JP7086451B2 - Fiber treatment agent - Google Patents

Description

The present invention relates to a fiber treatment agent. More specifically, the present invention relates to a fiber treatment agent preferably used for fibers such as polyester.

In recent years, consumers have been required to impart functions such as hygroscopicity, antibacterial / deodorant property, heat retention property, heat generation property, and flexibility to fibers from the viewpoint of hygiene / comfort, and various techniques have been developed. For example, as a method for imparting functionality to synthetic fibers, a technique for kneading functional components at the stage of the fiberization process has been developed. A method of imparting functionality at the stage of yarn or woven fabric after the fibrosis process has also been developed, and such a method can be applied regardless of the type of fiber such as synthetic fiber or natural fiber. No. 1 discloses a technique for imparting a texture or the like by coating a fiber with a fiber treatment agent. Further, Patent Documents 2 and 3 disclose a resin composition for processing a cellulosic base material using a carboxyl group-containing polymer (A) and a polyvalent oxazoline compound (B). Patent Document 4 discloses a fiber treatment agent containing a polyhydric alcohol and a polycarboxylic acid.

Japanese Unexamined Patent Publication No. 2008-280652 Japanese Unexamined Patent Publication No. 2000-129144 Japanese Unexamined Patent Publication No. 2000-119968 Japanese Unexamined Patent Publication No. 2016-79530

As described above, various fiber treatment agents have been disclosed, but the conventional fiber treatment agents are not sufficient in terms of both hygroscopicity and texture (touch, touch), and there is room for improvement.

The present invention has been made in view of the above situation, and an object of the present invention is to provide a fiber treatment agent capable of imparting sufficient hygroscopicity to a fiber and improving the texture of the fiber.

The present inventor has made various studies on fiber treatment agents, and found that a copolymer having a structural unit derived from a (poly) alkylene glycol-based monomer and a structural unit derived from a carboxylic acid-based monomer is sufficient for the fiber. We have found that it is possible to impart moisture absorption and improve the texture of fibers, and have come up with the idea that the above problems can be solved brilliantly, and have reached the present invention.

That is, the present invention has the following formula (1);

（式中、Ｒ^１、Ｒ^２及びＲ^３は、同一又は異なって、水素原子、又は、メチル基を表す。Ｒ^４は、水素原子、又は、炭素数１～３０の炭化水素基を表す。（ＡＯ）は、同一又は異なって、オキシアルキレン基を表す。ｎは、オキシアルキレン基の平均付加モル数を表し、１～３００の数である。ｙは、０～２の数を表す。ｚは、０又は１を表す。）で表される（ポリ）アルキレングリコール系単量体（Ａ）由来の構造単位（ａ）と不飽和カルボン酸系単量体（Ｂ）由来の構造単位（ｂ）とを有する共重合体を含む繊維処理剤である。
以下に本発明を詳述する。
なお、以下において記載する本発明の個々の好ましい形態を２つ以上組み合わせたものもまた、本発明の好ましい形態である。

(In the formula, R ¹ , R ² and R ³ represent the same or different hydrogen atom or methyl group. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. (AO) represents the same or different oxyalkylene group. N represents the average number of added moles of the oxyalkylene group. The number is 1 to 300. Y represents the number of 0 to 2. z. Represents 0 or 1), a structural unit (a) derived from the (poly) alkylene glycol-based monomer (A) and a structural unit (b) derived from the unsaturated carboxylic acid-based monomer (B). ) And a fiber treatment agent containing a copolymer.
The present invention will be described in detail below.
It should be noted that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

<Copolymer>
The fiber treatment agent of the present invention has a structural unit (a) derived from the (poly) alkylene glycol-based monomer (A) and a structural unit (b) derived from the unsaturated carboxylic acid-based monomer (B). It contains a polymer. The copolymer has a (poly) alkylene glycol chain derived from the structural unit (a) and a carboxyl group derived from the structural unit (b), and these hydrophilic groups make the fiber treatment agent of the present invention a fiber. It is possible to impart hygroscopicity to the material. Further, the copolymer has the above (poly) alkylene glycol chain in the side chain, and by having the side chain having a suitable size, the glass transition temperature (Tg) of the copolymer is sufficiently lowered. The fiber treatment agent of the present invention containing such a copolymer can impart flexibility to the fiber and can improve the texture of the fiber.

The (poly) alkylene glycol-based monomer (A) (hereinafter, also referred to as a monomer (A)) is a compound represented by the above formula (1).
R ¹ , R ² and R ³ in the above formula (1) are the same or different, and are hydrogen atoms or methyl groups. Preferably, R ¹ and R ² are hydrogen atoms, and R ³ is a hydrogen atom or a methyl group.
^R4 in the above formula (1) is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
As ^R4 , a hydrocarbon group having 1 to 30 carbon atoms is preferable. In this case, the (poly) alkylene glycol chain derived from the structural unit (a) and the carboxyl group derived from the structural unit (b) do not undergo a condensation reaction. The self-crosslinking reaction in the copolymer is suppressed. Since the self-crosslinking reaction is suppressed, the flexibility of the copolymer is further improved, so that the fiber treatment agent containing such a copolymer can further improve the texture of the fiber.
Hydrocarbon groups having 1 to 30 carbon atoms include an aliphatic alkyl group having 1 to 30 carbon atoms, an alicyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and 2 to 30 carbon atoms. Examples thereof include an alkynyl group, a phenyl group having 6 to 30 carbon atoms, an alkylphenyl key group, a phenylalkyl group, a phenyl group substituted with a (alkyl) phenyl group, an aromatic group having a benzene ring such as a naphthyl group, and the like. The hydrocarbon group having 1 to 30 carbon atoms has preferably 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, further preferably 1 to 12 carbon atoms, and particularly preferably 1 to 4 carbon atoms. The hydrocarbon group having 1 to 30 carbon atoms is preferably an aliphatic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group.

In the above formula (1), AO represents an oxyalkylene group "same or different", which may be the same for all n oxyalkylene groups of AO present in the polyalkylene glycol. It means that they can be different.
In the above formula (1), the oxyalkylene group represented by AO is an alkylene oxide adduct, and examples of such an alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, and 2-. Examples thereof include alkylene oxides having 2 to 8 carbon atoms such as butene oxide and styrene oxide. More preferably, it is an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide and butylene oxide, and more preferably ethylene oxide and propylene oxide.
When the polyalkylene glycol is any two or more kinds of alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like, any of random addition, block addition, alternate addition and the like. It may be in the form. As the oxyalkylene group in the polyalkylene glycol, it is preferable to have an oxyethylene group as an essential component, and it is more preferable that 50 mol% or more is an oxyethylene group. When 50 mol% or more is an oxyethylene group, the hydrophilicity of the polyalkylene glycol is further improved and the hygroscopicity is further improved. More preferably, 80 mol% or more is an oxyethylene group, particularly preferably 90 mol% or more, and most preferably 100 mol%.

In the above formula (1), n represents the average number of moles of substance added of the oxyalkylene group, and is 1 to 300. It is preferably 2 to 100, more preferably 4 to 100, still more preferably 4 to 50, particularly preferably 4 to 25, and most preferably 8 to 25.
When n is 1 to 300, the size of the side chain of the monomer (A) is in a more preferable range, and the flexibility of the copolymer is further improved. Therefore, the fiber containing such a copolymer The treatment agent can further improve the texture of the fiber.
When n is 1 to 12, the monomer (A) becomes a liquid, so that it is easy to handle and the productivity of the copolymer is further improved.
Further, when n is 4 or more, even if R ⁴ is a hydrogen atom, the polyalkylene glycol chain becomes sufficiently long, so that the self-crosslinking reaction with the carboxyl group is more sufficiently suppressed, and the copolymer It will be more flexible.
In the above formula (1), y represents a number of 0 to 2, z represents 0 or 1, but when z is 0, y is preferably 1 or 2.
When z is 1, y is preferably 0.

The (poly) alkylene glycol-based monomer (A) preferably has a glass transition temperature (Tg) of −70 to 0 ° C. when it is homopolymerized. By having the structural unit derived from the monomer (A) in which the Tg is in a preferable range, the flexibility of the copolymer is further improved, and the fiber treatment agent containing such a copolymer gives the texture of the fiber. It can be further improved.
The Tg is more preferably −65 to −10 ° C., and even more preferably −65 to −20 ° C. The glass transition temperature (Tg) of a homopolymer can be determined based on the findings already obtained and can also be measured by a differential scanning calorimeter.

Specifically, the monomer (A) includes (poly) alkylene glycol (meth) acrylates such as ethylene glycol (meth) acrylate and diethylene glycol (meth) acrylate; methoxyethylene glycol (meth) acrylate and methoxydiethylene glycol (meth). Alkoxy (poly) alkylene glycol (meth) acrylate having 1 to 300 moles of alkylene glycol such as acrylate; vinyl alcohol, allyl alcohol, methallyl alcohol, 3-methyl-3-butene-1-ol, 3-methyl- 1 to 300 mol of alkylene oxide in an unsaturated alcohol having 2 to 8 carbon atoms such as 2-butene-1-ol, 2-methyl-3-butene-1-ol, and 2-methyl-2-butene-1-ol. Examples thereof include added compounds and terminal hydrophobic modified products thereof. Among these, alkoxypolyethylene glycol (meth) acrylate having an alkoxy group having 1 to 4 carbon atoms; allyl alcohol, methallyl alcohol, 3-methyl-3-butene-1-ol with alkylene oxide added is preferable. .. More preferably, it is ethoxypolyethylene glycol (meth) acrylate or methoxypolyethylene glycol (meth) acrylate.

The unsaturated carboxylic acid-based monomer (B) is not particularly limited as long as it has a carboxyl group and an ethylenically unsaturated hydrocarbon group (unsaturated group), but the following formula (2);

(In the formula, R ⁵ , R ⁶ and R ⁷ are the same or different, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,-(CH ₂ ) _p1 COOM ² (-(CH ₂ ) _p1 COOM ² is -COOM ¹ or other- (CH ₂ ) _p1 may form anhydrate with COM ² ),-(CH ₂ ) _p2 (CO) _q1 -OR ⁸ or-(CH ₂ ) _p3 CONR ⁹ R ¹⁰ ; p1, p2, p3 represent the same or different integers from 0 to ² , q1 represents 0 or ^1. M1 and M2 represent the same or different hydrogen atoms. , Monovalent metal atom, divalent metal atom, trivalent metal atom, quaternary ammonium group, or organic amine group. R ⁸ , R ⁹ , R ¹⁰ are the same or different, hydrogen atom, or It is preferably a compound represented by (representing a hydrocarbon group having 1 to 30 carbon atoms).

The number of carbon atoms of the alkyl group having 1 to 10 carbon atoms in R ⁵ , R ⁶ and R ⁷ is preferably 1 to 8, and more preferably 1 to 4. The alkyl group having 1 to 10 carbon atoms is preferably a methyl group, an ethyl group, a propyl group or a butyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
It is preferable that at least one of the above R ⁵ , R ⁶ and R ⁷ is a hydrogen atom, and more preferably at least two are hydrogen atoms.
The hydrocarbon groups having 1 to 30 carbon atoms in R ⁸ , R ⁹ , and R ¹⁰ include an aliphatic alkyl group having 1 to 30 carbon atoms, an alicyclic alkyl group having 3 to 20 carbon atoms, and 2 to 30 carbon atoms. Examples thereof include an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, and an aryl group having 6 to 30 carbon atoms.
Examples of the monovalent metal atom in M ¹ and M ² include alkali metal atoms such as lithium, sodium and potassium. Examples of the divalent metal atom include alkaline earth metal atoms such as calcium and magnesium. Examples of the trivalent metal atom include aluminum and iron. Examples of the organic amine group include an alkanolamine group such as an ethanolamine group, a diethanolamine group and a triethanolamine group, and a triethylamine group and the like.
As the above M ¹ and M ² , a hydrogen atom or an alkali metal atom is preferable.

Specific examples of the unsaturated carboxylic acid-based monomer (B) include the following unsaturated monocarboxylic acid-based monomers and unsaturated dicarboxylic acid-based monomers.
Examples of the unsaturated monocarboxylic acid-based monomer include (meth) acrylic acid, crotonic acid, isocrotonic acid, tigric acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, α-hydroxyacrylic acid and the like; Monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt; half ester of the following unsaturated dicarboxylic acid-based monomer and alcohol having 1 to 22 carbon atoms or glycol having 2 to 4 carbon atoms; unsaturated Examples thereof include a halfamide of a dicarboxylic acid-based monomer and an amine having 1 to 22 carbon atoms.
The unsaturated dicarboxylic acid-based monomer may be a monomer having one unsaturated group and two groups capable of forming a carboanion in the molecule, and may be maleic acid, itaconic acid, mesaconic acid, or citracon. Examples thereof include acids, fumaric acids and the like, their monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts and the like, and their anhydrides.
As the unsaturated carboxylic acid-based monomer (B), (meth) acrylic acid (salt), maleic acid (salt) or maleic anhydride is preferable. From the viewpoint of improving the polymerizable property, (meth) acrylic acid (salt) is more preferable. That is, the fiber treatment agent in which the above-mentioned copolymer has a structural unit derived from (meth) acrylic acid (salt) is one of the preferable forms of the present invention. The unsaturated carboxylic acid-based monomer (B) is most preferably acrylic acid (salt).

The copolymer contained in the fiber treatment agent preferably has a sulfonic acid (salt) group.
The fiber treatment agent of the present invention can impart more sufficient hygroscopicity to the fiber because the copolymer has a sulfonic acid (salt) group.
The sulfonic acid (salt) group means a sulfonic acid group or a salt thereof, and examples of the salt include a metal salt, an ammonium salt, an organic amine salt and the like, and more specifically, a sodium salt as a metal salt. Alkali metal salts such as potassium salts; alkaline earth metal salts such as magnesium salts, calcium salts, strontium salts and barium salts; salts such as aluminum salts and iron salts. Examples of the organic amine salt include alkanolamine salts such as monoethanolamine salt, diethanolamine salt and triethanolamine salt; alkylamine salts such as monoethylamine salt, diethylamine salt and triethylamine salt; morpholinic salt and the like. Among these, sodium salt and potassium salt are preferable as the salt of the sulfonic acid group in order to fully exhibit the above effect.

The copolymer preferably has a structural unit (c) derived from a sulfonic acid (salt) group-containing monomer (C).
The sulfonic acid (salt) group-containing monomer (C) (hereinafter, also referred to as monomer (C)) is particularly limited as long as it has a sulfonic acid (salt) group and an ethylenically unsaturated hydrocarbon group. Not limited, for example, (poly) alkylene glycol-containing unsaturated sulfonic acid such as 2- (meth) allyloxyethylene sulfonic acid, 3- (meth) allyloxy-2-hydroxypropanesulfonic acid, 2- (meth) allyloxy. Ethylene sulfonic acid, 2-acrylamide-2-methylpropane sulfonic acid, p-styrene sulfonic acid, α-methyl-p-styrene sulfonic acid, vinyl sulfonic acid, vinyl sulfamic acid, (meth) allyl sulfonic acid, isoprene sulfonic acid, 4- (Allyloxy) benzene sulfonic acid, 1-methyl-2-propen-1-sulfonic acid, 1,1-dimethyl-2-propen-1-sulfonic acid, 3-butene-1-sulfonic acid, 1-buten- 3-sulfonic acid, 2-acrylamide-1-methylpropanesulfonic acid, 2-acrylamidepropanesulfonic acid, 2-acrylamide-n-butanesulfonic acid, 2-acrylamide-2-phenylpropanesulfonic acid, 2-((meth) Acryloyloxy) Unsaturated sulfonic acids such as ethanesulfonic acid and salts thereof can be mentioned.
As the sulfonic acid (salt) group-containing monomer (C), 2-acrylamide-2-methylpropanesulfonic acid, 2-((meth) acryloyloxy) ethanesulfonic acid and the like are preferable.

The copolymer is a single amount other than the (poly) alkylene glycol-based monomer (A), the unsaturated carboxylic acid-based monomer (B) and the sulfonic acid (salt) group-containing monomer (C). It may have a structural unit (e) derived from the body (E).
The other monomer (E) is not particularly limited, but is, for example, an N-vinyllactam-based monomer such as N-vinylpyrrolidone; methyl (meth) acrylate, ethyl (meth) acrylate, (meth). Propyl acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-nonyl (meth) acrylate, (meth) acrylate (Meta) acrylic acid esters such as dodecyl and stearyl (meth) acrylate; (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide and the like. N-substituted or unsubstituted (meth) acrylamide; vinyl aryl monomers such as styrene, α-methylstyrene, vinyltoluene, inden, vinylnaphthalene, phenylmaleimide, vinylaniline; ethylene, propylene, butadiene, isobutylene, octene, etc. Alkens; Vinyl carboxylic acids such as vinyl acetate and vinyl propionate; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether; Vinyl ethylene carbonate and its derivatives; N, N-dimethylaminoethyl (meth) acrylate, N, Saturated amines such as N-dimethylaminoethyl (meth) acrylamide, vinylpyridine, vinylimidazole and salts thereof or quaternized products thereof; vinyl cyanide-based monomers such as acrylonitrile and methacrylonitrile can be mentioned.

In the above copolymer, the ratio of the structural unit (a) derived from the (poly) alkylene glycol-based monomer (A) is preferably 10 to 90% by mass with respect to 100% by mass of the total structural unit. When the ratio of the structural unit (a) is the above-mentioned preferable ratio, it is possible to impart more sufficient hygroscopicity to the fiber and further improve the texture of the fiber. The ratio of the structural unit (a) is more preferably 15 to 90% by mass, still more preferably 25 to 75% by mass.
The copolymer also preferably has a structural unit (a) ratio of 15 to 400% by mass with respect to 100% by mass of the structural unit (b). When the ratio of the structural unit (a) to the structural unit (b) is in the above-mentioned preferable range, the balance between the hygroscopicity and the texture that can be imparted to the fiber becomes better. It is more preferably 40 to 250% by mass, and even more preferably 100 to 250% by mass.

In the above copolymer, the ratio of the structural unit (b) derived from the unsaturated carboxylic acid-based monomer (B) is preferably 10 to 90% by mass with respect to 100% by mass of the total structural unit. If the ratio of the structural unit (b) is the above-mentioned preferable ratio, more sufficient hygroscopicity can be imparted to the fiber. The ratio of the structural unit (b) is more preferably 25 to 75% by mass, still more preferably 25 to 55% by mass.

In the above copolymer, the ratio of the structural unit (c) derived from the sulfonic acid (salt) group-containing monomer (C) is preferably 0 to 50% by mass with respect to 100% by mass of the total structural unit. If the ratio of the structural unit (c) is the above-mentioned preferable ratio, more sufficient hygroscopicity can be imparted to the fiber. The ratio of the structural unit (c) is more preferably 0 to 30% by mass, still more preferably 10 to 30% by mass.

In the above copolymer, the ratio of the structural unit (e) derived from the other monomer (E) is preferably 0 to 30% by mass with respect to 100 mol% by mass of the total structural unit. It is more preferably 0 to 15% by mass, and most preferably 0 mol%.

The copolymer preferably has a weight average molecular weight of 5,000 to 200,000. When the weight average molecular weight is 5,000 or more, when the fiber treatment agent is used for the fiber, the fiber treatment agent is less likely to dissolve in water, and the washing durability is improved.
When the weight average molecular weight is 200,000 or less, the texture of the fiber treated with the fiber treatment agent of the present invention is further improved. The weight average molecular weight is more preferably 10,000 to 150,000, still more preferably 20,000 to 100,000, and particularly preferably 20,000 to 80,000.
The weight average molecular weight of the copolymer can be measured by the method described in Examples.

<Method for producing copolymer>
The method for producing the copolymer contained in the fiber treatment agent of the present invention is not particularly limited, but can be produced by polymerizing the monomer component, and specific examples and preferable examples of the monomer component, and The preferred proportions of each monomer are as described above.
The method for producing the polymer is also referred to as a step of polymerizing a monomer component containing a (poly) alkylene glycol-based monomer (A) and an unsaturated carboxylic acid-based monomer (B) (hereinafter, also referred to as a “polymerization step”). It is preferable to include).

The method for initiating the polymerization of the monomer component in the above polymerization step is not particularly limited, but for example, a method for adding a polymerization initiator, a method for irradiating UV, a method for applying heat, and a method in the presence of a light initiator. Examples thereof include a method of irradiating light.
It is preferable to use a polymerization initiator in the above polymerization step.
Examples of the polymerization initiator include hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-. Azobis (isobutyronitrile), 2,2'-azobis (2-methylpropion amidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropion amidine] 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) azo-based compounds such as dihydrochloride; benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydroperoxide and the like. Organic peroxides; oxidation-reduction initiators that generate radicals by combining an oxidizing agent and a reducing agent, such as ascorbic acid and hydrogen peroxide, and persulfates and metal salts, are suitable. Of these polymerization initiators, hydrogen peroxide, persulfates, and azo compounds are preferable, and persulfates are most preferable, because the residual monomer tends to decrease. These polymerization initiators may be used alone or in the form of a mixture of two or more.
The amount of the polymerization initiator used is preferably 0.1 g or more, 15 g or less, and more preferably 1 g to 12 g with respect to 1 mol of the total monomer used.

In the above polymerization step, a chain transfer agent may be used if necessary. Specific examples of the chain transfer agent include thiol-based chain transfer agents such as mercaptoethanol and mercaptopropionic acid; halides such as carbon tetrachloride and methylene chloride; secondary alcohols such as isopropyl alcohol and glycerin; hypophosphite. Hypophosphates (salts) such as acids and sodium hypophosphite (including hydrates); phosphite (salts) such as phosphite and sodium phosphite; sulfites such as sodium sulphate (salts) ); Heavy sulfite (salt) such as sodium hydrogen sulfite; subdithionic acid (salt) such as sodium dithionate; pyrosulfite (salt) such as potassium pyrosulfate, hydrogen peroxide and the like. The chain transfer agent is preferably hypophosphorous acid (salt), heavy sulfite (salt), or hydrogen peroxide. The chain transfer agent may be used alone or in the form of a mixture of two or more.
The amount of the chain transfer agent used is preferably 0 g or more and 20 g or less, and more preferably 0 g or more and 15 g or less, with respect to 1 mol of the monomer (total monomer) used.

When a solvent is used in the above polymerization step, an aqueous solvent is preferable as the solvent. Examples of the aqueous solvent include water, methyl alcohol, ethyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, alcohols such as diethylene glycol, glycol, glycerin, polyethylene glycol and the like, and water is preferable. ..
In order to improve the solubility of the monomer in the solvent, any suitable organic solvent may be appropriately added as long as it does not adversely affect the polymerization. Examples of such organic solvents include lower alcohols such as methanol, ethanol and isopropyl alcohol; lower ketones such as acetone, methyl ethyl ketone and diethyl ketone; ethers such as dimethyl ether, diethyl ether and dioxane; amides such as dimethyl formaldehyde. Kind and the like. Only one kind of these solvents may be used, or two or more kinds may be used.
The amount of the solvent used is preferably 40 to 300% by mass with respect to 100% by mass of the monomer.

In the above polymerization step, the polymerization temperature is not particularly limited, but is preferably 20 ° C to 110 ° C, more preferably 50 to 105 ° C, and even more preferably 60 to 105 ° C.
The reaction time should be appropriately set according to the reaction temperature, the type (property) of the monomer component, the polymerization initiator, the solvent, etc., the combination, the amount used, etc. so that the above-mentioned polymerization reaction is completed. Just do it.

The above-mentioned method for producing a copolymer preferably includes a step of aging the copolymer after the polymerization reaction. By performing the aging step, the amount of residual monomer can be reduced. The temperature in the aging step is not particularly limited, but is preferably 60 to 105 ° C. The aging time in the aging step is not particularly limited, but is preferably 10 minutes to 5 hours. More preferably, it is 30 minutes to 3 hours.

In order to keep the neutralization rate of the polymer in a suitable range, an unsaturated carboxylic acid-based monomer (B) and a sulfonic acid (salt) group-containing monomer (C) are used as a part of the raw material of the monomer. A salt may be used, or an alkali metal hydroxide such as sodium hydroxide may be added as a neutralizing agent during and after the polymerization.

<Fiber treatment agent>
The content ratio of the copolymer in the fiber treatment agent of the present invention is not particularly limited, but is preferably 5 to 50% by mass with respect to 100% by mass of the fiber treatment agent. It is more preferably 10 to 40% by mass, further preferably 10 to 30% by mass, and particularly preferably 10 to 20% by mass.

<Coating agent>
The fiber treatment agent of the present invention can be used not only as a fiber but also as a coating agent on the surface of various materials such as plastics, metals, concrete, wood and paper.
Such a coating agent, that is, the following formula (1);

(In the formula, R ¹ , R ² and R ³ represent the same or different hydrogen atom or methyl group. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. (AO) represents the same or different oxyalkylene group. N represents the average number of added moles of the oxyalkylene group. The number is 1 to 300. Y represents the number of 0 to 2. z. Represents 0 or 1), a structural unit (a) derived from the (poly) alkylene glycol-based monomer (A) and a structural unit (b) derived from the unsaturated carboxylic acid-based monomer (B). A coating agent containing a copolymer having) is also one of the present inventions.
The preferred copolymer contained in the coating agent is the same as the preferred copolymer contained in the fiber treatment agent of the present invention.

Examples of the plastic include polyethylene, polypropylene, polyacrylic, polyvinyl alcohol, polystyrene, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, ethylene-vinyl acetate copolymer, triacetyl cellulose, cycloolefin polymer, polycarbonate, polyamide, and the like. Examples thereof include resin molded products such as polyimide, nylon, polyvinyl chloride, and polyvinylidene chloride, and films. Examples of the metal include iron, aluminum, steel plate, tin-free steel plate, tin plate, polyethylene terephthalate film laminated steel plate and the like. The coating agent of the present invention is a self-crosslinking reaction of a copolymer even if there is no reaction point on the surface of the material (base material), and / or, when a cross-linking agent described later is contained, the copolymer and the cross-linking agent are used. A film can be formed on the surface of various materials by the cross-linking reaction of a plurality of compounds such as the cross-linking reaction of the above.

<Crosslinking agent>
The fiber treatment agent of the present invention may contain a cross-linking agent.
When the fiber treatment agent contains a cross-linking agent, by treating the fiber with such a fiber treatment agent, a cross-linking structure is formed on the fiber, and the fiber treatment agent is sufficiently immobilized by the fiber, so that the washing can be performed. Durability is improved.
The cross-linking agent is not particularly limited as long as it reacts with the carboxyl group and / or other reactive functional group of the copolymer to form a cross-linked structure.
The other reactive functional group of the copolymer is not particularly limited, and examples thereof include a sulfonic acid group and an ester or salt thereof; an amino group, a hydroxyl group and the like.
The cross-linking agent is not particularly limited, and examples thereof include ethylenediamine, hexamethylenediamine, phenylenediamine, diethanolamine, oxazoline group-containing polymer (Epocross manufactured by Nippon Catalyst Co., Ltd.), butanediol, tolylene diisocyanate, and hexamethylene diisocyanate. Be done.

In the fiber treatment agent of the present invention, the ratio of the reactive functional group of the cross-linking agent is preferably 0 to 50 mol% with respect to 100 mol% of the carboxyl group or the salt thereof of the copolymer. It is more preferably 0 to 30 mol%, still more preferably 0 to 20 mol%.

<Fiber treatment method using fiber treatment agent>
The method for treating a fiber using the fiber treatment agent of the present invention is not particularly limited, but preferably includes a step of immobilizing the fiber treatment agent on the fiber. That is, the present invention is also a fiber treatment method including a step of immobilizing a fiber treatment agent on the fiber. The fiber treatment method includes a step of drying the fiber dough (preliminary drying step), a step of immersing the dried fiber dough in an aqueous solution of the fiber treatment agent (immersion step), and a step of dehydrating the fiber dough (dehydration step). It is more preferable to include a step of immobilizing the fiber treatment agent on the fiber dough (immobilization step).

The temperature and time of the pre-drying step are not particularly limited, but it is preferably performed at 8 to 150 ° C. for 1 to 180 minutes.
The concentration of the fiber treatment agent in the aqueous solution of the fiber treatment agent is not particularly limited, but is preferably 1 to 15% by mass.
The immersion time in the immersion step is preferably 1 to 30 minutes.
In the above dehydration step, it is preferable to perform dehydration using, for example, a dehydrator or a mangle.

In the above treatment method, a medium drying step may be performed between the dehydration step and the immobilization step. The medium drying step is preferably carried out at 8 to 150 ° C. for 1 to 180 minutes.
When the fiber dough is a cellulose fiber, for example, the immobilization step is preferably performed at 100 to 160 ° C. for 1 to 30 minutes. When the fiber dough is a synthetic fiber such as a polyester fiber, it is preferably carried out at 100 to 220 ° C. for 1 to 30 minutes.

The fiber to be treated with the fiber treatment agent of the present invention is not particularly limited, and examples thereof include synthetic fibers such as polyester and nylon, regenerated cellulose fibers such as cupra, and cellulose fibers such as natural cellulose fibers such as cotton.
The fiber treatment agent of the present invention is preferably used for cellulose fibers and / or polyester fibers.
Cellulose fibers and / or polyester fibers treated with such a fiber treatment agent of the present invention are also one of the present inventions.

The fiber treatment agent of the present invention has the above-mentioned structure, can impart sufficient hygroscopicity to the fiber, and can improve the texture of the fiber, and therefore can be suitably used for fibers such as polyester. can.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".

<Measurement conditions for weight average molecular weight (GPC)>
Equipment: Tosoh HLC-8320GPC
Detector: RI
Column: Tosoh α-2500, α-m
Column temperature: 40 ° C
Flow velocity: 0.5 ml / min.
Calibration curve: GL Sciences (manufactured by Kurabo Industries) POLYACRYLIC ACID STANDARD
Eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio)

<Method for measuring solid content of aqueous polymer solution>
When the polymerization reaction was completed, 1 g of the polymerization solution was diluted with 1 g of deionized water and dried at 130 ° C. for 60 minutes, and the evaporation residue was measured and calculated from the following formula.
Solid content (%) = [Evaporation residue after drying (g) / Mass of polymerization solution before drying (g)] × 100

<Fiber treatment with fiber treatment agent for regenerated cellulose fabric>
A 10 cm square regenerated cellulose (cupra) test cloth was prepared, pre-dried at 130 ° C. for 60 minutes, and the mass (X) of the test cloth was measured. The test cloth was immersed in a fiber treatment agent adjusted to a concentration of 10% by mass, dehydrated so that the amount of the aqueous fiber treatment agent remaining on the test cloth was 150 ± 10% with respect to the test cloth, and the temperature was 130 ° C. for 15 minutes. It was dried to immobilize the fiber treatment agent. Then, the test cloth was washed once and then dried at 130 ° C. for 60 minutes to measure the mass (Y).
The ratio of the fiber treatment agent immobilized on the test cloth after washing was calculated from the following formula.
Immobilization amount (%) = [(Y / X) -1] × 100

<Fiber treatment with polyester fabric fiber treatment agent>
A 10 cm square polyester test cloth was prepared, pre-dried at 130 ° C. for 60 minutes, and the mass (X) of the test cloth was measured. The test cloth is dipped in a fiber treatment agent adjusted to a concentration of 10% by mass, dehydrated so that the amount of the fiber treatment agent aqueous solution remaining on the test cloth is 100 ± 10% with respect to the cloth, and dried at 130 ° C. for 5 minutes. After that, it was further dried at 190 ° C. for 1 minute to immobilize the fiber treatment agent. Then, the test cloth was washed once and then dried at 130 ° C. for 60 minutes to measure the mass (Y).
The ratio of the fiber treatment agent immobilized on the test cloth after washing was calculated from the following formula.
Immobilization amount (%) = [(Y / X) -1] × 100

<Hygroscopic evaluation>
The fiber-treated test cloth was dried at 105 ° C. for 2 hours, and the mass (M) was measured. Subsequently, the test cloth was placed in a weighing bottle, stored in a constant temperature bath at 30 ° C. and a relative humidity of 90%, taken out after 24 hours, and the mass (N) after moisture absorption was measured. The hygroscopicity was calculated by the following formula.
Moisture absorption rate (water absorption rate) (%) = [(NM) / M] × 100
The water absorption rate of the cloth not treated with fibers was as follows.
Regenerated cellulose; 11.0%
Polyester; 0.5%

<Texture evaluation>
The fiber-treated test cloth was evaluated according to the following criteria by touch.
The control was a single wash of untreated cloth.
5: Very soft than control 4: Much softer than control 3: Softer than control 2: Same as control 1: Not softer than control

<Example 1>
100 parts of deionized water was placed in a glass separable flask with a capacity of 500 mL equipped with a reflux condenser and a stirrer, the temperature was raised to 80 ° C. under stirring, and then 30 parts of methacrylic acid (hereinafter abbreviated as MAA) and methoxypolyethylene. Glycolmethacrylate (average number of added moles of EO chain: 2 mol, hereinafter abbreviated as PGM-2EO) 70 parts, 48% sodium hydroxide (hereinafter abbreviated as 48% NaOH) 10.4 parts, 10% aqueous sodium persulfate (hereinafter abbreviated) 19.3 parts of 10% NaPS (abbreviated as 10% NaPS) and 16.5 parts of 10% sodium hypophosphite monohydrate aqueous solution (hereinafter abbreviated as 10% SHP) were added dropwise from different dropping ports. The dropping time was 180 minutes for MAA, 180 minutes for PGM-2EO, 180 minutes for 48% NaOH, 210 minutes for 10% NaPS, and 210 minutes for 10% SHP. The dropping was started at the same time. The temperature was maintained at 80 ° C. until the completion of 10% NaPS dropping. Further, the same temperature was maintained for 30 minutes after the completion of dropping 10% NaPS and aged to complete the polymerization, and an aqueous solution of the polymer 1 was obtained. The solid content concentration of the aqueous solution of the polymer 1 was 43.2% by mass, and the weight average molecular weight was 71000.
Next, Epocross WS-300 (manufactured by Nippon Catalyst Co., Ltd., oxazoline group-containing acrylic weight) which is a cross-linking agent having an oxazoline group so as to be 5 mol% with respect to the carboxyl group contained in the aqueous solution of the obtained polymer 1. Combined, oxazoline group weight: 7.7 mmol / g, weight average molecular weight: 12 × 10 ⁴ , hereinafter also referred to as “WS-300”) was added, and the solid content concentration was reduced to 10% by mass using deionized water. After adjustment, a fiber treatment agent (1) was obtained. Using this, the regenerated cellulose fabric and the polyester fabric were subjected to fiber treatment, and hygroscopicity evaluation and texture evaluation were performed. The results are shown in Table 1.

<Examples 2 to 17 and Comparative Examples 1 and 2>
The polymers of Examples 2 to 17 and Comparative Examples 1 and 2 were synthesized according to the formulations shown in Tables 1 and 2. To these polymers, as in Example 1, Epocross WS-300 was added so as to be 5 mol% with respect to the carboxyl group of the polymer, and the solid content concentration was further increased to 10% by mass with deionized water. It was adjusted to obtain a fiber treatment agent. Using these, the regenerated cellulose fabric and the polyester fabric were subjected to fiber treatment, and hygroscopicity evaluation and texture evaluation were performed. The results are shown in Tables 1 and 2.

The compounds described using abbreviations in Tables 1 and 2 are as follows.
PGM-2EO: Methoxypolyethylene glycol (average EO addition number 2) methacrylate, Tg = -26 ° C.
PGM-4EO: Methoxypolyethylene glycol (average EO addition number 4) methacrylate, Tg = -59 ° C.
PGM-9EO: Methoxypolyethylene glycol (average EO addition number 9) methacrylate, Tg = -60 ° C.
PGM-23EO: Methoxypolyethylene glycol (average EO addition number 23) methacrylate, Tg = -52 ° C.
PG-8EO: Polyethylene glycol (average EO addition number 8) methacrylate, Tg = -65 ° C.
PGM-9EO-A: Methoxypolyethylene glycol (average EO addition number 9) acrylate, Tg = -58 ° C.
PG-10EO-A: Polyethylene glycol (average EO addition number 10) acrylate, Tg = -64 ° C.
APPS 50% aqueous solution: 2-acrylamide-2-methylpropanesulfonic acid 50% aqueous solution

Claims (5)

The following formula (1);

(In the formula, R ¹ , R ² and R ³ represent the same or different hydrogen atom or methyl group. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. (AO) represents the same or different oxyalkylene group. N represents the average number of moles of oxyalkylene group added. Y represents a number of 2 to 50. Z represents a number of 0 to 2. Represents 0 or 1), a structural unit (a) derived from the (poly) alkylene glycol-based monomer (A) and a structural unit (b) derived from the unsaturated carboxylic acid-based monomer (B). ) And a cross-linking agent
The copolymer has a weight average molecular weight of 20,000 to 200,000 and has a weight average molecular weight of 20,000 to 200,000.
80 mol% or more of the oxyalkylene group in the polyalkylene glycol in the (poly) alkylene glycol-based monomer (A) is an oxyethylene group.
The unsaturated carboxylic acid-based monomer (B) has the following formula (2);

(In the formula, R ⁵ , R ⁶ and R ⁷ are the same or different, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,-(CH ₂ ) _p1 COOM ² (-(CH ₂ ) _p1 COOM ² is -COOM ¹ or other- (CH ₂ ) _p1 may form anhydrate with COM ² ),-(CH ₂ ) _p2 (CO) _q1 -OR ⁸ or-(CH ₂ ) _p3 CONR ⁹ R ¹⁰ ; p1, p2, p3 represent the same or different integers from 0 to ² , q1 represents 0 or ^1. M1 and M2 represent the same or different hydrogen atoms. , Monovalent metal atom, divalent metal atom, trivalent metal atom, quaternary ammonium group, or organic amine group. R ⁸ , R ⁹ , R ¹⁰ are the same or different, hydrogen atom, or It is a compound represented by a hydrocarbon group having 1 to 30 carbon atoms.
The cross-linking agent is at least one selected from the group consisting of ethylene diamine, hexamethylene diamine, phenylenediamine , oxazoline group-containing polymer, butane diol, tolylene diisocyanate and hexamethylene diisocyanate. (However, chlorhexidine or a salt thereof, one having a polyamide polyamine chain, and a polymer of methoxypolyethylene glycol monomethacrylate (additional molar number of ethylene oxide 22 mol) and methacrylic acid (mass ratio 8: 2, weight average). Molecular weight: 25000), and a copolymer of methoxypolyethylene glycol monomethacrylate (22 mol of ethylene oxide added), methoxypolyethylene glycol monomethacrylate (45 mol of ethylene oxide added) and methacrylic acid (mass ratio 2). : 5: 3, weight average molecular weight: 28000)). The following formula (1);

(In the formula, R ¹ , R ² and R ³ represent the same or different hydrogen atom or methyl group. R ⁴ represents a hydrocarbon group having 1 to 30 carbon atoms. (AO) represents a hydrocarbon group. Identically or differently, it represents an oxyalkylene group. N represents the average number of moles of the oxyalkylene group added, 2 to 50. Y represents a number from 0 to 2. z represents 0 or 1. It has a structural unit (a) derived from the (poly) alkylene glycol-based monomer (A) represented by) and a structural unit (b) derived from the unsaturated carboxylic acid-based monomer (B). Contains polymers and cross-linking agents
The copolymer has a weight average molecular weight of 20,000 to 200,000 and has a weight average molecular weight of 20,000 to 200,000.
80 mol% or more of the oxyalkylene group in the polyalkylene glycol in the (poly) alkylene glycol-based monomer (A) is an oxyethylene group.
The unsaturated carboxylic acid-based monomer (B) has the following formula (2);

(In the formula, R ⁵ , R ⁶ and R ⁷ are the same or different, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,-(CH ₂ ) _p1 COOM ² (-(CH ₂ ) _p1 COOM ² is -COOM ¹ or other- (CH ₂ ) _p1 may form anhydrate with COM ² ),-(CH ₂ ) _p2 (CO) _q1 -OR ⁸ or-(CH ₂ ) _p3 CONR ⁹ R ¹⁰ ; p1, p2, p3 represent the same or different integers from 0 to ² , q1 represents 0 or ^1. M1 and M2 represent the same or different hydrogen atoms. , Monovalent metal atom, divalent metal atom, trivalent metal atom, quaternary ammonium group, or organic amine group. R ⁸ , R ⁹ , R ¹⁰ are the same or different, hydrogen atom, or A fiber treatment agent characterized by being a compound represented by a hydrocarbon group having 1 to 30 carbon atoms (provided that it has chlorhexidine or a salt thereof, a polyamide polyamine chain, and a methoxypolyethylene glycol mono. Copolymer of methacrylate (22 mol of ethylene oxide addition) and methacrylic acid (mass ratio 8: 2, weight average molecular weight: 25,000), and methoxypolyethylene glycol monomethacrylate (22 mol of ethylene oxide addition) And methoxypolyethylene glycol monomethacrylate (additional moles of ethylene oxide: 45 mol) and a copolymer of methacrylic acid (mass ratio 2: 5: 3, weight average molecular weight: 28000), excluding those containing at least one of them). The fiber treatment agent according to claim 1 or 2, wherein the copolymer has a sulfonic acid (salt) group. The fiber treatment agent according to any one of claims 1 to 3, wherein the fiber treatment agent is used for cellulose fibers and / or polyester fibers. Cellulose fiber and / or polyester fiber treated with the fiber treatment agent according to any one of claims 1 to 4.