Fiber additive, composition, solution and copolymer

Abstract

To provide: a fiber additive which can impart cationic dye dyeability to a fiber and has excellent solubility in N,N-dimethyl acetamide; a composition and a solution comprising such a fiber additive; and a copolymer applicable to such a fiber additive.SOLUTION: A fiber additive includes a copolymer comprising: a structural unit (A) derived from a monomer including a sulfo group or its salt; a structural unit (B) derived from a monomer including an amino group or its salt; and a structural unit (C) other than the structural unit (A) and the structural unit (B). In the copolymer, the content of the structural unit (A) is 5 mass% to 50 mass%, the content of the structural unit (B) is 5 mass% to 50 mass%, and the content of the structural unit (C) is 10 mass% to 90 mass%.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to additives for fibers, compositions, solutions, and copolymers.

Background Art

[0002] Cationic dyes are excellent in color development and dyeing fastness, and can dye fibers with vivid colors such as fluorescent colors. While this cationic dye is excellent in dyeability with respect to acrylic fibers and the like, it is difficult to dye fibers such as regenerated cellulose fibers, urethane fibers, and polyester fibers. For this reason, various methods for improving the cationic dyeability of fibers have been studied.

[0003] For example, in Patent Document 1, in order to impart cationic dyeability to regenerated cellulose fibers, a method of adding a compound having an acidic group to a spinning solution during the spinning of regenerated cellulose fibers has been proposed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] By the way, the method described in Patent Document 1 uses an aqueous solution containing a compound having an acidic group as a spinning solution. As a result of the study by the present inventor, it has become clear that it is difficult to apply the method described in Patent Document 1 to a method using an organic solvent solution as a spinning solution other than regenerated cellulose fibers. For example, the compound having an acidic group described in Patent Document 1 does not dissolve sufficiently in N,N-dimethylacetamide, which is widely used as a spinning solvent for urethane fibers, so it was difficult to apply the method described in Patent Document 1.

[0006] In view of the above circumstances, an object of the present invention is to provide a fiber additive capable of imparting cationic dye-dyeability to fibers and having excellent solubility in N,N-dimethylacetamide, a composition and a solution containing such a fiber additive, and a copolymer applicable to such a fiber additive.

Means for Solving the Problems

[0007] The present disclosure provides a fiber additive described in the following [1] to [5], a composition described in [6] to [8], a solution described in [9] to

[10] , and a copolymer described in

[11] to

[14] . [1] A fiber additive containing a copolymer composed of a structural unit (A) derived from a monomer containing a sulfo group or a salt thereof, a structural unit (B) derived from a monomer containing an amino group or a salt thereof, and a structural unit (C) other than the structural unit (A) and the structural unit (B), wherein the content of the structural unit (A) in the copolymer is 5% by mass or more and 50% by mass or less, the content of the structural unit (B) in the copolymer is 5% by mass or more and 50% by mass or less, and the content of the structural unit (C) in the copolymer is 10% by mass or more and 90% by mass or less. [2] The fiber additive according to [1], wherein the monomer containing a sulfo group or a salt thereof is vinyl aromatic sulfonic acid or a salt thereof. [3] The fiber additive according to [1] or [2], wherein the structural unit (C) includes a structural unit (D) derived from a hydroxyl group-containing monomer of more than 0% by mass and 50% by mass or less and a structural unit (E) derived from a hydrophobic monomer of 10% by mass or more and less than 90% by mass, based on the total amount of the copolymer. [4] The fiber additive according to any one of [1] to [3], wherein the copolymer dissolves in N,N-dimethylacetamide at 25°C in an amount of 5% by mass or more based on the total mass of N,N-dimethylacetamide and the copolymer. [5] The fiber additive according to any one of [1] to [4] for imparting cationic dye-dyeability to urethane fibers. [6] A copolymer comprising a structural unit (A) derived from a monomer containing a sulfo group or a salt thereof, a structural unit (B) derived from a monomer containing an amino group or a salt thereof, and a structural unit (C) other than the structural unit (A) and the structural unit (B), and a composition containing a urethane resin, wherein the content of the structural unit (A) in the copolymer is 5% by mass or more and 50% by mass or less, the content of the structural unit (B) in the copolymer is 5% by mass or more and 50% by mass or less, the content of the structural unit (C) in the copolymer is 10% by mass or more and 90% by mass or less, a composition. [7] The monomer containing a sulfo group or a salt thereof is vinyl aromatic sulfonic acid or a salt thereof, the structural unit (C) includes a structural unit (D) derived from a hydroxyl group-containing monomer of more than 0% by mass and 50% by mass or less based on the total amount of the copolymer, and a structural unit (E) derived from a hydrophobic monomer of 10% by mass or more and less than 90% by mass, the composition according to [6]. [8] The copolymer is soluble in N,N-dimethylacetamide at 25°C in an amount of 5% by mass or more based on the total mass of N,N-dimethylacetamide and the copolymer, the composition according to [6] or [7]. [9] A solution obtained by dissolving a copolymer having a structural unit (A) derived from a monomer containing a sulfo group or a salt thereof, a structural unit (B) derived from a monomer containing an amino group or a salt thereof, and a structural unit (C) other than the structural unit (A) and the structural unit (B) in an amide solvent, wherein the content of the structural unit (A) in the copolymer is 5% by mass or more and 50% by mass or less, the content of the structural unit (B) in the copolymer is 5% by mass or more and 50% by mass or less, the content of the structural unit (C) in the copolymer is 10% by mass or more and 90% by mass or less, a solution.

[10] The monomer containing a sulfo group or a salt thereof is vinyl aromatic sulfonic acid or a salt thereof, The solution according to [9], wherein the structural unit (C) contains a structural unit (D) derived from a hydroxyl group-containing monomer of more than 0% by mass and 50% by mass or less, and a structural unit (E) derived from a hydrophobic monomer of 10% by mass or more and less than 90% by mass, based on the total amount of the copolymer.

[11] A copolymer comprising a structural unit (A) derived from a monomer containing a sulfo group or a salt thereof, a structural unit (B) derived from a monomer containing an amino group or a salt thereof, a structural unit (D) derived from a hydroxyl group-containing monomer, and a structural unit (E) derived from a hydrophobic monomer, wherein the content of the structural unit (A) in the copolymer is 5% by mass or more and 50% by mass or less, the content of the structural unit (B) in the copolymer is 5% by mass or more and 50% by mass or less, the content of the structural unit (D) in the copolymer is more than 0% by mass and 50% by mass or less, and the content of the structural unit (E) in the copolymer is 10% by mass or more and less than 90% by mass.

[12] The copolymer according to

[11] , wherein the monomer containing a sulfo group or a salt thereof is vinyl aromatic sulfonic acid or a salt thereof.

[13] The copolymer according to

[11] or

[12] , wherein the hydrophobic monomer is a (meth)acrylate ester or a vinyl aryl compound.

[14] The copolymer according to any one of

[11] to

[13] , wherein the hydroxyl group-containing monomer is hydroxyalkyl (meth)acrylate or an alkylene oxide adduct thereof. [Advantages of the Invention]

[0008] According to the present invention, it is possible to provide a fiber additive capable of imparting functions such as cationic dyeability and deodorizing properties to fibers, and having excellent solubility in N,N-dimethylacetamide, a composition and a solution containing such a fiber additive, and a copolymer applicable to such a fiber additive. [Embodiments for Carrying Out the Invention]

[0009] Hereinafter, embodiments of the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following description, “(meth)acrylic” is used as a term encompassing both methacrylic and acrylic. Also, when a numerical range is indicated as X to Y, it means X or more and Y or less. For example, “5 to 100 nm” means 5 nm or more and 100 nm or less. Unless otherwise specified, the materials or components exemplified in this specification can be used alone or in combination of two or more.

[0010] [Additive for fibers] The additive for fibers according to this embodiment contains a copolymer described later.

[0011] The additive for fibers according to this embodiment may consist only of the above copolymer, or may contain a solvent and other components.

[0012] Examples of the solvent include water; alcohol solvents such as methanol, ethanol, propanol, butanol, 2-methylpropyl alcohol, and 2-methyl-2-propanol; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate; ether solvents such as dioxane, diethyl ether, and tetrahydrofuran; amide solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide; aromatic hydrocarbon solvents such as toluene and xylene; and the like. Among these, from the viewpoint of being able to be used as a solvent for the spinning solution, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, toluene, xylene, or tetrahydrofuran is preferable, and N,N-dimethylacetamide is more preferable.

[0013] When the above additive for fibers contains a solvent, the content of the solvent in the additive for fibers may be appropriately set according to the type of the solvent and the like, and is not particularly limited. For example, it may be 50 to 5000 parts by mass, or may be 80 to 1000 parts by mass with respect to 100 parts by mass of the total solid content.

[0014] As other components, components that can generally be added to fibers can be mentioned. For example, ultraviolet absorbers such as benzophenone-based compounds, salicylate-based compounds, benzoate-based compounds, triazole-based compounds, and triazine-based compounds; antioxidants such as phenol-based, phosphorus-based, and sulfur-based antioxidants; polymerization inhibitors such as 4-tert-butylcatechol (TBC), hydroquinone, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4H-TEMPO); stabilizers such as light stabilizers, weather stabilizers, and heat stabilizers; antistatic agents containing anionic, cationic, and nonionic surfactants; colorants such as inorganic pigments, organic pigments, and dyes. When the fiber additive contains other components, the content thereof may be, for example, 10% by mass or less, or may be 5% by mass or less based on the total solid content.

[0015] The fiber to which the fiber additive according to this embodiment is applied is not particularly limited, but fibers having poor cationic dye-dyeability, such as regenerated cellulose fibers, urethane fibers, or polyester fibers, are preferable, and urethane fibers are more preferable. Urethane fibers produced using N,N-dimethylacetamide as a solvent for the spinning solution are even more preferable.

[0016] [Copolymer] The copolymer according to this embodiment is composed of a structural unit (A) derived from a monomer containing a sulfo group or a salt thereof, a structural unit (B) derived from a monomer containing an amino group or a salt thereof, and a structural unit (C) other than the structural unit (A) and the structural unit (B). Hereinafter, each structural unit will be described.

[0017] [Structural unit (A) derived from a monomer containing a sulfo group or a salt thereof]< Examples of the monomer containing a sulfo group or a salt thereof in the constitutional unit (A) include 3-(meth)allyloxy-2-hydroxypropanesulfonic acid, 2-(meth)allyloxyethylenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, (meth)allylsulfonic acid, isoprenesulfonic acid, 1-methyl-2-propene-1-sulfonic acid, 1,1-dimethyl-2-propene-1-sulfonic acid, 3-butene-1-sulfonic acid, 1-butene-3-sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamidopropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-((meth)acryloyloxy)ethanesulfonic acid, styrenesulfonic acid, α-methylstyrenesulfonic acid, vinyltoluenesulfonic acid, vinylxylenesulfonic acid, vinylnaphthalenesulfonic acid, 4-(allyloxy)benzenesulfonic acid, 2-acrylamido-2-phenylpropanesulfonic acid, and other unsaturated sulfonic acids or salts thereof. Among these, vinyl aromatic sulfonic acids or salts thereof in which a vinyl group and a sulfo group are directly bonded to an aromatic ring are preferred, and styrenesulfonic acid or a salt thereof is more preferred.

[0018] Examples of the salt in the constitutional unit (A) include alkali metal salts such as lithium salt, sodium salt, and potassium salt; alkaline earth metal salts such as calcium salt and magnesium salt; transition metal salts such as iron and aluminum; ammonium salts; organic amine salts, etc. Examples of the organic amine salt include salts of alkylamines such as methylamine and n-butylamine; salts of alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, and dipropanolamine; salts of polyamines such as ethylenediamine and diethylenetriamine, etc. Among these, from the viewpoint of improving the solubility of the copolymer in N,N-dimethylacetamide, alkali metal salts, ammonium salts, or organic amine salts are preferred, and lithium salt or sodium salt is more preferred.

[0019] The method for forming the constitutional unit (A) is not particularly limited. For example, it may be formed by polymerizing a monomer containing the above-mentioned sulfo group or its salt, or it may be formed by introducing a sulfo group or its salt after polymerizing a monomer not containing a sulfo group or its salt. For example, the constitutional unit (A) may be formed by introducing a sulfo group by reacting a compound such as 1,4-butanesultone after polymerizing a monomer containing a functional group such as an amino group.

[0020] The content of the constitutional unit (A) in the copolymer is 5% by mass or more and 50% by mass or less, preferably 7.5% by mass or more and 40% by mass or less, and more preferably 10% by mass or more and 35% by mass or less. By including the constitutional unit (A) in the content within the above range, cationic dye-dyeability can be efficiently imparted.

[0021] <Constitutional unit (B) derived from a monomer containing an amino group or its salt> The amino group in the constitutional unit (B) may be any of primary to quaternary. That is, the amino group is a primary amino group (-NH2) having no substituent on the nitrogen atom, a secondary amino group (-NHR) having one substituent on the nitrogen atom, a tertiary amino group (-NR2) having two substituents on the nitrogen atom, or a quaternary amino group (quaternary ammonium group: -N + R3) (wherein R represents a substituent such as an alkyl group or an aryl group). Among these, from the viewpoint of the safety of the compound, the amino group in the constitutional unit (B) is preferably a secondary to quaternary amino group, and more preferably a tertiary amino group.

[0022] Examples of the monomer containing an amino group or a salt thereof include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, N,N-dimethylaminoethyl vinyl ether, N,N-diethylaminoethyl vinyl ether, N-[3-(dimethylamino)propyl]acrylamide-methyl chloride quaternary salt, 2-(dimethylamino)ethyl acrylate-benzyl chloride quaternary salt, and the like.

[0023] Examples of the salt in the structural unit (B) include chloride salts, bromide salts, iodide salts, carbonate salts, sulfate salts, and the like.

[0024] The method for forming the structural unit (B) is not particularly limited. For example, it may be formed by polymerizing the above-mentioned monomer containing an amino group or a salt thereof, or may be formed by introducing an amino group or a salt thereof after polymerizing a monomer not containing an amino group or a salt thereof. For example, the structural unit (B) may be formed by deprotecting a protecting group after polymerizing a monomer in which the amino group is protected.

[0025] The content of the structural unit (B) in the copolymer is 5% by mass or more and 50% by mass or less, preferably 7.5% by mass or more and 40% by mass or less, and more preferably 10% by mass or more and 35% by mass or less. By including the structural unit (B) in the content within the above range, deodorizing performance can be efficiently imparted. Also, if the content of the structural unit (B) is within the above range, dyeability with an acid dye can be efficiently imparted.

[0026] <Structural unit (C) other than structural unit (A) and structural unit (B)> The structural unit (C) is preferably a nonionic monomer from the viewpoint of further improving the solubility in N,N-dimethylacetamide. Further, the structural unit (C) may contain a structural unit (D) derived from a hydroxyl group-containing monomer, may contain a structural unit (E) derived from a hydrophobic monomer, or may contain both of them. The structural unit (C) may further contain a structural unit derived from other monomers.

[0027] The content of the structural unit (C) in the copolymer is 10% by mass or more and 90% by mass or less, preferably 25% by mass or more and 85% by mass or less, and more preferably 40% by mass or more and 80% by mass or less.

[0028] <Structural unit (D) derived from a hydroxyl group-containing monomer> Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2,3-hydroxypropyl (meth)acrylate; mono(meth)acrylates of polyols such as glycerin mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, mono(meth)acrylate of pentaerythritol, ditrimethylolpropane mono(meth)acrylate, and dipentaerythritol mono(meth)acrylate; hydroxyalkylacrylamides such as N-hydroxyethylacrylamide; and 2-(hydroxyalkyl)acrylate esters such as methyl 2-(hydroxymethyl)acrylate.

[0029] The hydroxyl group-containing monomer may be an alkylene oxide adduct obtained by adding an alkylene oxide to the hydroxyl group of these hydroxyl group-containing monomers, particularly hydroxyalkyl (meth)acrylates.

[0030] The method for forming the structural unit (C) is not particularly limited. For example, it may be formed by polymerizing the above-mentioned hydroxyl group-containing monomer, or it may be formed by introducing a hydroxyl group after polymerizing a monomer that does not contain a hydroxyl group. For example, the structural unit (C) may be formed by deprotecting a protecting group after polymerizing a monomer in which the hydroxyl group is protected.

[0031] The content of the structural unit (D) in the copolymer is preferably more than 0% by mass and 50% by mass or less, more preferably 5% by mass or more and 45% by mass or less, and still more preferably 10% by mass or more and 40% by mass or less. By including the structural unit (D) in the content within the above range, for example, water resistance can be efficiently imparted by coating the fiber surface in combination with a crosslinking agent. Further, it can be added during the polymerization of the urethane resin and copolymerized to efficiently impart water resistance. Also, if the content of the structural unit (D) is within the above range, dyeability with a reactive dye can be efficiently imparted.

[0032] <Structural unit (E) derived from a hydrophobic monomer> The hydrophobic monomer refers to a monomer having a solubility in water at 25 °C of 10% by mass or less. Specific examples thereof include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate, vinyl aryl compounds such as styrene, α- or β-methylstyrene, methylstyrene, and vinylnaphthalene, and vinyl cyanide-based monomers such as acrylonitrile and methacrylonitrile.

[0033] The solubility of the hydrophobic monomer in water at 25 °C is preferably 5% by mass or less, and more preferably 2% by mass or less.

[0034] The method for forming the structural unit (E) is not particularly limited. For example, it can be formed by polymerizing the above-mentioned hydrophobic monomer.

[0035] The content of the constitutional unit (E) in the copolymer is preferably 10% by mass or more and less than 90% by mass, more preferably 20% by mass or more and 80% by mass or less, and still more preferably 30% by mass or more and 70% by mass or less. By containing the constitutional unit (E) in the content within the above range, solubility in N,N-dimethylacetamide can be efficiently imparted.

[0036] <Constitutional units derived from other monomers> Examples of other monomers include (meth)acrylic acid, crotonic acid, and the like.

[0037] The content of the constitutional units derived from other monomers in the copolymer is preferably less than 10% by mass, more preferably less than 5% by mass, and still more preferably less than 1% by mass.

[0038] The copolymer according to the present embodiment preferably dissolves 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more in N,N-dimethylacetamide at 25°C based on the total mass of N,N-dimethylacetamide and the copolymer.

[0039] The solubility of the copolymer according to the present embodiment in N,N-dimethylacetamide can be evaluated, for example, by adding N,N-dimethylacetamide to the copolymer in a specified ratio, stirring overnight at 25°C, and then visually observing whether it has dissolved.

[0040] According to the fiber additive of the present embodiment containing the copolymer according to the present embodiment, functions derived from the copolymer, dye-dyeability (especially cationic dye-dyeability), and deodorizing properties can be imparted to the fiber.

[0041] The weight average molecular weight (Mw) of the copolymer according to this embodiment is preferably from 5,000 to 500,000, more preferably from 10,000 to 400,000, still more preferably from 20,000 to 250,000, and particularly preferably from 30,000 to 200,000. When the weight average molecular weight is 5,000 or more, the fiber additive according to this embodiment tends to remain inside the fiber when the fiber to which the fiber additive is applied is washed, and the washing durability tends to be improved. Further, when the weight average molecular weight is 500,000 or less, the viscosity when the copolymer is made into a solution is low, and it tends to be excellent in handling.

[0042] (Method for producing copolymer) The method for producing the copolymer according to this embodiment is not particularly limited. For example, it can be produced by a method characterized by including a polymerization step of polymerizing monomers corresponding to the above-described structural units in a solvent, and continuously introducing these monomers, a polymerization initiator, and a chain transfer agent into the system, respectively.

[0043] The solvent may be a non-aqueous solvent (particularly a water-soluble organic solvent) alone or may contain an aqueous solvent. Examples of the water-soluble organic solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, 2-methylpropyl alcohol, and 2-methyl-2-propanol; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate; ether solvents such as dioxane, diethyl ether, and tetrahydrofuran; and amide solvents such as N,N-dimethylacetamide. The proportion of the aqueous solvent in the water-soluble organic solvent can be, for example, 20% by mass or less.

[0044] Examples of the polymerization initiator include organic polymerization initiators and inorganic polymerization initiators. Examples of the organic polymerization initiators include azo compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(isobutyronitrile), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride; organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-tert-butyl peroxide, cumene hydroperoxide and the like. Examples of the inorganic polymerization initiators include hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; redox initiators that generate radicals by combining an oxidizing agent and a reducing agent such as ascorbic acid and hydrogen peroxide, persulfate and metal salts and the like.

[0045] From the viewpoint of improving the solubility of the copolymer in N,N-dimethylacetamide, an organic polymerization initiator is preferred as the polymerization initiator, an azo compound is more preferred, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate) are even more preferred, and 2,2'-azobis(2,4-dimethylvaleronitrile) is particularly preferred.

[0046] The addition amount of the polymerization initiator may be appropriately set according to the combination of monomers used, reaction conditions, etc., and is not particularly limited. For example, it may be 0.01 to 15% by mass, or 0.1 to 10% by mass based on all the monomers.

[0047] Examples of the chain transfer agent include organic chain transfer agents and inorganic chain transfer agents. Examples of the organic chain transfer agents include butanethiol, octanethiol, 1-dodecanethiol (also referred to as n-dodecyl mercaptan), octadecanethiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, 2-mercaptoethyl octanoate, 1,8-dimercapto-3,6-dioxaoctane, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhiobutyrate, 1,3,5-triazine-2,4,6-trithiol, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis(4-mercaptobutyrate), pentaerythritol tetrakis(6-mercaptohexanoate), dipentaerythritol hexakis(3-mercaptopropionate), mercaptopropionic acid, thiol-based chain transfer such as mercaptoethanol; halides such as carbon tetrachloride and methylene chloride; secondary or tertiary alcohols such as isopropyl alcohol and glycerin. Examples of the inorganic chain transfer agents include hypophosphorous acid or salts or hydrates thereof such as sodium hypophosphite and hypophosphorous acid; phosphorous acid or salts thereof such as phosphorous acid and sodium phosphite; sulfurous acid or salts thereof such as sodium sulfite; bisulfite or salts thereof such as sodium bisulfite; dithionous acid or salts thereof such as sodium dithionite; pyrosulfurous acid or salts thereof such as potassium pyrosulfite.

[0048] From the viewpoint of improving the solubility of the copolymer in N,N-dimethylacetamide, the chain transfer agent is preferably an organic chain transfer agent, hypophosphorous acid, or phosphorous acid, more preferably an organic chain transfer agent, still more preferably a thiol-based chain transfer agent, and particularly preferably mercaptopropionic acid.

[0049] The addition amount of the chain transfer agent may be appropriately set according to the combination of monomers used, reaction conditions, etc., and is not particularly limited. For example, it may be 0.01 to 10% by mass, or may be 0.1 to 5% by mass, based on all the monomers.

[0050] In the polymerization step, it is preferable to continuously drop the monomer, polymerization initiator, and chain transfer agent into the system, respectively. The dropping rate may be constant or may be changed stepwise. As a method of continuously introducing the monomer, polymerization initiator, and chain transfer agent into the system, for example, after raising the solvent in the system to a predetermined temperature, it is preferable to continuously drop the monomer, polymerization initiator, and chain transfer agent from separate routes. Note that the monomer may be dropped into the system as a mixture of some or all of the monomers.

[0051] When dispersing the monomer in the solvent, it may be dispersed by stirring with a paddle blade or the like, or may be dispersed using an emulsifying and dispersing device such as a high-speed shear turbine type disperser, a high-pressure jet homogenizer, an ultrasonic emulsifying and dispersing machine, a medium stirring disperser, or a forced gap passing type disperser.

[0052] After the polymerization reaction, it is preferable to include a ripening step of ripening the copolymer. By the ripening step, the polymerization reaction is completed, and the remaining monomers can be reduced. In the ripening step, although not particularly limited, it is preferable to maintain the system at the temperature during the polymerization step.

[0053] After the polymerization step or the ripening step, the copolymer may be recovered by drying the solution containing the copolymer. The copolymer recovered by drying may be ground in a mortar or the like to obtain a polymer powder.

[0054] An acidic aqueous solution may be allowed to act on the obtained copolymer. For example, when the copolymer contains a constitutional unit derived from a salt, the constitutional unit derived from the salt can be converted to an acid form by allowing an acidic aqueous solution, such as hydrochloric acid, to act thereon.

[0055] The method for producing the copolymer may include other steps. Examples of other steps include a neutralization step, a step for deactivating a polymerization initiator and a chain transfer agent, a dilution step, a concentration step, a purification step, and the like.

[0056] The copolymer according to this embodiment having a predetermined solubility in N,N-dimethylacetamide can be obtained by appropriately adjusting the production method.

[0057] [Composition containing a copolymer and a urethane resin] The composition containing the copolymer and the urethane resin according to this embodiment (hereinafter also referred to as "the composition according to this embodiment") includes the above copolymer and urethane resin.

[0058] The composition according to this embodiment can be used, for example, in the production of urethane fibers excellent in cationic dyeability, deodorizing properties, and the like.

[0059] In the composition according to this embodiment, the content of the copolymer is preferably 1 to 30% by mass, more preferably 1.5 to 25% by mass, and still more preferably 2 to 20% by mass based on the total solid content.

[0060] In the composition according to this embodiment, the content of the urethane resin is preferably 70 to 99% by mass, more preferably 75 to 98.5% by mass, and still more preferably 80 to 98% by mass based on the total solid content.

[0061] The composition according to this embodiment may contain a solvent depending on the intended use. As the solvent, the solvents described above for the fiber additives can be used. The content of the solvent in the composition according to this embodiment may be appropriately set according to the type of the solvent and the like, and is not particularly limited, but may be 0.001 to 5 parts by mass or 0.01 to 1 part by mass with respect to 100 parts by mass of the total solid content.

[0062] (Urethane resin) The urethane resin according to this embodiment is not particularly limited as long as it has structural units derived from polyols and structural units derived from polyisocyanates.

[0063] The polyols may be any compounds having two or more hydroxyl groups, and examples thereof include polyester polyols, polycarbonate polyols, polyether polyols and the like. Examples of the polyester polyols include polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, polybutylene sebacate diol, poly-ε-caprolactone diol, poly(3-methyl-1,5-pentylene) adipate diol, polycondensate of 1,6-hexanediol and dimer acid, polycondensate of 1,6-hexanediol, adipic acid and dimer acid, polycondensate of nonanediol and dimer acid, polycondensate of ethylene glycol, adipic acid and dimer acid, and the like. The polycarbonate polyol is a polyol having a carbonate bond in the molecule and two or more hydroxyl groups, and can be obtained, for example, by reacting polyols with an organic carbonate compound or phosgene. Examples of the polyols include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,10-decanediol and isosorbide. The polycarbonate polyol can have one or more kinds of structural units derived from the above polyols. Examples of the organic carbonate compound or phosgene include diphenyl carbonate.Examples of the polyether polyol include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, polyethylene glycol / polypropylene glycol block copolymer, propylene glycol propylene oxide adduct, bisphenol A propylene oxide adduct, glycerin propylene oxide adduct, ethylenediamine propylene oxide adduct, ethylenediamine propylene oxide adduct, sorbitol-based propylene oxide adduct, sucrose-based propylene oxide adduct, propylene oxide / ethylene oxide random polyether, and the like.

[0064] The polyisocyanates may be compounds having two or more isocyanate groups, and may be aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates. Examples of such polyisocyanates include aliphatic diisocyanate compounds such as hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, and trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane; and aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate.

[0065] (Method for producing urethane resin) The urethane resin is not particularly limited as long as it includes a step of polymerizing polyols and polyisocyanates, and can be produced by a known method such as a melt polymerization method or a solution polymerization method.

[0066] In the polymerization process, a chain extender, a terminal capping agent, a catalyst, etc. may be appropriately used. Examples of the chain extender include low molecular weight diamines such as ethylenediamine and 1,2-propanediamine; low molecular weight diols such as ethylene glycol and 1,3-propanediol. Examples of the terminal capping agent include ethanol, propanol, butanol, etc. Examples of the catalyst include organic amine compounds such as N,N-dimethylcyclohexylamine and N,N-dimethylbenzylamine; organometallic compounds such as tin octoate.

[0067] [Solution containing a copolymer and an amide solvent] A solution obtained by dissolving the copolymer according to the present embodiment in an amide solvent (hereinafter also referred to as "the solution according to the present embodiment") contains the above copolymer and amide solvent.

[0068] The solution according to the present embodiment can be used, for example, in the production of urethane fibers excellent in cationic dyeability, deodorizing property, etc.

[0069] Examples of the amide solvent include N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, etc.

[0070] The content of the amide solvent in the solution according to the present embodiment may be, for example, 50 to 5000 parts by mass, or 80 to 1000 parts by mass with respect to 100 parts by mass of the total solid content.

[0071] [Method for imparting functions to fibers] The method for imparting functions to fibers using a fiber additive is not particularly limited. For example, a method of adding a fiber additive to a spinning solution containing a fiber raw material in dry spinning or wet spinning, a method of adding a fiber additive to a chip of a fiber raw material before hot melting in melt spinning, a method of diffusing and adsorbing a fiber additive on the surface and / or inside of a fiber by post-processing of the fiber, etc. can be mentioned.

[0072] The fiber additive can be suitably used to impart functions to urethane fibers. The method of imparting functions to urethane fibers using the fiber additive is not particularly limited. For example, the fiber additive can be dispersed in the urethane resin by adding the fiber additive to a spinning solution containing a urethane resin in dry spinning and kneading, and then the spinning solution can be extruded from a spinning nozzle and the solvent can be evaporated by hot air or the like to form fibers. The content of the copolymer in the spinning solution can be, for example, 20% by mass or less. Further, as the solvent of the spinning solution, for example, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, toluene, xylene, or tetrahydrofuran can be used.

[0073] The composition according to this embodiment can also be suitably used for the production of urethane fibers imparted with functions. The method of producing urethane fibers imparted with functions using the composition is not particularly limited. For example, in dry spinning, the composition can be added to a spinning solution, kneaded, and then the spinning solution can be extruded from a spinning nozzle and the solvent can be evaporated by hot air or the like to form fibers. The total content of the copolymer and the urethane resin in the spinning solution can be, for example, 20 to 65% by mass. Further, as the solvent of the spinning solution, for example, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, toluene, xylene, or tetrahydrofuran can be used.

[0074] The dry spinning method is not particularly limited except that the spinning solution contains a fiber additive, or the composition or solution according to this embodiment, and can be appropriately set according to the desired properties of the urethane fibers and the like.

Examples

[0075] Examples are given below to explain the present invention in more detail, but the present invention is not limited to only these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0076] <Measurement Conditions (1) of Weight-Average Molecular Weight> The weight-average molecular weights of the polymers of Production Examples 1 to 5 were determined by measuring under the following conditions by gel permeation chromatography (GPC) method. Apparatus: HLC-8320GPC manufactured by Tosoh Corporation Detector: RI Column: Shodex KD-806M (two pieces), KD-G 4A manufactured by Showa Denko K.K. Column temperature: 40 °C Flow rate: 0.8 mL / min. Sample solution injection volume: 100 μL (sample concentration is 0.5%) Calibration curve: Polystyrene Standards Eluent: N,N-dimethylformamide (containing 0.1% LiBr)

[0077] <Measurement Conditions (GPC) (2) of Weight-Average Molecular Weight> The weight-average molecular weights of the polymers of Production Examples 6 and 7 were determined by measuring under the following conditions by gel permeation chromatography (GPC) method. Apparatus: Waters Alliance (2695) Detector: RI Column: OHpak SB-806M HQ manufactured by Shodex (three pieces in series) Column temperature: 40 °C Flow rate: 1.0 mL / min. Sample solution injection volume: 50 μL (sample concentration is 0.5%) Calibration curve: Polyacrylic acid standards (Mp = 900, 1250, 2925, 4100, 16000, 62900, 392600, 1310000, 2250000) manufactured by American Polymer Standards Corporation were used, and a cubic equation was created based on Mp and elution time. Eluent: A solution obtained by adding 752 g of acetonitrile to an aqueous solution prepared by diluting a mixture of sodium dihydrogen phosphate dodecahydrate / disodium hydrogen phosphate dihydrate (67.46 g / 154.86 g) to 8648 g with pure water.

[0078] <Deodorizing Property Evaluation Method (Target Odor: Acetic Acid)> The test cloth was placed in a sampling bag with a cock (Smart Bag PA, manufactured by GL Sciences Inc., capacity 3 L, model AAK), heat-sealed, and completely sealed. After evacuating the inside of the sampling bag, 2 L of nitrogen gas was measured and introduced. Then, 5 mL of acetic acid-containing air was measured and introduced into the sampling bag using a gastight syringe. After standing for 2 hours, a gas detector tube (No. 81 for acetic acid, manufactured by Gastech) was used, and 50 mL of the gas inside the bag was aspirated once with a gas sampler (model GV-100S, manufactured by Gastech Co., Ltd.) to measure the acetic acid concentration, and the following determination was made. Note that a test cloth not containing a polymer was used as a reference (the evaluation of Comparative Example 4 described below corresponds to the reference). (Judgment Criteria) ◎: Compared with the reference, the acetic acid concentration decreased ×: Compared with the reference, the acetic acid concentration was about the same.

[0079] <Production Example 1> Sodium styrenesulfonate with a purity of 87.9% (hereinafter referred to as "SSNa"): 45.6 g (i.e., pure content: 40.1 g), N,N-dimethylacetamide (hereinafter referred to as "DMAc"): 42.4 g, 2-hydroxyethyl methacrylate (hereinafter referred to as "HEMA"): 100.2 g, 2-(dimethylamino)ethyl methacrylate (hereinafter referred to as "DAM"): 100.2 g, acetic acid: 36.4 g, and ion-exchanged water: 93.2 g were mixed to prepare a monomer feed solution (1). A 2.5 L SUS reaction vessel equipped with a stirring blade, a glass lid, a stirrer with a stirring seal, a nitrogen inlet pipe, a reflux condenser, and a temperature sensor was charged with 257.4 g of DMAc. While stirring under a nitrogen stream, the temperature was raised to 90 °C. Then, while maintaining 90 °C and stirring under a nitrogen stream, the above monomer feed solution (1) was added dropwise from the tip nozzle over 180 minutes, 260.6 g of styrene (hereinafter referred to as "St") was added dropwise over 150 minutes, and 73.7 g of a DMAc solution of 25 mass% 2,2'-azobis(2,4-dimethylvaleronitrile) (hereinafter referred to as "25% V-65") was added dropwise over 240 minutes, each through a separate supply path. The dropping of each component was carried out continuously at a constant dropping rate. After the dropping of the monomer feed solution (1) was completed, the reaction solution was maintained at 90 °C for an additional 120 minutes (aged) to complete the polymerization, thereby obtaining a copolymer solution (A-1) with a polymerization average molecular weight (Mw) of 103,000. After charging 10.0 g of the obtained copolymer solution (A-1) into a container with a volume of 200 mL, 40.0 g of DMAc and 1.1 g of blocked isocyanate (Coronate 2507 manufactured by Tosoh Corporation) were added, and the mixture was stirred well to obtain a copolymer solution (A-2). A fabric of polyurethane / polyester cross-weave (15 / 85) manufactured by Shikisya Co., Ltd. cut into 10 cm squares was immersed in the copolymer solution (A-2), the solution was removed so that 25% by weight of the copolymer remained on the fabric, air-dried, and then heat-treated at 150 °C for 3 minutes to obtain a test cloth (A-3).

[0080] <Production Example 2> 93.2 g of SSNa with a purity of 87.9% (i.e., pure content: 81.9 g), 56.3 g of DMAc, 146.5 g of HEMA, 99.3 g of DAM, 36.0 g of acetic acid, and 142.6 g of ion-exchanged water were mixed to prepare a monomer feed solution (2). A 2.5 L SUS reaction vessel equipped with a stirring blade, a glass lid, a stirrer with a stirring seal, a nitrogen inlet pipe, a reflux condenser, and a temperature sensor was charged with 198.6 g of DMAc and heated to 90 °C with stirring under a nitrogen stream. Then, while maintaining 90 °C, the above monomer feed solution (2) was dropped from the tip nozzle through separate supply paths over 180 minutes, 168.9 g of St over 150 minutes, and 68.2 g of 25% V-65 over 240 minutes, respectively, with stirring under a nitrogen stream. The dropping of each component was carried out continuously at a constant dropping rate. After the dropping of the monomer feed solution (2) was completed, the reaction solution was further held at 90 °C for 120 minutes (aged) to complete the polymerization, thereby obtaining a copolymer solution (B-1) with a polymerization average molecular weight (Mw) of 225,000. After charging 10.0 g of the obtained copolymer solution (B-1) into a container with a volume of 200 mL, 40.0 g of DMAc and 1.1 g of block isocyanate (Coronate 2507 manufactured by Tosoh Corporation) were added and stirred well to obtain a copolymer solution (B-2). A fabric of polyurethane / polyester cross-weave (15 / 85) manufactured by Shikisya Co., Ltd. cut into 10 cm squares was immersed in the copolymer solution (B-2), the solution was removed so that 25% by weight of the copolymer remained on the fabric, air-dried, and then heat-treated at 150 °C for 3 minutes to obtain a test cloth (B-3).

[0081] <Production Example 3> 41.9 g of SSNa with a purity of 87.9% (i.e., pure content: 36.8 g), 124.8 g of DMAc, 92.1 g of HEMA, 92.1 g of DAM, 33.4 g of acetic acid, and 124.8 g of ion-exchanged water were mixed to prepare a monomer feed solution (3). A 2.5 L SUS reaction vessel equipped with a stirring blade, a glass lid, a stirrer with a stirring seal, a nitrogen inlet pipe, a reflux condenser, and a temperature sensor was charged with 116.0 g of DMAc and 116.0 g of ion-exchanged water, and heated to 80°C with stirring under a nitrogen stream. Then, while maintaining 80°C, the above monomer feed solution (3) was added dropwise from the tip nozzle over 180 minutes, 239.5 g of methyl methacrylate (hereinafter referred to as "MMA") was added dropwise over 180 minutes, and 69.4 g of 25% V-65 was added dropwise over 240 minutes, each through separate supply routes. The dropping of each component was carried out continuously at a constant dropping rate. After the dropping of the monomer feed solution (3) was completed, the reaction solution was maintained at 80°C for an additional 120 minutes (aged) to complete the polymerization, thereby obtaining a copolymer solution (C-1) with a polymerization average molecular weight (Mw) of 125,000. After charging 10.0 g of the obtained copolymer solution (C-1) into a 200 mL container, 40.0 g of DMAc and 1.1 g of blocked isocyanate (Coronate 2507 manufactured by Tosoh Corporation) were added, and the mixture was stirred well to obtain a copolymer solution (C-2). A fabric of polyurethane / polyester cross-weave (15 / 85) manufactured by Shikisya Co., Ltd. cut into 10 cm squares was immersed in the copolymer solution (C-2), the solution was removed so that 25% by weight of the copolymer remained on the fabric, air-dried, and then heat-treated at 150°C for 3 minutes to obtain a test cloth (C-3).

[0082] <Production Example 4> 74.6 g of SSNa with a purity of 87.9% (i.e., pure content: 65.6 g), 45.0 g of DMAc, 117.3 g of HEMA, 79.5 g of DAM, 28.8 g of acetic acid, and 134.2 g of ion-exchanged water were mixed to prepare a monomer feed solution (4). A 2.5 L SUS reaction vessel equipped with a stirring blade, a glass lid, a stirrer with a stirring seal, a nitrogen inlet pipe, a reflux condenser, and a temperature sensor was charged with 121.5 g of DMAc and 121.5 g of ion-exchanged water. While stirring under a nitrogen stream, the temperature was raised to 80°C. Then, while maintaining 80°C and stirring under a nitrogen stream, the above monomer feed solution (4) was dropped from the tip nozzle through separate supply paths for 180 minutes, 135.1 g of MMA was dropped for 180 minutes, and 55.4 g of 25% V-65 was dropped for 240 minutes. The dropping of each component was continuously carried out at a constant dropping rate. After the dropping of the monomer feed solution (4) was completed, the reaction solution was further held at 80°C for 120 minutes (aged) to complete the polymerization, thereby obtaining a copolymer solution (D-1) with a polymerization average molecular weight (Mw) of 228,000. After charging 10.0 g of the obtained copolymer solution (D-1) into a container with a volume of 200 mL, 40.0 g of DMAc and 1.1 g of blocked isocyanate (Coronate 2507 manufactured by Tosoh Corporation) were added, and the mixture was stirred well to obtain a copolymer solution (D-2). A fabric of polyurethane / polyester interwoven (15 / 85) manufactured by Shikisya Co., Ltd. cut into 10 cm squares was immersed in the copolymer solution (D-2). After removing the solution so that 25% by weight of the copolymer remained on the fabric and air-drying, heat treatment was carried out at 150°C for 3 minutes to obtain a test cloth (D-3).

[0083] <Production Example 5> 11.9 g of SSNa with a purity of 87.9% (i.e., pure content: 10.5 g), 39.0 g of DMAc, 105.0 g of HEMA, 105.0 g of DAM, 38.1 g of acetic acid, and 98.8 g of ion-exchanged water were mixed to prepare a monomer feed solution (5). A 2.5-L SUS reaction vessel equipped with a stirring blade, a glass lid, a stirrer with a stirring seal, a nitrogen inlet tube, a reflux condenser, and a temperature sensor was charged with 268.0 g of DMAc. While stirring under a nitrogen stream, the temperature was raised to 90°C. Then, while maintaining 90°C and stirring under a nitrogen stream, the above monomer feed solution (5) was added dropwise from the tip nozzle over 180 minutes, 304.5 g of St over 150 minutes, and 79.6 g of 25% V-65 over 240 minutes, respectively, through separate supply routes. The dropping of each component was continuously carried out at a constant dropping rate. After the dropping of the monomer feed solution (5) was completed, the reaction solution was further held at 90°C for 120 minutes (aged) to complete the polymerization, thereby obtaining a copolymer solution (E-1) with a polymerization average molecular weight (Mw) of 52,000. After charging 10.0 g of the obtained copolymer solution (E-1) into a container with a volume of 200 mL, 40.0 g of DMAc and 1.1 g of blocked isocyanate (Coronate 2507 manufactured by Tosoh Corporation) were added, and the mixture was stirred well to obtain a copolymer solution (E-2). A fabric of polyurethane / polyester cross-weave (15 / 85) manufactured by Shikisya Co., Ltd. cut into 10 cm squares was immersed in the copolymer solution (E-2). After removing the solution so that 25% by weight of the copolymer remained on the fabric and air-drying, heat treatment was carried out at 150°C for 3 minutes to obtain a test cloth (E-3).

[0084] <Production Example 6> 42.7 g of SSNa with a purity of 87.9% (i.e., pure content: 37.5 g), 539.6 g of an 80 wt% aqueous acrylic acid solution (hereinafter referred to as "80% AA"), and 102.7 g of ion-exchanged water were mixed to prepare a monomer feed solution (6). Into a 2.5 L SUS reaction vessel equipped with a reflux condenser and a stirrer, 218.6 g of ion-exchanged water was charged, and the temperature was raised to the boiling point with stirring. Next, under stirring, into the polymerization reaction system at the boiling point, the above monomer feed solution (6) was added dropwise from the tip nozzle through separate feed paths at a supply rate of 134.7 g of a 10% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (hereinafter also referred to as "10% V-50") for 180 minutes, 1.7 g of a 30% aqueous solution of mercaptopropionic acid (hereinafter also referred to as "30% MPA") for 18 minutes, and then 10.0 g for 162 minutes in two stages. The addition of components other than 30% MPA was carried out continuously at a constant dropping rate. After the completion of the dropping of the monomer feed solution (6), the reaction solution was maintained at the boiling point (aged) for an additional 30 minutes to complete the polymerization, thereby obtaining an aqueous polymer solution (F-1) with a polymerization average molecular weight (Mw) of 25,000. After charging 30.0 g of the obtained copolymer aqueous solution (F-1) into a container with a volume of 200 mL, 5.9 g of 25% aqueous ammonia solution (hereinafter referred to as "25% aqueous ammonia"), and 120.0 g of ion-exchanged water were added and mixed well. 19.0 g of Epocros WS-700 (manufactured by Nippon Shokubai Co., Ltd., an oxazoline group-containing polymer, hereinafter also referred to as "10% WS-700") previously diluted so that the solid content in the obtained aqueous solution was 10% by weight was added and stirred to obtain a copolymer aqueous solution (F-2). A fabric of polyurethane / polyester cross-weave (15 / 85) manufactured by Shikisya Co., Ltd. cut into 10 cm squares was immersed in the copolymer aqueous solution (F-2), dehydrated so that 25% by weight of the copolymer remained on the fabric, and then heat-treated at 120 °C for 30 minutes to obtain a test cloth (F-3).

[0085] <Production Example 7> Into a 2.5 L SUS reaction vessel equipped with a reflux condenser and a stirrer, 253.8 g of ion-exchanged water was charged and heated to the boiling point with stirring. Next, with stirring, into the polymerization reaction system at the boiling point, 626.3 g of 80% AA was added dropwise from the tip nozzle through separate supply paths at a constant dropping rate for 180 minutes, 156.4 g of 10% V-50 was added dropwise for 195 minutes, 1.9 g of 30% MPA was added dropwise for 18 minutes and then 11.6 g was added dropwise for 162 minutes in two stages. The dropping of components other than 30% MPA was carried out continuously at a constant dropping rate. After the dropping of 80% AA was completed, the above reaction solution was maintained at the boiling point (aged) for an additional 30 minutes to complete the polymerization, thereby obtaining an aqueous polymer solution (G-1) with a polymerization average molecular weight (Mw) of 28,000. After charging 30.0 g of the obtained copolymer aqueous solution (G-1) into a container with a volume of 200 mL, 5.9 g of 25% aqueous ammonia and 120.0 g of ion-exchanged water were added and mixed well. 19.0 g of 10% WS-700 was added to the obtained aqueous solution and stirred to obtain a copolymer aqueous solution (G-2). A fabric of polyurethane / polyester cross-weaving (15 / 85) manufactured by Shikisya Co., Ltd. cut into 10 cm squares was immersed in the copolymer aqueous solution (G-2), dehydrated so that 25% by weight of the copolymer remained on the fabric, and then heat-treated at 120 °C for 30 minutes to obtain a test cloth (G-3).

[0086] <Production Example 8> 0.27 g of a cationic dye (Nichilon Black KSL (300%)) manufactured by Nisshin Kasei Co., Ltd. and 450 g of a buffer solution (an aqueous solution consisting of 0.050% acetic acid and 0.041% sodium acetate trihydrate) were mixed to obtain a cationic dye solution (H).

[0087] <Production Example 9> 0.22 g of an acid dye (Kayanol Milling Black TLB) manufactured by Nippon Kayaku Co., Ltd. and 325.78 g of a 0.2% aqueous ammonium sulfate solution were mixed to obtain an acid dye solution (I).

[0088] <Production Example 10> By mixing 0.53 g of the reactive dye (Synozol blue SHF-BRF 150%) manufactured by Inaba Fine Tech Co., Ltd. and 499.47 g of a 4.2% aqueous sodium carbonate solution, a reactive dye solution (J) was obtained.

[0089] <Example 1> After removing the solvent by heating the copolymer solution (A-1) obtained in Production Example 1 under reduced pressure, DMAc was added so that the concentration of the copolymer became 15% by weight, and the mixture was stirred at 25°C overnight to obtain a uniform solution. Subsequently, the test cloth (A-3) obtained in Production Example 1 was immersed in the cationic dye solution (H) at room temperature for 30 minutes, and then thoroughly washed with water to wash away the excess dye, and it was confirmed visually that it was dyed. Finally, the deodorizing performance of the test cloth (A-3) obtained in Production Example 1 was evaluated by the above method. The judgment was "◎".

[0090] <Example 2> After removing the solvent by heating the copolymer solution (B-1) obtained in Production Example 2 under reduced pressure, DMAc was added so that the concentration of the copolymer became 15% by weight, and the mixture was stirred at 25°C overnight to obtain a uniform solution. Subsequently, the test cloth (B-3) obtained in Production Example 2 was immersed in the cationic dye solution (H) at room temperature for 30 minutes, and then thoroughly washed with water to wash away the excess dye, and it was confirmed visually that it was brightly dyed. Finally, the deodorizing performance of the test cloth (B-3) obtained in Production Example 2 was evaluated by the above method. The judgment was "◎".

[0091] <Example 3> After removing the solvent by heating the copolymer solution (C-1) obtained in Production Example 3 under reduced pressure, DMAc was added so that the concentration of the copolymer became 15% by weight, and the mixture was stirred at 25°C overnight to obtain a uniform solution. Subsequently, the test cloth (C-3) obtained in Production Example 3 was immersed in the cationic dye solution (H) at room temperature for 30 minutes, and then thoroughly washed with water to wash away the excess dye, and it was confirmed visually that it was dyed. Finally, the test cloth (C-3) obtained in Production Example 3 was evaluated for deodorizing performance by the above method. The judgment was "◎".

[0092] <Example 4> The copolymer solution (D-1) obtained in Production Example 4 was heated under reduced pressure to remove the solvent. Then, DMAc was added so that the concentration of the copolymer became 15% by weight, and the mixture was stirred at 25 °C overnight to obtain a uniform solution. Subsequently, the test cloth (D-3) obtained in Production Example 4 was immersed in the cationic dye solution (H) at room temperature for 30 minutes, and then thoroughly washed with water to wash away the excess dye. It was confirmed visually that the cloth was vividly dyed. Finally, the test cloth (D-3) obtained in Production Example 4 was evaluated for deodorizing performance by the above method. The judgment was "◎".

[0093] <Comparative Example 1> The copolymer solution (E-1) obtained in Production Example 5 was heated under reduced pressure to remove the ion-exchanged water. Then, DMAc was added so that the concentration of the copolymer became 15% by weight, and the mixture was stirred at 25 °C overnight to obtain a uniform solution. Subsequently, the test cloth (E-3) obtained in Production Example 5 was immersed in the cationic dye solution (H) at room temperature for 30 minutes, and then thoroughly washed with water to wash away the excess dye. It was confirmed that the cloth was hardly dyed. Finally, the test cloth (E-3) obtained in Production Example 5 was evaluated for deodorizing performance by the above method. The judgment was "◎".

[0094] <Comparative Example 2> The solid obtained by heating and drying the aqueous copolymer solution (F-1) obtained in Production Example 6 under reduced pressure was ground in a mortar to obtain a powder (F-4). DMAc was added to the powder (F-4) obtained so that the concentration of the copolymer became 15% by weight, and the mixture was stirred at 25 °C overnight. It was confirmed that there was undissolved copolymer. Subsequently, the test cloth (F-3) obtained in Production Example 6 was immersed in the cationic dye solution (H) at room temperature for 30 minutes, and then thoroughly washed with water to wash away the excess dye. It was confirmed visually that the cloth was vividly dyed. Finally, the test cloth (F-3) obtained in Production Example 6 was evaluated for deodorizing performance by the above method. The judgment was "×".

[0095] <Comparative Example 3> The solid obtained by heating and drying the copolymer aqueous solution (G-1) obtained in Production Example 7 under reduced pressure was ground in a mortar to obtain a powder (G-4). When DMAc was added to the powder (G-4) obtained so that the concentration of the copolymer was 15% by weight and stirred at 25°C overnight, a uniform solution was obtained. Comparing with the results of Comparative Example 2, it was suggested that the solubility in DMAc decreased by copolymerizing SSNa. Subsequently, the test cloth (G-3) obtained in Production Example 7 was immersed in the cationic dye solution (H) at room temperature for 30 minutes and then thoroughly washed with water to wash away the excess dye. It was confirmed that it was hardly dyed. Finally, the test cloth (G-3) obtained in Production Example 7 was evaluated for deodorizing performance by the above method. The judgment was "×".

[0096] <Comparative Example 4> A fabric of polyurethane / polyester cross-weave (15 / 85) manufactured by Shikisya Co., Ltd. cut into a 10 cm square was immersed in the cationic dye solution (H) at room temperature for 30 minutes and then thoroughly washed with water to wash away the excess dye. It was confirmed that it was hardly dyed. Also, the fabric of polyurethane / polyester cross-weave (15 / 85) manufactured by Shikisya Co., Ltd. cut into a 10 cm square was evaluated for deodorizing performance by the above method. The judgment was "×".

[0097] The results of the above Examples and Comparative Examples are summarized in Table 1.

Table 1

[0098] <Reference Examples 1 to 3: Dyeability with Acid Dyes and Reactive Dyes> The test fabrics (B-3) to (D-3) obtained in Production Examples 2 to 4 were immersed in the acid dye solution (I) at 95°C for 60 minutes, and then thoroughly washed with water to wash away the excess dye. It was confirmed visually that they were vividly dyed. Also, the test fabrics (B-3) to (D-3) were immersed in the reactive dye solution (J) at room temperature for 40 minutes and at 95°C for 60 minutes, and then thoroughly washed with water to wash away the excess dye. It was confirmed visually that they were vividly dyed.

[0099] The results of the above reference examples are summarized in Table 2.

Table 2

Claims

1. A fiber additive containing a copolymer composed of a structural unit (A) derived from a monomer containing a sulfo group or a salt thereof, a structural unit (B) derived from a monomer containing an amino group or a salt thereof, and a structural unit (C) other than the structural unit (A) and the structural unit (B), wherein the content of the structural unit (A) in the copolymer is 5% by mass or more and 50% by mass or less, the content of the structural unit (B) in the copolymer is 5% by mass or more and 50% by mass or less, and the content of the structural unit (C) in the copolymer is 10% by mass or more and 90% by mass or less. The fiber additive.

2. The fiber additive according to claim 1, wherein the monomer containing a sulfo group or a salt thereof is vinyl aromatic sulfonic acid or a salt thereof.

3. The structural unit (C) contains a structural unit (D) derived from a hydroxyl group-containing monomer of more than 0% by mass and 50% by mass or less, and a structural unit (E) derived from a hydrophobic monomer of 10% by mass or more and less than 90% by mass, based on the total amount of the copolymer. The fiber additive according to claim 1 or 2.

4. The fiber additive according to claim 1 or 2, wherein the copolymer dissolves in N,N-dimethylacetamide at 25°C in an amount of 5% by mass or more based on the total mass of N,N-dimethylacetamide and the copolymer.

5. The fiber additive according to claim 1 or 2 for imparting cationic dye-dyeability to urethane fibers.

6. A composition containing a copolymer composed of a structural unit (A) derived from a monomer containing a sulfo group or a salt thereof, a structural unit (B) derived from a monomer containing an amino group or a salt thereof, and a structural unit (C) other than the structural unit (A) and the structural unit (B), and a urethane resin, wherein the content of the structural unit (A) in the copolymer is 5% by mass or more and 50% by mass or less, the content of the structural unit (B) in the copolymer is 5% by mass or more and 50% by mass or less, and the content of the structural unit (C) in the copolymer is 10% by mass or more and 90% by mass or less. The composition.

7. The monomer containing a sulfo group or a salt thereof is vinyl aromatic sulfonic acid or a salt thereof, and the structural unit (C) contains a structural unit (D) derived from a hydroxyl group-containing monomer of more than 0% by mass and 50% by mass or less, and a structural unit (E) derived from a hydrophobic monomer of 10% by mass or more and less than 90% by mass, based on the total amount of the copolymer. The composition according to claim 6.

8. The composition according to claim 6 or 7, wherein the copolymer is soluble in N,N-dimethylacetamide at 25°C in an amount of 5% by mass or more based on the total mass of N,N-dimethylacetamide and the copolymer.

9. A solution obtained by dissolving a copolymer having a structural unit (A) derived from a monomer containing a sulfo group or a salt thereof, a structural unit (B) derived from a monomer containing an amino group or a salt thereof, and a structural unit (C) other than the structural unit (A) and the structural unit (B) in an amide-based solvent, wherein the content of the structural unit (A) in the copolymer is 5% by mass or more and 50% by mass or less, the content of the structural unit (B) in the copolymer is 5% by mass or more and 50% by mass or less, and the content of the structural unit (C) in the copolymer is 10% by mass or more and 90% by mass or less.

10. wherein the monomer containing a sulfo group or a salt thereof is vinyl aromatic sulfonic acid or a salt thereof, and the structural unit (C) includes a structural unit (D) derived from a hydroxyl group-containing monomer in an amount of more than 0% by mass and 50% by mass or less, and a structural unit (E) derived from a hydrophobic monomer in an amount of 10% by mass or more and less than 90% by mass, based on the total amount of the copolymer, according to the solution of claim 9.

11. A copolymer comprising a structural unit (A) derived from a monomer containing a sulfo group or a salt thereof, a structural unit (B) derived from a monomer containing an amino group or a salt thereof, a structural unit (D) derived from a hydroxyl group-containing monomer, and a structural unit (E) derived from a hydrophobic monomer, wherein the content of the structural unit (A) in the copolymer is 5% by mass or more and 50% by mass or less, the content of the structural unit (B) in the copolymer is 5% by mass or more and 50% by mass or less, the content of the structural unit (D) in the copolymer is more than 0% by mass and 50% by mass or less, and the content of the structural unit (E) in the copolymer is 10% by mass or more and less than 90% by mass.

12. The copolymer according to claim 11, wherein the monomer containing a sulfo group or a salt thereof is vinyl aromatic sulfonic acid or a salt thereof.

13. The copolymer according to claim 11 or 12, wherein the hydrophobic monomer is a (meth)acrylate ester or a vinyl aryl compound.

14. The copolymer according to claim 11 or 12, wherein the hydroxyl group-containing monomer is hydroxyalkyl (meth)acrylate or an alkylene oxide adduct thereof.

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