Surface treatment composition for fibers

Abstract

The purpose of the present invention is to provide a surface treatment composition for fibers, which is excellent in terms of compounding stability of the composition, and which is capable of sufficiently imparting soil release properties to fibers. The present invention provides a surface treatment composition for fibers, which contains: an amino group-containing copolymer that has at least one structural unit (a) which is represented by one of formulae (1)-(3) (in the formulae, R1, R2, and R3 are the same or different and each represent a hydrogen atom or an alkyl group having 1-5 carbon atoms, R4 and R5 are the same or different and each represent a hydrogen atom or an organic group having 1-12 carbon atoms, R6 to R8 are the same or different and each represent an organic group having 1-12 carbon atoms, X represents a direct bond or a divalent linking group, Y- represents an anion, and the asterisk represents an atom that is contained in another structural unit of the same type or a different type to which the structural units represented by formulae (1) to (3) are bonded) and a structural unit (b) which is derived from a polyalkylene glycol-containing monomer, and / or an ester group-containing polymer that has a structure represented by formula (14) (in the formula, R24 moieties are the same or different and each represent an anionic group or a (poly)oxyalkylene group-containing group, x1 represents a number of 0 to 4, and the asterisk represents an atom that is contained in another structure of the same type or a different type to which the structure represented by formula (14) is bonded) and a polyalkylene glycol structure; and a surfactant. This surface treatment composition for fibers has a pH of 6 or less.

Description

Fiber surface treatment composition

[0001] The present invention relates to a fiber surface treatment composition, and more particularly to a fiber surface treatment composition useful in the rinsing step of laundry, etc.

[0002] It is expected that sebum stains and other dirt adhering to clothing will be easier to remove during washing if the fabric is pre-treated with a compound that adsorbs to the fabric. This function is called soil release. Meanwhile, an increasing number of consumers are using fabric surface treatment agents such as fabric softeners in the rinsing process of washing clothes to give fabrics functionality such as softness. With regard to surface agents for fibers such as fabric softeners, Patent Document 1 discloses a fabric treatment composition comprising a polymer and a fabric softening active, wherein (iii) the polymer comprises cationic repeating units and non-cationic repeating units, the polymer has a weight average molecular weight of 40,000 to 600,000 daltons, preferably 50,000 to 550,000 daltons, and more preferably 100,000 to 500,000 daltons, the polymer has a calculated cationic charge density of 0.05 to 2 meq / g at pH 2 to 8, the polymer comprises less than 0.1 mol % of a crosslinking agent, preferably less than 0.05 mol % of a crosslinking agent, and more preferably less than 0.01 mol % of a crosslinking agent, and (iv) the fabric softening active comprises a quaternary ammonium compound, and the composition comprises less than 5% by weight of the composition of an anionic surfactant.

[0003] Patent Document 2 discloses a surface treatment and / or modification composition comprising a copolymer containing a cationic unit A and another unit B, characterized in that the cationic unit A contains at least one kind of quaternary ammonium group or one inium group, and the other unit B is a unit derived from vinyl lactam.

[0004] Patent Document 3 discloses a liquid fabric softener composition that contains (a) a polymeric compound having a weight average molecular weight of 2,000 to 90,000 and containing specific monomer units (A) and (B) in a specific molar ratio, (b) one or more compounds selected from specific quaternary ammonium salts and amine compounds, and (c) at least one compound selected from water and solvents having a ClogP of 2 or less, each in a specific range, and that has a pH of 2 to 5 at 20°C.

[0005] Patent Document 4 discloses a liquid fabric care composition comprising 0.1% to 20% by weight of the fabric care composition of vinegar, 0.1% to 20% by weight of the fabric care composition of a fragrance material, the fragrance material being characterized by a log P of less than 2.5, and at least 30% by weight of the fabric care composition of water, wherein the fabric care composition has an undiluted pH of 1 to 6.

[0006] JP 2019-535920 A JP 2011-516616 A JP 2008 / 072780 A JP 2022-046637 A

[0007] As described above, various compositions for use as surface treatment agents for fibers have been disclosed, but conventional compositions have had problems with the formulation stability of the compositions and have not provided sufficient soil release properties to fibers.

[0008] The present invention has been made in consideration of the above-mentioned current situation, and aims to provide a fiber surface treatment composition that has excellent formulation stability and can impart sufficient soil release properties to fibers.

[0009] The present inventors have conducted extensive research into fiber surface treatment compositions and have found that when a composition containing an amino group-containing copolymer having a structural unit derived from an amino group-containing monomer represented by a predetermined structure and a structural unit derived from a polyalkylene glycol-containing monomer, and / or an ester group-containing polymer of a predetermined structure, a surfactant, and an acid is used in the rinsing step of laundry, it is possible to impart sufficient soil release properties to fibers after the rinsing step and the composition also has excellent formulation stability. This led to the realization that the above-mentioned problems can be successfully solved, and has led to the present invention.

[0010] The present invention includes the following fiber surface treatment compositions, etc.: [1] A composition represented by the following formulas (1) to (3): (In the formula, R １ , R ２ , R ３ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ４ , R ５ are the same or different and represent a hydrogen atom or an organic group having 1 to 12 carbon atoms. ６ ~R ８ are the same or different and represent an organic group having 1 to 12 carbon atoms. X represents a direct bond or a divalent linking group. Y － represents an anion. An asterisk represents an atom contained in another structural unit of the same type or a different type to which the structural unit represented by formulas (1) to (3) is bonded.) and a structural unit (b) derived from a polyalkylene glycol-containing monomer, and / or an amino group-containing copolymer having at least one structural unit (a) represented by any one of the following formulas (14): (In the formula, R ２４are the same or different and represent an anionic group or a (poly)oxyalkylene group-containing group. x1 is a number from 0 to 4. An asterisk represents an atom contained in another structure of the same or different type to which the structure represented by formula (14) is bonded. A fiber surface treatment composition comprising an ester group-containing polymer having a structure represented by formula (14) and a polyalkylene glycol structure, and a surfactant, and having a pH of 6 or less. [2] The fiber surface treatment composition according to [1] above, which contains an acid. [3] The fiber surface treatment composition according to [2] above, in which the acid comprises an organic acid. [4] The fiber surface treatment composition according to [3] above, in which the organic acid comprises citric acid. [5] The fiber surface treatment composition according to any one of [1] to [4] above, in which the amino group-containing copolymer further comprises a structural unit (c) derived from an unsaturated carboxylic acid monomer. [6] The fiber surface treatment composition according to any one of [1] to [5] above, in which the amino group-containing copolymer further comprises a structural unit (d) derived from a hydrophobic monomer. [7] The fiber surface treatment composition according to any one of [1] to [6] above, wherein the amino group-containing copolymer has a proportion of the structural unit (a) of 5 to 80% by weight relative to 100% by mass of all structural units. [8] The fiber surface treatment composition according to any one of [1] to [7] above, wherein the amino group-containing copolymer has a weight average molecular weight of 4,000 or more and 500,000 or less. [9] The ester group-containing polymer is represented by the following formula (15): (In the formula, R ２４ are the same or different and represent an anionic group or a (poly)oxyalkylene group-containing group. x1 is a number from 0 to 4. ４ The fiber surface treatment composition according to any one of the above items [1] to [8], which has a structural unit (f) represented by the following formula (16): (In the formula, R ２４ , R ２７ are the same or different and represent an anionic group or a (poly)oxyalkylene group-containing group. x1 and x2 are the same or different and represent a number from 0 to 4. y is a number from 4 to 9. R ２５ , R２６ are the same or different and represent a hydrogen atom or a hydrocarbon group. ５ O.A. ６ O may be the same or different and represents an oxyalkylene group. ５ n5 represents the average number of moles of oxyalkylene groups added, and is an integer of 1 to 150. ６

[10] represents the average number of moles of oxyalkylene groups added, and is an integer of 1 to 150.

[11] A rinse agent comprising the fiber surface treatment composition according to any one of [1] to

[10] above.

[12] A method for treating fibers, comprising a step of washing fibers and a step of rinsing the fibers after the washing step, wherein the fiber surface treatment composition according to any one of [1] to

[10] above is brought into contact with the fibers in the rinsing step.

[0011] The fiber surface treatment composition of the present invention has the above-mentioned constitution, has excellent compounding stability, and can impart sufficient soil release properties to fibers, and therefore can be suitably used as a rinse aid in the rinsing step of laundry.

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

[0013] [Textile Surface Treatment Composition] The present invention provides a fiber surface treatment composition comprising an amino group-containing copolymer having at least one structural unit (a) represented by any one of the above formulas (1) to (3) and a structural unit (b) derived from a polyalkylene glycol-containing monomer, and / or an ester group-containing polymer having a structure represented by the above formula (14) and a polyalkylene glycol structure, a surfactant, and an acid. The composition contains an amino group-containing copolymer and / or ester group-containing polymer of a predetermined structure, and a surfactant. By adjusting the pH to 6 or less, the composition can impart sufficient soil releasability to fibers. Furthermore, while the acid content of the composition increases ionicity and tends to precipitate hydrophobic components, the use of the above-described predetermined polymer sufficiently suppresses precipitation and other problems by providing the solubilizing or dispersing ability of the hydrophobic components, thereby achieving excellent formulation stability. The total content of the amino group-containing copolymer and ester group-containing polymer in the fiber surface treatment composition is not particularly limited, but is preferably 0.1 to 20% by mass relative to 100% by mass of the composition. The content is more preferably 0.2 to 15% by mass, even more preferably 0.3 to 10% by mass, and most preferably 0.5 to 7% by mass.

[0014] The content of the surfactant in the fiber surface treatment composition is not particularly limited, but is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, and even more preferably 2 to 10% by mass, relative to 100% by mass of the composition.

[0015] The mass ratio of the total of the amino group-containing copolymer and the ester group-containing polymer to the surfactant in the fiber surface treatment composition (amino group-containing copolymer and ester group-containing polymer / surfactant) is preferably 0.002 to 100, more preferably 0.01 to 10, and even more preferably 0.1 to 5.

[0016] The mass ratio of the amino group-containing copolymer to the surfactant in the fiber surface treatment composition (amino group-containing copolymer / surfactant) is preferably 0.002 to 100, more preferably 0.01 to 10, and even more preferably 0.1 to 5. In one embodiment, the mass ratio of the amino group-containing copolymer to the surfactant may be 0.002 to 10, 0.01 to 5, or 0.1 to 2.5.

[0017] The mass ratio of the ester group-containing polymer to the surfactant in the fiber surface treatment composition (ester group-containing polymer / surfactant) is preferably 0.002 to 100, more preferably 0.01 to 10, and even more preferably 0.1 to 5.

[0018] The fiber surface treatment composition contains an acid, which can impart a deodorizing effect to the fiber. The type of acid is not particularly limited and may be an inorganic acid such as sulfuric acid, hydrochloric acid, or phosphoric acid, but preferably contains an organic acid. The organic acid is not particularly limited, but examples include citric acid, acetic acid, tartaric acid, toluenesulfonic acid, lactic acid, succinic acid, glycolic acid, and salts thereof. Among these, polycarboxylic acids such as citric acid, tartaric acid, succinic acid, and glycolic acid, and acetic acid are preferred, and citric acid is more preferred.

[0019] The content of the organic acid in the fiber surface treatment composition is not particularly limited, but is preferably 0.1 to 40% by mass, more preferably 3 to 35% by mass, even more preferably 10 to 30% by mass, and most preferably 15 to 25% by mass, relative to 100% by mass of the composition. In one embodiment, the content of the organic acid may be 3 to 30% by mass or 5 to 25% by mass.

[0020] The pH of the fiber surface treatment composition is 6 or less, preferably 5.5 or less, more preferably 5 or less, even more preferably 4 or less, even more preferably 3.5 or less, and most preferably 3 or less. The pH of the fiber surface treatment composition is preferably 1 or more. The pH of the fiber surface treatment composition can be measured at 25°C using a pH meter.

[0021] The essential components and optional components contained in the fiber surface treatment composition of the present invention will be further described below.

[0022] The amino group-containing copolymer contained in the fiber surface treatment composition of the present invention has at least one structural unit (a) represented by any one of the above formulas (1) to (3) and a structural unit (b) derived from a polyalkylene glycol-containing monomer, thereby exhibiting excellent soil release properties and improving blend stability when used in the rinsing step of laundry.

[0023] The content of the structural unit (a) in the amino group-containing copolymer is not particularly limited, but is preferably 1 to 80% by mass relative to 100% by mass of all structural units. It is more preferably 2 to 60% by mass, even more preferably 3 to 40% by mass, particularly preferably 5 to 30% by mass, and most preferably 8 to 25% by mass. In one embodiment, the content of the structural unit (a) may be 7 to 60% by mass, 8 to 40% by mass, 10 to 30% by mass, or 15 to 25% by mass.

[0024] The content of the structural unit (b) in the amino group-containing copolymer is not particularly limited, but is preferably 5 to 90% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, particularly preferably 40 to 65% by mass, and most preferably 40 to 60% by mass, relative to 100% by mass of all structural units.

[0025] The amino group-containing copolymer preferably further contains a structural unit (c) derived from an unsaturated carboxylic acid monomer. A preferred embodiment of the present invention is one in which the amino group-containing copolymer contains the structural units (a), (b), and (c). The content of the structural unit (c) in the amino group-containing copolymer is not particularly limited, but is preferably 1 to 20% by mass relative to 100% by mass of all structural units. It is more preferably 1 to 10% by mass, and even more preferably 1 to 5% by mass.

[0026] The amino group-containing copolymer may further have a structural unit (d) derived from a hydrophobic monomer. A preferred embodiment of the present invention is one in which the amino group-containing copolymer has the structural units (a), (b), (c), and (d), or (a), (b), and (d). The content of the structural unit (d) in the amino group-containing copolymer is not particularly limited, but is preferably 0 to 70% by mass relative to 100% by mass of all structural units. It is more preferably 2 to 60% by mass, even more preferably 5 to 50% by mass, particularly preferably 10 to 50% by mass, and most preferably 20 to 45% by mass.

[0027] The amino group-containing copolymer may have a structural unit (e) derived from a monomer other than the structural units (a), (b), (c), and (d). The content of the structural unit (e) in the amino group-containing copolymer is not particularly limited, but is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0 to 0.1% by mass, relative to 100% by mass of all structural units.

[0028] The weight average molecular weight of the amino group-containing copolymer is not particularly limited, but is preferably 4,000 to 500,000. It is more preferably 6,000 to 400,000, even more preferably 10,000 to 300,000, still more preferably 10,000 to 200,000, even more preferably 10,000 to 100,000, still more preferably 12,000 to 50,000, particularly preferably 15,000 to 40,000, and most preferably 18,000 to 35,000. The weight average molecular weight can be measured by the method described in the Examples.

[0029] (Amino Group-Containing Monomer) The method for forming the structural unit (a) represented by any one of formulas (1) to (3) in the amino group-containing copolymer is not limited, and examples thereof include the following formulas (4) to (6): (In the formula, R ４ , R ５ are the same or different and represent a hydrogen atom or an organic group having 1 to 12 carbon atoms. ６ ~R８ are the same or different and represent an organic group having 1 to 12 carbon atoms. X represents a direct bond or a divalent linking group. Y － represents an anion.)

[0030] R in the above formulas (1) to (6) １ , R ２ , R ３ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. １ , R ２ , R ３ are preferably the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, or a propyl group. １ , R ２ More preferably, R is a hydrogen atom. ３ A methyl group is more preferred.

[0031] The above R ４ , R ５ are the same or different and represent a hydrogen atom or an organic group having 1 to 12 carbon atoms. ６ ~R ８ are the same or different and represent an organic group having 1 to 12 carbon atoms. ４ ~R ８ The organic group in is not particularly limited, but is preferably a hydrocarbon group. The hydrocarbon group may have a chain structure or a ring structure, but is preferably a chain structure. When the hydrocarbon group has a chain structure, it may be linear or branched. The hydrocarbon group is preferably an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, and more preferably an alkyl group. The number of carbon atoms in the organic group is preferably 1 to 10, more preferably 1 to 8, particularly preferably 1 to 5, even more preferably 1 to 2, and most preferably 1.

[0032] The above R ４ , R ５ At least one of R is preferably a hydrocarbon group having 1 to 12 carbon atoms. ４ and R ５and (b) are more preferably hydrocarbon groups having 1 to 12 carbon atoms. That is, among the primary to tertiary amino groups, a tertiary amino group is preferred.

[0033] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group (amyl group), an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-icosyl group, an i-propyl group, a sec-butyl group, an i-butyl group, a t-butyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a 2-methylbutyl group, an i-amyl group, a neopentyl group, a 1,2-dimethylpropyl group, a 1,1-dimethylpropyl group, a t-amyl group, a 1,3-dimethylbutyl group, and a 3,3-dimethylbutyl group. aliphatic alkyl groups such as a 2-ethylbutyl group, a 2-ethyl-2-methylpropyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 1,5-dimethylhexyl group, a t-octyl group, a branched nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, a stearyl group, and an icosyl group; and alicyclic alkyl groups such as a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a cycloheptyl group, a cyclooctyl group, a cyclohexylpropyl group, a cyclododecyl group, a norbornyl group (C7), an adamantyl group (C10), and a cyclopentylethyl group. The number of carbon atoms in the alkyl group having 1 to 30 carbon atoms is preferably 1 to 22, more preferably 1 to 18, even more preferably 1 to 12, still more preferably 1 to 8, and particularly preferably 1 to 4.

[0034] Examples of the alkenyl group include vinyl, allyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, octadecenyl, and icosenyl groups. Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, dodecynyl, octadecenyl, and icosenyl groups. The number of carbon atoms in the alkenyl and alkynyl groups is preferably 2 to 22, more preferably 2 to 18, even more preferably 2 to 12, still more preferably 2 to 8, and particularly preferably 2 to 4.

[0035] Examples of the aryl group include a phenyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a propylphenyl group, and a naphthyl group. Examples of the aralkyl group include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. The number of carbon atoms in the aryl group and the aralkyl group is preferably 6 to 22, more preferably 6 to 18, even more preferably 6 to 12, and particularly preferably 6 to 8.

[0036] In the above formulas (1) to (6), -X- represents a direct bond or a divalent linking group. The divalent linking group is not particularly limited, but may be -C(=O)-O-, -C(=O)-, -C(=O)-O-(CH ２ ) ｐ -(p is 1 to 5) or -C(=O)-N(-H)-(CH ２ )p- (p is 1 to 5). In particular, -X- preferably contains a structural unit represented by -C(=O)-O-(CH ２ ) ｐ Preferably, p is -, more preferably p=1 to 3, and particularly preferably n=2.

[0037] Above Y －is not particularly limited, and examples thereof include halide ions such as chloride ions, bromide ions, and iodide ions; alkyl sulfate ions such as methyl sulfate ions; and ions of organic acids such as acetate ions and citrate ions. － is preferably an ion of an organic acid. － is preferably a halide ion or an alkyl sulfate ion.

[0038] 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, as well as their neutralization products with acids and quaternization products; 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, as well as their neutralization products with acids and quaternization products; monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, monomethylaminopropyl (meth)acrylate, monoethylaminopropyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, etc. monoalkylamino group-containing (meth)acrylates such as monomethylaminoethyl(meth)acrylamide, monoethylaminoethyl(meth)acrylamide, monomethylaminopropyl(meth)acrylamide, monoethylaminopropyl(meth)acrylamide, and the like, and the neutralized and quaternized products thereof with acids such as hydrochloric acid and acetic acid; (meth)acrylic acid and acrylic acid compounds such as 2-aminoethyl(meth)acrylate; and esters of N,N-diallylmethylamine and their neutralization with acids and quaternization products; allylamine and their neutralization with acids and quaternization products; addition reaction products of unsaturated monomers having a cyclic ether 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 and quaternization products.

[0039] As the structural unit (a) derived from the amino group-containing monomer, particularly, a structural unit represented by the following formula (7)

[0040] (In the formula, R３ represents a hydrogen atom or a methyl group. An asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit represented by formula (7) is bonded. A structural unit derived from N,N-dimethylaminoethyl (meth)acrylate represented by the formula (7) or a product thereof neutralized with an acid or quaternized with methyl chloride is preferred. Most preferred is a structural unit derived from N,N-dimethylaminoethyl methacrylate or a product thereof neutralized with acetic acid or quaternized with methyl chloride.

[0041] Y in the above formulas (4) to (6) － Although there are no particular limitations on the degree of neutralization, from the viewpoint of blend stability in the composition, the degree of neutralization (mol %) in the amino group-containing monomer is preferably 0 to 100 mol %, more preferably 50 to 100 mol %, even more preferably 70 to 100 mol %, and most preferably 85 to 95 mol %. In one embodiment, the degree of neutralization (mol %) in the amino group-containing copolymer may be 0 to 50 mol %, 0.1 to 40 mol %, or 0.1 to 30 mol %.

[0042] (Polyalkylene glycol-containing monomer) The amino group-containing copolymer of the present invention has a structural unit (b) derived from a polyalkylene glycol-containing monomer. In this specification, "structural unit derived from a monomer" means a structural unit having the same structure as a structural unit formed by polymerization of a monomer (a structure in which the ethylenically unsaturated double bond of a monomer having each unsaturated double bond is opened (a structure in which the double bond (C=C) becomes a single bond (-C-C-))). Note that the structural unit having the same structure as a structural unit formed by polymerization of a monomer is not limited to only a structural unit formed by actual polymerization of a monomer, but may also be a structural unit formed by another method as long as it has the same structure as a structural unit formed by polymerization of a monomer.

[0043] The structural unit (b) is represented by the following formula (8):

[0044] (In the formula, R ９ , R １０ , R １１are the same or different and 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 phosphate group, an amino group, or a salt thereof. A represents an alkylene group having 1 to 10 carbon atoms which may have a substituent. The number of carbon atoms in the alkylene group is preferably 2 to 4, more preferably 2 to 3, and even more preferably 2. q represents the average number of moles of (AO) added and is a number from 1 to 200. The average number of moles added is preferably 3 to 50, more preferably 4 to 25, and even more preferably 9 to 25. n represents a number from 0 to 4. m represents 0 or 1. An asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit represented by formula (8) is bonded. ) is preferably represented by the formula (8).

[0045] (Unsaturated Carboxylic Acid Monomer) The unsaturated carboxylic acid monomer is not particularly limited as long as it has at least one unsaturated hydrocarbon group and one carboxyl group, and examples thereof include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, isocrotonic acid, tiglic acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, and α-hydroxyacrylic acid, or salts thereof; and unsaturated dicarboxylic acids having 4 to 6 carbon atoms such as fumaric acid, maleic acid, itaconic acid, and citraconic acid, or salts thereof.

[0046] The salt is preferably a metal salt, an ammonium salt, an organic amine salt, or the like. Suitable metal atoms forming the metal salt include, for example, monovalent metal atoms such as alkali metal atoms (lithium, sodium, potassium, etc.); divalent metal atoms such as alkaline earth metal atoms (calcium, magnesium, etc.); and trivalent metal atoms (aluminum, iron, etc.). Suitable organic amine salts include alkanolamine salts (ethanolamine salts, diethanolamine salts, triethanolamine salts, etc.), and triethylamine salts. The salt is preferably an alkali metal salt, more preferably a sodium salt.

[0047] The unsaturated carboxylic acid monomer is preferably acrylic acid, methacrylic acid, or a salt thereof.

[0048] (Hydrophobic Monomer) The hydrophobic monomer is not particularly limited as long as the solubility parameter of the homopolymer obtained by homopolymerization is 13 or less. Here, the solubility parameter is a value calculated by the method described on pages 147-154 of "POLYMER ENGINEERING AND SCIENCE" (1974, Vol. 14, No. 2). The method is outlined below. Solubility parameter (δ) (cal / cm) of the homopolymer ３ ) １／２ is calculated by the following calculation method based on the evaporation energy (Δei) and molar volume (Δvi) of the structural units forming the polymer: δ=(Δei / Δvi) １／２ (cal / cm ３ ) １／２

[0049] If the solubility parameter of the homopolymer obtained by polymerizing the hydrophobic monomer alone is 13 or less, the hydrophobicity of the copolymer of the present invention is sufficient and the copolymer has excellent adsorption properties to hydrophobic fibers. The solubility parameter is preferably 12 or less, more preferably 11 or less. The solubility parameter is usually 5 or more.

[0050] The hydrophobic monomer is not particularly limited as long as the solubility parameter of the homopolymer is 13 or less, but is preferably a monomer having an ethylenically unsaturated group and an alkyl group having 1 to 30 carbon atoms. Examples of the hydrophobic monomer include esters of unsaturated carboxylic acids such as (meth)acrylic acid and alcohols having 1 to 30 carbon atoms which may have a substituent; aromatic vinyl monomers such as styrene; olefin monomers such as ethylene and propylene; esters of unsaturated alcohols such as vinyl acetate and carboxylic acids having 3 to 8 carbon atoms; vinyl halides such as vinyl chloride; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; cyclic vinyl monomers such as N-vinylpyrrolidone; and acrylonitrile.

[0051] The substituent that the alcohol may have may be any substituent other than a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, or a salt thereof, and examples thereof include a halogen atom. The number of carbon atoms in the alcohol is preferably 2 to 22, more preferably 2 to 16, and even more preferably 4 to 8. Preferred examples of the alcohol having 1 to 30 carbon atoms include aromatic alcohols such as alkyl alcohols having 1 to 30 carbon atoms and aryl alcohols having 6 to 30 carbon atoms.

[0052] Examples of the alkyl alcohol having 1 to 30 carbon atoms include methanol, ethanol, propanol, butanol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, and icosyl alcohol.

[0053] Preferred examples of the aromatic alcohol having 6 to 30 carbon atoms include phenol, benzyl alcohol, methylphenyl alcohol (o-cresol, m-cresol, p-cresol), creosol, ethylphenyl alcohol, propylphenyl alcohol, butylphenyl alcohol, butylmethylphenyl alcohol, dimethylphenyl alcohol, diethylphenyl alcohol, dibutylphenyl alcohol, hydroxybiphenyl, 4-hydroxymethylbiphenyl, 3-hydroxymethylbiphenyl, 4-hydroxyethylbiphenyl, 3-hydroxyethylbiphenyl, naphthol, 1-hydroxymethylnaphthalene, 1-hydroxyethylnaphthalene, 2-hydroxymethylnaphthalene, and 2-hydroxyethylnaphthalene.

[0054] The hydrophobic monomer is preferably a compound represented by the following formula (9):

[0055] (In the formula, R １２ , R １３ , R１４ , are the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. １５ represents a hydrocarbon group having 1 to 30 carbon atoms. That is, the structural unit (d) derived from the hydrophobic monomer is a compound represented by the following general formula (10):

[0056] (In the formula, R １２ , R １３ , R １４ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. １５ represents a hydrocarbon group having 1 to 30 carbon atoms. An asterisk represents an atom contained in another structural unit of the same type or a different type to which the structural unit represented by formula (10) is bonded. ) is preferred. When the amino group-containing copolymer of the present disclosure has a structural unit represented by formula (10), the structural unit may be obtained by polymerization using a compound represented by formula (9) above, or may be obtained by any other method.

[0057] The above R １２ , R １３ , R １４ The alkyl group in R is preferably a methyl group, an ethyl group, or a propyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. １２ , R １３ , R １４ are preferably the same or different and each is a hydrogen atom or a methyl group. More preferably, R １２ , R １３ is a hydrogen atom, and R １４ is a hydrogen atom or a methyl group.

[0058] The above R １５ The number of carbon atoms in the hydrocarbon group is preferably 1 to 22, more preferably 2 to 16, even more preferably 2 to 12, particularly preferably 4 to 12, and most preferably 4 to 8.

[0059] The above R １５The hydrocarbon group in is not particularly limited, and may have a chain structure or a cyclic structure, but a cyclic structure is preferred. When the hydrocarbon group has a chain structure, it may be linear or branched. The hydrocarbon group is preferably an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, more preferably an alkyl group, an aryl group, or an aralkyl group, and even more preferably an aralkyl group. Specific examples of the alkyl group, the alkenyl group, the alkynyl group, the aryl group, and the aralkyl group are as described above. In one embodiment, the hydrocarbon group in the R １５ The hydrocarbon group in may or may not have an aralkyl group, but R １５ is a hydrocarbon group not containing an aralkyl group is also one of the preferred embodiments of the present invention.

[0060] The above R １５ The number of carbon atoms in the alkyl group in the above R is preferably 2 to 22, more preferably 2 to 16, and particularly preferably 2 to 12. The most preferred is 4 to 8. １５ The aryl group and aralkyl group preferably have 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably 6 to 8 carbon atoms.

[0061] The above R １５ The hydrocarbon group in the formula (I) is preferably an alkyl group or an aromatic hydrocarbon group such as an aryl group or an aralkyl group, more preferably an aralkyl group. The hydrophobic monomer is preferably an alkyl (meth)acrylate or an aromatic (meth)acrylate, more preferably an aromatic (meth)acrylate.

[0062] Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and icosyl (meth)acrylate. Of these, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, and dodecyl (meth)acrylate are preferred, and ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, and dodecyl (meth)acrylate are more preferred.

[0063] Examples of the aromatic (meth)acrylate include phenyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylphenyl (meth)acrylate, propylphenyl (meth)acrylate, butylphenyl (meth)acrylate, pentylphenyl (meth)acrylate, hexylphenyl (meth)acrylate, butylmethylphenyl (meth)acrylate, dimethylphenyl (meth)acrylate, diethylphenyl (meth)acrylate, dibutylphenyl (meth)acrylate, 2-phenylethyl (meth)acrylate, 4-methylphenyl (meth)acrylate, ) acrylate, 4-methylbenzyl (meth)acrylate, 1-methoxy-4-methylphenyl (meth)acrylate, 2-(2-methylphenyl)ethyl (meth)acrylate, 2-(3-methylphenyl)ethyl (meth)acrylate, 2-(4-methylphenyl)ethyl (meth)acrylate, 2-(4-propylphenyl)ethyl (meth)acrylate, biphenylmethyl (meth)acrylate, biphenylethyl (meth)acrylate, naphthyl (meth)acrylate, naphthylmethyl (meth)acrylate, naphthylethyl (meth)acrylate, etc. Of these, phenyl (meth)acrylate and benzyl (meth)acrylate are preferred.

[0064] (Other Monomers) The amino group-containing copolymer may have a structural unit (e) derived from a monomer other than the structural units (a), (b), (c), and (d). The other monomer is not particularly limited, and examples thereof include sulfonic acid group-containing monomers such as styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 3-allyloxy-2-hydroxy-1-propanesulfonic acid, and salts thereof, and phosphoric acid group-containing monomers such as 2-methacryloyloxyethyl acid phosphate.

[0065] <Method for producing amino group-containing copolymer> The method for producing the amino group-containing copolymer is not particularly limited, but it can be produced by polymerizing monomer components, and specific examples and preferred examples of the monomer components and the preferred ratios of each monomer are as described above. The method for producing the amino group-containing copolymer also constitutes one aspect of the present invention.

[0066] The method for producing the amino group-containing copolymer preferably includes a step of polymerizing a monomer component containing an amino group-containing monomer and a polyalkylene glycol-containing monomer (hereinafter referred to as the polymerization step). Examples of methods for initiating the polymerization of the monomer component in the polymerization step include adding a polymerization initiator, irradiating with UV light, applying heat, and irradiating with light in the presence of a photopolymerization initiator. The use of a polymerization initiator is particularly preferred.

[0067] Examples of the polymerization initiator include persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; azo compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(isobutyronitrile), and 2,2'-azobis(2-methylpropionamidine) dihydrochloride; organic peroxides such as benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, and cumene hydroperoxide; and redox initiators that generate radicals by combining an oxidizing agent and a reducing agent, such as ascorbic acid and hydrogen peroxide, or persulfates and metal salts. Among these, persulfates and azo compounds are preferred, and azo compounds are more preferred, as they tend to reduce residual monomers. These polymerization initiators may be used alone or in the form of a mixture of two or more.

[0068] The amount of the polymerization initiator used is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 8% by mass or less, even more preferably 0.03% by mass or more and 7% by mass or less, and most preferably 0.04% by mass or more and 4% by mass or less, based on the total amount of the monomers constituting the structural units used.

[0069] In the polymerization step, a chain transfer agent may be used as a molecular weight modifier for the polymer, if necessary. Examples of chain transfer agents include mercaptocarboxylic acids such as thioglycolic acid (mercaptoacetic acid), 3-mercaptopropionic acid, 2-mercaptopropionic acid (thiolactic acid), 4-mercaptobutanoic acid, thiomalic acid, and salts thereof; mercaptoethanol, thioglycerol, 2-mercaptoethanesulfonic acid; halides such as carbon tetrachloride, methylene chloride, bromoform, and bromotrichloroethane; secondary alcohols such as isopropanol and glycerin; phosphorous acid, hypophosphorous acid, hypophosphites, and hydrates thereof; hydrogen sulfite (salt); and compounds capable of generating hydrogen sulfite (salt), such as bisulfite (salt), pyrosulfite (salt), dithionous acid (salt), and sulfurous acid (salt). Among these, compounds having a mercapto group are preferred, and mercapto group-containing compounds having a carboxyl group are more preferred.

[0070] The amount of the chain transfer agent used in producing the copolymer is preferably 0.1 mol % or more and 20 mol % or less, more preferably 0.2 mol % or more and 15 mol % or less, still more preferably 0.3 mol % or more and 10 mol % or less, and particularly preferably 0.5 mol % or more and 5 mol % or less, relative to 100 mol % of the total amount of the monomers constituting the structural units. In producing the copolymer, it is not necessary to use a chain transfer agent.

[0071] The solvent used during polymerization can be selected as needed from those capable of dissolving the monomer components, polymerization initiator, chain transfer agent, and copolymer after production. While not particularly limited, preferred solvents include water, alcohols having 1 to 8 carbon atoms such as ethanol, 1-propanol, 2-propanol, 1-butanol, and phenoxyethanol; glycols such as ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol; and glycol ethers such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and propylene glycol monomethyl ether. Of these, water, ethanol, ethylene glycol, propylene glycol, diethylene glycol monobutyl ether, and propylene glycol monomethyl ether are preferred, and a mixture of two or more of these solvents may also be used.

[0072] In the polymerization step, the polymerization temperature is preferably 40° C. or higher and 150° C. or lower, more preferably 45° C. or higher, and even more preferably 50° C. or higher. Also, the polymerization temperature is more preferably 100° C. or lower, and even more preferably 90° C. or lower.

[0073] In the polymerization step, the method for charging the monomer components, polymerization initiator, and chain transfer agent into a reaction vessel is not particularly limited, and examples thereof include a method in which the entire amount is charged into the reaction vessel all at once at the beginning, a method in which the entire amount is charged into the reaction vessel in portions or continuously, a method in which a portion is charged into the reaction vessel at the beginning and the remainder is charged into the reaction vessel in portions or continuously, etc. A preferred method is a method in which a solvent described below is charged at the beginning and the monomer components, polymerization initiator, and chain transfer agent are continuously charged.

[0074] The monomer components may be neutralized with an organic acid such as acetic acid, citric acid, or propionic acid, or a mineral acid such as hydrochloric acid, sulfuric acid, or nitric acid before polymerization. Neutralization may also be carried out after polymerization, if necessary. This embodiment is also one of the preferred embodiments of the present invention.

[0075] The copolymer obtained by polymerization can be used as it is as a detergent additive, such as an additive for liquid detergents, but if necessary, it may be further neutralized with an alkaline substance. Examples of alkaline substances that can be used include inorganic salts such as hydroxides and carbonates of monovalent or divalent metals, ammonia, and organic amines. Furthermore, the concentration of the copolymer can be adjusted as necessary after the reaction is complete.

[0076] <Ester Group-Containing Polymer> The ester group-containing polymer contained in the fiber surface treatment composition of the present invention is a polymer represented by the following formula (14):

[0077] (In the formula, R ２４ are the same or different and represent an anionic group or a (poly)oxyalkylene group-containing group. x1 is a number from 0 to 4. An asterisk represents an atom contained in another structure of the same or different type to which the structure represented by formula (14) is bonded. The composition has an ester group-containing structure represented by formula (14) and a polyalkylene glycol structure. This allows the composition to exhibit excellent soil release properties and improve formulation stability when used in the rinsing step of laundry.

[0078] R in the above formula (14) ２４ are the same or different and are an anionic group or a (poly)oxyalkylene group-containing group. ２４ When the benzene ring and R １４ The position at which R is bonded is not particularly limited. ２４ The anionic group in is not particularly limited, but examples thereof include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and salts thereof. Of these, a sulfonic acid group or a salt thereof is preferred.

[0079] The above R ２４ The (poly)oxyalkylene group-containing group in is not particularly limited as long as it is a group having a (poly)oxyalkylene group, but is preferably a group represented by the following formula (17): ７ O) ｎ６ -R ２８ (17) (wherein X represents —CONH—, —C(O)O—, or —O—. R ２８ represents a hydrogen atom or a hydrocarbon group.７ O may be the same or different and represents an oxyalkylene group. ７ represents the average number of moles of oxyalkylene groups added, and is an integer of 1 to 300.

[0080] In the above formula (14), x1 is a number of 0 to 4, preferably 0 or 1, and more preferably 0. The ester group-containing structure represented by the above formula (14) is R ２４ The embodiment not having the above is one of the preferred embodiments of the present invention.

[0081] The ester group-containing polymer may be any polymer as long as it has the ester group-containing structure and a polyalkylene glycol structure. The ester group-containing structure may be a polymer represented by the following formula (15):

[0082] (In the formula, R ２４ are the same or different and represent an anionic group or a (poly)oxyalkylene group-containing group. x1 is a number of 0 to 4. ４ O represents an oxyalkylene group. The asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit represented by formula (15) is bonded.

[0083] A in the above formula (15) ４ O is an oxyalkylene group, preferably an oxyalkylene group having 2 to 18 carbon atoms, and the number of carbon atoms in the oxyalkylene group is preferably 2 to 8, more preferably 2 to 4. ４ The embodiment in which O is an oxypropylene group is one of the preferred embodiments of the present invention.

[0084] The ester group-containing polymer preferably has a structural unit (f) represented by the above formula (15) and a polyalkylene glycol structure. (In the formula, R ２４ , R ２７ are the same or different and represent an anionic group or a (poly)oxyalkylene group-containing group. x1 and x2 are the same or different and represent a number from 0 to 4. y is a number from 4 to 9. R２５ , R ２６ are the same or different and represent a hydrogen atom or a hydrocarbon group. ５ O.A. ６ O may be the same or different and represents an oxyalkylene group. ５ n5 represents the average number of moles of oxyalkylene groups added, and is an integer of 1 to 150. ６ represents the average number of moles of oxyalkylene groups added, represented by O, and is an integer of 1 to 150. The embodiment represented by

[0085] The above x2 is a number from 0 to 4. Preferably, it is 0 to 2, and more preferably 0. The above y is a number from 4 to 9. Preferably, it is 5 to 8, and more preferably 6 to 7.

[0086] Above A ５ O.A. ６ Specific examples and preferred forms of O are: A １ The above n4 and n5 are the same as A. ５ O.A. ６ It represents the average number of moles of oxyalkylene groups added, represented by O, and is an integer of 1 to 150. The above n4 is preferably 30 to 80, more preferably 40 to 60. The above n5 is preferably 30 to 80, more preferably 40 to 60.

[0087] R in the above formula (16) ２５ - (A ５ O) ｎ４ - but R ２５ - (EO) ｎ４’ - (PO) ｎ４’’ In the above formula, n4' is the average number of moles of EO added, and is preferably 12 to 120, and more preferably 40 to 50. n4'' is the average number of moles of PO added, and is preferably 0 to 10, and more preferably 1 to 7.

[0088] R in the above formula (16) ２６ - (A ６ O) ｎ５ - but R ２６ - (EO) ｎ５’- (PO) ｎ５’’ In the above formula, n5' is the average number of moles of EO added, and is preferably 12 to 120, and more preferably 40 to 50. n5'' is the average number of moles of PO added, and is preferably 0 to 10, and more preferably 1 to 7.

[0089] R in the above formula (16) ２５ , R ２６ are the same or different and are a hydrogen atom or a hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 4. The hydrocarbon group is preferably an alkyl group having 1 to 4 carbon atoms. ２５ , R ２６ is a methyl group is one of the preferred embodiments of the present invention.

[0090] Examples of compounds satisfying the above formula (14) include TEXCARE SRN100, 170, 172, TEXCARE SRA300F, TEXCARE SRN260, 260 LIFE, and 260 SG TERRA, all of which are manufactured by CLARIANT; Repwl-O-Tex SRP6, SF2, Crystal, and Crystal Plus, all of which are manufactured by Solvay; Sorez (registered trademark) 100, all of which are manufactured by Ashland; CIRRASOL (registered trademark) PE113, and Permalose™, all of which are manufactured by CRODA.

[0091] <Method for producing ester group-containing polymer> The method for producing the ester group-containing polymer is not particularly limited, but it is preferable to react, in the presence of a catalyst, an aromatic dicarboxylic acid or a derivative thereof which may have a substituent and which forms the structural unit (f) represented by the above formula (15), and a diol with a polyalkylene glycol compound which forms a polyalkylene glycol structure.

[0092] The aromatic dicarboxylic acid is preferably terephthalic acid, and its derivative is preferably a dialkyl terephthalate such as dimethyl terephthalate. Of these, dialkyl terephthalate is preferred, and dimethyl terephthalate is more preferred. The diol includes ethylene glycol, propylene glycol, butylene glycol, etc. Of these, ethylene glycol and 1,2-propylene glycol are preferred, and 1,2-propylene glycol is more preferred.

[0093] The polyalkylene glycol compound forming the polyalkylene glycol structure is preferably R ２５ - (A ５ O) ｎ４ -OH or R ２６ - (A ６ O) ｎ５ It is a compound represented by —OH.

[0094] Examples of the catalyst include sodium acetate, titanium tetraisopropionate, dibutyltin oxide, antimony trioxide / calcium acetate, etc. Among these, sodium acetate and titanium tetraisopropionate are preferred.

[0095] The method for producing the ester group-containing polymer preferably includes the steps of adding a dialkyl terephthalate, a diol, a polyalkylene glycol compound, and a catalyst to a reaction vessel and carrying out transesterification at atmospheric pressure and a reaction temperature of 160 to 220°C, and polycondensing the reaction product obtained in the transesterification step at a pressure below atmospheric pressure and a temperature of 210 to 240°C.

[0096] <Surfactant> The surfactant contained in the fiber surface treatment composition of the present invention is not particularly limited as long as it has a surface-active effect, and examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants, etc. Among these, nonionic surfactants are preferred. An embodiment in which the fiber surface treatment composition of the present invention contains a nonionic surfactant is one of the preferred embodiments of the present invention. In this case, the fiber surface treatment composition of the present invention can exhibit better soil release properties.

[0097] (Anionic Surfactant) The anionic surfactant is not particularly limited as long as it is a surfactant having a hydrophobic group and a hydrophilic group that dissociates into anions. For example, anionic surfactants may be those represented by the following formula (11): １６ -(O) ｍ１ - (A １ O) ｎ１ -Q (11) (wherein, R １６ are the same or different and represent a hydrocarbon group having 6 to 24 carbon atoms. １ O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. １ m1 represents the average number of moles of oxyalkylene groups added, represented by O, and is an integer of 0 to 50. m1 is 0 or 1. Q represents a hydrophilic group that dissociates into anions.

[0098] Above A １ Each O is the same or different and is an oxyalkylene group having 2 to 18 carbon atoms, preferably 2 to 8, more preferably 2 to 4 carbon atoms. These oxyalkylene groups are alkylene oxide adducts, and specific examples of alkylene oxides are as described above. Preferably, they are ethylene oxide, propylene oxide, or butylene oxide, more preferably ethylene oxide or propylene oxide. Furthermore, when the oxyalkylene group is an adduct of any two or more alkylene oxides selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc., it may be in any form such as random addition, block addition, or alternating addition. In order to ensure a balance between hydrophilicity and hydrophobicity, it is preferable that the oxyalkylene groups in the polyalkylene glycol contain oxyethylene groups as an essential component, more preferably 50 mol % or more of oxyethylene groups, even more preferably 80 mol % or more of oxyethylene groups, and particularly preferably 90 mol % or more of oxyethylene groups.

[0099] The above n1 may be any value from 0 to 50, preferably from 0 to 40, and more preferably from 0 to 30.

[0100] R １６The hydrocarbon group in is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, an aryl group, and an aralkyl group. The alkyl group and the alkenyl group may be linear or branched. Specific examples of the alkyl group, the alkenyl group, the aryl group, and the aralkyl group are as described above.

[0101] R １６ The hydrocarbon group has 6 to 24 carbon atoms, preferably 6 to 22 carbon atoms, more preferably 8 to 20 carbon atoms, and even more preferably 8 to 18 carbon atoms.

[0102] The hydrophilic group in Q that dissociates into an anion is not particularly limited, and examples thereof include a sulfate (salt) group, a sulfonic acid (salt) group, a carboxylic acid (salt) group, and a phosphate (salt) group. Preferred are sulfate groups, sulfonate groups, and carboxylate groups.

[0103] Examples of anionic surfactants include alkyl or alkenyl sulfate salts; polyoxyalkylene alkyl or alkenyl ether sulfate salts having an oxyalkylene group; anionic surfactants having a sulfonate group; fatty acids or salts thereof, and sulfosuccinate esters.

[0104] More specific examples of the alkyl or alkenyl sulfate ester salts include alkyl sulfate ester salts in which the alkyl group has 10 to 18 carbon atoms, and alkenyl sulfate ester salts in which the alkenyl group has 10 to 18 carbon atoms.

[0105] More specific examples of the polyoxyalkylene alkyl or alkenyl ether sulfate salts having an oxyalkylene group include polyoxyalkylene alkyl ether sulfate salts having an alkyl group with 10 to 18 carbon atoms and an average number of added moles of alkylene oxide of 1 to 5; and polyoxyalkylene alkenyl ether sulfate salts having an alkenyl group with 10 to 18 carbon atoms and an average number of added moles of alkylene oxide of 1 to 5. Among these, polyoxyethylene alkyl ether sulfate salts having an average number of added moles of ethylene oxide of 1 to 3 are preferred, and polyoxyethylene alkyl ether sulfate salts having an alkyl group with 12 to 14 carbon atoms and an average number of added moles of ethylene oxide of 1 to 3 are more preferred, and sodium salts thereof are even more preferred.

[0106] More specific examples of the anionic surfactant having a sulfonate group include one or more anionic surfactants selected from alkylbenzenesulfonates having an alkyl group containing 10 to 18 carbon atoms, alkenylbenzenesulfonates having an alkenyl group containing 10 to 18 carbon atoms, alkanesulfonates having an alkyl group containing 10 to 18 carbon atoms, α-olefinsulfonates having an α-olefin moiety containing 10 to 18 carbon atoms, α-sulfofatty acid salts having a fatty acid moiety containing 10 to 18 carbon atoms, α-sulfofatty acid lower alkyl ester salts having a fatty acid moiety containing 10 to 18 carbon atoms and an ester moiety containing 1 to 5 carbon atoms, and internal olefinsulfonates having 12 to 16 carbon atoms. Among these, alkylbenzenesulfonates having an alkyl group containing 11 to 16 carbon atoms are preferred, and sodium alkylbenzenesulfonate having an alkyl group containing 11 to 16 carbon atoms is more preferred.

[0107] The fatty acid or salt thereof may be a fatty acid or salt thereof having 10 to 20 carbon atoms. The fatty acid or salt thereof preferably has 12 to 18 carbon atoms, and more preferably has 14 to 18 carbon atoms.

[0108] The sulfosuccinate ester or salt thereof may be a sulfosuccinate ester or salt thereof having a hydrocarbon group having from 5 to 18 carbon atoms.

[0109] (Nonionic Surfactant) The nonionic surfactant is not particularly limited as long as it has a hydrophobic group and a hydrophilic group that does not dissociate into ions, such as a hydroxy group, an ether group, or an ester group. Examples of the nonionic surfactant include surfactants represented by the following formula (12-1) and / or (12-2): １７ -O-(A ２ O) ｎ２ -H (12-1) R １８ -COO-(A ３ O) ｎ３ -R １９ (12-2) (wherein, R １７ , R １８ are the same or different and represent a hydrocarbon group having 6 to 24 carbon atoms. １９ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ２ O.A. ３ O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. ２ n3 represents the average number of moles of oxyalkylene groups added, and is an integer of 1 to 50. ３ represents the average number of moles of oxyalkylene groups added, represented by O, and is an integer of 5 to 50.

[0110] The above R １７ , R １８ The hydrocarbon group in is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, an aryl group, and an aralkyl group. The alkyl group and the alkenyl group may be linear or branched. Specific examples of the alkyl group, the alkenyl group, the aryl group, and the aralkyl group are as described above.

[0111] The above R １７ , R １８ The hydrocarbon group has 6 to 24 carbon atoms, preferably 6 to 22 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 18 carbon atoms.

[0112] Above A ２ O.A. ３ Specific examples and preferred forms of O are: A １ Same as O.

[0113] The above n2 and n3 are preferably 1 to 30, more preferably 1 to 22, even more preferably 2 to 18, and particularly preferably 3 to 16.

[0114] -(A ２ O) ｎ２ -ga,-(EO) ｎ２’ - (PO) ｎ２’’ In the above formula, n2' is the average number of moles of EO added and is a number from 1 to 20, preferably from 2 to 10. n2'' is the average number of moles of PO added and is a number from 1 to 20, preferably from 2 to 10.

[0115] Specific examples of the nonionic surfactant include compounds in which 1 to 50 moles of ethylene oxide (EO) and / or propylene oxide (PO) are added to an alkyl alcohol having 6 to 24 carbon atoms. The total number of moles of EO and PO added is more preferably 2 to 30, even more preferably 2 to 25, and particularly preferably 3 to 20. The alkyl alcohol may be linear or branched, and an embodiment in which the alkyl alcohol is a primary or secondary alcohol is one of the preferred embodiments of the present invention. Furthermore, an embodiment in which only ethylene oxide is added to the alkyl alcohol, and an embodiment in which propylene oxide and ethylene oxide are block-added to the alkyl alcohol in this order are also preferred embodiments of the present invention.

[0116] (Cationic Surfactant) The cationic surfactant is not particularly limited as long as it is a surfactant having a hydrophobic group and a hydrophilic group that dissociates into a cation, and examples thereof include quaternary ammonium salt type cationic surfactants. Examples of quaternary ammonium salt type cationic surfactants include quaternary ammonium salts in which, of the four groups bonded to a nitrogen atom, one or two are hydrocarbon groups having 6 to 24 carbon atoms, and the remaining are hydrocarbon groups having 1 to 3 carbon atoms. Examples of cationic surfactants include those represented by the following formula (13):

[0117] (In the formula, R ２０is a chain hydrocarbon group having 8 to 24 carbon atoms, and R ２１ is a chain hydrocarbon group having 8 to 24 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ２２ and R ２３ are the same or different and are alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl groups having 1 to 3 carbon atoms; W － is an alkyl sulfate ion having 1 to 3 carbon atoms, or a halide ion.

[0118] In the above formula (13), R ２０ The number of carbon atoms in the chain hydrocarbon group is preferably 9 to 18, more preferably 10 to 14, and even more preferably 10 to 12. ２１ is a chain hydrocarbon group having 8 to 24 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ２１ The number of carbon atoms in the chain hydrocarbon group is preferably 9 to 18, more preferably 10 to 14, and even more preferably 10 to 12. ２１ The chain hydrocarbon group of R is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. ２２ , R ２３ are the same or different and are a methyl group, an ethyl group, or a hydroxyalkyl group having 1 to 3 carbon atoms. ５ , R ６ Specific examples of the chain hydrocarbon group include an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and a hexadecyl group, with a nonyl group and a decyl group being preferred, and a decyl group being more preferred.Specific examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group. － is CH ３ SO ４ － , C.H. ３ CH ２ SO ４ － , or a halide ion.

[0119] More specific examples of the compound represented by formula (13) include one or more compounds selected from N-ethyl-N,N-dimethyltetradecylammonium salt, trimethylhexadecyl salt, N,N-dioctyl-N,N-dimethylammonium salt, N,N-dinonyl-N,N-dimethylammonium salt, N,N-didecyl-N,N-dimethylammonium salt, N,N-dioctyl-N-ethyl-N-methylammonium salt, N,N-dinonyl-N-ethyl-N-methylammonium salt, and N,N-didecyl-N-ethyl-N-methylammonium salt. Mono-long chain ammonium salts and di-long chain ammonium salts can also be used in combination. Of these, N,N-didecyl-N-ethyl-N-methylammonium salt is preferred. The counter ion for these salts is CH ３ SO ４ － , C.H. ３ CH ２ SO ４ － , or a halide ion such as chloride ion.

[0120] The content of the cationic surfactant is not particularly limited, but is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, and even more preferably 0 to 30% by mass, relative to 100% by mass of the composition.

[0121] <Other Components> The fiber surface treatment composition of the present invention may contain other components in addition to the amino group-containing copolymer, ester group-containing polymer, surfactant, and acid. The other components are not particularly limited, and examples thereof include deodorants, stabilizers, pH adjusters, fragrances, antifoaming agents, metal ion scavengers (chelating agents), enzymes, antibacterial agents, antioxidants, preservatives, soil release agents other than the amino group-containing copolymer and ester group-containing polymer, dispersants, colorants, fluorescent agents, bleaching agents, texture improvers, dye transfer inhibitors, anti-soiling agents, pearlizing agents, and emulsifiers. Among these, deodorants, stabilizers, pH adjusters, and fragrances are preferred.

[0122] [Uses of the Fiber Surface Treatment Composition] The fiber surface treatment composition of the present invention has excellent formulation stability and can impart sufficient soil releasability to fibers, and is therefore preferably used when washing household, commercial, and industrial fibers, more preferably in the rinsing step of household and commercial laundry. A rinse agent containing the fiber surface treatment composition of the present invention also constitutes the present invention. As described above, the fiber surface treatment composition of the present invention is preferably used at an acidic pH, and an acidic detergent containing the fiber surface treatment composition of the present invention also constitutes the present invention. Use of the fiber surface treatment composition of the present invention as a rinse agent also constitutes the present invention. The present invention also relates to a method of using the fiber surface treatment composition, which comprises the steps of washing fibers and contacting the fibers after the washing step with the fiber surface treatment composition of the present invention.

[0123] The surface treatment composition can be used on any fiber, including textile products such as clothing, dishcloths, sheets, curtains, pillowcases, etc. The material of the textile product is also not particularly limited, including natural fibers such as cotton, silk, wool, etc.; regenerated cellulose fibers such as rayon, etc.; synthetic fibers such as polyester, polyamide, etc.; semi-synthetic fibers such as acetate, etc.

[0124] [Method for treating fibers] The present invention also relates to a method for treating fibers, which comprises a step of washing fibers and a step of rinsing the fibers after the washing step, and in the rinsing step, the fiber surface treatment composition of the present invention is brought into contact with the fibers.

[0125] The washing step is not particularly limited as long as it washes the fibers, but it is preferable to apply an external force to the fibers to transfer the dirt on the fibers into the washing liquid, and then separate the fibers from the washing liquid by dehydration, etc. In the washing step, the method of applying an external force to the textile product may be, for example, a method of applying mechanical force using a washing machine, or a method of hand washing such as rubbing washing, pushing washing, beating washing, grabbing washing, pinching washing, or shaking washing.

[0126] The cleaning solution used in the cleaning step is not particularly limited, but preferably contains the surfactant described above. The surfactant used in the cleaning step is not particularly limited, and regardless of the surfactant used, sufficient soil releasability can be imparted to the fibers by using the fiber surface treatment composition of the present invention in the rinsing step. The surfactant used in the cleaning step is preferably an anionic surfactant or a nonionic surfactant, more preferably a nonionic surfactant.

[0127] The ratio of the amount of washing water to the weight of laundry used in the washing step (bath ratio) is not particularly limited, but is preferably 1 to 1,000, more preferably 3 to 100, and even more preferably 5 to 50.

[0128] The temperature of the washing water in the washing step is not particularly limited, but is preferably 15 to 40°C, and more preferably 20 to 30°C.

[0129] The rinsing step is not particularly limited as long as the fibers after the washing step are rinsed by contacting them with the fiber surface treatment composition of the present invention, but it is preferable to immerse the fibers in a rinse solution containing the fiber surface treatment composition.

[0130] The total concentration of the amino group-containing copolymer and the ester group-containing polymer in the rinse solution is not particularly limited, but is preferably 1 to 100 ppm, more preferably 3 to 50 ppm, and even more preferably 5 to 40 ppm.

[0131] The concentration of the surfactant in the rinse solution is not particularly limited, but is preferably 5 to 200 ppm, more preferably 10 to 150 ppm, and even more preferably 20 to 100 ppm.

[0132] The pH of the rinse solution is not particularly limited, but is preferably 2 to 6, more preferably 3 to 5.5, and even more preferably 4 to 5.

[0133] The temperature of the rinse solution in the rinsing step is not particularly limited, but is preferably 15 to 40°C, and more preferably 20 to 30°C.

[0134] The water used for the rinse may be soft water or hard water.

[0135] The weight ratio (liquor ratio) of the rinse liquid to the laundry used in the rinsing step is not particularly limited, but is preferably 1 to 1,000, more preferably 3 to 100, and even more preferably 5 to 50.

[0136] The above-described fiber treatment method can be incorporated into a fiber washing process. By performing the above-described fiber treatment method every time a fiber is washed, the fiber surface treatment composition of the present invention adheres more effectively to the fiber, thereby effectively exhibiting soil release properties.

[0137] Each step in the above-mentioned fiber treatment method may be performed manually or by a machine such as a washing machine or a cleaning machine. The machine for performing the above-mentioned steps may be a home washing machine, a commercial washing machine, or an industrial cleaning machine, but a home washing machine or a commercial washing machine is preferred.

[0138] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "% by mass."

[0139] <Measurement of Weight-Average Molecular Weight of Copolymer> The weight-average molecular weight (Mw) of the copolymer was measured by GPC (gel permeation chromatography) under the following conditions and using the following apparatus. Apparatus: EcoSEC HLC-8320GPC manufactured by Tosoh Corporation Detector: Differential refractometer (RI) detector Column: TSKgel α-M, α-2500 manufactured by Tosoh Corporation Column temperature: 40°C Flow rate: 0.8 mL / min Injection volume: 20 μL (eluent preparation solution with sample concentration of 0.5 wt%) Calibration curve: Polyethylene glycol manufactured by GL Sciences, Mw = 194, 410, 615, 1020, 1450, 3860, 8160, 16100, 21160, 49930, 67600, 96100, 205500, 542500, 942000 Calibration curve order: 3 GPC software: EcoSEC-WS manufactured by Tosoh Corporation Eluent: 0.5 M acetic acid + 0.2 M Na nitrate / acetonitrile = 50 / 50 (v / v)

[0140] <Soil Release Property Evaluation 1> As an evaluation method when using a textile surface treatment composition as a rinse aid, soil release property was evaluated 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 make 1,000 g. (1)-2: Preparation of Hard Water 1.54 g of sodium bicarbonate, 10 g of 0.1 N hydrogen chloride, and 200 g of hardness mother liquor (1)-1 were placed in a beaker and diluted with ion-exchanged water to make 20,000 g. (1)-3: Preparation of Rinse Agent Composition A rinse agent composition was prepared by mixing the copolymer prepared in the Synthesis Example with a commercially available rinse agent (Reno Citric Acid in Super Deodorizer (containing polyoxyethylene alkyl ether as a surfactant and citric acid as an acid), manufactured by P&G Japan LLC) so that the nonvolatile content was 5%. (1)-4 Polyester taffeta (polyester fiber manufactured by Shikisen Co., Ltd.) cut into 5 x 5 cm pieces was prepared. 55 g of an aqueous rinse aid solution was prepared using hard water (1)-2) so that the rinse aid composition prepared in (1)-3 was 600 ppm (copolymer concentration: 30 ppm). 2.7 g of the above fabric was added, stirred with a roller shaker for 30 minutes, then dehydrated and air-dried for 1 day. (Preparation of Soiled Fabric) 61.5 g of olive oil, 37 g of oleic acid, 1 g of iron (III) oxide, and 0.5 g of oil red were mixed to prepare an oil-stained solution. 15 μL of this stained solution was dropped onto the polymer-treated fabric obtained by the above pretreatment method and left at 40°C for 1 hour to prepare a stained fabric. (Detergency Evaluation) (2)-1: Preparation of Surfactant Aqueous Solution 10 g of Emulgen 108 (Kao Corporation) (polyoxyethylene lauryl ether, hereinafter also referred to as PAE) was weighed into a beaker and ion-exchanged water was added to make 100 g, preparing a 10% surfactant solution. (2)-2: Detergency Test A tergot meter was set to 25°C, and 498.8 g of hard water (1)-2) and 0.85 g of surfactant solution (2)-1) were added to a pot and mixed. Five soiled cloths whose Z values ​​had been measured in advance using a spectrophotometer (SE6000, Nippon Denshoku Industries Co., Ltd.) and a liquor ratio adjustment cloth were added to a pot totaling 16.7 g, and the cloths were washed by stirring at 120 rpm for 10 minutes. The water in the pot was discarded, and the cloths were rinsed once with hard water (1)-2 for 3 minutes, after which they were dehydrated and air-dried for 1 day.After air drying, the Z value of the soiled cloth after washing was measured again using a color difference meter, and the cleaning rate was calculated using the following formula. Based on the obtained cleaning rate, the cleaning power was evaluated according to the following criteria: ◎: The difference in cleaning rate from the blank (no pretreatment) was 5% or more. ○: The difference in cleaning rate from the blank (no pretreatment) was 1% or more but less than 5%. ×: The difference in cleaning rate from the blank (no pretreatment) was less than 1%.

[0141] <Soil Release Property Evaluation 2> As an evaluation method when using a textile surface treatment composition as a detergent, soil release property was evaluated 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 make 1,000 g. (1)-2: Preparation of Hard Water 1.54 g of sodium bicarbonate, 10 g of 0.1 N hydrogen chloride, and 200 g of hardness mother liquor (1)-1 were placed in a beaker and diluted with ion-exchanged water to make 20,000 g. (1)-3: Preparation of Detergent Composition 15.4 g of Neopelex G-65 (sodium dodecylbenzenesulfonate, hereinafter also referred to as LAS) was weighed into a beaker, and the copolymer prepared in Synthesis Example was added so that the nonvolatile content was 0.33%, and then the mixture was adjusted with ion-exchanged water to prepare 100 g of a detergent composition. (1)-4 Polyester taffeta (polyester fiber manufactured by Shikisen Co., Ltd.) cut into 5 x 5 cm pieces was prepared. 55 g of the detergent aqueous solution prepared in (1)-2 was prepared using hard water so that the surfactant concentration of the detergent composition prepared in (1)-3 was 1% (copolymer concentration: 33 ppm). 2.7 g of the above cloth was added, and the mixture was stirred for 30 minutes using a roller shaker. After stirring, the cloth was rinsed with hard water for 3 minutes, then dehydrated and air-dried for 1 day. (Preparation of Soiled Cloth) 61.5 g of olive oil, 37 g of oleic acid, 1 g of iron (III) oxide, and 0.5 g of oil red were mixed to prepare an oil-stained solution. 15 μL of this stained solution was added dropwise to the polymer-treated cloth obtained in the pretreatment method 1 above, and the cloth was left to stand at 40°C for 1 hour to prepare a soiled cloth. (Detergency Evaluation) (2)-1: Detergency Test The tergot meter was set to 25°C, and 498.8 g of the hard water (1)-2) was placed in a pot. The detergent composition (1)-4 was then added and mixed so that the surfactant concentration in the pot was 220 ppm (copolymer concentration 7.3 ppm). Five stained cloths whose Z values ​​had been previously measured using a spectrophotometer (SE6000, manufactured by Nippon Denshoku Industries Co., Ltd.) and a liquor ratio adjustment cloth were placed in a pot totaling 16.7 g, and the cloths were washed by stirring at 120 rpm for 10 minutes. The water in the pot was discarded, and the cloths were rinsed once with the hard water (1)-2) for 3 minutes. The cloths were then dehydrated and air-dried for 1 day. After air-drying, the Z values ​​of the stained cloths after washing were measured again using the colorimeter, and the cleaning rate was calculated using the following formula: Based on the obtained cleaning rate, the cleaning power was evaluated according to the following criteria: ◎: The difference in cleaning rate from the blank (no pretreatment) was 5% or more. ○: The difference in cleaning rate from the blank (no pretreatment) was 1% or more but less than 5%. ×: The difference in cleaning rate from the blank (no pretreatment) was less than 1%.

[0142] <Soil Release Property Evaluation 3> As an evaluation method when using a textile surface treatment composition as a rinse aid, soil release property was evaluated by the following method. (Preparation of Rinse Aid Model Formulation) (1)-1: Preparation of Surfactant Aqueous Solution 10 g of Emulgen 108 (Kao Corporation) (polyoxyethylene lauryl ether) was weighed into a beaker and ion-exchanged water was added to make 100 g, preparing a 10% surfactant solution. (1)-2: Preparation of Rinse Aid Base Formulation 70 g of citric acid, 102.78 g of ion-exchanged water, 1.05 g of acetic acid, 105 g of the surfactant aqueous solution (1)-1, and 17.5 g of propylene glycol were mixed and completely dissolved, and then 53.67 g of a 10% aqueous sodium hydroxide solution was added. (1)-3: Preparation of rinse aid model formulation The rinse aid base formulation (1)-2 was mixed with the copolymer prepared in Synthesis Example so that the nonvolatile content was 3%, to prepare a rinse aid model formulation. The rinse aid model formulation had the following composition: 20% citric acid, 0.3% acetic acid, 3% surfactant, 5% propylene glycol, 1.5% sodium hydroxide (neutralizer), and 3% copolymer. (Fabric pretreatment method) (2)-1: Preparation of hardness mother liquor 8.39 g of calcium chloride dihydrate and 2.9 g of magnesium chloride hexahydrate were weighed into a beaker, and ion-exchanged water was added to make 1,000 g. (2)-2: Preparation of hard water 1.54 g of sodium bicarbonate, 10 g of 0.1 N hydrogen chloride, and 200 g of hardness mother liquor (1)-1 were placed in a beaker and diluted with ion-exchanged water to make 20,000 g. (2)-3: Preparation of Rinse Aid Model Aqueous Solution The prepared rinse aid model formulation was diluted 10 times with ion-exchanged water to prepare a 10% rinse aid model formulation. (2)-4: Fabric Pretreatment Polyester crepe (polyester fiber manufactured by Shikisen Co., Ltd.) cut into 5 x 5 cm pieces was prepared. 55 g of a detergent aqueous solution prepared with hard water (2)-2) was prepared so that the rinse aid model formulation prepared in (1)-3 had a concentration of 600 ppm (copolymer concentration 18 ppm). 2.7 g of the above fabric was added, stirred for 10 minutes with a roller shaker, then dehydrated and air-dried for 1 day. (Preparation of Soiled Fabric) 61.5 g of olive oil, 37 g of oleic acid, 1 g of iron (III) oxide, and 0.5 g of oil red were mixed to prepare an oil-stained solution.15 μL of this soiling solution was dropped onto the polymer-treated fabric obtained by the above pretreatment method, and the fabric was left at 40°C for 1 hour to prepare a soiled fabric. (Evaluation of Detergency) (3)-1: Preparation of Surfactant Aqueous Solution (3)-2: Detergency Test The tergot meter was set to 25°C, and 498.8 g of hard water (2)-2) and 0.85 g of surfactant solution (2)-1 were mixed in a pot. Five soiled fabrics whose Z values ​​had been measured in advance using a spectrophotometer (SE7700, manufactured by Nippon Denshoku Industries Co., Ltd.) and a liquor ratio-adjusted fabric were added to a 16.7 g pot and washed by stirring at 120 rpm for 10 minutes. In a separate pot, 497.0 g of hard water (2)-2) and 3.0 g of the rinse aid model aqueous solution (2)-3 were mixed, and rinsed once for 3 minutes. The fabrics were then dehydrated and air-dried for 1 day. After air drying, the Z value of the soiled cloth after washing was measured again using a color difference meter, and the cleaning rate was calculated using the following formula. Based on the obtained cleaning rates, the cleaning power was evaluated according to the following criteria: +++: The rate of increase in cleaning rate compared to the blank (no pretreatment) was 20% or more. ++: The rate of increase in cleaning rate compared to the blank (no pretreatment) was 15% or more but less than 20%. +: The rate of increase in cleaning rate compared to the blank (no pretreatment) was 5% or more but less than 15%. -: The rate of increase in cleaning rate compared to the blank (no pretreatment) was less than 5%.

[0143] <Evaluation of Soil Release Property 4> As an evaluation method when using a textile surface treatment composition as a rinse aid, soil release property was evaluated 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 make 1,000 g. (1)-2: Preparation of hard water 1.54 g of sodium bicarbonate, 10 g of 0.1 N hydrogen chloride, and 200 g of hardness mother liquor (1)-1 were placed in a beaker and diluted with ion-exchanged water to make 20,000 g. (1)-3: Preparation of Rinse Agent Compositions A rinse agent composition was prepared by mixing the copolymer prepared in the Synthesis Examples or a polyalkylene (ethylene oxide / propylene oxide)-added aryl ester polymer (TexCare SRN260Terra manufactured by Clariant) with a commercially available rinse agent (Rhenor Citric Acid in Super Deodorizer, manufactured by P&G Japan, LLC) so that the nonvolatile content was 0.4%, 1%, or 5%. (1)-4 Polyester crepe (polyester fiber manufactured by Shikisen Co., Ltd.) cut into 5 x 5 cm pieces was prepared. 55 g of the rinse agent aqueous solution prepared in (1)-2 was prepared using hard water so that the rinse agent composition prepared in (1)-3 had a concentration of 600 ppm (copolymer concentration 30 ppm). 2.7 g of the above fabric was added, and the mixture was stirred with a roller shaker for 30 minutes, then dehydrated and air-dried for 1 day. (Preparation of Soiled Fabric) 61.5 g of olive oil, 37 g of oleic acid, 1 g of iron (III) oxide, and 0.5 g of oil red were mixed to prepare an oil-stained solution. 15 μL of this stained solution was dropped onto the polymer-treated fabric obtained by the above pretreatment method and left at 40°C for 1 hour to prepare a stained fabric. (Evaluation of Detergency) (2)-1: Preparation of Surfactant Aqueous Solution 10 g of Emulgen 108 (Kao Corporation) (polyoxyethylene lauryl ether) was weighed into a beaker and ion-exchanged water was added to make 100 g to prepare a 10% surfactant solution. (2)-2: Detergency Test A tergotometer was set to 25°C, and 498.8 g of the hard water (1)-2) and 0.85 g of the surfactant solution (2)-1) were added to a pot and mixed. Five stained cloths whose Z values ​​had been measured in advance using a spectrophotometer (SE6000 manufactured by Nippon Denshoku Industries Co., Ltd.) and a liquor ratio adjustment cloth were placed in a pot weighing 16.7 g, and washed by stirring at 120 rpm for 10 minutes.The water in the pot was discarded, and 497.0 g of the hard water (1)-2 and 3.0 g of a 10% aqueous solution of the rinse aid composition (1)-3 were mixed, and the cloth was rinsed once for 3 minutes, then dehydrated and air-dried for 1 day. After air-drying, the Z value of the soiled cloth after washing was measured again using a color difference meter, and the cleaning rate was calculated using the following formula. Based on the obtained cleaning rates, the cleaning power was evaluated according to the following criteria: +++: The rate of increase in cleaning rate compared to the blank (no pretreatment) was 20% or more. ++: The rate of increase in cleaning rate compared to the blank (no pretreatment) was 15% or more but less than 20%. +: The rate of increase in cleaning rate compared to the blank (no pretreatment) was 5% or more but less than 15%. -: The rate of increase in cleaning rate compared to the blank (no pretreatment) was less than 5%.

[0144] Synthesis Example 1 A separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 76.2 g of diethylene glycol monobutyl ether (hereinafter also referred to as BDG), and after flowing nitrogen at 200 ml / min for 30 minutes while stirring, the mixture was heated to 80°C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 27.0 g of dimethylaminoethyl methacrylate (hereinafter also referred to as DAM), 56.0 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 25, hereinafter also referred to as PGM25E), 4.7 g of methacrylic acid (hereinafter also referred to as MAA), 47.3 g of benzyl methacrylate (hereinafter also referred to as BzMA), 9.8 g of acetic acid, and 36.6 g of BDG, and an aqueous initiator solution consisting of 26.9 g of a 6.5% BDG solution of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were each added dropwise from separate dropping nozzles into the polymerization reaction system under stirring at a constant temperature of 80°C. The monomer solution and the aqueous initiator solution were added dropwise for 180 minutes and 240 minutes, respectively. After the completion of all the dropwise addition, the reaction solution was kept at 80° C. for an additional 60 minutes to mature and complete the polymerization. Thereafter, 68.0 g of ion-exchanged water was added, and the obtained copolymer 1 had a Mw of 26,000.

[0145] Synthesis Example 2 A separable glass flask equipped with a thermometer, reflux condenser, and stirrer was charged with 72.8 g of BDG. Under stirring, nitrogen was flowed at 200 ml / min for 30 minutes, and then the temperature was raised to 80 ° C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 40.5 g of DAM, 43.6 g of PGM25E, 3.7 g of MAA, 47.3 g of BzMA, 14.7 g of acetic acid, and 37.8 g of BDG, and an aqueous initiator solution consisting of 27.7 g of a 6.5% BDG solution of V-65 were each added dropwise from separate dropping nozzles into the polymerization reaction system at a constant temperature of 80 ° C. Regarding the dropping time, the monomer solution and the aqueous initiator solution were simultaneously added dropwise, with the monomer solution being added dropwise for 180 minutes and the aqueous initiator solution being added dropwise for 240 minutes. After the completion of all the droppings, the reaction solution was maintained at 80 ° C. for an additional 60 minutes to mature and complete the polymerization. Thereafter, 64.0 g of ion-exchanged water was added, and the resulting copolymer 2 had a Mw of 27,000.

[0146] Synthesis Example 3 A separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 80.2 g of diethylene glycol monobutyl ether (hereinafter also referred to as BDG). Under stirring, nitrogen was flowed at 200 ml / min for 30 minutes, and then the temperature was raised to 80°C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 13.5 g of DAM, 68.5 g of PGM25E, 5.8 g of MAA, 47.3 g of BzMA, 4.9 g of acetic acid, and 35.5 g of BDG, and an aqueous initiator solution consisting of 25.6 g of a 6.5% BDG solution of V-65 were each added dropwise from separate dropping nozzles into the polymerization reaction system, which was kept at a constant temperature of 80°C. The monomer solution and the aqueous initiator solution were added dropwise simultaneously, with the monomer solution added dropwise for 180 minutes and the aqueous initiator solution added dropwise for 240 minutes. After the completion of all the dropwise addition, the reaction solution was kept at 80° C. for an additional 60 minutes to mature and complete the polymerization. Thereafter, 72.2 g of ion-exchanged water was added, and the obtained copolymer 3 had a Mw of 24,000.

[0147] Synthesis Example 4 A separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 64.6 g of diethylene glycol monobutyl ether (hereinafter also referred to as BDG), and after stirring, nitrogen was flowed at 200 ml / min for 30 minutes, and the temperature was raised to 80 ° C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 27.0 g of DAM, 80.9 g of PGM25E, 6.8 g of MAA, 20.3 g of BzMA, 9.8 g of acetic acid, and 36.8 g of BDG, and an aqueous initiator solution consisting of 31.5 g of a 6.5% BDG solution of V-65 were each added dropwise from separate dropping nozzles into the polymerization reaction system at a constant temperature of 80 ° C. With regard to the dropping time, the monomer solution and the aqueous initiator solution started dropping simultaneously, and the monomer solution was added dropwise for 180 minutes, and the aqueous initiator solution was added dropwise for 240 minutes. After the completion of all the dropwise addition, the reaction solution was kept at 80° C. for an additional 60 minutes to mature and complete the polymerization. Thereafter, 48.9 g of ion-exchanged water was added, and the obtained copolymer 4 had a Mw of 27,000.

[0148] <Synthesis Example 5> A separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 50.3 g of 95% ethanol, and after stirring, nitrogen was flowed at 200 ml / min for 30 minutes, and the temperature was raised to 70 ° C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 40.5 g of DAM, 68.4 g of PGM25E, 5.8 g of MAA, 20.3 g of BzMA, 14.7 g of acetic acid, and 37.9 g of 95% ethanol, and an aqueous initiator solution consisting of 43.2 g of a 6.0% ethanol solution of V-65 were each added dropwise from separate dropping nozzles into the polymerization reaction system at a constant state of 70 ° C. With regard to the dropping time, the monomer solution and the aqueous initiator solution were simultaneously added dropwise, and the monomer solution was added dropwise for 180 minutes, and the aqueous initiator solution was added dropwise for 240 minutes. After the completion of all the droppings, the reaction solution was maintained at 80 ° C. for an additional 60 minutes, and the polymerization was completed by aging. The resulting copolymer 5 had a Mw of 25,000.

[0149] <Synthesis Example 6> A separable glass flask equipped with a thermometer, reflux condenser, and stirrer was charged with 47.9 g of 95% ethanol, and after stirring, nitrogen was flowed at 200 ml / min for 30 minutes, and the temperature was raised to 70 ° C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 60.8 g of DAM, 49.7 g of MePGM25E, 4.3 g of MAA, 20.3 g of BzMA, 22.0 g of acetic acid, and 39.6 g of 95% ethanol, and an aqueous initiator solution consisting of 41.7 g of a 6.0% ethanol solution of V-65 were each added dropwise from separate dropping nozzles into the polymerization reaction system at a constant state of 70 ° C. The monomer solution and the aqueous initiator solution were added dropwise simultaneously, with the monomer solution being added dropwise for 180 minutes and the aqueous initiator solution being added dropwise for 240 minutes. After completion of all additions, the reaction solution was maintained at 70 ° C. for an additional 60 minutes, and the polymerization was completed by aging. The resulting copolymer 6 had a Mw of 26,000.

[0150] Synthesis Example 7 A separable glass flask equipped with a thermometer, reflux condenser, and stirrer was charged with 50.0 g of 95% ethanol. Under stirring, nitrogen was flowed at 200 ml / min for 30 minutes, and then the temperature was raised to 70°C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 60.8 g of DAM, 68.5 g of PGM25E, 5.7 g of MAA, 22.0 g of acetic acid, and 36.5 g of ethanol, and an aqueous initiator solution consisting of 38.0 g of a 7.0% ethanol solution of V-65 were each added dropwise from separate dropping nozzles into the polymerization reaction system, which was kept at a constant temperature of 70°C. Regarding the dropwise addition time, the monomer solution and the aqueous initiator solution were added simultaneously, with the monomer solution being added over 180 minutes and the aqueous initiator solution being added over 240 minutes. After the completion of all additions, the reaction solution was maintained at 70°C for an additional 60 minutes to mature and complete the polymerization. The resulting copolymer 7 had a Mw of 25,000.

[0151] <Synthesis Example 8> A separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 77.0 g of 95% ethanol, and after stirring, nitrogen was flowed at 200 ml / min for 30 minutes, and the temperature was raised to 70 ° C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 17.8 g of DAM, 99.9 g of PGM25E, 8.3 g of MAA, 8.9 g of BzMA, 6.5 g of acetic acid, and 24.1 g of ethanol, and an aqueous initiator solution consisting of 30.5 g of a 7.0% ethanol solution of V-65 were each added dropwise from separate dropping nozzles into the polymerization reaction system at a constant state of 70 ° C. With regard to the dropping time, the monomer solution and the aqueous initiator solution were simultaneously added dropwise, and the monomer solution was added dropwise for 180 minutes, and the aqueous initiator solution was added dropwise for 240 minutes. After the completion of all the droppings, the reaction solution was maintained at 80 ° C. for an additional 60 minutes, and the polymerization was completed by aging. The resulting copolymer 8 had a Mw of 28,000.

[0152] <Synthesis Example 9> A separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 56.1 g of 95% ethanol, and after stirring, nitrogen was flowed at 200 ml / min for 30 minutes, and the temperature was raised to 70 ° C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 67.5 g of DAM, 31.2 g of PGM25E, 2.6 g of MAA, 33.8 g of BzMA, 24.5 g of acetic acid, and 46.0 g of ethanol, and an aqueous initiator solution consisting of 30.0 g of a 7.0% ethanol solution of V-65 were each added dropwise from separate dropping nozzles into the polymerization reaction system at a constant state of 70 ° C. With regard to the dropping time, the monomer solution and the aqueous initiator solution were simultaneously started to be dropped, and the monomer solution was added dropwise for 180 minutes, and the aqueous initiator solution was added dropwise for 240 minutes. After the completion of all the dropping, the reaction solution was maintained at 70 ° C. for an additional 60 minutes, and the polymerization was completed by aging. The resulting copolymer 9 had a Mw of 26,000.

[0153] Synthesis Example 10 A separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 72.3 g of 95% ethanol, and after stirring, nitrogen was flowed at 200 ml / min for 30 minutes, and the temperature was raised to 70 ° C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 20.6 g of quaternized dimethylaminoethyl methacrylate (hereinafter also referred to as quaternized DAM), 115.7 g of PGM25E, 9.8 g of MAA, 10.3 g of BzMA, and 40.3 g of 95% ethanol, and an aqueous initiator solution consisting of 39.1 g of a 7% ethanol solution of V-65 were each added dropwise from separate dropping nozzles into the polymerization reaction system at a constant temperature of 70 ° C. With regard to the dropping time, the monomer solution and the aqueous initiator solution started dropping simultaneously, and the monomer solution was added dropwise for 180 minutes, and the aqueous initiator solution was added dropwise for 240 minutes. After the completion of all the dropwise addition, the reaction solution was kept at 70° C. for an additional 60 minutes to mature and complete the polymerization. Copolymer 10 thus obtained had a Mw of 31,000.

[0154] Synthesis Example 11 A separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 42.9 g of 95% ethanol, and after stirring, nitrogen was flowed at 200 ml / min for 30 minutes, and the temperature was raised to 70 ° C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 108.2 g of quaternized DAM, 32.5 g of PGM25E, 2.7 g of MAA, 13.0 g of BzMA, and 97.0 g of 95% ethanol, and an aqueous initiator solution consisting of 34.8 g of a 7% ethanol solution of V-65 were each added dropwise from separate dropping nozzles into the polymerization reaction system, which was kept at a constant temperature of 70 ° C. The monomer solution and the aqueous initiator solution were added dropwise simultaneously, with the monomer solution being added dropwise for 180 minutes and the aqueous initiator solution being added dropwise for 240 minutes. After the completion of all the dropwise addition, the reaction solution was kept at 70° C. for an additional 60 minutes to mature and complete the polymerization. The resulting copolymer 11 had a Mw of 29,000.

[0155] Synthesis Example 12 A separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 76.1 g of 95% ethanol, and after stirring, nitrogen was flowed at 200 ml / min for 30 minutes, and the temperature was raised to 70°C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 31.3 g of quaternized DAM, 28.9 g of PGM25E, 2.4 g of MAA, 93.8 g of BzMA, and 60.4 g of 95% ethanol, and an aqueous initiator solution consisting of 39.1 g of a 7% ethanol solution of V-65 were each added dropwise from separate dropping nozzles into the polymerization reaction system, which was kept at a constant temperature of 70°C. With regard to the dropping times, the monomer solution and the aqueous initiator solution were simultaneously started to be dropped, and the monomer solution was added dropwise over 180 minutes, and the aqueous initiator solution was added dropwise over 240 minutes. After the completion of all the dropwise addition, the reaction solution was kept at 70° C. for an additional 60 minutes to mature and complete the polymerization. The resulting copolymer 12 had a Mw of 15,000.

[0156] Synthesis Example 13 A separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 53.9 g of 95% ethanol, and after stirring, nitrogen was flowed at 200 ml / min for 30 minutes, and the temperature was raised to 70 ° C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 57.9 g of quaternized DAM, 54.8 g of PGM25E, 4.6 g of MAA, 39.1 g of BzMA, and 61.0 g of 95% ethanol, and an aqueous initiator solution consisting of 53.6 g of a 5.0% ethanol solution of V-65 were each added dropwise from separate dropping nozzles into the polymerization reaction system, which was kept at a constant temperature of 80 ° C. The monomer solution and the aqueous initiator solution were added dropwise simultaneously, with the monomer solution being added dropwise for 180 minutes and the aqueous initiator solution being added dropwise for 240 minutes. After the completion of all the dropwise addition, the reaction solution was kept at 70° C. for an additional 60 minutes to mature and complete the polymerization. The resulting copolymer 13 had a Mw of 29,000.

[0157] Synthesis Example 14 A separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 205.0 g of BDG, and after stirring, nitrogen was flowed at 200 ml / min for 30 minutes, and the temperature was raised to 80 ° C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 98.5 g of DAM, 204.4 g of PGM25E, 17.2 g of MAA, 172.4 g of BzMA, 0.5 g of acetic acid, and 109.1 g of BDG, and an aqueous initiator solution consisting of 105.2 g of a 7% BDG solution of V-65 were each added dropwise from separate dropping nozzles into the polymerization reaction system at a constant temperature of 80 ° C. The monomer solution and the aqueous initiator solution were added dropwise simultaneously, and the monomer solution was added dropwise for 180 minutes and the aqueous initiator solution for 240 minutes. After the completion of all additions, the reaction solution was maintained at 80 ° C. for an additional 60 minutes, and the polymerization was completed by aging. Thereafter, 265.9 g of ion-exchanged water was added, and the resulting copolymer 14 had a Mw of 25,000.

[0158] Synthesis Example 15 A separable glass flask equipped with a thermometer, reflux condenser, and stirrer was charged with 212.5 g of BDG, and after stirring, nitrogen was flowed at 200 ml / min for 30 minutes, and the temperature was raised to 80 ° C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 48.6 g of DAM, 246.6 g of PGM25E, 20.8 g of MAA, 170.2 g of BzMA, 0.6 g of acetic acid, and 104.0 g of BDG, and an aqueous initiator solution consisting of 97.8 g of a 7% BDG solution of V-65 were each added dropwise from separate dropping nozzles into the polymerization reaction system at a constant temperature of 80 ° C. The monomer solution and the aqueous initiator solution were added dropwise simultaneously, with the monomer solution added dropwise for 180 minutes and the aqueous initiator solution added dropwise for 240 minutes. After the completion of all additions, the reaction solution was maintained at 80 ° C. for an additional 60 minutes, and the polymerization was completed by aging. Thereafter, 252.0 g of ion-exchanged water was added, and the resulting copolymer 15 had a Mw of 25,000.

[0159] Synthesis Example 16 A separable glass flask equipped with a thermometer, reflux condenser, and stirrer was charged with 203.1 g of BDG, and after stirring, nitrogen was flowed at 200 ml / min for 30 minutes, and the temperature was raised to 80 ° C. After the nitrogen flow was increased to 50 ml / min, a monomer solution consisting of 48.6 g of DAM, 296.7 g of PGM25E, 25.0 g of MAA, 74.3 g of BzMA, 7.0 g of acetic acid, and 96.8 g of BDG, and an aqueous initiator solution consisting of 118.4 g of a 7% BDG solution of V-65 were each added dropwise from separate dropping nozzles into the polymerization reaction system at a constant temperature of 80 ° C. The monomer solution and the aqueous initiator solution were added dropwise simultaneously, with the monomer solution added dropwise for 180 minutes and the aqueous initiator solution added dropwise for 240 minutes. After completion of all additions, the reaction solution was maintained at 80 ° C. for an additional 60 minutes, and the polymerization was completed by aging. Thereafter, 240.7 g of ion-exchanged water was added, and the resulting copolymer 16 had a Mw of 26,000.

[0160] The monomer compositions and weight average molecular weights (Mw) of the copolymers obtained in Synthesis Examples 1 to 16 are shown in Table 1.

[0161]

[0162] Example 1 Soil releasability evaluation 1 was performed using copolymer 1 of Synthesis Example 1 and a commercially available rinse agent (Rheno Citric Acid in Super Deodorizer (manufactured by P&G Japan LLC), pH 2.6) as a rinse agent, and the results are shown in Table 2.

[0163] Comparative Example 1 In Example 1, soil release evaluation 1 was carried out using a rinse aid (Reno Citric Acid in Super Deodorizer (manufactured by P&G Japan LLC), pH 2.6) containing no copolymer. The results are shown in Table 2.

[0164] Comparative Example 2 Evaluation of soil release properties 2 was carried out using a cleaning composition containing Copolymer 1 of Synthesis Example 1. The results are shown in Table 2.

[0165]

[0166] As shown in Table 2, it was revealed that the fiber surface treatment composition of the present invention has excellent soil release properties.

[0167] Example 2 Copolymer 1 produced in Synthesis Example 1 was mixed with 100 g of a commercially available rinse aid (Rheno Citric Acid in Super Deodorizer (manufactured by P&G Japan LLC)) that had become cloudy over time, so that the non-volatile content was 5%. After mixing, the rinse aid solution became transparent and no longer cloudy. As described above, it was revealed that the fiber surface treatment composition of the present invention has the effect of improving blend stability.

[0168] Examples 3 to 15: Soil releasability evaluation 3 was carried out using copolymers 1 to 13 prepared in Synthesis Examples 1 to 13 in Examples 3 to 15. In addition, evaluation was carried out in the same manner without the copolymer in Comparative Example 3. The evaluation results of the pH, appearance and soil releasability of the rinse aid model blend compositions are shown in Table 3.

[0169]

[0170] Examples 16 to 19 In Examples 16 to 18, the copolymer 1 prepared in Synthesis Example 1 was used at different concentrations, and in Example 19, a polyalkylene (ethylene oxide / propylene oxide) adduct polyester polymer (TexCare SRN 260Terra, manufactured by Crariant) was used, and soil releasability evaluation 4 was performed. In addition, in Comparative Example 4, the evaluation was performed in the same manner without the copolymer. The evaluation results for the concentration of each copolymer, the pH of the rinse agent composition, its appearance, and soil releasability are shown in Table 4.

[0171]

[0172] As shown in Tables 3 and 4, it was revealed that the fiber surface treatment composition of the present invention has excellent soil release properties.

Claims

1. The following formulas (1) to (3): (In the formula, R １ , R ２ , R ３ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ４ , R ５ are the same or different and represent a hydrogen atom or an organic group having 1 to 12 carbon atoms. ６ ~R ８ are the same or different and represent an organic group having 1 to 12 carbon atoms. X represents a direct bond or a divalent linking group. Y － represents an anion. An asterisk represents an atom contained in another structural unit of the same type or a different type to which the structural unit represented by formulas (1) to (3) is bonded. An amino group-containing copolymer having at least one structural unit (a) represented by any one of the following formulas (14): (In the formula, R ２４ are the same or different and represent an anionic group or a (poly)oxyalkylene group-containing group. x1 is a number from 0 to 4. An asterisk represents an atom contained in another structure of the same or different type to which the structure represented by formula (14) is bonded. A fiber surface treatment composition comprising an ester group-containing polymer having a structure represented by formula (13) and a polyalkylene glycol structure, and a surfactant, and having a pH of 6 or less.

2. The fiber surface treatment composition of claim 1, which comprises an acid.

3. The fiber surface treatment composition of claim 2, wherein the acid comprises an organic acid.

4. The fiber surface treatment composition of claim 3, wherein the organic acid comprises citric acid.

5. The fiber surface treatment composition according to any one of claims 1 to 4, wherein the amino group-containing copolymer further has a structural unit (c) derived from an unsaturated carboxylic acid monomer.

6. The fiber surface treatment composition according to any one of claims 1 to 5, wherein the amino group-containing copolymer further has a structural unit (d) derived from a hydrophobic monomer.

7. A fiber surface treatment composition according to any one of claims 1 to 6, wherein the amino group-containing copolymer has a proportion of the structural unit (a) of 5 to 80% by weight relative to 100% by mass of all structural units.

8. The fiber surface treatment composition according to any one of claims 1 to 7, wherein the amino group-containing copolymer has a weight average molecular weight of 4,000 or more and 500,000 or less.

9. The ester group-containing polymer is represented by the following formula (15): (In the formula, R ２４ are the same or different and represent an anionic group or a (poly)oxyalkylene group-containing group. x1 is a number from 0 to 4. ４ The fiber surface treatment composition according to any one of claims 1 to 8, which has a structural unit (f) represented by the formula (15):

10. The ester group-containing polymer is represented by the following formula (16): (In the formula, R ２４ , R ２７ are the same or different and represent an anionic group or a (poly)oxyalkylene group-containing group. x1 and x2 are the same or different and represent a number from 0 to 4. y is a number from 4 to 9. R ２５ , R ２６ are the same or different and represent a hydrogen atom or a hydrocarbon group. ５ O.A. ６ O may be the same or different and represents an oxyalkylene group. ５ n5 represents the average number of moles of oxyalkylene groups added, and is an integer of 1 to 150. ６ 10. The fiber surface treatment composition according to claim 1, wherein R represents the average number of moles of oxyalkylene groups added, and R represents an integer of 1 to 150.

11. A rinse agent comprising the fiber surface treatment composition according to any one of claims 1 to 10.

12. A method for treating fibers, comprising the steps of washing fibers and rinsing the fibers after the washing step, wherein the fiber surface treatment composition according to any one of claims 1 to 10 is brought into contact with the fibers in the rinsing step.

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