Amino group-containing copolymer

Abstract

The purpose of the present invention is to provide an amino-group-containing copolymer having excellent detergency and a method for producing a detergent using the copolymer. The present invention is an amino group-containing copolymer containing 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 (d) derived from an unsaturated carboxylic acid-based monomer.

Description

Technical Field

[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. Background Art

[0002] For sebum dirt and the like attached to clothes, by treating the fibers with a compound that adsorbs to the fibers in advance, it is expected that the dirt will be easily removed during washing. This function is called detergency.

[0003] Various compounds that exhibit soil release properties have been proposed. For example, Patent Document 1 discloses a polymer composed of a (meth)acrylate having primary to tertiary amino groups and an unsaturated bond-containing monomer having a hydrophobic group, which has an excellent soil release effect on cotton cloth.

[0004] For example, Patent Document 2 discloses that a composition containing a polymer having a quaternary ammonium group and a hydrophilic group has a dirt-releasing effect on cotton cloth.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent No. 5014739

[0008] Patent Document 2: Japanese Patent Publication No. 11-505568 Summary of the invention

[0009] Problems to be solved by the invention

[0010] As described above, the detergency of amino group-containing polymers is disclosed. However, there is still room for further improvement in detergency, particularly for polyester fibers that easily adsorb sebum dirt.

[0011] The present invention has been made in view 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 copolymer.

[0012] Means for solving problems

[0013] The present inventors have conducted various studies to achieve the above-mentioned object and have arrived at the present invention.

[0014] That is, the present disclosure relates to an amino group-containing copolymer comprising:

[0015] The structural unit (a) derived from an amino group-containing monomer represented by the following general formula (1),

[0016] Structural units (b) derived from monomers having a polyalkylene glycol chain,

[0017] Structural units (c) derived from hydrophobic monomers, and

[0018] The structural unit (d) is derived from an unsaturated carboxylic acid monomer.

[0019] [Chemistry 1]

[0020]

[0021] 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, and R 4 , R 5 Each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms, and X represents a divalent linking group. The asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit represented by the general formula (1) is bonded.

[0022] The solubility parameter of the homopolymer of the hydrophobic monomer is preferably 13 or less.

[0023] The ratio 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.

[0024] The ratio 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.

[0025] The ratio 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.

[0026] The ratio of the structural unit (d) derived from the unsaturated carboxylic acid-based monomer is preferably 1 to 20% by weight relative to 100% by weight of all structural units.

[0027] The weight average molecular weight of the amino group-containing copolymer is preferably 4,000 to 500,000.

[0028] In addition, the present invention also relates to a detergent comprising the amino group-containing copolymer.

[0029] In addition, the present invention also relates to a method for using the amino group-containing copolymer as a soil release agent.

[0030] In addition, the present invention also relates to a method for producing a detergent, wherein the method comprises the step of mixing the amino group-containing copolymer with a surfactant.

[0031] Effects of the Invention

[0032] The amino group-containing copolymer disclosed in the present invention has excellent soil release properties and can therefore be particularly suitably used in detergents and the like for fiber products such as polyester. DETAILED DESCRIPTION

[0033] Hereinafter, the present invention will be described in detail.

[0034] In addition, the preferred aspects of the present invention described below may be combined in two or more forms, which are also preferred aspects of the present invention.

[0035] [Amino Group-Containing Copolymer of the Present Disclosure]

[0036] The amino group-containing copolymer of the present disclosure (hereinafter also referred to as the copolymer of the present disclosure) is a copolymer comprising the structural unit (a) derived from the amino group-containing monomer described below, the structural unit (b) derived from the monomer having a polyalkylene glycol chain, the structural unit (c) derived from the hydrophobic monomer, and the structural unit (d) derived from the unsaturated carboxylic acid monomer.

[0037] The copolymer disclosed in the present invention has such a structure and is excellent in detergency, antimicrobial property and anti-refouling property.

[0038] <Structural Unit (a) Derived from Amino Group-Containing Monomer>

[0039] The structural unit (a) derived from the amino group-containing monomer of the present disclosure is a structural unit represented by the following general formula (1).

[0040] [Chemistry 2]

[0041]

[0042] 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, and R 4 , R 5 Each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms, and X represents a divalent linking group. The asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit represented by the general formula (1) is bonded.

[0043] It should be noted that, in the present disclosure, “atoms contained in another structural unit of the same type”, for example, with respect to the structural unit represented by the general formula (1), refers to atoms contained in another structural unit represented by the general formula (1), and “atoms contained in another structural unit of a different type”, for example, with respect to the structural unit represented by the general formula (1), refers to atoms contained in a structural unit other than the structural unit represented by the general formula (1).

[0044] The structural unit derived from the amino group-containing monomer preferably includes a structural unit in which -X- in the general formula (1) is a direct bond, or is represented by -C(=O)-O-, -C(=O)-, -C(=O)-O-(CH2)n- (n is 1 to 5), or -C(=O)-N(-H)-(CH2)n- (n is 1 to 5). It is particularly preferred that -X- is -C(=O)-O-(CH2)n-, more preferably n=1 to 3, and particularly preferably n=2.

[0045] 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 or tertiary amino group represented by the following general formula (2) or a neutralized product of a primary or tertiary amino group neutralized with an acid, but is not limited thereto.

[0046] [Chemistry 3]

[0047]

[0048] R in the above general formula (2) 4 , R 5 R of the above general formula (1) 4 , R 5 same.

[0049] 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 (meth)acrylic acid esters containing N,N-dialkylamino groups 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 neutralized products neutralized with an acid such as hydrochloric acid and acetic acid; (meth)acrylic acid amides containing N,N-dialkylamino groups 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 neutralized products neutralized with an acid such as hydrochloric acid and acetic acid; (meth)acrylic acid monomethylaminoethyl, (meth)acrylate monoethylaminoethyl, (meth)acrylate monomethylaminopropyl, (meth)acrylate monoethylaminopropyl, (meth)acrylate-2-(tert-butylamino)-propene; (Meth)acrylic acid esters containing monoalkylamino groups such as (meth)acrylic acid esters, such as (meth)acrylic acid esters containing monoalkylamino groups such as (meth)ethyl (meth)acrylamide, and their neutralization products neutralized with acids such as hydrochloric acid and acetic acid; (meth)acrylic acid esters containing monoalkylamino groups such as (meth)acrylamide, monomethylaminoethyl (meth)acrylamide, monoethylaminoethyl (meth)acrylamide, monomethylaminopropyl (meth)acrylamide, and monoethylaminopropyl (meth)acrylamide, and their neutralization products neutralized with acids such as hydrochloric acid and acetic acid; (meth)acrylic acid esters containing monoalkylamino groups such as (meth)acrylic acid esters and alkanolamines such as (meth)acrylic acid esters containing monoalkylamino groups such as (meth)acrylic acid esters containing monoalkylamino groups such as (meth)ethyl (meth)acrylamide, and their neutralization products neutralized with acids such as hydrochloric acid and acetic acid; (meth)acrylic acid esters containing (meth)acrylic acid esters containing monoalkylamino groups such as (meth)acrylamide, monomethylaminoethyl (meth)acrylamide, monoethylaminoethyl (meth)acrylamide, monomethylaminopropyl (meth)acrylamide, and their neutralization products neutralized with acids such as hydrochloric acid and acetic acid; (meth)acrylic acid esters containing (meth)acrylic acid esters containing monoalkylamino groups such as ... Esters and their neutralization products neutralized with acids such as hydrochloric acid and acetic acid; N,N-diallylmethylamine and its neutralization products neutralized with acids such as hydrochloric acid and acetic acid; allylamine and its neutralization products neutralized with acids such as hydrochloric acid and acetic acid; addition reaction products of unsaturated monomers containing cyclic ether groups having 2 to 8 carbon atoms such as 1-allyloxy-3-dibutylamino-2-ol and 1-allyloxy-3-diethanolamino-2-ol and amine compounds having 1 to 24 carbon atoms, and their neutralization products neutralized with acids such as hydrochloric acid and acetic acid, etc.

[0050] As the structural unit (a) derived from the amino group-containing monomer, a structural unit derived from N,N-dimethylaminoethyl (meth)acrylate represented by the following general formula (3) is particularly preferred.

[0051] [Chemistry 4]

[0052]

[0053] R in the above general formula (3) 6 represents a hydrogen atom or a methyl group. The asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit represented by the general formula (3) is bonded. The most preferred structural unit is a structural unit derived from N,N-dimethylaminoethyl methacrylate.

[0054] The content of the structural unit (a) derived from the amino group-containing monomer in the copolymer of the present disclosure 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, relative to 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).

[0055] In one embodiment, the content of the structural unit (a) is preferably 8 mass % to 45 mass % relative to 100 mass % of all structural units, more preferably 10 mass % to 40 mass %, particularly preferably 15 mass % to 38 mass %, and most preferably 20 mass % to 35 mass %.

[0056] By being within the above range, the proportion of the cationic sites that can act on a substrate such as a fiber to which detergency is to be imparted becomes appropriate, and the detergency and antimicrobial performance of the detergent additive of the present disclosure tend to be improved.

[0057] <Structural Unit (b) Derived from Monomer Having a Polyalkylene Glycol Chain>

[0058] 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. This structural unit (b) is represented by the following general formula (4), for example.

[0059] [Chemistry 5]

[0060]

[0061] In the formula, R 7 , R 8 , R 9 Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted, and 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, and a salt thereof. A represents an alkylene group having 1 to 10 carbon atoms which may be substituted. q represents the average number of added moles of (AO), which is a number of 1 to 200. n represents a number of 0 to 4. m represents 0 or 1.

[0062] The above R 7 , R 8 , R 9 Each is 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 phosphoric acid group, an amino group, and salts thereof.

[0063] The alkyl group is preferably a methyl group, an ethyl group, or a propyl group, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

[0064] Preferred R 7 , R 8 , R 9 Each independently represents a hydrogen atom or a methyl group. 7 , R 9 is a hydrogen atom, R 8 is a hydrogen atom or a methyl group. 7 , R 9 is a hydrogen atom, R 8 It is methyl.

[0065] 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, and salts thereof. The hydrocarbon group is not particularly limited, and examples thereof include chain hydrocarbon groups such as alkyl, alkenyl, and alkynyl, and cyclic hydrocarbon groups such as aryl, cycloalkyl, and cycloalkenyl. The hydrocarbon group may have a branched chain, and the carbon number of the hydrocarbon group in the case of having a branched chain refers to the total carbon number of the main chain and the branched chain.

[0066] Examples of the alkyl group include ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, stearyl, and eicosyl.

[0067] Examples of the alkenyl group include vinyl, allyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, octadecenyl, eicosenyl, etc. Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, dodecynyl, octadecynyl, eicosynyl, etc.

[0068] Examples of the aryl group include phenyl, benzyl, methylphenyl, 1-methoxy-4-methylphenyl, ethylphenyl, propylphenyl, butylphenyl, butylmethylphenyl, dimethylphenyl, diethylphenyl, dibutylphenyl, biphenylyl, biphenylmethyl, biphenylethyl, naphthyl, naphthylmethyl, and naphthylethyl.

[0069] Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the cycloalkenyl group include cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl.

[0070] The hydrocarbon group is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. The hydrocarbon group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, further preferably 2 to 10 carbon atoms, and particularly preferably 2 to 5 carbon atoms.

[0071] As the above-mentioned Z, a hydrogen atom or a methyl group is preferable.

[0072] A represents an optionally substituted alkylene group having 1 to 10 carbon atoms. 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.

[0073] All of the q oxyalkylene groups of AO present in the polyalkylene glycol represented by (AO)q may be the same or different.

[0074] The alkylene group represented by A preferably has 2 to 10 carbon atoms, and more preferably has 2 to 4 carbon atoms.

[0075] As the oxyalkylene group represented by AO, for example, oxyethylene, oxypropylene, oxybutylene, oxyisobutylene, oxy2,3-butylene, oxystyrene, and alkylene groups having 2 to 10 carbon atoms can be cited. Oxyalkylene groups having 2 to 4 carbon atoms such as oxyethylene, oxypropylene, and oxybutylene are more preferred, and oxyethylene and oxypropylene are further preferred. It should be noted that the oxyalkylene group represented by AO is not limited to the group formed by the addition reaction of oxyalkylene. In addition, when the above-mentioned polyalkylene glycol is a product of two or more oxyalkylene adducts, it can be any of random addition, block addition, alternating addition, etc. As the oxyalkylene group in the polyalkylene glycol, it is preferred to have oxyethylene as an essential component, more preferably 50 mol% or more of oxyethylene, and more preferably 90 mol% or more of oxyethylene.

[0076] The above q represents the average number of added moles of AO, and is a number of 1 to 200. It is preferably 1 to 180, more preferably 2 to 150, more preferably 2 to 100, further preferably 2 to 80, particularly preferably 2 to 50, and most preferably 20 to 30.

[0077] In one embodiment, q is preferably 2-180, more preferably 3-150, more preferably 4-100, further preferably 5-80, and particularly preferably 9-50.

[0078] The above n represents a number of 0 to 4, and m represents 0 or 1.

[0079] As n, 0 to 3 is preferable, 0 to 2 is more preferable, and 0 is still more preferable. As m, 1 is more preferable.

[0080] The structural unit (b) having a polyalkylene glycol chain is formed, for example, by radical polymerization of a monomer having a polyalkylene glycol chain.

[0081] As the monomer having a polyalkylene glycol chain, specifically, for example, 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 obtained by adding 10 to 100 mol of alkylene oxide to any one of vinyl alcohol, (meth)allyl alcohol, 3-methyl-3-butene-1-ol (isoprenol), 3-methyl-2-butene-1-ol, 2-methyl-3-butene-2-ol, 2-methyl-2-butene-1-ol, and 2-methyl-3-butene-1-ol are preferred. (Poly)ethylene glycol mono(meth)acrylate and methoxy (poly)ethylene glycol mono(meth)acrylate are particularly preferred.

[0082] The content of the structural unit (b) having a polyalkylene glycol chain in the copolymer of the present disclosure is preferably 5% by mass or more and 75% by mass or less, more preferably 20% by mass or more and 70% by mass or less, further 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 monomers constituting the copolymer of the present disclosure.

[0083] In one embodiment, the content of the structural unit (b) is preferably 10% by mass to 75% by mass, more preferably 15% by mass to 70% by mass, and even more preferably 17% by mass to 65% by mass, based on 100% by mass of all structural units.

[0084] By being within the above range, the ratio of the hydrophilic part becomes appropriate, and there is a tendency that the detergency and anti-recontamination performance of the detergent additive of the present disclosure are improved.

[0085] <Structural Unit (c) Derived from Hydrophobic Monomer>

[0086] 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.

[0087] Here, the solubility parameter is a value calculated according to the method described in "POLYMER ENGINEERING AND SCIENCE" (1974, Vol. 14, No. 2), pages 147 to 154.

[0088] The method is briefly described below. The solubility parameter (δ) (cal / cm 3 ) 1 / 2 The following calculation method is used to calculate the vaporization energy (Δei) and the molar volume (Δvi) of the structural unit constituting the polymer.

[0089] δ=(△ei / △vi) 1 / 2 (cal / cm 3 ) 1 / 2

[0090] If the solubility parameter of the homopolymer obtained by homopolymerizing the hydrophobic monomer disclosed in the present invention is 13 or less, the copolymer of the present invention has sufficient hydrophobicity and excellent adsorption to hydrophobic fibers. The solubility parameter is preferably 12 or less, and more preferably 11 or less. The solubility parameter is usually 5 or more.

[0091] The hydrophobic monomer of the present disclosure is not particularly limited as long as the solubility parameter of the homopolymer is 13 or less, and is preferably a monomer having an ethylenically unsaturated group and an alkyl group having 1 to 30 carbon atoms.

[0092] 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 or may not 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-vinyl pyrrolidone, acrylonitrile, and the like.

[0093] The substituent that the alcohol may have is any substituent other than a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, and a salt thereof, and examples thereof include a halogen atom.

[0094] The alcohol has preferably 2 to 22 carbon atoms, more preferably 2 to 16 carbon atoms, and even more preferably 4 to 8 carbon atoms.

[0095] Preferred examples of the alcohol having 1 to 30 carbon atoms include alkyl alcohol having 1 to 30 carbon atoms and aryl alcohol having 6 to 30 carbon atoms.

[0096] Examples of the alkyl alcohol having 1 to 30 carbon atoms include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol and eicosanol.

[0097] Preferred examples of the aromatic alcohol having 6 to 30 carbon atoms include phenol, benzyl alcohol, methylphenyl alcohol (o-cresol, m-cresol, p-cresol), wood tar alcohol, 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, 2-hydroxyethylnaphthalene, and the like.

[0098] As the hydrophobic monomer, a compound represented by the following general formula (5) is preferred.

[0099] [Chemistry 6]

[0100]

[0101] (In the general formula, 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. )

[0102] That is, the structural unit (c) derived from the hydrophobic monomer of the present disclosure is preferably a structural unit represented by the following general formula (6).

[0103] [Chemistry 7]

[0104]

[0105] (Where R 10 ~R 13 Same as in general formula (5). Wherein, 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.)

[0106] When the amino group-containing copolymer of the present disclosure has a structural unit represented by the general formula (6), the structural unit may be obtained by polymerizing a compound represented by the general formula (5) or by other methods.

[0107] As the above R 10 , R 11 , R 12 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.

[0108] R 10 , R 11 and R 12 are the same or different, preferably a hydrogen atom or a methyl group. More preferably R 10 , R11 is a hydrogen atom, R 12 A hydrogen atom or a methyl group.

[0109] The above R 13 The number of carbon atoms in the hydrocarbon group is preferably 1 to 22, more preferably 2 to 16, further preferably 2 to 12, particularly preferably 4 to 12, and most preferably 4 to 8.

[0110] As the above R 13 The hydrocarbon group is not particularly limited, and examples thereof include chain hydrocarbon groups such as alkyl, alkenyl, and alkynyl, and cyclic hydrocarbon groups such as aryl, cycloalkyl, and cycloalkenyl. The above hydrocarbon group may have a branched chain, and the carbon number of the hydrocarbon group with a branched chain refers to the total carbon number of the main chain and the branched chain.

[0111] In one embodiment, the above R 13 The hydrocarbon group may or may not have an aromatic group, and R 13 An embodiment in which the hydrocarbon group has no aromatic group is also one of the preferred embodiments of the present invention.

[0112] As the above R 13 The number of carbon atoms in the alkyl group is preferably 2 to 22, more preferably 2 to 16, particularly preferably 2 to 12, and most preferably 4 to 8.

[0113] As the above R 13 The number of carbon atoms in the aryl group is preferably 6-12, more preferably 6-10, particularly preferably 6-8.

[0114] As the above R 13 Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, stearyl and eicosyl.

[0115] As the above R 13 Examples of the alkenyl group include vinyl, allyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, octadecenyl and eicosenyl.

[0116] As the above R 7 Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, dodecynyl, octadecynyl and eicosynyl.

[0117] As the above R 13Examples of the aryl group include phenyl, benzyl, methylphenyl, 1-methoxy-4-methylphenyl, ethylphenyl, propylphenyl, butylphenyl, butylmethylphenyl, dimethylphenyl, diethylphenyl, dibutylphenyl, 2-(2-methylphenyl)ethyl, 2-(3-methylphenyl)ethyl, 2-(4-methylphenyl)ethyl, 2-(4-propylphenyl)ethyl, biphenylyl, biphenylmethyl, biphenylethyl, naphthyl, naphthylmethyl, and naphthylethyl.

[0118] As the above R 13 Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0119] Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.

[0120] As the above R 13 The hydrocarbon group is preferably an alkyl group or an aryl group, and more preferably an alkyl group.

[0121] As the hydrophobic monomer, alkyl (meth)acrylates and aryl (meth)acrylates are preferred, and alkyl (meth)acrylates are more preferred.

[0122] 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 eicosyl (meth)acrylate. Among them, preferred are methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, and dodecyl (meth)acrylate; more preferred are ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, and dodecyl (meth)acrylate.

[0123] 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, and the like. ethyl (meth)acrylate, 2-(4-methylphenyl)ethyl (meth)acrylate, 2-(4-propylphenyl)ethyl (meth)acrylate, methyl biphenyl (meth)acrylate, ethyl biphenyl (meth)acrylate, naphthyl (meth)acrylate, naphthyl methyl (meth)acrylate, and naphthyl ethyl (meth)acrylate.

[0124] Among them, phenyl (meth)acrylate and benzyl (meth)acrylate are preferred.

[0125] The content of the structural unit (c) derived from the hydrophobic monomer in the copolymer of the present invention 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, further 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, relative to 100% by mass of the structural units derived from all monomers constituting the copolymer of the present invention. By being within the above range, the proportion of the hydrophobic part becomes appropriate, and there is a tendency that the detergency, anti-recontamination property, and antibacterial performance of the detergent additive of the present invention are improved.

[0126] In one embodiment, the content of the structural unit (c) may be 5 to 40% by weight, and preferably 5 to 35% by weight, based on 100% by weight of all the structural units.

[0127] <Structural Unit (d) Derived from Unsaturated Carboxylic Acid Monomer>

[0128] The structural unit (d) derived from the unsaturated carboxylic acid monomer of the present disclosure is not particularly limited as long as it is a structural unit derived from a monomer having a carboxyl group and an ethylenically unsaturated hydrocarbon group (unsaturated group), but is preferably a structural unit represented by the following general formula (7).

[0129] [Chemistry 8]

[0130]

[0131] In the general formula (7), R 14is one or more selected from a hydrogen atom, a methyl group, and a -CH2COOH group, R 15 , R 16 The same or different groups are at least one selected from a hydrogen atom, a methyl group, an ethyl group, a carboxyl group, and a -CH2COOH group.

[0132] As a preferred embodiment of the above general formula (7), R 14 is one or more selected from a hydrogen atom, a methyl group, and R 15 , R 16 The same or different groups are at least one selected from a hydrogen atom and a carboxyl group.

[0133] As a more preferred embodiment, R 14 is one or more selected from a hydrogen atom, a methyl group, and R 15 , R 16 A hydrogen atom.

[0134] As unsaturated carboxylic acid monomers that are precursors of structural units (d) derived from unsaturated carboxylic acid monomers before polymerization, for example, (meth) acrylic acid, crotonic acid, tiliac acid, 3-methyl crotonic acid, 2-methyl-2-pentenoic acid, and the like, and unsaturated carboxylic acid monomers such as their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts; unsaturated dicarboxylic acid monomers such as maleic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid, and the like, and their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts, and their anhydrides or semi-fat. Among these, (meth) acrylic acid, maleic acid, and their salts are preferred, and (meth) acrylic acid is more preferred.

[0135] The content of the structural unit (d) derived from the unsaturated carboxylic acid monomer in the copolymer of the present invention is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass, relative to 100% by mass of the structural units derived from all monomers constituting the copolymer of the present invention. By being within the above range, the ratio of the hydrophobic part to the hydrophilic part becomes appropriate, and there is a tendency that the detergency and anti-recontamination performance of the detergent additive of the present invention are improved.

[0136] <Structural Units (e) Derived from Other Monomers>

[0137] 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 other monomers in addition to the structural unit (d) derived from an unsaturated carboxylic acid monomer.

[0138] The other monomers are not particularly limited, and examples thereof include sulfonic acid group-containing monomers such as styrenesulfonic acid, 2-acrylamide-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.

[0139] The content of the structural units derived from other monomers in the copolymer of the present disclosure 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 the structural units derived from all monomers constituting the copolymer of the present disclosure.

[0140] <Physical Properties of the Copolymer Disclosed in the Present Invention>

[0141] The weight average molecular weight (Mw) of the amino group-containing copolymer disclosed herein is preferably 4,000 to 500,000, more preferably 6,000 to 400,000, and even more preferably 10,000 to 300,000. Further, it is preferably 10,000 to 200,000, more preferably 10,000 to 100,000, even more preferably 12,000 to 50,000, particularly preferably 15,000 to 40,000, and most preferably 18,000 to 30,000. By being within the above range, there is a tendency that the soil removal performance of the copolymer disclosed herein is further improved.

[0142] [Method for producing amino group-containing copolymer disclosed herein]

[0143] The method for producing the amino group-containing copolymer disclosed in the present invention is not particularly limited, and the copolymer can be produced by polymerizing monomer components. Specific examples and preferred examples of the monomer components and preferred ratios of the monomers are as described above.

[0144] The method for producing the amino group-containing copolymer disclosed in the present invention is also one of the present invention.

[0145] The method for producing the amino-containing copolymer includes, for example, a step of polymerizing an amino-containing monomer or a precursor thereof, a monomer or a precursor thereof having a polyalkylene glycol chain, a hydrophobic group monomer or a precursor thereof, and an unsaturated carboxylic acid monomer (hereinafter referred to as a polymerization step). As a method for initiating polymerization of the monomer component in the polymerization step, for example, a method of adding a polymerization initiator, a method of irradiating UV, a method of heating, a method of irradiating light in the presence of a photopolymerization initiator, etc. It is particularly preferred to use a polymerization initiator.

[0146] As the above-mentioned polymerization initiator, for example, there are persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate, azo compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 2,2'-azobis(isobutyronitrile), and 2,2'-azobis(2-methylpropionamidine) dihydrochloride; organic peroxides such as benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, and isopropylbenzene hydroperoxide; redox initiators that generate free radicals by combining oxidants and reducing agents such as ascorbic acid and hydrogen peroxide, persulfates and metal salts, etc. Among them, persulfates and azo compounds are preferred, and azo compounds are more preferred from the perspective of having a tendency to reduce residual monomers. These polymerization initiators can be used alone or in the form of a mixture of two or more.

[0147] The amount of the polymerization initiator used is preferably from 0.01% by mass to 10% by mass, more preferably from 0.02% by mass to 8% by mass, further preferably from 0.03% by mass to 7% by mass, and most preferably from 0.04% by mass to 4% by mass, relative to the total amount of the monomers constituting the structural units.

[0148] In the above-mentioned polymerization step, a chain transfer agent can be used as a molecular weight regulator of the polymer as needed. As the chain transfer agent, there can be mentioned mercaptocarboxylic acids such as thioglycolic acid (thioglycolic acid), 3-mercaptopropionic acid, 2-mercaptopropionic acid (thiolactic acid), 4-mercaptobutyric acid, thiomalic acid and their salts; mercaptoethanol, thioglycerol, 2-mercaptoethanesulfonic acid, etc.; halides such as carbon tetrachloride, dichloromethane, bromoform, bromotrichloroethane; secondary alcohols such as isopropyl alcohol and glycerol; phosphorous acid, hypophosphorous acid, hypophosphite and their hydrates; hydrogen sulfite (salt) or compounds that can generate hydrogen sulfite (salt) (bisulfurous acid (salt)), pyrosulfite (salt), dithionite (salt), sulfurous acid (salt), etc.). Among them, compounds having a mercapto group are preferred, and mercapto-containing compounds having a carboxyl group are more preferred.

[0149] The amount of the chain transfer agent used in the production of the copolymer of the present invention is preferably 0.1 mol% to 20 mol%, more preferably 0.2 mol% to 15 mol%, further preferably 0.3 mol% to 10 mol%, and most preferably 0.5 mol% to 5 mol%, relative to 100 mol% of the total amount of the monomers constituting the structural units.

[0150] The solvent used in the polymerization can be selected from solvents that can dissolve the monomer components used, polymerization initiators, chain transfer agents, and copolymers after production as needed. There are no particular restrictions, but preferably water, ethanol, 1-propanol, 2-propanol, 1-butanol, phenoxyethanol and other alcohols with 1 to 8 carbon atoms, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and other glycol ethers such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether and the like are used. Among them, water, ethanol, ethylene glycol, propylene glycol, diethylene glycol monobutyl ether, propylene glycol monomethyl ether are preferred, and a mixture of two or more of them may also be used.

[0151] In the polymerization step, the polymerization temperature is preferably 40° C. or higher and preferably 150° C. or lower, more preferably 45° C. or higher, and further preferably 50° C. or higher, and more preferably 100° C. or lower, and further preferably 90° C. or lower.

[0152] The method for adding the monomer components, polymerization initiator, and chain transfer agent to the reaction vessel in the above-mentioned polymerization step is not particularly limited, and examples thereof include a method of adding the total amount to the reaction vessel at the initial stage; a method of adding the total amount to the reaction vessel in batches or continuously; a method of adding a part to the reaction vessel at the initial stage and adding the remaining part to the reaction vessel in batches or continuously, etc. A method of adding the solvent described later at the initial stage and continuously adding the monomer components, polymerization initiator, and chain transfer agent is preferred.

[0153] The monomer components may be polymerized after being neutralized with an organic acid such as acetic acid or propionic acid, or an inorganic acid such as hydrochloric acid, sulfuric acid, or nitric acid.

[0154] The multipolymer obtained by polymerization can be directly used as a detergent additive such as a liquid detergent additive, or can be further neutralized and used using an alkaline substance as required. As the alkaline substance, inorganic salts such as hydroxides and carbonates of monovalent metals or divalent metals, ammonia, and organic amines can be used. In addition, the concentration of the multipolymer can be adjusted as required after the reaction is completed.

[0155] [Use of the amino group-containing copolymer disclosed herein]

[0156] The amino-containing copolymers disclosed herein can be used in detergent, antimicrobial and anti-resoiling applications.

[0157] Detergents, antimicrobial agents and anti-recontamination agents can be used as additives for detergents. For example, detergents that use detergents, antimicrobial agents and anti-recontamination agents are detergents for fibers or hard surfaces. Detergents mentioned here also include detergents for household clothing, kitchen use, household use, fiber industry use, and other industrial use.

[0158] In addition, the present invention also relates to a method for using the above amino group-containing copolymer as a soil release agent, antibacterial agent or anti-refouling agent.

[0159] In the above method, it is preferred that the amino group-containing copolymer is brought into contact with the object to be cleaned.

[0160] In addition, the present invention also relates to a method for producing a detergent, wherein the method comprises the step of mixing the amino group-containing copolymer and a surfactant.

[0161] [Detergent of the present disclosure]

[0162] The detergent disclosed in the present invention is a detergent containing the amino group-containing copolymer disclosed in the present invention. Detergent property refers to the cleaning performance that can be measured by the method described in the examples described below. The detergent disclosed in the present invention can exert its effect under any of the immersion conditions and the cleaning conditions.

[0163] The detergent of the present invention may be the amino group-containing copolymer of the present invention alone, or may contain additives commonly used in detergents in addition to the amino group-containing copolymer of the present invention without particular limitation. The detergent of the present invention preferably contains 0.1 to 100% by mass of the amino group-containing copolymer. Examples of the additive include surfactants, including anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

[0164] Examples of additives other than the above-mentioned surfactants include anti-reattachment agents such as sodium carboxymethylcellulose, anti-color transfer agents, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishing agents, bactericides, bleaching agents, bleaching aids, enzymes, dyes, solvents, etc. In the case of a powder detergent composition, zeolite is also preferably blended.

[0165] [Antibacterial agent of the present disclosure]

[0166] The antimicrobial agent disclosed herein comprises the above-mentioned amino-containing copolymer and exhibits excellent antimicrobial performance. Antimicrobial performance refers to the antimicrobial performance in a substrate such as fiber treated with an antimicrobial agent, which can be evaluated using the method described in the embodiments described below. The antimicrobial agent disclosed herein preferably comprises 0.1 to 100% by mass of the above-mentioned amino-containing copolymer. Antimicrobial performance refers to the performance of bactericidal (killing microorganisms), bacteriostatic (inhibiting the reproduction of microorganisms), sterilization, disinfection, bacteria control, sterilization, antiseptic, mildew-proof, etc., and the target microorganisms are bacteria and fungi.

[0167] Examples of the above-mentioned bacteria include gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, Salmonella, Moraxella, and Legionella; gram-positive bacteria such as Staphylococcus aureus and Clostridium bacteria. Examples of the above-mentioned fungi include yeasts such as Candida, red yeast, and baker's yeast; and molds such as red mold and black mold.

[0168] The reason why the antibacterial agent of the present invention exhibits antibacterial properties by including such an amino-containing copolymer is presumed to be as follows. When the antibacterial agent of the present invention acts on microorganisms, the cationic group derived from the structural unit represented by the above general formula (1) possessed by the above amino-containing copolymer is adsorbed on the surface of the microorganism having a negative charge. It is further presumed that the hydrophobic group possessed by the amino-containing copolymer exhibits affinity for the cell membrane portion, and by interacting with the cell membrane, the interaction between lipids constituting the cell membrane is destroyed and / or the function of proteins bound to the membrane is hindered, thereby destroying the cell and / or hindering the physiological activity of the cell, thereby killing the microorganism.

[0169] The antimicrobial agent of the present invention may be the amino-containing copolymer of the present invention alone, and in addition to the amino-containing copolymer of the present invention, may also contain additives used in conventional detergent compositions without particular limitation. The antimicrobial agent of the present invention preferably contains 0.1 to 100% by mass of the amino-containing copolymer. As the additive, for example, there is a surfactant, and examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

[0170] Examples of additives other than the surfactant include other antimicrobial agents or anti-reattachment agents such as sodium carboxymethylcellulose, anti-color transfer agents, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishing agents, bactericides, bleaching agents, bleaching aids, enzymes, dyes, solvents, etc. In the case of a powder detergent composition, zeolite is also preferably blended.

[0171] [Anti-recontamination agent of the present disclosure]

[0172] The anti-recontamination agent of the present disclosure comprises the amino group-containing copolymer and exhibits excellent anti-recontamination performance. The anti-recontamination agent of the present disclosure preferably comprises 0.1 to 100% by mass of the amino group-containing copolymer.

[0173] The anti-recontamination 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 liquid, solid, powder, or the like.

[0174] The detergent composition of the present disclosure may contain various components used in detergent compositions in addition to detergents, antimicrobial agents, and anti-recontamination agents. As components contained in the detergent composition, surfactants and detergent additives commonly used in detergent compositions may be used.

[0175] The surfactant may be any of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, and one or more of them may be used.

[0176] Preferred anionic surfactants include alkylbenzene sulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, α-olefin sulfonates, α-sulfofatty acids or their ester salts, alkane sulfonates, 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 have a branched chain of an alkyl group such as a methyl group.

[0177] Examples of the nonionic surfactant include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycolates (glycoxides), fatty acid glycerol monoesters, alkylamine oxides, etc. The alkyl and alkenyl groups in these nonionic surfactants may have a branched chain of an alkyl group such as a methyl group.

[0178] Examples of the cationic surfactant include quaternary ammonium salts, etc. Examples of the amphoteric surfactant include carboxyl amphoteric surfactants, sulfobetaine amphoteric surfactants, etc. The alkyl and alkenyl groups in these cationic surfactants and amphoteric surfactants may have a branched chain of an alkyl group such as a methyl group.

[0179] The content of the above-mentioned surfactant is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, further 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 have both detergency and economy.

[0180] Example

[0181] The present invention will be described in further detail below with reference to Examples, but the present invention is not limited to these Examples. It should be noted that "%" means "mass %" unless otherwise specified.

[0182] <Measurement of Weight Average Molecular Weight of Copolymer>

[0183] The weight average molecular weight (Mw) of the copolymer is measured by GPC (gel permeation chromatography).

[0184] The measurement conditions, apparatus, etc. are as follows.

[0185] Equipment: EcoSEC HLC-8320GPC manufactured by Tosoh Corporation

[0186] Detector: Differential Refractive Index (RI) detector

[0187] Column: TSKgel α-M, α-2500 manufactured by Tosoh Corporation

[0188] Column temperature: 40°C

[0189] Flow rate: 0.8 mL / min

[0190] Injection volume: 20 μL (sample concentration 0.5 wt% eluent preparation solution)

[0191] Calibration curve: polyethylene glycol manufactured by GL Sciences, Mw = 194, 410, 615, 1020, 1450, 3860, 8160, 16100, 21160, 49930, 67600, 96100, 205500, 542500, 942000

[0192] Number of calibration curves: 3

[0193] GPC software: EcoSEC-WS manufactured by Tosoh Corporation

[0194] Eluent: 0.5M acetic acid + 0.2M sodium nitrate / acetonitrile = 50 / 50 (v / v)

[0195] <Evaluation of Decontamination Performance 1>

[0196] The copolymers produced in Production Examples 2, 4, 6, 8 to 17, and 19 were evaluated for stain removal properties by the following method.

[0197] (Fabric pretreatment method)

[0198] (1)-1: Preparation of hardness mother solution

[0199] 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 adjust the amount to 1000 g.

[0200] (1)-2: Preparation of hard water

[0201] 1.54 g of sodium bicarbonate, 10 g of 0.1 N hydrogen chloride, and 200 g of hardness mother solution (1)-1 were added to a beaker, and diluted with ion-exchanged water to 20,000 g.

[0202] (1)-3

[0203] Prepare a polyester taffeta (polyester fiber manufactured by Seisen Co., Ltd.) cut into 5×5 cm cloth. Prepare 55 g of an aqueous solution of the copolymer obtained in Example (1)-2 adjusted to 33 ppm using hard water, add 2.7 g of the above cloth, and stir for 10 minutes using a roller shaker. After stirring, rinse for 3 minutes, then dehydrate and air-dry for 1 day.

[0204] (Production of Contaminated Cloth)

[0205] 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 a grease contaminated liquid. 15 μL of the contaminated liquid 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 contaminated cloth.

[0206] (Evaluation of cleaning power)

[0207] (2)-1: Preparation of surfactant aqueous solution

[0208] 10 g of EMULGEN 108 (manufactured by Kao Corporation) was weighed into a beaker, and ion-exchanged water was added to make 100 g to prepare a 10% surfactant solution.

[0209] (2)-2: Cleaning power test

[0210] Set the oscillating detergent to 25°C, add 498.8g of hard water (1)-2 and 0.85g of surfactant solution (1)-3 to the tank, add 1% copolymer aqueous solution so that the copolymer concentration in the tank is 7.3ppm and mix. Add 5 pieces of contaminated cloth whose Z value has been measured in advance by a spectrophotometer (SE6000 manufactured by Nippon Denshoku Industries Co., Ltd.) and a total of 16.7g of cloth adjusted by bath ratio to the tank, stir at 120rpm for 10 minutes, and wash. Discard the water in the tank, rinse once for 3 minutes, then dehydrate the cloth and air-dry for 1 day.

[0211] After air drying, the Z value of the soiled cloth after washing was measured again using a colorimeter, and the washing rate was calculated using the following formula.

[0212] Cleaning rate (%) = ((Zs-Zw) / (Zs-Zo)) × 100

[0213] Zs represents the Z value of the contaminated cloth before washing, Zw represents the Z value of the contaminated cloth after washing, and Zo represents the Z value of the white cloth before contamination.

[0214] The cleaning power was evaluated based on the obtained cleaning rates according to the following criteria.

[0215] ◎: Cleaning rate over 88%

[0216] ○: Cleaning rate 86% or more and less than 88%

[0217] ×: Cleaning rate is less than 86%

[0218] <Repollution Prevention Evaluation>

[0219] (1) As a surfactant solution, EMULGEN 108 (PAE, manufactured by Kao Corporation) was diluted with ion-exchanged water to prepare a 10% solution.

[0220] (2) Preparation of hardness mother solution

[0221] 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 adjust the amount to 100 g.

[0222] (3) Preparation of sodium bicarbonate aqueous solution

[0223] 1.54 g of sodium bicarbonate and 10 g of 0.1 N hydrogen chloride were added to a beaker, and the mixture was diluted with ion-exchanged water to 100 g.

[0224] (4) Measurement of the color tone of white cloth

[0225] The whiteness of the white cloth used for the re-soiling prevention evaluation was measured for reflectance using a colorimeter (SE-6000 manufactured by Nippon Denshoku Industries) before the evaluation.

[0226] (5) Cleaning power evaluation

[0227] Set the oscillating scale washer to 25°C, add 891.3g of ion exchange water, 1.2g of hardness mother solution, 4.5g of sodium bicarbonate aqueous solution, 2.25g of surfactant aqueous solution, and 0.75g of polymer aqueous solution converted to 1% of solid content into a tank, and stir at 120rpm for 3 minutes. Then, add 0.05g of carbon black (carbon black #10 manufactured by Mitsubishi Chemical), 5 pieces of cotton knitwear (cotton cloth manufactured by Dyeing Test Material Co., Ltd.) or 5 pieces of Style730 and 30g of bath ratio adjustment cloth (cotton white cloth), stir at 120rpm for 10 minutes, and wash. Discard the water in the tank, rinse twice, and then dehydrate the white cloth.

[0228] A cloth was placed on the white cloth, and the cloth was dried while smoothing out wrinkles with an iron. Then, the whiteness of the white cloth was measured again as reflectance using the colorimeter.

[0229] Based on the above measurement results, the recontamination prevention rate was calculated by the following formula.

[0230] Anti-recontamination rate (%) = [(whiteness after cleaning) / (whiteness of original white cloth)] × 100

[0231] The anti-recontamination capability is determined according to the following criteria.

[0232] Anti-recontamination ability of cotton

[0233] Compared with the condition without adding polymer, the anti-recontamination rate is more than +1.0%:◎

[0234] The anti-recontamination rate relative to the condition without adding polymer is +0.5% or more and less than +1.0%:

[0235] The anti-recontamination rate is less than +0.5% compared to the condition without adding polymer: ×

[0236] Anti-recontamination capability for polyester

[0237] Compared with the condition without adding polymer, the anti-recontamination rate is more than +4.0%:◎

[0238] The anti-recontamination rate relative to the condition without adding polymer is +2.0% or more and less than +4.0%: ○

[0239] The anti-recontamination rate is less than +2.0% compared to the condition without adding polymer: ×

[0240] <Antibacterial Evaluation>

[0241] (1) Preparation of hard water

[0242] 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, which was used as a hardness mother solution.

[0243] 1.54 g of sodium bicarbonate, 10 g of 0.1 N hydrogen chloride, and 200 g of the hardness mother solution were added to a beaker, and diluted with ion exchange water to 20,000 g to prepare hard water.

[0244] (2) Fabric pretreatment method

[0245] Style 730 was cut into 5×5 cm cloth. 55 g of an aqueous solution prepared by hard water described in (1) above so that the content of the copolymer obtained in the example was 100 ppm was added to a 70 cc mayonnaise bottle, and then 5.5 g of Style 730 was added and stirred for 1 hour. After stirring, the mixture was dehydrated and air-dried for 1 day.

[0246] (3) Antibacterial test

[0247] The antibacterial property of the pretreated test cloth was evaluated by JIS L 1902:2015 (Test method for antibacterial property of fiber products - bacterial solution absorption method). In the evaluation of antibacterial property, Staphylococcus aureus (NBRC 12732) was used to measure the number of viable bacteria by pour plate culture method to evaluate the antibacterial performance. The antibacterial performance was evaluated by comparing with untreated 100% cotton test cloth, and the antibacterial property against Staphylococcus aureus was evaluated by the antibacterial activity value expressed by the following formula.

[0248] Antimicrobial activity value = {log (number of viable bacteria after culture of control sample) - log (number of viable bacteria just after inoculation of control sample)} - {log (number of viable bacteria after culture of test sample) - log (number of viable bacteria just after inoculation of test sample)}

[0249] The antibacterial property was evaluated according to the following criteria.

[0250] Antibacterial activity value is 2.5 or more: ◎

[0251] Antibacterial activity value is 2.0 or more and less than 2.5: ○

[0252] Antibacterial activity value less than 2.0: ×

[0253] <Production Example 1>

[0254] 62.3 g of ethanol was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer. After nitrogen purge was performed at 100 ml / min for 60 minutes under stirring, the temperature was raised to 70°C. After nitrogen purge 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 referred to as DAM), 11.8 g of ethanol, and 7.3 g of acetic acid; and a monomer solution 1 consisting of methoxypolyethylene glycol monomethacrylate (average number of ethylene oxide added moles 23, trade name "M-230G" manufactured by Shin-Nakamura Chemical, hereinafter referred to as "M-230G") were added dropwise to the polymerization reaction system at a constant temperature of 70°C under stirring using different droppers. The monomer solution 2 was composed of 72.2 g of methyl methacrylate (hereinafter referred to as PGM23E), 6.0 g of methacrylic acid (hereinafter referred to as MAA), and 33.5 g of ethanol; the monomer solution 3 was composed of 36.5 g of benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter referred to as BnMA); and the initiator aqueous solution was composed 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.). Regarding the dropping time, the monomer solution and the initiator aqueous solution were started to be dropped at the same time, and the monomer solutions 1, 2, and 3 were dropped for 180 minutes, and the initiator aqueous solution was dropped for 240 minutes.

[0255] After all the dropwise addition was completed, the reaction solution was further kept at 70° C. for 60 minutes to age and complete the polymerization, thereby obtaining Copolymer 1. The results are shown in Table 1.

[0256] <Production Examples 2 to 20>

[0257] In Preparation Example 1, the amount of solvent, the amount of monomer, the type of monomer, and the amount of initiator used were changed to the composition and molecular weight of Table 1. Except for this, copolymers 2 to 20 were obtained by the same method as in Preparation Example 1. The types of monomers not used in Preparation Example 1 but used in the polymerization of Preparation Examples 2 to 20 are as follows. Lauryl methacrylate (trade name "LIGHT ESTERL" of 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), methoxypolyethylene glycol monomethacrylate (average addition mole number of ethylene oxide 9, trade name "BLEMMERPME-400" of NOF Corporation, hereinafter also referred to as PGM9E). The results are shown in Table 1.

[0258] [Table 1]

[0259]

[0260] <Comparative Production Example 1>

[0261] 33.3 g of 2-butanone, 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 to a glass detachable flask equipped with a thermometer, a reflux condenser, and a stirrer, 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 the temperature was lowered to room temperature. The reaction solution was added dropwise to 4000.0 g of n-hexane, and reprecipitation was performed and the precipitate was dried to obtain a comparative copolymer 1.

[0262] <Comparative Production Example 2>

[0263] Into a glass detachable flask equipped with a thermometer, a reflux condenser, and a stirrer, 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 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 8 hours to polymerize and mature. 50.0 g of ethanol was added thereto for dilution, and the temperature was lowered to room temperature. The reaction solution was added dropwise to 2000.0 g of ion exchange water, and reprecipitation was performed and the precipitate was dried to obtain a comparative copolymer 2.

[0264] Table 2 shows the results of stain removal evaluation 1 for Examples 1 to 14 using the copolymers produced in Production Examples 2, 4, 6, 8 to 17, and 19, Comparative Example 1 without a polymer, and Comparative Production Example 2 as Comparative Example 2.

[0265] [Table 2]

[0266] Copolymer Detergency Evaluation 1 Example 1 Copolymer 2 〇 Example 2 Copolymer 4 〇 Example 3 Copolymer 6 ◎ Example 4 Copolymer 8 〇 Example 5 Copolymer 9 ◎ Example 6 Copolymer 10 〇 Example 7 Copolymer 11 〇 Example 8 Copolymer 12 ◎ Example 9 Copolymer 13 〇 Example 10 Copolymer 14 〇 Embodiment 11 Copolymer 15 ◎ Example 12 Copolymer 16 ◎ Example 13 Copolymer 17 〇 Embodiment 14 Copolymer 19 〇 Comparative Example 1 Polymer-free × Comparative Example 2 Comparative Copolymer 2 ×

[0267] As shown in Table 2, it can be seen that the copolymer of the present disclosure has excellent soil release properties.

[0268] The results of evaluating the anti-recontamination property on cotton using the copolymers produced in the Production Examples are shown in Table 3 as Examples 15 to 23, and the results of evaluating the comparative copolymer 1 produced in the Comparative Production Examples are shown in Table 3 as Comparative Example 3.

[0269] [Table 3]

[0270] Copolymer Anti-recontamination of cotton Embodiment 15 Copolymer 1 〇 Example 16 Copolymer 3 〇 Embodiment 17 Copolymer 5 ◎ Embodiment 18 Copolymer 8 〇 Embodiment 19 Copolymer 9 〇 Embodiment 20 Copolymer 11 〇 Embodiment 21 Copolymer 13 〇 Embodiment 22 Copolymer 18 ◎ Embodiment 23 Copolymer 20 ◎ Comparative Example 3 Comparative Copolymer 1 ×

[0271] In addition, the results of evaluating the anti-recontamination property for polyester using the copolymers produced in the Production Examples are shown in Table 4 as Examples 24 to 41, and the results of evaluating the anti-recontamination property for polyester using the comparative copolymer 1 produced in the comparative Production Example are shown in Table 4 as Comparative Example 4.

[0272] [Table 4]

[0273] Copolymer Anti-recontamination of polyester Embodiment 24 Copolymer 1 〇 Embodiment 25 Copolymer 2 ◎ Embodiment 26 Copolymer 3 〇 Embodiment 27 Copolymer 4 〇 Embodiment 28 Copolymer 5 〇 Embodiment 29 Copolymer 8 〇 Embodiment 30 Copolymer 9 ◎ Embodiment 31 Copolymer 10 ◎ Embodiment 32 Copolymer 11 ◎ Embodiment 33 Copolymer 12 ◎ Embodiment 34 Copolymer 13 ◎ Embodiment 35 Copolymer 14 ◎ Embodiment 36 Copolymer 15 〇 Embodiment 37 Copolymer 16 ◎ Embodiment 38 Copolymer 17 〇 Embodiment 39 Copolymer 18 ◎ Embodiment 40 Copolymer 19 ◎ Embodiment 41 Copolymer 20 ◎ Comparative Example 4 Comparative Copolymer 1 ×

[0274] Table 5 shows the results of antimicrobial evaluation of Examples 42 to 46 using the copolymers produced in the Production Examples and Comparative Example 5 in which no polymer was used.

[0275] [Table 5]

[0276] Copolymer Antimicrobial Embodiment 42 Copolymer 6 ◎ Embodiment 43 Copolymer 7 ◎ Embodiment 44 Copolymer 8 ◎ Embodiment 45 Copolymer 9 ◎ Embodiment 46 Copolymer 10 ◎ Comparative Example 5 Polymer-free ×

[0277] As shown in Tables 3 to 5, it can be seen that the copolymer of the present disclosure is also excellent in anti-recontamination property and antimicrobial property.

Claims

1. An amino group-containing copolymer comprising: The structural unit (a) derived from an amino group-containing monomer represented by the following general formula (1), Structural units (b) derived from monomers having a polyalkylene glycol chain, Structural units (c) derived from hydrophobic monomers, and The structural unit (d) derived from an unsaturated carboxylic acid monomer, [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, and R 4 , R 5 Each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms, X represents a divalent linking group, and the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit represented by the general formula (1) is bonded.

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

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

4. The amino group-containing copolymer according to claim 1, wherein The weight average molecular weight of the amino group-containing copolymer is 4,000 to 500,000.

5. A detergent, characterized in that It comprises the amino group-containing copolymer according to claim 1.

6. A method of using the amino group-containing copolymer according to claim 1 as a detergent.

7. A method for producing a detergent, characterized in that: The method comprises the step of mixing the amino group-containing copolymer according to claim 1 with a surfactant.

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