JP7637230B2 - Amino group-containing copolymer - Google Patents

Description

The present invention relates to an amino group-containing copolymer. More specifically, the present invention relates to an amino group-containing copolymer that is useful for detergent applications such as liquid detergents and powder detergents.

It is expected that sebum stains on clothes will be easily removed when washing if the fabric is treated with a compound that will adsorb to the fabric. This function is called soil release property.
Various compounds exhibiting soil release properties have been proposed. For example, Patent Document 1 discloses that a polymer composed of a (meth)acrylic acid ester having a primary to tertiary amino group and an unsaturated bond-containing monomer having a hydrophobic group has an excellent soil release effect on cotton fabric.
For example, Patent Document 2 discloses that a composition containing a polymer having a quaternary ammonium group and a hydrophilic group has a stain removing effect on cotton fabric.

Patent No. 5014739 Special Publication No. 11-505568

As described above, the soil releasability of polymers containing amino groups has been disclosed. However, there is still room for improvement in the soil releasability, particularly for polyester fibers which tend to adsorb sebum stains.
The present invention has been made in consideration of the above-mentioned current situation, and an object of the present invention is to provide an amino group-containing copolymer having excellent soil release properties and a method for producing a soil release agent using the same.

The present inventors have conducted various investigations to achieve the above object and have arrived at the present invention.
That is, the present disclosure provides 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, and a structural unit (c) derived from a (meth)acrylic acid ester containing an aryl group which may have a substituent, wherein the proportion of the structural unit (a) derived from the amino group-containing monomer is 5 to 50 mass% with respect to 100 mass% of all structural units:

In general formula (1), R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₄ and R ₅ each independently represent a hydrogen atom or an organic group having 1 to 12 carbon atoms, and X represents a divalent linking group, with the exception that 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) is bonded.

The proportion of structural unit (b) derived from the monomer having the above-mentioned polyalkylene glycol chain is preferably 5 to 70 weight % relative to 100 mass % of all structural units.

It is preferable that the proportion of structural units (c) derived from a (meth)acrylic acid ester containing an aryl group which may have the above-mentioned substituent is 10 to 70 weight % relative to 100 mass % of all structural units.

It is preferable that the above amino group-containing copolymer has a weight average molecular weight of 4,000 or more and 500,000 or less.

The present invention is also a soil release agent containing the above-mentioned amino group-containing copolymer.

The present invention further relates to a method of using the above-mentioned amino group-containing copolymer as a soil release agent.

The present invention further relates to a method for producing a soil release agent, which includes a step of mixing the amino group-containing copolymer with a surfactant.

The amino group-containing copolymer disclosed herein has excellent soil release properties and can therefore be suitably used in detergents, etc., for textile products such as polyester.

The present invention will be described in detail below.
In addition, 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.

[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 characterized in that it contains a structural unit (a) derived from an amino group-containing monomer described below, a structural unit (b) derived from a monomer having a polyalkylene glycol chain, and a structural unit (c) derived from a (meth)acrylic acid ester containing an aryl group which may have a substituent, and the proportion of the structural unit (a) is 5 to 50 mass% with respect to 100 mass% of all structural units.
The copolymer of the present disclosure has such a structure and thus has excellent soil release properties, as well as excellent antibacterial properties and anti-redeposition properties.

<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).

一般式（１）において、Ｒ_１、Ｒ_２、Ｒ_３は、それぞれ独立に、水素原子または炭素数１～５のアルキル基を表し、Ｒ_４、Ｒ_５は、それぞれ独立に、水素原子または炭素数１～１２の有機基を表し、Ｘは２価の連結基を表す。ただし、アスタリスクは、一般式（１）で表される構造単位が結合している同種もしくは異種の他の構造単位に含まれる原子を表す。
なお、本開示において、「同種の他の構造単位に含まれる原子」とは、例えば一般式（１）で表される構造単位であれば、別の一般式（１）で表される構造単位に含まれる原子であることを表し、「異種の他の構造単位に含まれる原子」とは、例えば一般式（１）で表される構造単位であれば、一般式（１）で表される構造単位以外の構造単位に含まれる原子であることを表す。
上記アミノ基本含有単量体由来の構造単位は、一般式（１）において、－Ｘ－が、直接結合、又は－Ｃ（＝Ｏ）－Ｏ－又は－Ｃ（＝Ｏ）－Ｎ（－Ｈ）－又は－Ｃ（＝Ｏ）－Ｏ－（ＣＨ_２）ｎ－（ｎは１～５）又は－Ｃ（＝Ｏ）－Ｎ（－Ｈ）－（ＣＨ_２）ｎ－（ｎは１～５）で表される構造単位を含むことが好ましい。特に、－Ｘ－は、－Ｃ（＝Ｏ）－Ｏ－（ＣＨ_２）ｎ－であることが好ましく、ｎ＝１～３であることがより好ましく、ｎ＝２が特に好ましい。

In general formula (1), R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₄ and R ₅ each independently represent a hydrogen atom or an organic group having 1 to 12 carbon atoms, and X represents a divalent linking group, with the exception that 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) is bonded.
In the present disclosure, "an atom contained in another structural unit of the same type" refers to, for example, 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" refers to, for example, 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 preferably contains a structural unit represented by general formula (1) in which -X- is a direct bond, or -C(=O)-O-, or -C(=O)-N(-H)-, or -C(=O)-O-(CH ₂ )n- (n is 1 to 5), or -C(=O)-N(-H)-(CH ₂ )n- (n is 1 to 5). In particular, -X- is preferably -C(=O)-O-(CH ₂ )n-, with n being more preferably 1 to 3, and n being particularly preferably 2.

The structure derived from the above 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 to this.

上記一般式（２）のＲ_４、Ｒ_５は上記一般式（１）のＲ_４、Ｒ_５と同じである。

R ₄ and R ₅ in the above general formula (2) are the same as R ₄ and R ₅ in the above general formula (1).

The structural unit (a) derived from the above amino group-containing monomer is formed, for example, by radical polymerization of an 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 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 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 (meth)acrylate, 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 with acids such as hydrochloric acid, acetic acid, etc.; monoalkylamino group-containing (meth)acrylamides such as monomethylaminoethyl(meth)acrylamide, monoethylaminoethyl(meth)acrylamide, monomethylaminopropyl(meth)acrylamide and the like, and their neutralization with acids such as hydrochloric acid, acetic acid, etc.; (meth)acrylic acid and an alkali such as 2-aminoethyl(meth)acrylate, etc. Examples of such an amine compound include esters of allylamine and their neutralization with acids such as hydrochloric acid, acetic acid, etc.; N,N-diallylmethylamine and their neutralization with acids such as hydrochloric acid, acetic acid, etc.; allylamine and their neutralization with acids such as hydrochloric acid, acetic acid, etc.; and 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, acetic acid, etc.

As the structural unit (a) derived from the above amino group-containing monomer, it is particularly preferable that it is a structural unit derived from N,N-dimethylaminoethyl (meth)acrylate, as represented by the following general formula (3).

上記一般式（３）のＲ_６は水素原子又はメチル基を表す。ただし、アスタリスクは、一般式（３）で表される構造単位が結合している同種もしくは異種の他の構造単位に含まれる原子を表す。最も好ましくは、Ｎ，Ｎ－ジメチルアミノエチルメタアクリレート由来の構造単位である。

_R6 in the above general formula (3) represents a hydrogen atom or a methyl group. However, 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 (3) is bonded. Most preferred is a structural unit derived from N,N-dimethylaminoethyl methacrylate.

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 the monomers constituting the copolymer of the present disclosure (hereinafter also referred to as all structural units). By being in the above range, the proportion of cationic sites that can act on a substrate such as a fiber to which soil releasability is to be imparted becomes appropriate, and the performance of the detergent additive of the present disclosure tends to be improved.

<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 in that it contains a polyalkylene glycol chain in its structure. The structural unit (b) is represented, for example, by the following general formula (4).

式中、Ｒ_７、Ｒ_８、Ｒ_９は、それぞれ独立に、水素原子または置換基を有していてもよい炭素数１～５のアルキル基を表し、Ｚは、水素原子、炭素数１～３０の炭化水素基、又は、水酸基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩を表す。Ａは、置換基を有していてもよい炭素数１～１０のアルキレン基を表す。ｑは、（ＡＯ）の平均付加モル数を表し、１～２００の数である。ｎは、０～４の数を表す。ｍは０又は１を表す。

In the formula, R ₇ , R ₈ and R ₉ each independently represent 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 phosphoric acid 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.

The above R ₇ , R ₈ , and R ₉ each independently represent 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 phosphoric acid group, an amino group, and salt groups thereof.

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 further preferably a methyl group.
It is preferable that R ₇ , R ₈ , and R ₉ are each independently a hydrogen atom or a methyl group. More preferably, R ₇ and R ₉ are hydrogen atoms, and R ₈ is a hydrogen atom or a methyl group. Even more preferably, R ₇ and R ₉ are hydrogen atoms, and R ₈ is a methyl group.

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. The above-mentioned 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 above-mentioned hydrocarbon group may be branched, and when the hydrocarbon group is branched, the number of carbon atoms in the hydrocarbon group means the total number of carbon atoms in the main chain and the branched chains.

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

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.

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.

Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.

The hydrocarbon group is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 2 to 20, more preferably 2 to 15, even more preferably 2 to 10, and particularly preferably 2 to 5.
The above Z is preferably a hydrogen atom or a methyl group.

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, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a secondary or tertiary amino group, and salts thereof.
In the polyalkylene glycol represented by _q (AO), the q oxyalkylene groups of AO may all be the same or different.
The alkylene group represented by A preferably has 2 to 10 carbon atoms, and more preferably has 2 to 4 carbon atoms.

Examples of the oxyalkylene group represented by AO include oxyethylene, oxypropylene, oxybutylene, oxyisobutylene, oxy-2,3-butylene, oxystyrene, and oxyalkylene having 2 to 10 carbon atoms. More preferably, it is an alkylene oxide having 2 to 4 carbon atoms such as oxyethylene, oxypropylene, and oxybutylene, and even more preferably, it is oxyethylene and oxypropylene. The oxyalkylene group represented by AO is not limited to a group formed by an addition reaction of an alkylene oxide. In addition, when the above polyalkylene glycol is an adduct of two or more types of alkylene oxide, it may be in any form such as random addition, block addition, or alternating addition. As the oxyalkylene group in the polyalkylene glycol, it is preferable that the oxyethylene group is an essential component, and more preferably, 50 mol% or more of the oxyethylene group is an oxyethylene group, and even more preferably, 90 mol% or more of the oxyethylene group is an oxyethylene group.

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, even more preferably from 2 to 100, even more preferably from 2 to 80, and particularly preferably from 2 to 50.

The above n represents a number from 0 to 4, and m represents 0 or 1.
n is preferably 0 to 3, more preferably 0 to 2, and further preferably 0. m is more preferably 1.

The structural unit (b) having a 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; alkoxy polyalkylene 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 obtained by adding 10 to 100 moles of alkylene oxide 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.

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 70% 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, 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 proportion of hydrophilic sites becomes appropriate, and the performance of the detergent additive of the present disclosure tends to be improved.

<Structural Unit (c) Derived from a (Meth)acrylic Acid Ester Containing an Aryl Group Which May Have a Substitute>
The structural unit (c) derived from a (meth)acrylic acid ester containing an optionally substituted aryl group of the present disclosure is characterized in that it is derived from a (meth)acrylic acid ester containing an optionally substituted aryl group in its structure. The substituent is preferably a hydrophobic group, and is preferably a hydrocarbon group having 1 to 18 carbon atoms or an aryl group having 6 to 30 carbon atoms.

The structural unit (c) derived from the (meth)acrylic acid ester containing an aryl group which may have a substituent is formed, for example, by radical polymerization of a (meth)acrylic acid ester containing an aryl group which may have a substituent. Examples of the (meth)acrylic acid ester containing an aryl group which may have a substituent in the structure include esters of (meth)acrylic acid and an aryl alcohol having 6 to 30 carbon atoms which may have a substituent. 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-hydroxymethyl-naphthalene, 1-hydroxyethyl-naphthalene, 2-hydroxymethyl-naphthalene, 2-hydroxyethyl-naphthalene, and the like.

The above aryl (meth)acrylates include, for example, 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. Among these, phenyl (meth)acrylate and benzyl (meth)acrylate are preferred.

In the copolymer of the present disclosure, the content of the structural unit (c) derived from a (meth)acrylic acid ester containing an aryl group which may have a substituent is 10% by mass or more and 70% by mass or less, preferably 15% by mass or more and 65% by mass or less, more preferably 15% by mass or more and 60% by mass or less, even more preferably 15% by mass or more and 55% by mass or less, even more preferably 15% by mass or more and 50% by mass or less, particularly preferably 20% by mass or more and 45% by mass or less, and most preferably 20% by mass or more and 40% by mass or less, based on 100% by mass of the structural units derived from all the monomers constituting the copolymer of the present disclosure. The above ranges provide an appropriate proportion of hydrophobic sites, which tends to improve the performance of the detergent additive of the present disclosure.

<Structural Unit (d) 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, and a structural unit (d) derived from a monomer other than the structural unit (c) derived from a (meth)acrylic acid ester containing an optionally substituted aryl group.

Other monomers are not particularly limited, but examples include unsaturated carboxylic acid monomers; (meth)acrylic acid esters not containing aryl groups; olefin monomers having 2 to 4 carbon atoms such as ethylene and propylene, vinyl halides such as vinyl chloride, methyl vinyl ether, ethyl vinyl ether, acrylonitrile, etc.

The above-mentioned unsaturated carboxylic acid monomers include, for example, unsaturated carboxylic acid monomers such as (meth)acrylic acid, crotonic acid, tiglic acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, itaconic 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 their salts are preferred, and (meth)acrylic acid is more preferred.

The (meth)acrylic acid ester not containing an aryl group may be an ester of an alcohol not containing an aryl group and (meth)acrylic acid, and examples thereof 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, n-octyl (meth)acrylate, tridecyl (meth)acrylate, cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate, n-lauryl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isobornyl methacrylate, etc.

The other monomer is preferably an unsaturated carboxylic acid monomer, and a form in which the copolymer of the present disclosure has structural units derived from an unsaturated carboxylic acid monomer is also a preferred embodiment of the present invention.

In the copolymer of the present disclosure, the content of structural units derived from other monomers is preferably 10 mass% or less, more preferably 5 mass% or less, particularly preferably 3 mass% or less, and most preferably 1 mass% or less, relative to 100 mass% of structural units derived from all monomers constituting the copolymer of the present disclosure.

In the copolymer of the present disclosure, the content of the structural units derived from the unsaturated carboxylic acid monomer is preferably 0 to 10% by mass, more preferably 0 to 6% by mass, based on 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 proportion of dispersing groups becomes appropriate, and the performance of the detergent additive of the present disclosure tends to be improved.
An embodiment in which the copolymer of the present disclosure has 1 to 6% by mass of structural units derived from unsaturated carboxylic acid monomers relative to 100% by mass of all structural units is also one of the preferred embodiments of the present invention.

<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 4000 or more and 500000 or less, more preferably 6000 or more and 400000 or less, and even more preferably 10000 or more and 300000 or less. Furthermore, it is particularly preferably 10000 or more and 200000 or less, and most preferably 10000 or more and 100000 or less. By being in the above range, the soil release performance of the copolymer of the present disclosure tends to be further improved.

[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 it can be produced by polymerizing monomer components, and specific and preferred examples of the monomer components and the preferred ratio of each monomer are as described above.
The method for producing the amino group-containing copolymer of the present disclosure also constitutes the present invention.

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, and a (meth)acrylic acid ester containing an aryl group which may have a substituent (hereinafter referred to as the polymerization step). Methods for initiating the polymerization of the monomer components in the polymerization step include, for example, a method of adding a polymerization initiator, a method of irradiating with UV light, a method of applying heat, a method of irradiating with light in the presence of a photopolymerization initiator, and the like. In particular, it is preferable to use a polymerization initiator.

The above-mentioned polymerization initiators include, for example, 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, and persulfates and metal salts. Among these, persulfates and azo compounds are preferred, and azo compounds are more preferred, since they tend to reduce the amount of residual monomer. These polymerization initiators may be used alone or in the form of a mixture of two or more types.

The amount of the above 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 unit.

In the above polymerization step, a chain transfer agent may be used as a molecular weight regulator 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, and the like, 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 that can generate hydrogen sulfite (salt) (bisulfite (salt), pyrosulfite (salt), dithionous acid (salt), sulfurous acid (salt), etc.). Among these, compounds having a mercapto group are preferred, and more preferably mercapto group-containing compounds having a carboxyl group.

The amount of chain transfer agent used in the production of 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, even more preferably 0.3 mol% or more and 10 mol% or less, and most preferably 0.5 mol% or more and 5 mol% or less, relative to 100 mol% of the total amount of monomers constituting the structural units used.

The solvent used during polymerization can be selected as necessary from those capable of dissolving the monomer components, polymerization initiator, chain transfer agent, and copolymer after production. There are no particular restrictions, but water, alcohols having 1 to 8 carbon atoms such as ethanol, 1-propanol, 2-propanol, 1-butanol, and phenoxyethanol, and glycols such as propylene glycol, butylene glycol, and hexylene glycol are preferably used. Of these, water, ethanol, ethylene glycol, and propylene glycol are preferred, and a mixture of two or more of these may also be used.

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

In the above polymerization process, the method of feeding the monomer components, polymerization initiator, and chain transfer agent into the reaction vessel is not particularly limited, and examples of the method include feeding the entire amount into the reaction vessel all at once at the beginning, feeding the entire amount into the reaction vessel in portions or continuously, feeding a portion into the reaction vessel at the beginning and feeding the remainder into the reaction vessel in portions or continuously, etc. A preferred method is to charge the solvent described below at the beginning and then feed the monomer components, polymerization initiator, and chain transfer agent continuously.

The monomer components may also 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.

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 before use. As the alkaline substance, inorganic salts such as hydroxides and carbonates of monovalent or divalent metals, ammonia, and organic amines can be used. In addition, the concentration of the copolymer can be adjusted as necessary after the reaction is completed.

[Uses of the amino group-containing copolymer of the present disclosure]
The amino group-containing copolymers of the present disclosure are used in soil release, antibacterial and anti-redeposition applications.
Soil release agents, antibacterial agents and anti-resoiling agents can be used as additives in detergents. For example, soil release agents, antibacterial agents and anti-resoiling agents are used in detergents for textiles and hard surfaces. Detergents in this case include household detergents for clothing, kitchens, households, textile industry, and other industrial detergents.
The present invention further relates to a method for using the amino group-containing copolymer as a soil release agent, an antibacterial agent, or an anti-redeposition agent.
In the above method, it is preferable to contact the amino group-containing copolymer with an object to be washed.
The present invention also relates to a method for producing a soil release agent, which comprises the step of mixing the amino group-containing copolymer with a surfactant.

[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. The soil release property is a 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 soaking conditions and washing conditions.

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 typically used in detergents, without any 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 the additive include surfactants, such as anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

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

[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 is 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, antibacterial, antiseptic, antifungal, etc., and the target microorganisms are bacteria and fungi.

The above bacteria include gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, Salmonella, Moraxella, Legionella, etc.; and gram-positive bacteria such as Staphylococcus aureus and Clostridium bacteria. The above fungi include yeasts such as Candida, Rhodotorula, and baker's yeast; and molds such as red mold and black mold.

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 a microorganism, the cationic group derived from the structural unit represented by the general formula (1) of the amino group-containing copolymer is adsorbed to the surface of the microorganism having a negative charge. Furthermore, it is presumed that the hydrophobic group of the amino group-containing copolymer exhibits affinity for the cell membrane portion and interacts with the cell membrane, thereby destroying the interaction between lipids and the like that constitute the cell membrane and/or inhibiting the function of proteins and the like bound to the membrane, thereby destroying the cell and/or inhibiting the physiological activity of the cell, thereby killing the microorganism.

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 additive that is used in a typical detergent composition, without any particular limitation. The antibacterial agent of the present disclosure preferably contains 0.1 to 100% by mass of the amino group-containing copolymer. Examples of the additive include surfactants, such as anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

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

[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 %.

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

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.

The above surfactant may be any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants, and one or more of them may be used.

Preferred anionic surfactants include alkylbenzenesulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, α-olefinsulfonates, 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.

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 alkyl groups such as methyl groups.

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

The content of the above 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, relative to the total amount of the detergent composition. When the content of the surfactant is 10 to 60% by mass, relative to the total amount of the detergent composition, there is a tendency to achieve both cleaning power and economy.

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, "parts" means "parts by mass" and "%" means "% by mass."

<Measurement of weight average molecular weight of copolymer>
The weight average molecular weight (Mw) of the copolymer was measured by GPC (gel permeation chromatography).
The measurement conditions and the apparatus are as follows:
Apparatus: Tosoh EcoSEC HLC-8320GPC
Detector: Differential Refractometer (RI) Detector column: TSKgel α-M, α-2500 manufactured by Tosoh Corporation
Column temperature: 40°C
Flow rate: 0.8mL/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)

<Soil release evaluation 1>
Copolymers 1 to 9 produced in Examples 1 to 9 were evaluated for soil releasability by the following method.
(1) Preparation of hardness water: 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 to prepare a hardness mother liquor.
1.54 g of sodium hydrogen carbonate, 10 g of 0.1N hydrogen chloride, and 200 g of the above hardness mother liquor were placed in a beaker, and the mixture was diluted with ion-exchanged water to prepare 20,000 g of hard water.
(2) Fabric pretreatment method: Style 730 (polyester fiber manufactured by Testfabiric) was cut into 5 x 5 cm pieces. 360 g of an aqueous solution containing 1000 ppm of Emulgen 108 (manufactured by Kao Corporation) and 33 ppm of the copolymer obtained in the example was added to the fabric and stirred for 10 minutes while stirring with a magnetic stirrer. After stirring, the fabric was rinsed for 3 minutes using 360 g of ion-exchanged water, dehydrated, and air-dried for 1 day.
(3) Preparation of Contaminated 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-contaminated solution. 50 μL of the contaminated solution was dropped onto the polymer-treated cloth obtained by the above pretreatment method 1, and after leaving it for 1 hour, excess oil was wiped off by sandwiching it between filter paper to prepare a contaminated cloth.
(4) Detergency Evaluation (4)-1: Preparation of Surfactant Aqueous Solution 10 g of Emulgen 108 (Kao Corporation) was weighed out into a beaker, and ion-exchanged water was added to make up to 100 g to prepare a 10% surfactant solution.
(4)-2: Preparation of 1% copolymer aqueous solution Dilute with ion-exchanged water to a copolymer concentration of 1% to prepare a 1% copolymer aqueous solution. An appropriate concentration of sodium hydroxide aqueous solution was added to the prepared aqueous solution to adjust the pH to 7.5 to 8.5.
(4)-3: Detergency test The tergotometer was set to 25°C, and 493.3 g of the hard water (1) and 5.0 g of the surfactant solution (4)-1 were added to the pot, and 1.7 g of the 1% copolymer aqueous solution (4)-2 was added so that the copolymer concentration in the pot was 33 ppm, and mixed. Five stained cloths whose Z value had been measured in advance using a color difference observation device (Vervide: Digieye) and a liquor ratio adjustment cloth (cotton white cloth) were added to the pot in a total of 16.7 g, and washed by stirring at 120 rpm for 10 minutes. The water in the pot was discarded, and rinsing was performed once for 3 minutes using 500 g of ion-exchanged water, after which the cloths were dehydrated and air-dried for 1 day. After air-drying, the Z value of the stained cloths after washing was measured again using a color difference meter, and the cleaning rate was calculated using the following formula. Based on the obtained cleaning rate, the cleaning power was evaluated according to the following criteria.
Formula for calculating cleaning rate Cleaning rate (%) = ((Zs-Zw)/(Zs-Zo)) x 100
Zs represents the Z value of the soiled cloth before evaluation, Zw represents the Z value of the soiled cloth after evaluation, and Zo represents the Z value of the white cloth before soiling.
◎: Cleaning rate of 90% or more 〇: Cleaning rate of 60% or more, less than 90% ×: Cleaning rate of less than 60%

<Soil release evaluation 2>
Copolymers 10 to 20 produced in Examples 10 to 21 were evaluated for soil releasability by 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 bring the total weight to 1000 g.
(1)-2: Preparation of hard water 1.54 g of sodium hydrogen carbonate, 10 g of 0.1N hydrogen chloride, and 200 g of hardness mother liquor (1)-1 were placed in a beaker and diluted with ion-exchanged water to a total weight of 20,000 g.
(1)-3
Polyester taffeta (polyester fiber, manufactured by Shikisen Co., Ltd.) was cut into 5 x 5 cm pieces. (1)-2 hard water was used to prepare 55 g of an aqueous solution containing 1000 ppm of Emulgen 108 (manufactured by Kao Corporation) and 33 ppm of the copolymer obtained in the Example, to which 2.7 g of the above fabric was added and stirred for 10 minutes with a roller shaker. After stirring, the fabric was rinsed for 3 minutes, dehydrated, and air-dried for 1 day.
(Creating contaminated cloth)
An oil-stained solution was prepared by mixing 61.5 g of olive oil, 37 g of oleic acid, 1 g of iron (III) oxide, and 0.5 g of oil red. 15 μL of this stained solution was dropped onto the polymer-treated cloth obtained by the above pretreatment method 1, and left at 40° C. for 1 hour to prepare a stained cloth.
(Cleaning power evaluation)
(2)-1: Preparation of an aqueous surfactant solution 10 g of Emulgen 108 (Kao Corporation) was weighed out into a beaker, and ion-exchanged water was added to make up to 100 g to prepare a 10% surfactant solution.
(2)-2: Detergency test The tergot meter was set to 25°C, and 498.8 g of the hard water (1)-2) and 0.85 g of the surfactant solution (1)-3 were added to the pot, and a 1% copolymer aqueous solution was added so that the copolymer concentration in the pot was 7.3 ppm, and mixed. Five pieces of soiled cloth whose Z value had been measured in advance with a spectrophotometer (SE6000 manufactured by Nippon Denshoku Industries Co., Ltd.) and a liquor ratio adjustment cloth were added to the pot in a total of 16.7 g, and washed by stirring at 120 rpm for 10 minutes. The water in the pot was discarded, and after rinsing once for 3 minutes, the cloth was dehydrated and air-dried for 1 day.
After air drying, the Z value of the soiled cloth after washing was measured again using a color difference meter, and the cleaning rate was calculated using the above formula. Based on the obtained cleaning rate, the cleaning power was evaluated according to the following criteria. The results are shown in Table 5.
◎: Cleaning rate of 87% or more 〇: Cleaning rate of 85% or more, less than 87% ×: Cleaning rate of less than 85%

<Re-soiling prevention evaluation>
(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 bring the total weight to 100 g.
(3) Preparation of an aqueous sodium hydrogen carbonate solution: 1.54 g of sodium hydrogen carbonate and 10 g of 0.1N hydrogen chloride were placed in a beaker and diluted with ion-exchanged water to a total weight of 100 g.
(4) Measurement of color of white cloth The whiteness of the white cloth used in the evaluation of anti-resoiling was measured by measuring the reflectance with a color difference meter (SE-6000, manufactured by Nippon Denshoku Industries Co., Ltd.) before the evaluation.
(5) Detergency Evaluation The tergotometer was set to 25°C, and 891.3g of ion-exchanged water, 1.2g of hardness mother liquor, 4.5g of sodium bicarbonate aqueous solution, 2.25g of surfactant aqueous solution, and 0.75g of 1% polymer aqueous solution in terms of solid content were put into a pot and stirred at 120 rpm for 3 minutes. Then, 0.05g of carbon black (carbon black #10 manufactured by Mitsubishi Chemical) was put in, and 5 sheets of cotton knit (cotton cloth manufactured by Dyeing Test Materials Co., Ltd.) or 5 sheets of Style 730 and a liquor ratio adjustment cloth (white cotton cloth) were put in total of 30g, and the mixture was washed by stirring at 120 rpm for 10 minutes. The water in the pot was discarded, and after rinsing twice, the white cloth was dehydrated.
The white cloth was covered with a pressing cloth, and the cloth was dried while smoothing out any wrinkles with an iron. The whiteness of the white cloth was then measured again in terms of reflectance using the color difference meter.
From the above measurement results, the anti-soil redeposition rate was calculated according to the following formula.
Anti-redeposition rate (%) = [(whiteness after washing)/(whiteness of original white cloth)] x 100
The anti-redeposition ability was evaluated according to the following criteria.
Redeposition prevention rate compared to when no polymer was added is +1.0% or more: ◎
The redeposition prevention rate compared to the condition where no polymer was added is +0.5% or more but less than 1.0%: ◯ The redeposition prevention rate compared to the condition where no polymer was added is less than +0.5%: ×

<Antibacterial evaluation>
(1) Preparation of hardness water: 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 to prepare a hardness mother liquor.
1.54 g of sodium hydrogen carbonate, 10 g of 0.1N hydrogen chloride, and 200 g of the above hardness mother liquor were placed in a beaker, and the mixture was 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 adjusted to 100 ppm of the copolymer obtained in the example using the hard water described in (1) above 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 mixture was dehydrated and air-dried for 1 day.
(3) Antibacterial Test The antibacterial properties of the pretreated test cloth were evaluated by JIS L 1902:2015 (bacterial liquid absorption method of antibacterial test method for textile products). Staphylococcus aureus (Staphylococcus aureus NBRC 12732) was used to evaluate the antibacterial properties, and the number of live bacteria was measured by the pour plate culture method to evaluate the antibacterial performance. The antibacterial performance was compared with that of a test cloth made of 100% untreated cotton, and the antibacterial properties against Staphylococcus aureus were evaluated by the antibacterial activity value represented by the following formula.
Antibacterial activity value = {log (control sample, viable bacteria count after incubation) - log (control sample, viable bacteria count immediately after inoculation)} - {log (test sample, viable bacteria count after incubation) - log (test sample, viable bacteria 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 is 2.0 or more and less than 2.5: ○
Antibacterial activity value less than 2.0: ×

<Production Example 1>
A glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 65 g of ethanol, and nitrogen was flowed at 100 ml/min for 60 minutes under stirring, and then the temperature was raised to 70° C. After the nitrogen flow was increased to 50 ml/min, 78.3 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), 20.3 g of dimethylaminoethyl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter also referred to as DAM), ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter also referred to as DAM), and 10.0 g of dimethylaminoethyl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter also referred to as DAM) were added to the polymerization reaction system at a constant temperature of 70° C. under stirring. A monomer solution 1 consisting of 42.2 g of benzyl methacrylate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 7.4 g of acetic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), a monomer solution 2 consisting of 36.5 g of benzyl methacrylate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., hereinafter also referred to as BnMA), and an aqueous initiator solution consisting of 50.4 g of a 3% ethanol solution of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65" manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were each dropped from separate dropping nozzles. Regarding the dropping time, the dropping of the monomer solution and the aqueous initiator solution was started at the same time, and the dropping of the monomer solutions 1 and 2 was started for 180 minutes, and the aqueous initiator solution was dropped for 240 minutes.
After the entire dropwise addition was completed, the reaction solution was kept at 70° C. for an additional 60 minutes for maturation, and the polymerization was completed to obtain Copolymer 1.

<Production Examples 2 to 6, 8 to 11>
Copolymers 2 to 6 and 8 to 11 were obtained in the same manner as in Production Example 1, except that the amounts of the solvent, monomer, and initiator used were changed so as to obtain the compositions and molecular weights shown in Table 1.

<Production Example 7>
A separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 65 g of ethanol, and after stirring, nitrogen flow was performed at 100 ml/min for 60 minutes, and the temperature was raised to 70 ° C. After the nitrogen flow was changed to 50 ml/min, the polymerization reaction system was stirred at a constant temperature of 70 ° C., and monomer solution 1 consisting of 71.6 g of PGM23E, 27.0 g of DAM, 42.4 g of ethanol, 9.8 g of acetic acid, and 0.47 g of mercaptopropionic acid (manufactured by SC Organic Chemicals, hereinafter also referred to as MPA) was dropped from a separate dropping nozzle. Regarding the dropping time, the monomer solution and the aqueous initiator solution started dropping at the same time, and the monomer solutions 1 and 2 were dropped for 180 minutes, and the aqueous initiator solution was dropped for 240 minutes.
After the entire dropwise addition was completed, the reaction solution was kept at 70° C. for an additional 60 minutes for maturation, and the polymerization was completed to obtain Copolymer 7.

<Production Example 12>
A glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 62.3 g of ethanol, and after 60 minutes of nitrogen flow at 100 ml/min under stirring, the temperature was raised to 70 ° C. After the nitrogen flow was changed to 50 ml/min, the polymerization reaction system was stirred at a constant temperature of 70 ° C., and the following monomer solution 1 consisting of 20.3 g of DAM, 11.8 g of ethanol, and 7.3 g of acetic acid; monomer solution 2 consisting of 72.2 g of PGM23E, 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 BnMA; and an aqueous initiator solution consisting of 50.1 g of a 3.5% ethanol solution of 'V-65 were each dropped from a separate dropping nozzle. Regarding the dropping time, the monomer solution and the aqueous initiator solution started dropping at the same time, and the monomer solutions 1, 2, and 3 were dropped for 180 minutes, and the aqueous initiator solution was dropped for 240 minutes.
After the entire dropwise addition was completed, the reaction solution was kept at 70° C. for an additional 60 minutes for maturation, and the polymerization was completed to obtain Copolymer 12.

<Production Examples 13 to 21>
Copolymers 13 to 21 were obtained in the same manner as in Production Example 12, except that the amounts of the solvent, monomer, and initiator used were changed so as to obtain the compositions and molecular weights shown in Table 1.

<Comparative Production Example 1>
33.3 g of 2-butanone was charged into a glass separable flask equipped with a thermometer, a reflux condenser, and a 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 about 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 dropped into 4000.0 g of n-hexane to perform reprecipitation purification, and the precipitate was dried to obtain comparative copolymer 1.

<Comparative Production Example 2>
A separable glass flask equipped with a thermometer, reflux condenser, and stirrer was charged with 900 g of ethanol, 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, and stirred for a certain period of time under a nitrogen atmosphere. The solution was heated to about 60°C and maintained at 60°C for 8 hours for polymerization and aging. 50.0 g of ethanol was added thereto for dilution, and the temperature was then lowered to room temperature. This reaction solution was dropped into 2000.0 g of ion-exchanged water for reprecipitation and purification, and the precipitate was dried to obtain comparative copolymer 2.

The results of soil release evaluation 1 for Examples 1 to 9, which used copolymers 1 to 9 produced in Production Examples 1 to 9, and for Comparative Example 1, a system that did not use a polymer, are shown in Table 2.

The results of soil release evaluation 2 for Examples 10, 11, 13-17, 19-21, which used copolymers 10, 11, 13-17, 19-21 produced in Production Examples 10, 11, 13-17, 19-21, and Comparative Production Example 2 as Comparison Example 2, are shown in Table 3.

As shown in Tables 2 and 3, it has been revealed that the copolymers disclosed herein have excellent soil release properties.

The results of testing the copolymer produced in the manufacturing example for its anti-redeposition properties on cotton are shown in Examples 22 to 30, and the evaluation results of comparative copolymer 1 produced in comparative manufacturing example 1 are shown in Table 4 as Comparative Example 3.

In addition, the copolymer produced in the manufacturing example was used to test the anti-redeposition properties of polyester, and the results are shown in Examples 31 to 47, while the evaluation results of comparative copolymer 1 produced in comparative manufacturing example 1 are shown in Table 5 as Comparative Example 4.

The results of antibacterial evaluation of Examples 48 to 56, which used the copolymer produced in the manufacturing examples, and Comparative Example 5, a system that did not use a polymer, are shown in Table 6.

As shown in Tables 4 to 6, it was revealed that the copolymer of the present disclosure also has excellent anti-redeposition properties and antibacterial properties.

Claims (8)

An amino group-containing copolymer comprising structural units (a) derived from an amino group-containing monomer represented by the following general formula (1), structural units (b) derived from a monomer having a polyalkylene glycol chain represented by the following general formula (4) , and structural units (c) derived from an ester of (meth)acrylic acid and an aryl alcohol having 6 to 30 carbon atoms which may have a substituent, wherein the proportion of the structural units (a) derived from the amino group-containing monomer is 5 to 50 mass% relative to 100 mass% of all structural units, and the proportion of the structural units (b) derived from the monomer having a polyalkylene glycol chain is 30 to 70 mass% relative to 100 mass% of all structural units,
The amino group-containing copolymer is characterized in that the substituent which the aryl alcohol may have is a hydrocarbon group having 1 to 18 carbon atoms or an aryl group having 6 to 30 carbon atoms .
(In general formula (1), R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₄ and R ₅ each independently represent 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 different type to which the structural unit represented by general formula (1) is bonded.)
(In general formula (4), R ₇ , R ₈ , and R ₉ each independently represent a hydrogen atom or a methyl group; Z represents a hydrogen atom, a chain hydrocarbon group having 1 to 30 carbon atoms, or a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphate group, or a salt thereof; A represents an alkylene group having 1 to 10 carbon atoms which may have a substituent, and the substituent is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphate group, or a salt thereof; 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; and m represents 0 or 1.) 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 represented by the following general formula (4) , and a structural unit (c) derived from an ester of (meth)acrylic acid and an aryl alcohol having 6 to 30 carbon atoms which may have a substituent:
The amino group-containing copolymer has a ratio of structural units (a) derived from an amino group-containing monomer of 5 to 50 mass% relative to 100 mass% of all structural units, a ratio of structural units (b) derived from a monomer having a polyalkylene glycol chain of 20 to 70 mass% relative to 100 mass% of all structural units, and a weight average molecular weight of 10,000 or more and 500,000 or less ;
The amino group-containing copolymer is characterized in that the substituent which the aryl alcohol may have is a hydrocarbon group having 1 to 18 carbon atoms or an aryl group having 6 to 30 carbon atoms .
(In general formula (1), R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₄ and R ₅ each independently represent 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 different type to which the structural unit represented by general formula (1) is bonded.)
(In general formula (4), R ₇ , R ₈ , and R ₉ each independently represent a hydrogen atom or a methyl group; Z represents a hydrogen atom, a chain hydrocarbon group having 1 to 30 carbon atoms, or a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphate group, or a salt thereof; A represents an alkylene group having 1 to 10 carbon atoms which may have a substituent, and the substituent is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphate group, or a salt thereof; 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; and m represents 0 or 1.) The amino group-containing copolymer according to claim 1, characterized in that the proportion of structural units (c) derived from a (meth)acrylic acid ester containing an aryl group which may have a substituent is 10 to 65% by mass relative to 100% by mass of all structural units. The amino group-containing copolymer according to claim 2, characterized in that the proportion of structural units (c) derived from a (meth)acrylic acid ester containing an aryl group which may have a substituent is 10 to 70 mass% relative to 100 mass% of all structural units. The amino group-containing copolymer according to claim 1, characterized in that the weight average molecular weight of the amino group-containing copolymer is 10,000 or more and 500,000 or less. A soil release agent comprising an amino group-containing copolymer,
The amino group-containing copolymer contains structural units (a) derived from an amino group-containing monomer represented by the following general formula (1), structural units (b) derived from a monomer having a polyalkylene glycol chain represented by the following general formula (4) , and structural units (c) derived from an ester of (meth)acrylic acid and an aryl alcohol having 6 to 30 carbon atoms which may have a substituent, wherein the proportion of the structural units (a) derived from the amino group-containing monomer is 5 to 50% by mass with respect to 100% by mass of all structural units:
A soil release agent characterized in that the substituent that the aryl alcohol may have is a hydrocarbon group having 1 to 18 carbon atoms or an aryl group having 6 to 30 carbon atoms .
(In general formula (1), R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₄ and R ₅ each independently represent 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 different type to which the structural unit represented by general formula (1) is bonded.)
(In general formula (4), R ₇ , R ₈ , and R ₉ each independently represent a hydrogen atom or a methyl group; Z represents a hydrogen atom, a chain hydrocarbon group having 1 to 30 carbon atoms, or a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphate group, or a salt thereof; A represents an alkylene group having 1 to 10 carbon atoms which may have a substituent, and the substituent is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphate group, or a salt thereof; 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; and m represents 0 or 1.) the structural unit (a) derived from an amino group-containing monomer represented by the following general formula (1), the structural unit (b) derived from a monomer having a polyalkylene glycol chain represented by the following general formula (4) , and the structural unit (c) derived from an ester of (meth)acrylic acid and an aryl alcohol having 6 to 30 carbon atoms which may have a substituent, wherein the proportion of the structural unit (a) derived from the amino group-containing monomer is 5 to 50% by mass with respect to 100% by mass of all structural units,
The amino group-containing copolymer , in which the substituent that the aryl alcohol may have is a hydrocarbon group having 1 to 18 carbon atoms or an aryl group having 6 to 30 carbon atoms, is used as a soil release agent.
(In general formula (1), R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₄ and R ₅ each independently represent 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 different type to which the structural unit represented by general formula (1) is bonded.)
(In general formula (4), R ₇ , R ₈ , and R ₉ each independently represent a hydrogen atom or a methyl group; Z represents a hydrogen atom, a chain hydrocarbon group having 1 to 30 carbon atoms, or a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphate group, or a salt thereof; A represents an alkylene group having 1 to 10 carbon atoms which may have a substituent, and the substituent is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphate group, or a salt thereof; 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; and m represents 0 or 1.) A method for producing a soil release agent, comprising:
The method includes the step of mixing an amino group-containing copolymer and a surfactant,
The amino group-containing copolymer contains structural units (a) derived from an amino group-containing monomer represented by the following general formula (1), structural units (b) derived from a monomer having a polyalkylene glycol chain represented by the following general formula (4) , and structural units (c) derived from an ester of (meth)acrylic acid and an aryl alcohol having 6 to 30 carbon atoms which may have a substituent, wherein the proportion of the structural units (a) derived from the amino group-containing monomer is 5 to 50% by mass with respect to 100% by mass of all structural units:
The method for producing a soil release agent is characterized in that the substituent that the aryl alcohol may have is a hydrocarbon group having 1 to 18 carbon atoms or an aryl group having 6 to 30 carbon atoms .
(In general formula (1), R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₄ and R ₅ each independently represent 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 different type to which the structural unit represented by general formula (1) is bonded.)
(In general formula (4), R ₇ , R ₈ , and R ₉ each independently represent a hydrogen atom or a methyl group; Z represents a hydrogen atom, a chain hydrocarbon group having 1 to 30 carbon atoms, or a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphate group, or a salt thereof; A represents an alkylene group having 1 to 10 carbon atoms which may have a substituent, and the substituent is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphate group, or a salt thereof; 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; and m represents 0 or 1.)