Amino-group-containing copolymer

Abstract

The purpose of the present invention is to provide an amino-group-containing copolymer having exceptional soil release properties and a method for producing a soil release agent in which said amino-group-containing copolymer is used. The present invention is an amino-group-containing copolymer containing 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.

Description

Amino group-containing copolymer

[0001] The present invention relates to an amino group-containing copolymer, and more particularly to an amino group-containing copolymer useful for detergent applications such as liquid detergents and powder detergents.

[0002] For sebum stains and other stains adhering to clothing, pre-treating the fabric with a compound that adsorbs to the fabric can be expected to make the stains easier to remove during washing. This function is called soil release. Various compounds that exhibit soil release properties have been proposed. For example, Patent Document 1 discloses that a polymer composed of a (meth)acrylic acid ester having primary to tertiary amino groups and an unsaturated bond-containing monomer having a hydrophobic group has excellent soil release properties for cotton fabrics. For example, Patent Document 2 discloses that a composition containing a polymer having a quaternary ammonium group and a hydrophilic group has a soil release effect on cotton fabrics.

[0003] Patent No. 5014739 Publication Special Publication No. 11-505568

[0004] The soil release properties of amino group-containing polymers have been disclosed as described above. However, there is room for further improvement in soil release properties, particularly for polyester fibers that are prone to adsorbing sebum stains. The present invention has been made in light of the above-mentioned current situation, and aims to provide an amino group-containing copolymer with excellent soil release properties and a method for producing a soil release agent using the same.

[0005] The present inventors have conducted various studies to achieve the above object and have arrived at the present invention, which is an amino group-containing copolymer comprising a structural unit (a) derived from an amino group-containing monomer represented by the following general formula (1), 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 (d) derived from an unsaturated carboxylic acid monomer:

[0006]

[0007] In general formula (1), R １ , R ２ , R ３each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R ４ , R ５ each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms, and X represents a divalent linking group, provided that the asterisk represents an atom contained in another structural unit of the same type or different type to which the structural unit represented by general formula (1) is bonded.

[0008] The hydrophobic monomer preferably has a homopolymer having a solubility parameter of 13 or less.

[0009] The proportion of the structural unit (a) derived from the amino group-containing monomer is preferably 5 to 50% by weight relative to 100% by weight of all structural units.

[0010] The proportion of the structural unit (b) derived from the monomer having a polyalkylene glycol chain is preferably 5 to 75% by weight relative to 100% by weight of all structural units.

[0011] The proportion of the structural unit (c) derived from the hydrophobic monomer is preferably 5 to 70% by weight relative to 100% by weight of all structural units.

[0012] The proportion of the structural unit (d) derived from the unsaturated carboxylic acid monomer is preferably 1 to 20% by weight relative to 100% by weight of all structural units.

[0013] The amino group-containing copolymer preferably has a weight average molecular weight of 4,000 or more and 500,000 or less.

[0014] The present invention also relates to a soil release agent containing the amino group-containing copolymer.

[0015] The present invention also relates to a method for using the amino group-containing copolymer as a soil release agent.

[0016] The present invention also provides a method for producing a soil release agent, which includes a step of mixing the amino group-containing copolymer with a surfactant.

[0017] The amino group-containing copolymer of the present disclosure has excellent soil release properties and can therefore be suitably used in detergents and the like, particularly for textile products such as polyester.

[0018] The present invention will be described in detail below. It should be noted that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[0019] [Amino Group-Containing Copolymer of the Present Disclosure] The amino group-containing copolymer of the present disclosure (hereinafter also referred to as the copolymer of the present disclosure) is a copolymer containing the following 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. Due to having such a structure, the copolymer of the present disclosure has excellent soil release properties, as well as excellent antibacterial properties and anti-redeposition properties.

[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 ５ each 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)-(CH２ )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 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.

[0023] 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

[0024] 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.

[0025] The structural unit (a) derived from the amino group-containing monomer is particularly preferably a structural unit derived from N,N-dimethylaminoethyl (meth)acrylate, represented by the following general formula (3).

[0026] 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.

[0027] In the copolymer of the present disclosure, the content of the structural unit (a) derived from the amino group-containing monomer is 5% by mass or more and 50% by mass or less, preferably 7% by mass or more and 45% by mass or less, more preferably 8% by mass or more and 40% by mass or less, particularly preferably 10% by mass or more and 30% by mass or less, and most preferably 15% by mass or more and 25% 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 embodiment, the content of the structural unit (a) is preferably 8% by mass or more and 45% by mass or less, more preferably 10% by mass or more and 40% by mass or less, particularly preferably 15% by mass or more and 38% by mass or less, and most preferably 20% by mass or more and 35% by mass or less, based on 100% by mass of all structural units. By being in the above range, the proportion of cationic moieties that can act on substrates such as fibers to which soil releasability is to be imparted becomes appropriate, and the soil releasability and antibacterial performance of the detergent additive of the present disclosure tend to be improved.

[0028] <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):

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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, 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 the branched chains.

[0033] 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.

[0034] 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.

[0035] Examples of the aryl group include a phenyl group, a benzyl group, a methylphenyl group, a 1-methoxy-4-methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a butylmethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a dibutylphenyl group, a biphenyl group, a biphenylmethyl group, a biphenylethyl group, a naphthyl group, a naphthylmethyl group, and a naphthylethyl group.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] Examples of oxyalkylene groups represented by AO include oxyethylene, oxypropylene, oxybutylene, oxyisobutylene, oxy-2,3-butylene, oxystyrene, and oxyalkylene groups 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] In the copolymer of the present disclosure, the content of the structural unit (b) having a polyalkylene glycol chain is preferably 5% by mass or more and 75% by mass or less, more preferably 20% by mass or more and 70% by mass or less, even more preferably 30% by mass or more and 70% by mass or less, particularly preferably 40% by mass or more and 65% by mass or less, and most preferably 45% by mass or more and 60% by mass or less, based on 100% by mass of all structural units derived from all monomers constituting the copolymer of the present disclosure. In one embodiment, the content of the structural unit (b) is preferably 10% by mass or more and 75% by mass or less, more preferably 15% by mass or more and 70% by mass or less, even more preferably 17% by mass or more and 65% by mass or less. By being in the above range, the proportion of hydrophilic moieties becomes appropriate, and the soil release properties and anti-redeposition performance of the detergent additive of the present disclosure tend to be improved.

[0044] <Structural unit (c) derived from hydrophobic monomer> 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 the solubility parameter of the 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. The solubility parameter (δ) (cal / cm) of the 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

[0045] 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 invention will be sufficient and the copolymer will have excellent adsorption to hydrophobic fibers. The solubility parameter is preferably 12 or less, more preferably 11 or less. The solubility parameter is usually 5 or more.

[0046] 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.

[0047] 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 aryl alcohols having 6 to 30 carbon atoms.

[0048] 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.

[0049] Preferred examples of the aryl 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.

[0050] The hydrophobic monomer is preferably a monomer represented by the following general formula (5):

[0051]

[0052] (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):

[0053] (In the formula, R １０ ~R １３ is 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.

[0054] The above R １０ , R １１ , R １２The 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.

[0055] 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.

[0056] 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 aryl 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 may or may not have an aryl group, but R １３ is a hydrocarbon group having no aryl group is also one of the preferred embodiments of the present invention.

[0057] The above R １３ The 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 aryl group in the formula (I) preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably 6 to 8 carbon atoms.

[0058] The above R １３Examples 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. ７ 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.

[0059] The above R １３ Examples of the aryl group in the formula (I) include a phenyl group, a benzyl group, a methylphenyl group, a 1-methoxy-4-methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a butylmethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a dibutylphenyl group, a 2-(2-methylphenyl)ethyl group, a 2-(3-methylphenyl)ethyl group, a 2-(4-methylphenyl)ethyl group, a 2-(4-propylphenyl)ethyl group, a biphenyl group, a biphenylmethyl group, a biphenylethyl group, a naphthyl group, a naphthylmethyl group, and a naphthylethyl group.

[0060] The above R １３ Examples 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.

[0061] The above R １３The hydrocarbon group in the formula (I) is preferably an alkyl group or an aryl group, more preferably an alkyl group. The hydrophobic monomer is preferably an alkyl (meth)acrylate or an aryl (meth)acrylate, more preferably an alkyl (meth)acrylate.

[0062] 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.

[0063] Examples of the aryl(meth)acrylate 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, 4-methylphenyl(meth)acrylate, ) acrylate, 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. Of these, phenyl (meth)acrylate and benzyl (meth)acrylate are preferred.

[0064] In the copolymer of the present disclosure, the content of the structural unit (c) derived from a hydrophobic monomer is preferably 5% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 60% by mass or less, even more preferably 15% by mass or more and 50% by mass or less, and most preferably 20% by mass or more and 45% by mass or less, based on 100% by mass of the structural units derived from all monomers constituting the copolymer of the present disclosure. The above ranges result in an appropriate proportion of hydrophobic moieties, which tends to improve the soil releasability, anti-redeposition properties, and antibacterial performance of the detergent additive of the present disclosure. In one embodiment, the content of the structural unit (c) may be 5 to 40% by mass, and preferably 5 to 35% by mass, based on 100% by mass of all structural units.

[0065] <Structural Unit (d) Derived from Unsaturated Carboxylic Acid Monomer> The structural unit (d) derived from an unsaturated carboxylic acid monomer according to 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 is preferably a structural unit represented by the following general formula (7):

[0066] 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.

[0067] A preferred embodiment of the general formula (7) is R １４ is 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.

[0068] 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.

[0069] In the copolymer of the present disclosure, the content of the structural unit (d) derived from an unsaturated carboxylic acid monomer 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, relative to 100% by mass of the structural units derived from all the 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 the soil release properties and anti-soil redeposition properties of the detergent additive of the present disclosure tend to be improved.

[0070] <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.

[0071] The other monomer is not particularly limited, and examples thereof include sulfonic acid group-containing monomers such as styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 3-allyloxy-2-hydroxy-1-propanesulfonic acid, and salts thereof; and phosphoric acid group-containing monomers such as 2-methacryloyloxyethyl acid phosphate.

[0072] 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.

[0073] <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 18,000 or more and 30,000 or less. When it is in the above range, the soil release performance of the copolymer of the present disclosure tends to be further improved.

[0074] [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. The method for producing the amino group-containing copolymer of the present disclosure also constitutes one aspect of the present invention.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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 used that constitute the structural units.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] [Uses of the Amino Group-Containing Copolymer of the Present Disclosure] The amino group-containing copolymer of the present disclosure is used as a soil release agent, antibacterial agent, and anti-redeposition agent. The soil release agent, antibacterial agent, and anti-redeposition agent can be used as a detergent additive. For example, soil release agents, antibacterial agents, and anti-redeposition agents are used in detergents for fibers and hard surfaces. Detergents here include detergents for household clothing, kitchens, homes, the textile industry, and other industrial uses. The present invention also relates to a method for using the amino group-containing copolymer as a soil release agent, antibacterial agent, or anti-redeposition agent. In the above method, it is preferable to contact the amino group-containing copolymer with an object to be cleaned. The present invention also relates to a method for producing a soil release agent, the production method including a step of mixing the amino group-containing copolymer with a surfactant.

[0086] [Soil release agent of the present disclosure] The soil release agent of the present disclosure is a soil release agent containing the amino group-containing copolymer of the present disclosure. Soil release property is detergency performance that can be measured by the method described in the examples below. The soil release agent of the present disclosure can be effective under both immersion conditions and washing conditions.

[0087] The soil release agent of the present disclosure may be the amino group-containing copolymer of the present disclosure alone, or may contain, in addition to the amino group-containing copolymer of the present disclosure, any additive commonly used in detergents, without particular limitation. The soil release agent of the present disclosure preferably contains 0.1 to 100 mass% of the amino group-containing copolymer. Examples of such additives include surfactants, such as anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

[0088] Examples of additives other than the surfactants include anti-redeposition agents such as sodium carboxymethylcellulose, color transfer inhibitors, softeners, alkaline substances for adjusting pH, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, glossing agents, disinfectants, bleaching agents, bleaching aids, enzymes, dyes, solvents, etc. In the case of powder detergent compositions, it is also preferable to incorporate zeolite.

[0089] [Antibacterial Agent of the Present Disclosure] The antibacterial agent of the present disclosure contains the amino group-containing copolymer and exhibits excellent antibacterial performance. The antibacterial performance refers to the antibacterial performance of a substrate such as a fiber treated with the antibacterial agent, which can be evaluated by the method described in the Examples below. The antibacterial agent of the present disclosure preferably contains 0.1 to 100 mass% of the amino group-containing copolymer. The antibacterial performance refers to the performance of bactericidal (killing microorganisms), bacteriostatic (suppressing the growth of microorganisms), sterilization, disinfection, bacteriostatic, antiseptic, antifungal, etc., and the target microorganisms are bacteria and fungi.

[0090] Examples of the bacteria include gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, Salmonella, Moraxella, and Legionella; and gram-positive bacteria such as Staphylococcus aureus and Clostridium bacteria. Examples of the fungi include yeasts such as Candida, Rhodotorula, and baker's yeast; and molds such as red mold and black mold.

[0091] The reason why the antibacterial agent of the present disclosure exhibits antibacterial properties by including such an amino group-containing copolymer is presumed to be as follows: When the antibacterial agent of the present invention is applied to microorganisms, the cationic groups derived from the structural units represented by the general formula (1) possessed by the amino group-containing copolymer are adsorbed to the negatively charged surface of the microorganism. Furthermore, it is presumed that the hydrophobic groups possessed by the amino group-containing copolymer exhibit affinity for the cell membrane portion and interact with the cell membrane, thereby disrupting the interaction between lipids and the like constituting the cell membrane and / or inhibiting the function of proteins and the like bound to the membrane, thereby destroying the cells and / or inhibiting the physiological activity of the cells, thereby killing the microorganisms.

[0092] The antibacterial agent of the present disclosure may be the amino group-containing copolymer of the present disclosure alone, or may contain, in addition to the amino group-containing copolymer of the present disclosure, any additives used in conventional detergent compositions, without particular limitation. The antibacterial agent of the present disclosure preferably contains the amino group-containing copolymer in an amount of 0.1 to 100 mass%. Examples of such additives include surfactants, such as anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

[0093] Examples of additives other than the surfactants include other antibacterial agents, anti-redeposition agents such as sodium carboxymethyl cellulose, color transfer inhibitors, softeners, alkaline substances for adjusting pH, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishing agents, disinfectants, bleaching agents, bleaching aids, enzymes, dyes, solvents, etc. In the case of powder detergent compositions, it is also preferable to incorporate zeolite.

[0094] [Anti-redeposition Agent of the Present Disclosure] The anti-redeposition agent of the present disclosure contains the amino group-containing copolymer and exhibits excellent anti-redeposition ability. The anti-redeposition agent of the present disclosure preferably contains the amino group-containing copolymer in an amount of 0.1 to 100 mass %.

[0095] The anti-redeposition agent of the present disclosure can be added to a detergent composition. The form of the detergent composition is not particularly limited, and may be in the form of a liquid, solid, powder, or the like.

[0096] The detergent composition of the present disclosure may contain various components used in detergent compositions in addition to the soil release agent, antibacterial agent, and anti-redeposition agent. The components contained in the detergent composition may include surfactants and detergent additives typically used in detergent compositions.

[0097] The surfactant may be any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants, and one or more of these may be used.

[0098] Suitable anionic surfactants include alkylbenzenesulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, α-olefin sulfonates, α-sulfofatty acids or their 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 their salts, alkenyl phosphates or their salts, etc. The alkyl and alkenyl groups in these anionic surfactants may be branched with an alkyl group such as a methyl group.

[0099] Examples of 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 these nonionic surfactants may be branched with an alkyl group such as a methyl group.

[0100] Examples of cationic surfactants include quaternary ammonium salts. Examples of amphoteric surfactants include carboxyl-type amphoteric surfactants and sulfobetaine-type amphoteric surfactants. The alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may have a branched alkyl group such as a methyl group.

[0101] The content of the surfactant is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, even more preferably 20 to 45% by mass, and particularly preferably 25 to 40% by mass, based on the total amount of the detergent composition. When the content of the surfactant is 10 to 60% by mass, based on the total amount of the detergent composition, both detergency and economy tend to be achieved.

[0102] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "% by mass."

[0103] <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)

[0104] <Soil Releasability Evaluation 1> The soil releasability of the copolymers produced in Production Examples 2, 4, 6, 8 to 17, and 19 was evaluated using the following method. (Fabric 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 1,000 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 20,000 g. (1)-3 Polyester taffeta (polyester fiber, manufactured by Shikisen Co., Ltd.) cut into 5 x 5 cm pieces was prepared. 55 g of an aqueous solution of the copolymer obtained in the Examples (1)-2, adjusted to 33 ppm, was prepared using the hard water. 2.7 g of the above fabric was added and stirred for 10 minutes using a roller shaker. After stirring, the mixture was rinsed for 3 minutes, then 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 stained solution was dropped onto the polymer-treated fabric obtained by pretreatment method 1 above and left at 40°C for 1 hour to prepare a stained fabric. (Evaluation of Detergency) (2)-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 a total of 100 g to prepare a 10% surfactant solution. (2)-2: Detergency Test A tergot meter was set to 25°C, and 498.8 g of hard water (1)-2) and 0.85 g of surfactant solution (1)-3) were placed in a pot. A 1% copolymer aqueous solution was added and mixed so that the copolymer concentration in the pot was 7.3 ppm. Five stained cloths whose Z values ​​had been previously measured using a spectrophotometer (SE6000 manufactured by Nippon Denshoku Industries Co., Ltd.) and a liquor ratio-adjusted cloth were placed in a 16.7 g pot and washed by stirring at 120 rpm for 10 minutes. The water in the pot was discarded, and the cloths were rinsed once for 3 minutes, then dehydrated and air-dried for 1 day. After air-drying, the Z values ​​of the stained cloths after washing were measured again using the colorimeter, and the cleaning rate was calculated using the following formula: Cleaning rate (%) = ((Zs - Zw) / (Zs - Zo)) x 100, where Zs represents the Z value of the stained cloth before washing, Zw represents the Z value of the stained cloth after washing, and Zo represents the Z value of the white cloth before contamination. Based on the obtained cleaning rate, detergency was evaluated using the following criteria.The results are shown in Table 5. ⊚: cleaning rate of 88% or more ◯: cleaning rate of 86% or more but less than 88% ×: cleaning rate of less than 86%.

[0105] <Evaluation of Anti-Resoiling> (1) As a surfactant solution, Emulgen 108 (PAE, manufactured by Kao Corporation) was diluted with ion-exchanged water to prepare a 10% solution. (2) 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. (3) 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. (4) Measurement of color of white cloth: The whiteness of the white cloth used in the anti-resoiling evaluation was measured for reflectance using a color difference meter (SE-6000, manufactured by Nippon Denshoku Industries Co., Ltd.) before evaluation. (5) Detergency Evaluation: The tergotometer was set to 25°C, and 891.3 g of ion-exchanged water, 1.2 g of hardness mother liquor, 4.5 g of sodium bicarbonate aqueous solution, 2.25 g of surfactant aqueous solution, and 0.75 g of a 1% polymer aqueous solution (solids equivalent) were added to a pot and stirred at 120 rpm for 3 minutes. Then, 0.05 g of carbon black (Mitsubishi Chemical Carbon Black #10) was added, and 5 sheets of cotton knitted fabric (dyeing test materials Co., Ltd. cotton fabric) or 5 sheets of Style 730 and a 30 g liquor ratio adjustment cloth (white cotton fabric) were added, and the mixture was stirred at 120 rpm for 10 minutes for washing. The water in the pot was discarded, and the white fabric was rinsed twice, after which it was dehydrated. After drying with a pressing cloth and ironing out any wrinkles, the whiteness of the white fabric was measured again using the color difference meter in terms of reflectance. From the above measurement results, the anti-redeposition rate was calculated using the following formula: Anti-redeposition rate (%) = [(whiteness after washing) / (whiteness of original white cloth)] x 100 Anti-redeposition rate was evaluated according to the following criteria: Anti-redeposition rate on cotton: +1.0% or more compared to the condition where no polymer was added: ⊚ Anti-redeposition rate on cotton: +0.5% or more but less than +1.0% compared to the condition where no polymer was added: 〇 Anti-redeposition rate on polyester: +4.0% or more compared to the condition where no polymer was added: ⊚ Anti-redeposition rate on polyester: +2.0% or more but less than +4.0% compared to the condition where no polymer was added: 〇 Anti-redeposition rate on polyester: +2.0% or more but less than +2.0% compared to the condition where no polymer was added: ×

[0106] <Antibacterial Evaluation> (1) Preparation of Hard Water: 8.39 g of calcium chloride dihydrate and 2.9 g of magnesium chloride hexahydrate were weighed into a beaker and added with ion-exchanged water to make 1,000 g, forming a hardness mother liquor. 1.54 g of sodium bicarbonate, 10 g of 0.1 N hydrogen chloride, and 200 g of the above hardness mother liquor were placed in a beaker and diluted with ion-exchanged water to prepare 20,000 g of hard water. (2) Fabric Pretreatment Method: Style 730 was cut into 5 x 5 cm pieces. 55 g of an aqueous solution prepared using the hard water described in (1) above to contain 100 ppm of the copolymer obtained in the Examples was placed in a 70 cc mayonnaise bottle, and 5.5 g of Style 730 was then added and stirred for 1 hour. After stirring, the solution was dehydrated and air-dried for 1 day. (3) Antibacterial Test The antibacterial properties of the pretreated test cloth were evaluated according to JIS L 1902:2015 (bacterial liquid absorption method for testing antibacterial properties of textile products). Staphylococcus aureus (Staphylococcus aureus NBRC 12732) was used to evaluate the antibacterial properties, and the viable cell count was measured by the pour plate culture method to evaluate the antibacterial performance. The antibacterial performance was compared with an untreated 100% cotton test cloth, and the antibacterial properties against Staphylococcus aureus were evaluated using the antibacterial activity value expressed by the following formula: Antibacterial activity value = {log (control sample, viable cell count after incubation) - log (control sample, viable cell count immediately after inoculation)} - {log (test sample, viable cell count after incubation) - log (test sample, viable cell count immediately after inoculation)} The antibacterial properties were evaluated according to the following criteria. Antibacterial activity value of 2.5 or more: ◎ Antibacterial activity value of 2.0 or more but less than 2.5: ○ Antibacterial activity value of less than 2.0: ×

[0107] <Production Example 1> 62.3 g of ethanol was placed in a separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer, and after stirring, nitrogen was flowed at 100 mL / min for 60 minutes, and the temperature was then raised to 70° C. After the nitrogen flow was increased to 50 mL / min, a monomer solution 1 consisting of 20.3 g of dimethylaminoethyl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, hereinafter also referred to as DAM), 11.8 g of ethanol, and 7.3 g of acetic acid; and 72.2 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 also referred to as PGM23E) were added to the polymerization reaction system, which was kept at a constant temperature of 70° C. under stirring. Monomer solution 2 consisting of 6.0 g of methacrylic acid (hereinafter also referred to as MAA) and 33.5 g of ethanol; monomer solution 3 consisting of 36.5 g of benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, hereinafter also referred to as BnMA); and an aqueous initiator solution consisting of 50.1 g of a 3.5% 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. Regarding the dropping time, the monomer solution and the aqueous initiator solution were added simultaneously, with Monomer Solutions 1, 2, and 3 added over 180 minutes, and the aqueous initiator solution added over 240 minutes. After the completion of all the droppings, the reaction solution was maintained at 70°C for an additional 60 minutes to mature, completing the polymerization and obtaining Copolymer 1. The results are shown in Table 1.

[0108] <Preparation Examples 2 to 20> Copolymers 2 to 20 were obtained by the same method as in Preparation Example 1, except that the amount of solvent, amount of monomer, type of monomer, and amount of initiator used in Preparation Example 1 were changed so as to obtain the compositions and molecular weights shown in Table 1. The types of monomers used in the polymerization of Preparation Examples 2 to 20 but not in Preparation Example 1 are listed below: lauryl methacrylate (trade name "Light Ester L" available from Kyoeisha Chemical Co., Ltd., hereinafter also referred to as LMA), butyl methacrylate (hereinafter also referred to as BMA), cyclohexyl methacrylate (hereinafter also referred to as CHMA), 2-ethylhexyl acrylate (hereinafter also referred to as 2EHA), and methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 9, trade name "Blemmer PME-400" available from NOF Corporation, hereinafter also referred to as PGM9E). The results are shown in Table 1.

[0109]

[0110] Comparative Production Example 1: 33.3 g of 2-butanone was placed in a separable glass flask equipped with a thermometer, reflux condenser, and stirrer, and 10.00 g of DAM, 6.67 g of lauryl acrylate (hereinafter also referred to as LA), 33.33 g of PGM23E, and 0.80 g of V-65 were added and stirred for a certain period of time under a nitrogen atmosphere. The solution was heated to around 60°C and maintained at 60°C for 7 hours to polymerize and mature. 200.0 g of 2-butanone was added thereto for dilution, and then the temperature was lowered to room temperature. This reaction solution was added dropwise to 4000.0 g of n-hexane to perform reprecipitation purification, and the precipitate was dried to obtain Comparative Copolymer 1.

[0111] Comparative Production Example 2: 900 g of ethanol was placed in a separable glass flask equipped with a thermometer, reflux condenser, and stirrer, and 17.8 g of DAM, 7.2 g of lauryl methacrylate (hereinafter also referred to as LMA), and 10.6 g of 6.6% V-65 were added and stirred for a certain period of time under a nitrogen atmosphere. The solution was heated to around 60°C and maintained at 60°C for 8 hours to polymerize and mature. 50.0 g of ethanol was added thereto for dilution, and then the temperature was lowered to room temperature. This reaction solution was added dropwise to 2000.0 g of ion-exchanged water to perform reprecipitation purification, and the precipitate was dried to obtain Comparative Copolymer 2.

[0112] Table 2 shows the results of soil releasability evaluation 1 for Examples 1 to 14, which used the copolymers produced in Production Examples 2, 4, 6, 8 to 17, and 19, as well as for Comparative Example 1, which contained no polymer, and Comparative Production Example 2, which was used as Comparative Example 2.

[0113]

[0114] As shown in Table 2, it was revealed that the copolymer of the present disclosure has excellent soil release properties.

[0115] The copolymers produced in the Production Examples were used to test the anti-soil redeposition properties on cotton, and the results are shown in Examples 15 to 23, and the evaluation result using Comparative Copolymer 1 produced in Comparative Production Example is shown in Table 3 as Comparative Example 3.

[0116]

[0117] The copolymers produced in the Production Examples were used to test the anti-soil redeposition properties of polyester, and the results are shown in Examples 24 to 41. The evaluation results of Comparative Copolymer 1 produced in Comparative Production Example are shown in Table 4 as Comparative Example 4.

[0118]

[0119] Table 5 shows the results of antibacterial evaluation of Examples 42 to 46, which used the copolymers produced in the Production Examples, and Comparative Example 5, which was a system using no polymer.

[0120]

[0121] As shown in Tables 3 to 5, it was revealed that the copolymer of the present disclosure also has excellent anti-redeposition properties and antibacterial properties.

Claims

1. A structural unit (a) derived from an amino group-containing monomer represented by the following general formula (1): A structural unit (b) derived from a monomer having a polyalkylene glycol chain; A structural unit (c) derived from a hydrophobic monomer, and Structural unit (d) derived from an unsaturated carboxylic acid monomer (However, excluding polymers having structural units derived from a monomer having a primary amino group or an amino group-containing monomer having two or more nitrogen atoms). 【Chemistry 1】 (In the 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 ５ each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms, and X represents a divalent linking group. In addition, an asterisk represents an atom contained in another structural unit of the same type or different type to which the structural unit represented by general formula (1) is bonded.

2. 2. The amino group-containing copolymer according to claim 1, wherein the hydrophobic monomer has a solubility parameter of 13 or less when formed into a homopolymer.

3. The ratio of the structural unit (a) derived from the amino group-containing monomer is 5 to 50% by weight based on 100% by weight of all structural units The amino group-containing copolymer according to claim 1 .

4. The weight average molecular weight is 4,000 or more and 500,000 or less. The amino group-containing copolymer according to claim 1 .

5. A soil release agent comprising the amino group-containing copolymer according to claim 1.

6. A method for using the amino group-containing copolymer according to claim 1 as a soil release agent.

7. The amino group-containing copolymer according to claim 1. and a surfactant. A method for producing a soil release agent, comprising:

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