esterases, cutinases, pectinases, keratinases, reductases, oxidases, phenol oxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanases, maranases, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, amylases, or combinations thereof. Preferably, proteases and amylases are used, and more preferably, proteases.

[0100] [Surfactants] When used in combination with nonionic surfactants, the combined usage ratio of sulfonic acid group-containing anionic surfactants and nonionic surfactants is preferably 5 to 100% by mass relative to 100% by mass of the total 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.

[0101] In the detergent composition of this disclosure, the ratio of sulfonic acid group-containing anionic surfactant to nonionic surfactant is preferably 0.5 to 70% by mass of the sulfonic acid group-containing anionic surfactant relative to the total content of sulfonic acid group-containing anionic surfactant and nonionic surfactant, from the viewpoint of achieving both sebum stain removal and re-soiling prevention. More preferably it is 1 to 60% by mass, even more preferably 2 to 50% by mass, and most preferably 3 to 40% by mass.

[0102] Suitable sulfonic acid group-containing anionic surfactants include alkylbenzene sulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, α-olefin sulfonates, α-sulfo fatty acids or ester salts, alkane sulfonates, sulfosuccinate esters, and dialkyl sulfosuccinates. The alkyl and alkenyl groups in the sulfonic acid group-containing anionic surfactants may be branched alkyl groups such as methyl groups.

[0103] 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 glycosides, fatty acid glycerol monoesters, alkylamine oxides, and the like. The alkyl and alkenyl groups in the nonionic surfactants may be branched alkyl groups such as methyl groups.

[0104] The detergent compositions of this disclosure may contain other surfactants other than the nonionic surfactant and the sulfonic acid group-containing anionic surfactant described above. The other surfactants are not particularly limited, but for example, as anionic surfactants, saturated fatty acid salts, unsaturated fatty acid salts, alkyl ether carboxylates, alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl phosphate esters or salts thereof, alkenyl phosphate esters or salts thereof are preferred; as cationic surfactants, quaternary ammonium salts are preferred; and as amphoteric surfactants, carboxyl-type amphoteric surfactants, sulfobetaine-type amphoteric surfactants are preferred. The alkyl groups and alkenyl groups in the cationic surfactants and amphoteric surfactants may be branched alkyl groups such as methyl groups.

[0105] The content of the above-mentioned other surfactants is not particularly limited, but it is preferably 0 to 30% by mass based on 100% by mass of the detergent composition. More preferably 0 to 20% by mass, and even more preferably 0 to 10% by mass. A form in which the content of the above-mentioned other surfactants is 0% by mass is also one of the preferred embodiments of the present invention.

[0106] In the above-mentioned detergent composition, the mass ratio of surfactant to amino group-containing copolymer (surfactant / amino group-containing copolymer) is preferably 1 to 200. More preferably 1 to 150, even more preferably 1 to 100, even more preferably 5 to 80, and particularly preferably 10 to 50.

[0107] [Other Components] The detergent composition of this disclosure may contain other components besides the copolymer, enzyme, and surfactant described above. These other components are not particularly limited, but examples include antibacterial agents, anti-redeposition agents such as sodium carboxymethylcellulose, 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, enzymes, dyes, solvents, etc. In the case of a powder detergent composition, it is also preferable to include zeolite.

[0108] The above-mentioned detergent builders are not particularly limited, but examples include alkali builders such as carbonates, bicarbonates, and silicates; chelate builders such as tripolyphosphates, pyrophosphates, sodium sulfate, nitrilotriacetate, ethylenediaminetetraacetate, citrates, copolymer salts of (meth)acrylic acid, acrylic acid-maleic acid copolymers, fumarates, and zeolites; and carboxyl derivatives of polysaccharides such as carboxymethylcellulose. Examples of counter salts used with the above-mentioned 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.

[0109] The above solvents are not particularly limited, but for example: water; C1-C8 alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, phenoxyethanol; glycols such as propylene glycol, butylene glycol, hexylene glycol; polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol; diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl Hydrophilic solvents such as alkyl ethers like ruethers; sulfoxides such as sulfones, diethyl sulfone, and bis(2-hydroxyethyl) sulfone (dimethyl sulfoxide, etc.); cyclic ethers (tetrahydrofuran, tetrahydropyran, etc.); nitriles (acetonitrile, propionitrile, butyronitrile, acrylonitrile, and methacrylicnitrile, etc.); carbonates (ethylene carbonate, propionate carbonate, etc.); and ketones (acetone, diethyl ketone, acetophenone, methyl ethyl ketone, cyclohexanone, cyclopentanone, and diacetone alcohol, etc.) are preferred.

[0110] When the above-mentioned detergent composition contains a detergent builder, the blending ratio is usually preferably 0.1 to 20% by mass per 100% by mass of the detergent composition. More preferably 0.2 to 15% by mass, even 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.

[0111] When the above-mentioned detergent composition is a liquid detergent, the percentage of water content 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, based on 100% by mass of the liquid detergent.

[0112] <Method of Use of the Cleaning Composition> The cleaning composition of this disclosure is intended for clothing use, and this disclosure includes a method of using the above-mentioned detergent for cleaning soiled materials. As will be understood by those skilled in the art, the cleaning composition of this disclosure is suitable for use in pre-washing, washing, and home care applications.

[0113] The above method of use includes, but is not limited to, the steps of diluting the detergent in neat form or in a cleaning solution, bringing it into contact with at least a portion of the soiled material, and then optionally rinsing the soiled material. The soiled material may be subjected to a cleaning step before any rinsing step.

[0114] Specific uses of the present invention include liquid detergents, powder detergents, bleaches, topical detergents, soaking detergents, rinsing agents, etc., but are not limited to these, and are also suitable for use as other cleaning agents and treatment agents.

[0115] A machine washing method may include treating soiled laundry with an aqueous washing solution in a washing machine having an effective amount of the laundry detergent composition of the Disclosure dissolved or dispersed therein. An "effective amount" of the detergent composition means about 20 g to about 300 g of the product dissolved or dispersed in a washing solution with a volume of about 5 L to about 65 L. The water temperature may be in the range of about 5°C to about 50°C. The ratio of water to soiled material (e.g., fabric) may be about 1:1 to about 30:1. The detergent composition of the Disclosure may be used at a concentration of about 50 ppm to about 15,000 ppm in the solution. In the context of fabric washing compositions, the concentration used may also vary depending on the type and degree of soiling and stains, as well as the temperature of the washing water, the amount of washing water, and the type of washing machine (e.g., top-loading, front-loading, top-loading, vertical-axis Japanese-type automatic washing machine).

[0116] The detergent compositions described herein may be used to wash fabrics at low washing temperatures. These methods for washing fabrics include the steps of delivering the detergent composition to water to form a washing solution, and adding the fabric to be washed to the washing solution, wherein the washing solution has a temperature of about 0°C to about 20°C, or about 0°C to about 15°C, or about 0°C to about 9°C. The fabric may be brought into contact with water before, after, or simultaneously with the contact of the detergent composition with water.

[0117] The present disclosure will be further described below with reference to examples, but the present disclosure is not limited to these examples. Unless otherwise specified, "%" means "mass%".

[0118] <Measurement of Weight-Average Molecular Weight of Copolymers> The weight-average molecular weight (Mw) of copolymers was measured by GPC (gel permulation chromatography). The measurement conditions and equipment are as follows. Instrument: Tosoh EcoSEC HLC-8320GPC Detector: Differential Refractometer (RI) Detector Column: Tosoh TSKgel α-M, α-2500 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: GL Sciences polyethylene glycol, Mw = 194, 410, 615, 1020, 1450, 3860, 8160, 16100, 21160, 49930, 67600, 96100, 205500, 542500, 942000 Calibration Curve Order: 3 GPC Software: Tosoh EcoSEC-WS Eluent: 0.5 M acetic acid + 0.2 M sodium nitrate / acetonitrile = 50 / 50 (v / v)

[0119] <Sebum Stain Cleaning Performance Test 1> Sebum stain cleaning performance test 1 was performed on the copolymers produced in Production Examples 1 to 9 using the following method. (Cloth Pretreatment Method) (1)-1: Preparation of Hardness Mother Liquor 8.39 g of calcium chloride dihydrate and 2.9 g of magnesium chloride hexahydrate were weighed into a beaker and ion-exchanged water was added to make 1000 g. (1)-2: Preparation of Hard Water 1.54 g of sodium bicarbonate, 10 g of 0.1 N hydrogen chloride, and 200 g of hardness mother liquor (1)-1 were placed in a beaker and diluted with ion-exchanged water to make 20000 g. (1)-3: Preparation of Test Cloth Polyester taffeta (polyester fiber manufactured by Irozome Co., Ltd.) was cut into 5 x 5 cm pieces. Using the same copolymer as the detergent composition used in the cleaning power evaluation for the hard water and surfactant in (1)-2, the pretreatment solutions were prepared as shown in Tables 2 and 3. 55 g of pretreatment solution was prepared, 2.7 g of the above cloth was added, and the mixture was stirred for 10 minutes using a roller-type shaker. After stirring, it was rinsed for 3 minutes, then dewatered and air-dried for 1 day. (Preparation of soiled cloth) 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 soiled solution was dropped onto the polymer-treated cloth obtained by the above pretreatment method, and left at 40°C for 1 hour to prepare a soiled cloth. (Evaluation of cleaning power) (2)-1: Preparation of cleaning agent composition The cleaning agent compositions shown in Tables 4 to 9 were prepared. (2)-2: Cleaning power test The turgot meter was set to 25°C, and 498.7 g of the hard water from (1)-2 and 0.425 g of the cleaning agent composition from (2)-1 were placed in a pot and mixed. Five soiled cloths, whose Z values ​​were previously measured using a spectrophotometer (SE6000, manufactured by Nippon Denshoku Industries Co., Ltd.), were combined with a bath ratio adjustment cloth and placed in a 16.7g pot. The mixture was then stirred at 120 rpm for 10 minutes for washing. After discarding the water from the pot, the cloths were rinsed once for 3 minutes, then dewatered and air-dried for one day. After air-drying, the Z values ​​of the soiled cloths after washing were measured again using a colorimeter, and the cleaning rate was calculated using the formula described above. Based on the obtained cleaning rate, the cleaning power was evaluated according to the following criteria. The results are shown in Tables 4 to 9. +++: More than +10% compared to the cleaning rate without polymer ++: More than +3% and less than +10% compared to the cleaning rate without polymer +: More than +0.5% and less than +3% compared to the cleaning rate without polymer -: Less than +0.5% compared to the cleaning rate without polymer

[0120] <Re-soiling Prevention Evaluation> (1) As a detergent composition, the cleaning solution shown in Table 8 was prepared. (2)-1: Preparation of hardness mother liquor 5.90 g of calcium chloride dihydrate and 2.72 g of magnesium chloride hexahydrate were weighed into a beaker and ion-exchanged water was added to make 100 g. (2)-2: Preparation of sodium bicarbonate aqueous solution 1.54 g of sodium bicarbonate and 10 g of 0.1 N hydrogen chloride were placed in a beaker and diluted with ion-exchanged water to make 100 g. (3): Preparation of 15 degree hard water 20.0 g of the hardness mother liquor prepared above and 20.0 g of the sodium bicarbonate aqueous solution were weighed into a beaker and ion-exchanged water was added to make 4000 g. (4) Color measurement of white cloth The whiteness of the white cloth used in the re-soiling prevention evaluation was measured by the reflectance using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd.: SE-6000) before the evaluation. (5) Cleaning power evaluation The turgot meter was set to 25°C, and 499.1g of 15°C hard water and 0.48g of the cleaning agent composition prepared as shown in Table 8 were placed in the pot and stirred at 120 rpm for 3 minutes. Then, 0.1g of mud (standard strained red clay) was added, and 30g of cotton knit fabric (cotton cloth manufactured by Dyeing Test Materials Co., Ltd.) and bath ratio adjustment cloth (white cotton cloth) were added together and the mixture was stirred at 120 rpm for 10 minutes to wash. The water in the pot was discarded, and after rinsing twice, the white cloth was dewatered. A pressing cloth was placed over the white cloth, and it was dried while smoothing out wrinkles with an iron. The whiteness of the white cloth was then measured again by reflectance using the above colorimeter. From the above measurement results, the re-soiling prevention rate was calculated using the following formula: Re-soiling prevention rate (%) = [(whiteness after washing) / (whiteness of original white cloth)] × 100 The re-soiling prevention performance was judged according to the following criteria. Compared to Comparative Example 2, which does not contain sulfonic acid-based anionic surfactants: ++: Re-soiling prevention rate of +1.0% or more +: Re-soiling prevention rate of +0.5% to less than +1.0% -: Re-soiling prevention rate of less than +0.5%

[0121] <Sebum Stain Cleaning Performance Test 2> The copolymers produced in Production Examples 10 to 12 were subjected to Sebum Stain Cleaning Performance Test 2 in the same manner as in Sebum Stain Cleaning Performance Test 1, except that the preparation of hard water was carried out as in the Re-soiling Prevention Evaluation described above.

[0122] <Sebum Stain Cleaning Test 3> The copolymer produced in Production Example 12 was subjected to Sebum Stain Cleaning Test 3 by the following method. (Test Preparation) (1)-1: Preparation of Hardness Mother Liquor 8.39 g of calcium chloride dihydrate and 2.9 g of magnesium chloride hexahydrate were weighed into a beaker and deionized water was added to make 1000 g. (1)-2: Preparation of Hard Water 1.54 g of sodium bicarbonate, 10 g of 0.1 N hydrogen chloride, and 200 g of hardness mother liquor (1)-1 were placed in a beaker and diluted with deionized water to make 20000 g. (1)-3: Preparation of Test Cloth Polyester taffeta (polyester fiber manufactured by Irozome Co., Ltd.) was cut into 5 x 5 cm pieces. (Preparation of Stained Cloth) (2)-1: Preparation of Stained Cloth 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 stain solution. 15 μL of this contaminated liquid was dropped onto the test cloth described in (1)-3 above, and left at 40°C for 1 hour to prepare a contaminated cloth. (2)-2: Preparation of pretreatment solution Using the hard water, surfactant, and copolymer 12 described in (1)-2, a pretreatment solution was prepared as shown in Table 12. 0.2 g of the prepared pretreatment solution was applied to each contaminated cloth prepared in (2)-1, and a cleaning power test was performed 5 minutes after application.

[0123] (Evaluation of cleaning power) (2)-1: Preparation of cleaning agent composition The cleaning agent composition shown in Table 12 was prepared. (2)-2: Cleaning power test The targot meter was set to 25°C, and 498.7 g of the hard water from (1)-2 and 0.425 g of the cleaning agent composition shown in Table 12 were added to the pot and mixed. Five soiled cloths whose Z values ​​had been measured in advance using a spectrophotometer (SE6000 manufactured by Nippon Denshoku Industries Co., Ltd.), along with a cloth for adjusting the bath ratio, were added to the pot, totaling 16.7 g, and the cloths were washed by stirring at 120 rpm for 10 minutes. The water in the pot was discarded, and after one rinse for 3 minutes, the cloths were dewatered and air-dried for 1 day. After air-drying, the Z values ​​of the soiled cloths after washing were measured again using a colorimeter, and the cleaning rate was calculated using the above formula. Based on the obtained cleaning rate, the cleaning power was evaluated according to the following criteria. The results are shown in Table 12. +++: +10% or more compared to cleaning without polymer ++: +3% or more and less than +10% compared to cleaning without polymer +: +0.5% or more and less than +3% compared to cleaning without polymer -: Less than +0.5% compared to cleaning without polymer

[0124] <Sebum Stain Cleaning Performance Test 4> The copolymer produced in Production Example 12 was subjected to sebum stain cleaning performance test 4 by the following method. (Test preparation) (1)-1: Preparation of hardness mother liquor 8.39 g of calcium chloride dihydrate and 2.9 g of magnesium chloride hexahydrate were weighed into a beaker and deionized water was added to make 1000 g. (1)-2: Preparation of hard water 1.54 g of sodium bicarbonate, 10 g of 0.1 N hydrogen chloride, and 200 g of hardness mother liquor (1)-1 were placed in a beaker and diluted with deionized water to make 20000 g. (1)-3: Preparation of test cloth Polyester taffeta (polyester fiber manufactured by Irozome Co., Ltd.) was cut into 5 x 5 cm pieces. (Preparation of soiled cloth) (2)-1: Preparation of soiled cloth 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 liquid was dropped onto the test cloth described in (1)-3 above, and left at 40°C for 1 hour to prepare a contaminated cloth. (2)-2: Preparation of pretreatment solution Using the hard water, surfactant, and copolymer 12 described in (1)-2, a pretreatment solution was prepared as shown in Table 12. 30 ml of the prepared pretreatment solution was used to impregnate the contaminated cloth prepared in (2)-1, and after 30 minutes, it was removed and a cleaning power test was performed.

[0125] (Evaluation of cleaning power) (2)-1: Preparation of cleaning agent composition The cleaning agent composition shown in Table 12 was prepared. (2)-2: Cleaning power test The targot meter was set to 25°C, and 498.7 g of the hard water from (1)-2 and 0.425 g of the cleaning agent composition shown in Table 12 were added to the pot and mixed. Five soiled cloths whose Z values ​​had been measured in advance using a spectrophotometer (SE6000 manufactured by Nippon Denshoku Industries Co., Ltd.), along with a cloth for adjusting the bath ratio, were added to the pot, totaling 16.7 g, and the cloths were washed by stirring at 120 rpm for 10 minutes. The water in the pot was discarded, and after one rinse for 3 minutes, the cloths were dewatered and air-dried for 1 day. After air-drying, the Z values ​​of the soiled cloths after washing were measured again using a colorimeter, and the cleaning rate was calculated using the above formula. Based on the obtained cleaning rate, the cleaning power was evaluated according to the following criteria. The results are shown in Table 12. +++: +10% or more compared to cleaning without polymer ++: +3% or more and less than +10% compared to cleaning without polymer +: +0.5% or more and less than +3% compared to cleaning without polymer -: Less than +0.5% compared to cleaning without polymer

[0126] <Manufacturing Example 1> 50.1 g of ethanol was placed in a glass separable flask equipped with a thermometer, reflux condenser, and stirrer. Under stirring, nitrogen was flowed at 200 ml / min for 10 minutes, and then the temperature was raised to 70°C. After adjusting the nitrogen flow to 50 ml / min, and under stirring, the polymerization reaction system was kept at a constant temperature of 70°C. A monomer solution consisting of 72.1 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 25, hereafter referred to as PGM25E), 6.2 g of methacrylic acid (hereafter referred to as MAA), 50.0 g of dimethylaminoethyl methacrylate (hereafter referred to as DAM), 38.8 g of ethanol, 18.1 g of acetic acid, and 6.8 g of benzyl methacrylate (hereafter referred to as BnMA) (solubility parameter: 10.0) was added dropwise from separate dropping nozzles. An initiator aqueous solution consisting of 38.1 g of a 6% ethanol solution of 2,2'-azobis(2,4-dimethylvaleronitrile) (hereafter referred to as V-65) was added dropwise. The monomer solution and the initiator aqueous solution were added dropwise simultaneously, with the monomer solution added for 180 minutes and the initiator aqueous solution for 240 minutes. After all dropwise addition was complete, the reaction solution was kept at 70°C for another 60 minutes to mature and complete the polymerization, yielding amino group-containing copolymer 1.

[0127] <Production Example 2> The synthesis was carried out in the same manner as in Production Example 1, except that the amount of PGM25E was changed to 68.5 g, MAA to 5.7 g, DAM to 60.8 g, ethanol in the monomer solution to 36.5 g, acetic acid to 22.0 g, BnMA to 0 g, and the initiator aqueous solution to 38.0 g, to obtain amino group-containing copolymer 2.

[0128] <Production Example 3> The synthesis was carried out in the same manner as in Production Example 1, except that the amount of ethanol used for the starter was changed to 77.0 g, PGM25E to 99.9 g, MAA to 8.3 g, DAM to 17.8 g, the amount of ethanol in the monomer solution to 24.1 g, acetic acid to 6.5 g, BnMA to 8.9 g, and the amount of aqueous initiator solution to 30.5 g, to obtain amino group-containing copolymer 3.

[0129] <Production Example 4> The synthesis was carried out in the same manner as in Production Example 1, except that the amount of ethanol used in the initial stage was changed to 56.1 g, PGM25E to 31.2 g, MAA to 2.6 g, DAM to 67.5 g, the amount of ethanol in the monomer solution to 46.0 g, acetic acid to 24.5 g, BnMA to 33.8 g, and the amount of aqueous initiator solution to 30.0 g, to obtain amino group-containing copolymer 4.

[0130] <Production Example 5> The synthesis was carried out in the same manner as in Production Example 1, except that the amount of ethanol used for the starter was changed to 55.0 g, PGM25E to 24.9 g, MAA to 2.1 g, DAM to 108.0 g, the amount of ethanol in the monomer solution to 30.0 g, acetic acid to 39.3 g, BnMA to 0 g, and the amount of the initiator aqueous solution to 53.8 g, to obtain amino group-containing copolymer 5.

[0131] <Production Example 6> The synthesis was carried out in the same manner as in Production Example 1, except that the amount of ethanol used in the initial stage was changed to 76.2 g, PGM25E to 56.0 g, MAA to 4.7 g, DAM to 27.0 g, the amount of ethanol in the monomer solution to 36.6 g, acetic acid to 9.8 g, BnMA to 47.3 g, and the amount of the initiator aqueous solution to 26.9 g, to obtain amino group-containing copolymer 6.

[0132] <Production Example 7> In a glass separable flask equipped with a thermometer, reflux condenser, and stirrer, 53 g of ethanol was charged, and under stirring, nitrogen was flowed at 200 ml / min for 10 minutes, and then the temperature was raised to 70°C. After reducing the nitrogen flow to 50 ml / min, under stirring, a monomer solution consisting of 58 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 25, hereinafter referred to as PGM25E), 4.9 g of methacrylic acid (hereinafter referred to as MAA), 47 g of dimethylaminoethyl methacrylate (hereinafter referred to as DAM), 44 g of ethanol, 17 g of acetic acid, and 47 g of 2-(methacryloyloxy)ethyltrimethylammonium chloride (hereinafter referred to as METMAC); and an initiator solution consisting of 54 g of a 7% ethanol solution of 2,2'-azobis (2,4-dimethylvaleronitrile) (hereinafter referred to as V-65) was added dropwise from separate dropping nozzles to the polymerization reaction system maintained at a constant temperature of 70°C. Regarding the dropwise addition time, the monomer solution and the initiator aqueous solution were added simultaneously. The monomer solution was added for 180 minutes, and the initiator solution for 240 minutes. After all addition was complete, the reaction solution was kept at 70°C for another 60 minutes to mature and complete the polymerization, yielding amino group-containing copolymer 7.

[0133] <Production Example 8> The synthesis was carried out in the same manner as in Production Example 7, except that the amount of ethanol used in the preparation was changed to 56 g, PGM25E to 78 g, MAA to 6 g, METMAC to 31 g, the amount of ethanol in the monomer solution to 41 g, and the amount of the initiator solution to 49 g, to obtain amino group-containing copolymer 8.

[0134] <Production Example 9> The synthesis was carried out in the same manner as in Production Example 7, except that the amount of ethanol used in the preparation was changed to 60 g, PGM25E to 79 g, MAA to 6.7 g, METMAC to 23 g, the amount of ethanol in the monomer solution to 32 g, and the amount of the initiator solution to 47 g, to obtain amino group-containing copolymer 9.

[0135] <Production Example 10> The synthesis was carried out in the same manner as in Production Example 1, except that PGM25E was changed to 59.5 g, MAA to 5.4 g, DAM to 40.5 g, acetic acid to 16.3 g, and BnMA to 29.7 g, to obtain amino group-containing copolymer 10.

[0136] <Production Example 11> The synthesis was carried out in the same manner as in Production Example 1, except that PGM25E was changed to 83.8 g, MAA to 6.8 g, DAM to 31.1 g, acetic acid to 12.5 g, BnMA to 13.5 g, and the initiator aqueous solution to 44 g of 7% ethanol solution, to obtain an amino group-containing copolymer 11.

[0137] <Production Example 12> The synthesis was carried out in the same manner as in Production Example 1, except that PGM25E was changed to 54.0 g, MAA to 4.1 g, DAM to 70.3 g, acetic acid to 28.3 g, and BnMA to 6.8 g, to obtain amino group-containing copolymer 12.

[0138] Table 1 shows the monomer composition and weight-average molecular weight (Mw) of the amino group-containing copolymers 1 to 12 obtained in the above production examples 1 to 12.

[0139]

[0140]

[0141] Tables 4 to 7 show the results of Examples 1 to 22, which used the copolymers produced in Production Examples 1 to 5, and Comparative Example 1, which was evaluated without the polymer.

[0142]

[0143] The surfactants listed in Tables 2-4 are as follows: Anionic surfactant 1: LAS: Sodium linear alkylbenzene sulfonate (Kao Neoperex G-65) Anionic surfactant 2: AES: Sodium polyoxyethylene lauryl ether sulfate (Kao Emal 20C) Anionic surfactant 3: Sodium di-2-ethylhexyl sulfosuccinate Nonionic surfactant 1: PAE: Polyoxyethylene lauryl ether (Kao Emal 108) The same surfactants as above were used in Tables 5-12 below.

[0144]

[0145]

[0146]

[0147] Table 8 shows the results of cleaning power tests for sebum stain removal and re-soiling prevention conducted on Example 23 and 24 using copolymer 6, and Comparative Example 2, which does not use a sulfonic acid group-containing anionic surfactant.

[0148]

[0149] As shown in Tables 4 to 8, the detergent compositions of this disclosure have been shown to be excellent in sebum stain removal and re-soiling prevention.

[0150] Table 9 shows the results of the sebum stain cleaning performance test 1 for Examples 25-30, which used copolymers 7-9. For Examples 28-30, the sebum stain cleaning performance test 1 was performed without a pretreatment step. As a result, it was found that this copolymer is effective not only in soil release but also in primary cleaning performance.

[0151]

[0152] Examples 31 to 38, using copolymers 10 to 12, underwent a sebum stain cleansing test 2. Table 10 shows the mixing ratio of surfactants used in the above test, and the concentrations of copolymers and surfactants in the pretreatment solution. Table 11 shows the results of the sebum stain cleansing test 2. Examples 35 to 38 underwent the sebum stain cleansing test 2 without a pretreatment step. As a result, it was found that this copolymer is effective not only in soil release but also in primary cleaning.

[0153]

[0154]

[0155] Using copolymer 12, a sebum stain cleansing performance test 3 was performed on Example 39, and a sebum stain cleansing performance test 4 was performed on Example 40. The pretreatment conditions used in the above tests and the results of sebum stain cleansing performance tests 3 and 4 are shown in Table 12. As a result, it was found that this copolymer is effective not only when used as a liquid detergent, but also when used as a topical detergent or a soaking detergent.

[0156]

Claims

1. A detergent 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 (1-1) and / or (1-2) and a structural unit (b) derived from a monomer having a polyalkylene glycol chain, and a sulfonic acid group-containing anionic surfactant, wherein the ratio of the sulfonic acid group-containing anionic surfactant to the total amount of surfactants contained in the detergent composition is 0.5 to 90% by mass. (In general formulas (1-1) and / or (1-2), 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 direct bond or a divalent linking group. － The symbol represents an anion. However, the asterisk represents an atom contained within another structural unit of the same or different type to which the structural unit represented by general formula (1-1) and / or (1-2) is bonded.

2. The detergent composition according to claim 1, further comprising a nonionic surfactant.

3. The detergent 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 detergent composition according to any one of claims 1 to 3, wherein the amino group-containing copolymer further comprises a structural unit (d) derived from an unsaturated carboxylic acid.

5. The detergent composition according to any one of claims 1 to 4, wherein the weight-average molecular weight of the amino group-containing copolymer is 4,000 or more and 500,000 or less.

6. The detergent composition according to any one of claims 1 to 5, wherein the content of the sulfonic acid group-containing anionic surfactant is 1 to 60% by mass with respect to 100% by mass of the detergent composition.

7. The detergent composition according to any one of claims 2 to 6, wherein, when the total amount of the sulfonic acid group-containing anionic surfactant and the nonionic surfactant is 100% by mass, the content ratio of the sulfonic acid group-containing anionic surfactant is 0.5 to 90% by mass.

8. A laundry detergent composition comprising the detergent composition according to any one of claims 1 to 7.

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