JP2003020569A - Fiber treating agent to impart high moisture absorbing and releasing property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber treating agent to impart a moisture-absorbing and -releasing function and water-absorbing function resistant to washing to a synthetic fiber product made of polyamide fibers, polyester fibers, polyacrylonitrile fibers, etc., or a blended fiber product composed of these synthetic fibers or a synthetic fiber and a natural fiber. SOLUTION: The highly moisture-absorbing and -releasing fiber-treating agent is produced by copolymerizing (A) a polyalkylene glycol(meth)acrylate containing a polyethylene glycol unit having an oxyethylene addition molar number of 5-90 and (B) a (meth)acrylate monomer in the presence of (C) an aqueous dispersion of fine particles of a highly moisture-absorbing and -releasing organic material. The amount of the polyethylene glycol unit is 18-68 mass% based on the total solid component of the agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a synthetic fiber product obtained from a polyamide fiber, a polyester fiber, a polyacrylonitrile fiber, or the like, a mixed fiber product of these synthetic fibers, or a synthetic fiber and a natural fiber. ,
The present invention relates to a fiber treatment agent capable of imparting a moisture absorbing / releasing function and a water absorbing function which are excellent in washing resistance.

[0002]

2. Description of the Related Art Synthetic fiber products obtained from polyamide fibers, polyester fibers, polyacrylonitrile fibers, and mixed fiber products of these fibers have a high moisture absorption / desorption property as a method of imparting moisture absorption / desorption properties. A technique is disclosed in which fine particles are treated with a pad using a resin such as water-soluble polyurethane as a binder (JP-A-11-24).
7069).

This method utilizes high moisture absorbing / releasing organic fine particles having a reversible moisture absorbing / releasing function as disclosed in JP-A-8-225610 and which can be repeatedly used. This is a technology that imparts a moisture absorbing / releasing function to other fibers. However, the textile product obtained by this technique tends to have a reduced moisture absorbing / releasing function after washing, and thus there is room for improvement in terms of washing resistance of the moisture absorbing / releasing function.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems, and an object thereof is a synthetic fiber product obtained from a polyamide fiber, a polyester fiber, a polyacrylonitrile fiber, or the like, It is an object of the present invention to provide a fiber treatment agent capable of imparting a moisture absorbing / releasing function and a water absorbing function, which are excellent in washing resistance, to these synthetic fibers or a mixed fiber product of synthetic fibers and natural fibers.

[0005]

The highly moisture absorptive and desorptive fiber treating agent of the present invention which has achieved the above-mentioned object is oxyethylene (in the presence of an aqueous dispersion of the highly moisture absorptive and desorptive organic fine particles (A)). that is, obtained by copolymerizing polyalkylene glycol -CH ₂ CH ₂ O-) addition mole number having a polyethylene glycol unit of 5 to 90 (meth) acrylate (B) and (meth) acrylic monomer (C) The gist is that the polyethylene glycol unit is 18 to 68 mass% with respect to the total solid content.

The "solid content" referred to in the present invention means the solid content remaining when all the liquid content in the highly hygroscopic fiber treating agent is removed by evaporation.

The high moisture absorptive and desorptive fiber treating agent of the present invention is preferably used together with a binder resin capable of reacting with the functional group contained in the molecule of the (meth) acrylic monomer (C). In particular, (meth) acrylic monomer (C)
Has a hydroxyl group and / or an epoxy group in the molecule and is recommended to be used with a binder resin capable of reacting with the hydroxyl group and / or the epoxy group.

The highly moisture-absorbing and desorbing organic fine particles (A) are vinyl-based cross-linked copolymers, and at least one selected from the group consisting of sulfonic acid groups, carboxyl groups, phosphoric acid groups and metal salts thereof. Seed 1.0 mmol / g
Those having the above are preferable. Among them, an acrylic cross-linked polymer or a styrene cross-linked polymer, and at least one selected from the group consisting of (salt-type) sulfonic acid group, salt-type carboxyl group and salt-type phosphate group is 1.0 mmo.
Those having 1 / g or more are preferable, and more specifically, 2
An acrylonitrile cross-linked polymer having a cross-linked structure introduced by using a compound having a polymerizable vinyl group as a copolymerization component,
Alternatively, the acrylonitrile polymer is one of those obtained by chemically converting a nitrile group of an acrylonitrile crosslinked polymer having a crosslinked structure introduced by treatment with a hydrazine compound into a salt type carboxyl group by hydrolysis, wherein the salt type carboxyl group is Those having 1.0 mmol / g or more are recommended.

The above (salt-type) sulfonic acid group is
It is meant to include both a salt-type sulfonic acid group and a non-salt-type sulfonic acid group.

The amounts of the high moisture absorptive and desorptive organic fine particles (A), the polyalkylene glycol (meth) acrylate (B) component and the (meth) acrylic monomer (C) component contained in the solid content are (A). : 29-80 parts by mass, (B)
Component: 19-70 parts by mass, (C) component: 1-20 parts by mass is recommended.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION By adopting the above configuration,
Synthetic fiber products obtained from polyamide-based fibers, polyester-based fibers, polyacrylonitrile-based fibers, etc., as well as synthetic fiber products such as these synthetic fiber products, or mixed fiber products of synthetic fibers and natural fibers. It is also possible to provide a highly hygroscopic fiber treating agent capable of imparting a water absorbing function.
The above "moisture absorption / desorption function" means a function of absorbing and releasing moisture in the air, and "water absorption function" means a function of absorbing contacting water. Hereinafter, the moisture absorption / desorption function and the water absorption function may be collectively referred to as “moisture absorption / desorption / water absorption function”.

The above-mentioned high moisture absorbing / releasing organic fine particles (A) are, as the name suggests, organic fine particles having high moisture absorbing / releasing properties. Although it is possible to use organic fine particles having high water absorption and hygroscopicity and moisture releasing property, specifically, 20 ° C., 65% RH
The water content (relative humidity) is preferably 20% or more.

Preferred as such fine particles are those in which a cross-linked structure is introduced by post-treatment into a vinyl polymer obtained from a copolymer monomer composition containing a compound having a polymerizable vinyl group in the molecule, A raw material is a vinyl-based cross-linked polymer obtained by adding a copolymerization component capable of forming a cross-linking structure to the copolymerization monomer composition and forming a cross-linking structure simultaneously with polymerization. Is 1.0 mmo of at least one selected from the group consisting of sulfonic acid group, carboxyl group, phosphoric acid group and metal salts thereof.
Those having 1 / g are mentioned. Of the above sulfonic acid group, carboxyl group and phosphoric acid group, the carboxyl group and phosphoric acid group are preferably metal salts (that is, salt type carboxyl group and salt type phosphoric acid group).

Among the above organic fine particles, particularly preferable ones are those obtained by using an acrylic cross-linked polymer as a raw material. The "acrylic cross-linked polymer" means (meth) acrylic acid; ) Methyl acrylate,
(Meth) acrylic acid ester such as ethyl (meth) acrylate; (meth) acrylic acid amide; and other acrylic acid-based monomers, and (meth) acrylonitrile and other acrylonitrile-based monomers having at least a polymerizable vinyl group and a nitrile group It means an acrylic polymer having a crosslinked structure introduced into an acrylic polymer obtained by copolymerizing a copolymerizable monomer composition to which other copolymerizable monomer is added, if necessary.

The acrylic acid-based monomer or acrylonitrile-based monomer used in the above acrylic polymer may be used alone or in combination of two or more. Further, as the other copolymerizable monomer described above,
It is not particularly limited as long as it does not impair the action of the finally obtained high moisture absorptive and desorptive organic fine particles (A), and examples thereof include vinyl halides, vinylidene halides, sulfonic acid-containing monomers such as p-styrene sulfonate, and the like. Vinyl compounds such as salts, styrene and vinyl acetate, and vinylidene compounds can be used.

The introduction of the crosslinked structure is carried out by adding 2 to the above-mentioned copolymerizable monomer composition as a copolymerization component which further forms the crosslinked structure.
A method of adding the above-mentioned compound having a polymerizable vinyl group and copolymerizing this can be adopted. Examples of the compound having two or more polymerizable vinyl groups include triallyl isocyanurate,
Triallyl cyanurate, divinylbenzene, ethylene glycol di (meth) acrylate, methylenebisacrylamide and the like are preferably used.

The acrylic polymer is an acrylonitrile polymer obtained by copolymerizing an acrylonitrile monomer with a comonomer composition in which other comonomer is optionally added. In this case, it is possible to introduce a crosslinked structure by treatment with a hydrazine compound. Examples of hydrazine compounds that can be used in this case include hydrazine; hydrazine salts such as hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, hydrazine nitrate, hydrazine bromine, and hydrazine carbonate; ethylenediamine,
Examples thereof include hydrazine derivatives such as guadinine sulfate, guadinine hydrochloride, guadinine nitrate, guadinine phosphate, and melamine.

The above-mentioned other copolymerizable monomers, compounds having two or more polymerizable vinyl groups, and hydrazine compounds can be used alone or in combination of two or more.

All of the above acrylic cross-linked polymers are
A compound having a carboxyl group or a functional group capable of being modified into a carboxyl group, and by chemically converting the carboxyl group or a functional group capable of being modified into a carboxyl group into a salt-type carboxyl group, high absorption and release according to the present invention can be achieved. Wet organic fine particles (A) are obtained.

Examples of such highly moisture-absorbing and desorbing organic fine particles (A) include, for example, an acrylonitrile-based polymer obtained by copolymerizing a copolymerizable monomer composition containing 50% by mass or more of acrylonitrile, and a cross-linking structure of a hydrazine-based compound. Or an acrylonitrile crosslinked polymer obtained by copolymerizing a copolymerizable monomer composition containing 50 mass% or more of acrylonitrile and further containing a compound having two or more polymerizable vinyl groups. Which is obtained by chemically converting the nitrile group of 1. into a salt-type carboxyl group by hydrolysis, and the salt-type carboxyl group is 1.
Those containing 0 mmol / g are mentioned. In a more preferred embodiment, (I) an acrylonitrile-based polymer obtained by copolymerizing a copolymerizable monomer composition containing 85% by mass or more of acrylonitrile has an increase in nitrogen content of 1.0 to
A residual nitrile group of an acrylonitrile cross-linked polymer having a cross-linked structure introduced by treatment with a hydrazine-based compound to 15.0 mass% is chemically converted into a salt-type carboxyl group by hydrolysis, Highly moisture-absorbing and desorbing organic fine particles having a salt type carboxyl group of 1.0 mmol / g or more, (II) Acrylonitrile of 50% by mass or more, and further containing divinylbenzene or triallyl isocyanurate, and other copolymerizable monomers. A nitrile group of an acrylonitrile-based crosslinked polymer having a crosslinked structure introduced by copolymerizing a copolymerizable monomer composition to be chemically converted into a salt type carboxyl group by hydrolysis,
Highly moisture-absorbing and desorbing organic fine particles containing the salt-type carboxyl group in an amount of 2.0 mmol / g or more can be used.

In the (I) high moisture absorptive and desorptive organic fine particles, "increasing the nitrogen content" means that the nitrogen content (% by mass) in the acrylonitrile polymer as a raw material and the hydrazine compound in the resin are It means the difference in the nitrogen content (mass%) after introducing the crosslinked structure by the treatment. If the nitrogen content is less than the above range, the organic fine particles are dissolved in the hydrolysis step and the salt-type carboxyl group cannot be introduced. On the other hand, if it exceeds the above range, 1.0 mm of nitrile group
It is not possible to convert ol / g or more into a salt type carboxyl group. The method of introducing crosslinks with a hydrazine-based compound into an acrylonitrile-based polymer is not particularly limited as long as it is a means for increasing the nitrogen content by the crosslinkage to be 1.0 to 15.0% by mass. Industrially preferred is a means for treating at a concentration of 1 to 80% by mass and a temperature of 50 to 120 ° C. for 0.2 to 10 hours.

In addition to the above-mentioned acrylonitrile-based cross-linked polymer as a raw material, a copolymerization monomer containing 5% by mass or more of methyl acrylate and further containing divinylbenzene or triallyl isocyanurate, and other copolymerization monomers. A methyl ester acrylate cross-linked polymer in which a cross-linked structure is introduced by copolymerization of a monomer composition is chemically converted into a salt-type carboxyl group by hydrolysis. Highly moisture-absorbing and desorbing organic fine particles containing 0.0 mmol / g or more can also be preferably used.

In addition to the one having a salt type carboxyl group as described above, an acrylic cross-linked polymer having a (salt type) sulfonic acid group or a salt type phosphoric acid group of 1.0 mmol / g or more may be used. Examples of such compounds include (meth) acrylonitrile and sulfonic acid (salt) group-containing monomers such as p-styrene sulfonate, acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate, acid phosphooxyethyl acrylate, and the like. A nitrile group of a copolymer with a phosphoric acid (salt) group-containing monomer, which has been treated with the hydrazine compound to introduce a cross-linking structure, or a (meth) acrylonitrile and a sulfonic acid (salt) group-containing monomer as described above. Alternatively, a compound having a crosslinked structure introduced by copolymerizing a phosphoric acid (salt) group-containing monomer and the above-mentioned compound having two or more polymerizable vinyl groups can be used. When the sulfonic acid group or phosphoric acid group in the obtained acrylic crosslinked polymer is not a salt type, it may be converted to a salt type after that, but the sulfonic acid group does not have to be a salt type and may be a salt type. The non-salt group may be mixed with the above group.

In addition, a styrene-based cross-linked polymer,
At least 1.0 selected from the group consisting of (salt-type) sulfonic acid group, salt-type carboxyl group and salt-type phosphate group.
Highly moisture absorbing / releasing organic fine particles having a mmol / g or more can also be preferably used. Examples of such substances include styrene and sulfonic acids (salts) such as p-styrene sulfonate.
A group-containing monomer or a (salt-type) carboxyl group-containing monomer such as maleic acid, or a phosphoric acid (salt) group-containing monomer as exemplified above is copolymerized with a compound having two or more polymerizable vinyl groups described above. And a cross-linked structure is introduced. If the sulfonic acid group in the obtained styrene-based crosslinked polymer, the carboxyl group, or the phosphoric acid group is not a salt type, then it may be a salt type, but the same as above.
The sulfonic acid group does not have to be a salt type, and a salt type group and a non-salt type group may be mixed.

Only one kind of (salt-type) sulfonic acid group, salt-type carboxyl group or salt-type phosphate group contained in the highly moisture-absorbing and desorbing organic fine particles obtained from the above acrylic cross-linked polymer or styrene cross-linked polymer. However, it may have two or more kinds in total of 1.0 mmol / g or more.

(Salt type) in high moisture absorbing / releasing organic fine particles (A)
The amount of carboxyl groups can be measured as follows. The (salt-type) carboxyl group is meant to include both a salt-type carboxyl group and a non-salt-type carboxyl group.

About 1 g of sufficiently dried and highly hygroscopic organic fine particles (A) was precisely weighed (Xg), 200 g of water was added thereto, and hydrochloric acid (concentration: 1 mol /
L) is added to bring the pH to 2. Then, using a caustic soda aqueous solution (concentration: 0.1 mol / L), a titration curve is obtained by a conventional method. From this titration curve, the amount of caustic soda aqueous solution Y (mL) consumed by the (salt-type) carboxyl group was calculated,
The amount of (salt type) carboxyl group is calculated by the following formula. [(Salt type) carboxyl group amount] = 0.1 Y / X Separately from the above, a titration curve is obtained and the carboxyl group amount is calculated in the same manner except that the operation of adjusting the pH to 2 using hydrochloric acid is not performed. From these results, the amount of salt type carboxyl groups is calculated by the following formula. (Amount of salt type carboxyl group) = [Amount of (salt type) carboxyl group] − (Amount of carboxyl group).

The amount of the (salt-type) sulfonic acid group in the high moisture absorptive and desorptive organic fine particles (A) is determined by elemental analysis of the S amount in the sufficiently dried high moisture absorptive and desorptive organic fine particles (A). It can be calculated by dividing the obtained value by the atomic weight of S.

Further, the amount of (salt type) phosphate group in the highly moisture-absorbing and desorbing organic fine particles (A) is determined by fluorescent X-ray analysis of the amount of P in the sufficiently dried highly moisture-absorbing and desorbing organic fine particles (A). Then, it can be calculated by dividing the obtained value by the atomic weight of P. The (salt-type) phosphate group is meant to include both a salt-type phosphate group and a non-salt-type phosphate group.

By the way, as an aqueous dispersion of the above-mentioned highly moisture absorbing / releasing organic fine particles (A), an acrylic fine particle emulsion: HU-307 from Japan Exlan Co., Ltd.
E, HU-707E, HU-807E and the like are commercially available.

The particle size of the high moisture absorptive and desorptive organic fine particles (A) is not so long as it does not impair the properties of the textile product to be treated.
It is not particularly limited and can be appropriately selected depending on the application. For example, when it is desired to increase the moisture absorption / water absorption rate of the treated fiber product, it is preferable to use an average particle size of 10 μm or less, preferably 1 μm or less in order to increase the surface area of the highly moisture absorbing / releasing organic fine particles (A). desirable.

The polyalkylene glycol (meth) acrylate (B) used in the present invention has a polyethylene glycol unit having a molecular weight of 5 or more and 90 or less in the number of moles of oxyethylene added in the molecule.

The highly moisture absorptive and desorptive fiber treating agent of the present invention is a copolymer of polyalkylene glycol (meth) acrylate (B) and (meth) acrylic monomer (C) (hereinafter, simply referred to as "copolymer"). The solid content (hereinafter, simply referred to as “solid content”) in which the highly moisture-absorbing and desorbing organic fine particles (A) are incorporated into water is dispersed in water. Thus, by treating the fiber product with the highly moisture absorptive and desorptive fiber treatment agent in which the solid content particles are uniformly dispersed in the aqueous medium, the solid content as the active ingredient can be uniformly adsorbed to the fiber product. .
However, if the number of moles of oxyethylene added in the polyethylene glycol unit is less than 5, a stable dispersion cannot be obtained due to agglomeration of solid content particles, and it is difficult to perform uniform treatment with such a treatment agent. However, it is not possible to impart a sufficient moisture absorbing / releasing function to textiles and excellent wash resistance. It is preferably 13 or more. On the other hand, when the number of moles of oxyethylene added exceeds 90, the viscosity of the copolymer increases too much, and the copolymerization itself becomes difficult. Preferably 4
It is 6 or less.

The content of the polyethylene glycol unit must be 18% by mass or more and 68% by mass or less based on the total solid content. When the amount of the polyethylene glycol unit is less than 18% by mass, solid particles are aggregated and a stable dispersion cannot be obtained. Preferably 30
It is at least mass%. On the other hand, when it exceeds 68 mass%,
Since the amount of the high moisture absorptive and desorptive organic fine particles (A) becomes small, a sufficient moisture absorptive and desorptive function cannot be imparted to the fiber product. Preferably 6
It is 0 mass% or less.

Specific examples of such polyalkylene glycol (meth) acrylate (B) include, for example, polyethylene glycol (meth) acrylate [oxyethylene addition mole number 5 to 90], methoxypolyethylene glycol (meth) acrylate [oxy]. Ethylene addition mole number 5 to 90], phenoxy polyethylene glycol (meth) acrylate [oxyethylene addition mole number 5 to 90]
90], polyethylene glycol polypropylene glycol (meth) acrylate [oxyethylene addition mole number 7, oxypropylene addition mole number 3], polyethylene glycol polytetramethylene glycol (meth) acrylate [oxyethylene addition mole number 10, oxytetramethylene addition mole number Such as polyethylene glycol di (meth) acrylate [oxyethylene addition mole number 5 to 90], methoxy polyethylene glycol di (meth) acrylate [oxyethylene addition mole number 5 to 90], etc. Examples thereof include polyfunctional (meth) acrylates, and these may be used alone or in combination of two or more. The above-mentioned "mol number of oxyethylene added", "mol number of oxypropylene added", and "mol number of oxytetramethylene added" all represent the amount in the polyethylene glycol unit. The same applies hereinafter.

Specific examples of the (meth) acrylic monomer (C) include 2-hydroxyethyl (meth) acrylate in addition to those exemplified as the acrylic acid type monomer and acrylonitrile type monomer which can be used in the "acrylic crosslinked polymer". , 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2
-Hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 2-
Acryloyloxyethyl acid phosphate, 2
-Acryloyloxyethyl-2-hydroxyethylphthalic acid, hydroxyl group- and / or epoxy group-containing (meth) acrylic monomers such as glycidyl (meth) acrylate, and the like, and one or more of these are used in combination. can do.

As will be described later, the highly moisture absorptive and desorptive fiber treating agent of the present invention is used together with a binder resin capable of reacting with a functional group in the molecule of the (meth) acrylic monomer (C). It is preferable from the viewpoint of improving the washing resistance of moisture-releasing and water-absorbing functions, and particularly when used together with a binder resin capable of reacting with a hydroxyl group and / or an epoxy group, the above-mentioned (meth) acrylic group containing a hydroxyl group and / or an epoxy group. A system monomer is preferably used.

The polyalkylene glycol (meth) acrylate (B) and the (meth) acrylic monomer (C) are distinguished by whether or not they have a polyethylene glycol unit in the molecule.

The amount of the high moisture absorptive and desorptive organic fine particles (A) contained in the solid content of the high moisture absorptive and desorptive fiber treating agent is 29 parts by mass or more, preferably 40 parts by mass or more, and 80 parts by mass. Hereafter, it is recommended that the amount is preferably 70 parts by mass or less. When the content of the high moisture absorptive and desorptive organic fine particles (A) is less than the above range, the moisture absorptive and water absorbing functions of the treated fiber product are deteriorated. ) The content of acrylate (B) or (meth) acrylic monomer (C)] is reduced, and the washing resistance of moisture absorption / release and water absorption of the treated fiber product is reduced.

The amount of the polyalkylene glycol (meth) acrylate (B) component contained in the solid content is 1
9 parts by mass or more, preferably 30 parts by mass or more, 7
It is recommended that the amount is 0 parts by mass or less, preferably 65 parts by mass or less. The polyalkylene glycol (meth) acrylate (B) component plays a role of holding the high moisture absorptive and desorptive organic fine particles (A), and permeates the treated fiber with a solid content which is an active ingredient of the high moisture absorptive and desorptive fiber treating agent. It has a function and further imparts a water absorbing function to the treated fiber, but if the content of the component (B) is less than the above range, the function of retaining the highly hygroscopic organic fine particles (A) is not sufficient, Further, the permeability for inducing the solid content between the fibers is insufficient, so that the moisture absorbing / releasing / water absorbing functions cannot be sufficiently imparted. On the other hand, when the amount of the component (B) exceeds the above range, the moisture absorbing / releasing function is deteriorated due to the lack of the amount of the highly hygroscopic organic fine particles (A) and the amount of the (meth) acrylic monomer (C) component, and The water solubility becomes too high and washing resistance cannot be obtained.

Further, it is contained in the above solid content (meta).
The amount of the acrylic monomer (C) component is 1 part by mass or more,
It is preferably 4 parts by mass or more and 20 parts by mass or less, preferably 18 parts by mass or less. When the content of the (meth) acrylic monomer (C) component is less than the above range, the amount of the highly moisture-absorbing and desorbing organic fine particles (A) and the polyalkylene glycol (meth) acrylate (B) component increases, and particularly (C) When the component) has a hydroxyl group and / or an epoxy group and is used together with a binder resin that reacts with these functional groups, the amount of the functional groups decreases, so that the washing resistance of moisture absorption / desorption / water absorption functions is reduced. descend. On the other hand,
The greater the amount of the (meth) acrylic monomer (C) component, the more improved the moisture absorption / desorption / water absorption function is the washing resistance. However, when the amount exceeds the above range, the hydrophobicity of the solid content in the highly moisture-absorption / desorption fiber treatment agent is increased. It becomes strong and cannot form a stable dispersion.

In the highly moisture absorptive and desorptive fiber treating agent of the present invention, the aqueous dispersion of the highly moisture absorptive and desorptive organic fine particles (A) is a polyalkylene glycol (meth) acrylate (B) and a (meth) acrylic monomer (C). At the time of copolymerization of, the highly moisture-absorbing and desorbing organic fine particles (A) play a role as an emulsifier and a protective colloid, and the polyalkylene glycol (meth) acrylate (B) and the (meth) acrylic monomer (C) are mixed with each other. It is considered that it is retained well by being incorporated into the entanglement between the copolymer molecules. The incorporation of the highly moisture-absorbing and desorbing organic fine particles (A) into the entanglement between the above-mentioned copolymer molecules is caused by the copolymerization of the polyalkylene glycol (meth) acrylate (B) and the (meth) acrylic monomer (C). It is considered that this is achieved by the presence of the highly moisture-absorbing and desorbing organic fine particles (A), and actually, the copolymerization of the polyalkylene glycol (meth) acrylate (B) and the (meth) acrylic monomer (C). Even if the substance is simply mixed with an aqueous dispersion of the high moisture absorptive and desorptive organic fine particles (A), the high moisture absorptive and desorptive organic fine particles (A) are not sufficiently retained in the copolymer. The treatment of the textile does not improve the washing resistance of the moisture absorbing / releasing function.

In copolymerizing the polyalkylene glycol (meth) acrylate (B) and the (meth) acrylic monomer (C) in the presence of an aqueous dispersion of the highly moisture-absorbing and desorbing organic fine particles (A), an initiator is used. Examples include benzoyl peroxide, azobisbutyronitrile (AIBN), 2,2′-azobis (2-aminopropane) dihydrochloride, ammonium persulfate (APS), potassium persulfate (KPS), and persulfate salts. A redox initiator or the like using an oxidizing agent such as hydrogen peroxide and a reducing agent such as a copper salt, an iron salt, or sodium acid sulfite (SBS) may be appropriately selected and used.

In the above copolymerization, a known emulsifying dispersant such as a surfactant and a protective colloid agent such as polyvinyl alcohol or carboxymethyl cellulose (CMC) may be used in combination.

The high moisture absorptive and desorptive fiber treating agent of the present invention is capable of imparting water absorbability to synthetic fibers such as nylon fibers, polyester fibers and polyacrylonitrile fibers, and further dried high moisture absorptive and desorptive fiber treating agent, that is, The solid content of the active ingredient has a moisture absorption function such that the moisture content is 30% by mass or more at 20 ° C. and 80% RH.

In order to treat a synthetic fiber product with a highly moisture absorptive and desorptive fiber treatment agent, the highly moisture absorptive and desorptive fiber treatment agent is placed in a fiber treatment bath and heated to raise the solid content in the highly moisture absorptive and desorptive fiber treatment agent. A method of aggregating the resin and fixing it to the fiber can be adopted. The treatment conditions are generally a temperature of about 60 ° C. to 130 ° C. and a time of about 5 to 60 minutes.
At this time, a salting-out agent such as Glauber's salt or ammonium sulfate can be used in combination in order to accelerate the aggregation of the solid resin.

Further, when a synthetic fiber product is treated with a highly moisture-absorbing / desorbing fiber treating agent, a binder resin such as a thermosetting resin or a thermoplastic resin is used in combination to obtain a higher moisture-absorbing / desorbing / water-absorbing function. You can ensure good washing resistance.

Examples of the binder resin include thermosetting resins such as melamine resins, epoxy resins and urethane resins; thermoplastic resins such as thermoplastic polyester resins, nylon resins and acrylic resins; natural rubber, nitrile rubber, Rubber-based resins such as urethane rubber; starch, glue,
Examples include natural polymer resins such as dextrin. Of these, when a resin capable of reacting with a hydroxyl group and / or an epoxy group such as an epoxy resin or a urethane resin is used, the (meth) acrylic monomer (C) component in the solid content of the highly hygroscopic fiber treating agent is Hydroxyl groups and /
Alternatively, it is preferable to have an epoxy group, and since the copolymer can be bonded to the binder resin through these functional groups, it is possible to secure higher washing resistance of moisture absorption / release and water absorption. Further, among the above binder resins, urethane resins that do not inhibit the moisture absorption / release and water absorption functions of the treatment agent are particularly preferable.

[0049]

EXAMPLES The present invention will be described in detail below based on examples. However, the following examples do not limit the present invention, and all modifications made within a scope not departing from the gist of the preceding and the following are included in the technical scope of the present invention. The following "parts" and "%" are based on mass unless otherwise specified.

Polymerization Example 1 Aqueous dispersion A-1 of high moisture-absorbing and desorbing organic fine particles (A) in a reactor equipped with a stirrer, a thermometer and a condenser ["HU-707E" manufactured by Japan Exlan Industrial Co., Ltd., high 20% moisture absorbing / releasing organic fine particles, high moisture absorbing / releasing organic fine particles: acrylic cross-linked copolymer, salt type carboxyl group amount 5.5 mmol
/ G] 500 parts, as component (B), polyethylene glycol monomethacrylate [oxyethylene (EO) addition mole number 40] 90 parts, as component (C), 2-hydroxyethyl methacrylate [HEM] 20 parts, ion-exchanged water 240 parts were charged, and the mixture was stirred while substituting with nitrogen, and used as a polymerization initiator in an amount of 2 with respect to the total amount of components (A), (B) and (C).
% Ammonium persulfate and 2.4% sodium acid sulfite were dissolved in 200 parts of ion-exchanged water and added.
Copolymerization was performed at 40 to 45 ° C. for 3 hours with stirring to obtain a fiber treatment agent. The mass ratio of each of the components (A), (B), and (C) in the solid content contained in the obtained fiber treatment agent is (A) /
(B) / (C) = 47.6% / 42.9% / 9.5%. Polyethylene glycol (P
The amount of EG) units is 38.9%. The results are shown in Table 1. The obtained fiber treatment agent was a white emulsion and had a solid content of 20% as measured by an infrared moisture meter.
Met.

Polymerization Examples 2 to 11 Fiber treatment agents were obtained in the same manner as in Polymerization Example 1 with the compositions shown in Tables 1 and 2. The results are shown in Tables 1 and 2.

[0052]

[Table 1]

1) Aqueous dispersion of high moisture-absorbing and desorbing organic fine particles ["Hu-307E" manufactured by Nippon Exlan Industrial Co., Ltd., high moisture-absorbing and desorbing organic fine particles in an amount of 20%, high moisture-absorbing and desorbing organic fine particles: acrylonitrile crosslinked polymer Salt-type carboxyl group amount 5.
5 mmol / g]; 2) methoxy polyethylene glycol methacrylate (oxyethylene addition mole number 23); 3) polyethylene glycol polypropylene glycol methacrylate (oxyethylene addition mole number 23, oxypropylene addition mole number 7); 4) 2-hydroxypropyl Methacrylate; 5) Glycidyl methacrylate.

[0054]

[Table 2]

6) Methoxypolyethylene glycol methacrylate (4 moles of oxyethylene added); 7) Polyethylene glycol methacrylate (100 moles of oxyethylene added).

The fiber treatment agents of Polymerization Examples 2 to 5 satisfying the requirements of the present invention were dispersions having good stability over time. Further, although the fiber treatment agents of Polymerization Examples 6 to 9 are examples which do not partially satisfy the requirements of the present invention, these are also dispersions having good stability over time. On the other hand, in the fiber treating agent of Polymerization Example 10 in which the number of moles of oxyethylene added to the PEG unit was less than the range of the present invention, the dispersion particles were too large and unstable were obtained. In addition, in each of the fiber treatment agents of Polymerization Example 11 in which the number of moles of oxyethylene added to the PEG unit exceeds the range of the present invention and Polymerization Example 12 in which the (meth) acrylic monomer (C) component exceeds the range of the present invention, polymerization is performed. At times the viscosity increased and gelled.

With respect to the above fiber treating agent and the nylon knit (100% nylon) treated with the fiber treating agent, the moisture absorption rate was measured as follows, and the treated nylon knit was further evaluated for water absorption as follows. The fiber treatment agents of Polymerization Examples 10 to 12 were not evaluated as described below, because good fiber treatment agent dispersions were not obtained as described above.

[Measurement of moisture absorption rate of fiber treatment agent] 2 at 105 ° C.
About 1 g of fiber treatment agent (that is, solid content) dried for 2 hours
Scale (W ₀), 24 hours in an environment of 20 ° C and 80% RH
Mass after leaving (W₁) Is precisely weighed and
I asked for 1. Moisture absorption rate 1 (%) = [(W₁/ W₀) -1] x 100 Next, it was made to absorb moisture under the environment of 20 ° C. and 80% RH described above.
Allow the sample to stand in an environment of 20 ° C and 65% RH for 24 hours
Mass (W₂) Is accurately weighed and the moisture absorption rate of 2 is calculated by the following formula.
I have Moisture absorption rate 2 (%) = [(W₂/ W₀) -1] x 100.

[Measurement of moisture absorption rate of treated nylon knit] Table 1
And an aqueous solution in which the fiber treatment agent shown in Table 2, a water-soluble urethane TS-897 for binder (manufactured by Takamatsu Oil & Fat Co., Ltd.), and a catalyst for urethane CAT-908K (manufactured by Takamatsu Oil & Fat Co., Ltd.) (in the fiber treatment agent) Solid content of 25%,
Nylon knit is soaked in water-soluble urethane 6%, urethane catalyst 0.2%), dehydrated by mangle, dried at 100 ° C for 4 minutes, and heat-set at 160 ° C for 1 minute. A treated nylon knit was obtained in which the solid content and the binder resin were fixed to the nylon knit by 5% and 1.5%, respectively.

The treated nylon knit obtained was heated to 105 ° C.
After drying for 2 hours, weigh accurately (W ₃ ) and put it at 20 ° C, 95%
The mass (W ₄ ) after being left for 24 hours in the environment of RH was precisely weighed, and the moisture absorption rate 3 was obtained by the following formula. Moisture absorption rate 3 (%) = [(W ₄ / W ₃ ) −1] × 100 The moisture absorption rate of the treated nylon knit was measured under both the conditions after the above treatment (unwashed) and after 10 times of washing. Washing of treated nylon knit is JIS L0217103
I went according to the law.

[Evaluation of Water Absorption] A water drop extinction method was used in which water drops were dropped on the treated nylon knit using a 1 ml pipette and the time until the reflection of light by the water drops disappeared was measured.

The above results are shown in Tables 3 and 4. In addition, for comparison, an aqueous dispersion A- of highly moisture-absorbing and desorbing organic fine particles
1 and 50/1 of A-1 and the fiber treating agent of Polymerization Example 9
The 0 (%) mixture (hereinafter, referred to as "A-1 / Polymerization example 9 mixture") was also subjected to the above hygroscopicity measurement, and further, these treated nylon knits were produced by the above-mentioned method, and were treated with other treated nylon knits. Similarly, the moisture absorption rate was measured and the water absorption was evaluated. Further, the untreated nylon knit was also subjected to the above moisture absorption rate measurement and water absorption evaluation. These results are also shown in Tables 3 and 4.

[0063]

[Table 3]

[0064]

[Table 4]

As is clear from Table 3, in the fiber treating agents of Polymerization Examples 1 to 7, A-1, and the mixture of A-1 / Polymerization Example 9, 3
Although the moisture absorption rate of 0% or more is obtained, the fiber treatment agents of Polymerization Examples 8 and 9 in which the high moisture absorptive and desorptive organic fine particles (A) are below the range of the present invention do not have a sufficient hygroscopicity. Further, in the fiber treatment agents of Polymerization Examples 1 to 7, A-1, and the mixture of A-1 / Polymerization Example 9, the environmental humidity was changed from 80% RH to 65% RH.
It can be seen that the moisture absorption rate is lowered by lowering the value to 1, and the material has a moisture releasing function.

Further, as is clear from Table 4, Polymerization Example 1
The moisture absorption rate of the nylon knit treated with the fiber treatment agent of up to 5 is improved by about 3 points after the treatment as compared with the untreated nylon knit, and in addition, the moisture absorption function is maintained even after 10 times of washing. There is.

On the other hand, high moisture absorbing / releasing organic fine particles (A)
However, in the case of the treated nylon knits with the fiber treatment agents of Polymerization Examples 8 and 9 below the range of the present invention, the improvement is only about 0.5 to 0.6 points after the treatment as compared with the untreated nylon knit.

Further, the fiber treating agent of Polymerization Example 6 in which the component (C) is below the range of the present invention, the fiber treating agent of Polymerization Example 7 in which the component (B) is below the range of the present invention, A-1 and A- In the treated nylon knit with the mixture of 1 / Polymerization Example 9, the hygroscopicity after treatment is improved, but the hygroscopicity is largely reduced after 10 times of washing, and the washing resistance is insufficient.

Focusing on the water absorption evaluation results in Table 4, in the nylon knit treated with the fiber treatment agents of Polymerization Examples 1 to 5 satisfying the requirements of the present invention, 10 times after the treatment and 10 times after the washing.
It has a good water absorption of less than a second. On the other hand, in the fiber treatment agents of Polymerization Examples 6 to 8 and the treated nylon knit with A-1, the water absorbency after 10 times of washing is lowered, and the wash resistance is insufficient. The treated nylon knit with the mixture of Polymerization Example 9 and the mixture of A-1 / Polymerization Example 9 has a relatively high water-absorbing function after the treatment and after 10 times of washing, and has good wash resistance.

Next, nylon tights were treated with the fiber treatment agents of Polymerization Examples 1-5. The treatment is an aqueous solution in which a fiber treatment agent, water-soluble urethane TS-897 for a binder, and a urethane catalyst CAT-908K are dissolved (solid content 5% in the fiber treatment agent, water-soluble urethane 3%, urethane catalyst 0. Nylon tights is dipped in 2%) at 80 ° C. for 20 minutes for treatment [nylon tights: treatment bath = 1: 20 (mass ratio)], washed with running water for 5 minutes, and centrifugally dehydrated at 100 ° C.
And dried for 10 minutes. The treated nylon tights thus obtained were subjected to moisture absorption measurement and water absorption evaluation in the same manner as the treated nylon knit. The results are shown in Table 5.

[0071]

[Table 5]

The above nylon tights treatment was carried out at 80 ° C. for 2 hours.
Upon 0 minute immersion, the fiber treatment agents of Polymerization Examples 1 to 5 (white emulsion) and the fiber treatment agent of Polymerization Example 4 (light orange emulsion) became lighter in color and the solid content of the active ingredient was nylon. Adsorbed on tights. In contrast,
The fiber treatment agents of Polymerization Examples 6 to 8, A-1, and the mixture of A-1 / Polymerization Example 9 were also subjected to the nylon tights treatment described above. Even when the amount of adsorbed polymer was low or the color of the treating agent became light, the washing water became cloudy in the washing step and the solid content was removed.

In the fiber treating agent of Polymerization Example 6, since the amount of the (meth) acrylic monomer (C) component was below the range of the present invention, the adhesion to nylon tights was insufficient and the fiber treatment agent fell off during washing with water. In the fiber treatment agent, the amount of the polyalkylene glycol (meth) acrylate (B) component was below the range of the present invention, so that the adsorption on the nylon tights during the treatment was insufficient. Since the amount of component B) exceeds the range of the present invention, it has high water solubility and is considered to have fallen off by washing with water. Also, A-1 / Polymerization Example 9
In the mixture, since the component (B) and the component (C) are not copolymerized in the presence of the aqueous dispersion of the highly moisture-absorbing and desorbing organic fine particles (A), the retention of the highly moisture-absorbing and desorbing organic fine particles (A) is performed. It is considered that the function was insufficient and the high moisture absorptive and desorptive organic fine particles (A) did not adhere to the nylon tights.

On the other hand, in the treated nylon tights shown in Table 5, even if treated with any of the fiber treatment agents of Polymerization Examples 1 to 5, it was excellent in less than 10 seconds after the treatment and 10 times of washing. Shows water absorption function.

Although the fiber treatment agents of Polymerization Examples 1 to 5 shown in Table 3 are inferior in moisture absorption rate to A-1,
High humidity of nylon knit treated with these (95% R
The reason why the moisture absorption rate in H) (Table 4) is not inferior to that of the nylon knit treated in A-1 is considered to be due to the excellent water absorption function as described above.

[0076]

As described above, in the present invention, polyalkylene glycol (meth) acrylate (B) and (meth) acrylic monomer (C) are present in the presence of an aqueous dispersion of highly moisture-absorbing and desorbing organic fine particles (A). It was possible to obtain a highly moisture-absorbing and desorbing fiber treatment agent by copolymerizing with the above). The highly moisture-absorbing and desorbing fiber treatment agent of the present invention is excellent in the function of retaining the highly moisture-absorbing and desorbing organic fine particles (A), and is made of synthetic fibers such as nylon-based fibers, polyester-based fibers, polyacrylonitrile-based fibers having poor hygroscopicity. It is possible to impart the moisture absorbing / releasing / water absorbing functions excellent in washing resistance to the obtained fiber products and the mixed-spun fiber products of these synthetic fibers and natural fibers.

Continued front page    (72) Inventor Kenji Shimizu             Toyobo, 2-8, Dojimahama, Kita-ku, Osaka-shi             Koki Co., Ltd. (72) Inventor Soichi Takamoto             68-13 Nakamachi, Negami-cho, Nomi-gun, Ishikawa Prefecture Takamatsu oil             Fat Co., Ltd. (72) Inventor Ryosuke Nishida             3-3-1 Kanaokahigashi-cho, Okayama City, Okayama Prefecture             Within Exlan Industrial Co., Ltd. F-term (reference) 4L033 AB01 AC15 BA49 CA20 CA26

Claims (8)

[Claims] 1. A polyalkylene glycol (meth) acrylate (B) having a polyethylene glycol unit having an oxyethylene addition mole number of 5 to 90 in the presence of an aqueous dispersion of highly moisture-absorbing and desorbing organic fine particles (A) and ( A highly hygroscopic fiber treating agent obtained by copolymerizing a (meth) acrylic monomer (C), wherein the polyethylene glycol unit is 18 to 68% by mass based on the total solid content. 2. The (meth) acrylic monomer (C)
The high moisture absorptive and desorptive fiber treatment agent according to claim 1, wherein is used together with a binder resin capable of reacting with a functional group contained in the molecule. 3. The (meth) acrylic monomer (C)
The high moisture absorptive and desorptive fiber treatment agent according to claim 2, wherein the agent has a hydroxyl group and / or an epoxy group in the molecule and is used together with a binder resin capable of reacting with the hydroxyl group and / or the epoxy group. 4. The highly moisture-absorbing and desorbing organic fine particles (A) are vinyl-based cross-linked copolymers, and are at least selected from the group consisting of sulfonic acid groups, carboxyl groups, phosphoric acid groups and metal salts thereof. The highly hygroscopic fiber treating agent according to any one of claims 1 to 3, which has one or more of 1.0 mmol / g or more. 5. The highly moisture-absorbing and desorbing organic fine particles (A) are an acrylic cross-linked polymer or a styrene cross-linked copolymer, wherein a (salt-type) sulfonic acid group, a salt-type carboxyl group and a salt-type phosphoric acid are used. At least one selected from the group consisting of
A compound having 1.0 mmol / g or more of seeds.
The highly moisture absorptive and desorptive fiber treatment agent according to. 6. The high moisture absorbing / releasing organic fine particles (A) are 2
A compound obtained by chemically converting a nitrile group of an acrylonitrile cross-linked polymer having a cross-linked structure using the compound having a polymerizable vinyl group as a copolymerization component into a salt-type carboxyl group by hydrolysis. The highly moisture-absorbing and desorbing fiber treatment agent according to claim 5, which has a content of 1.0 mmol / g or more. 7. The highly moisture-absorbing and desorbing organic fine particles (A) are chemically converted into salt-type carboxyl groups by hydrolyzing a nitrile group of an acrylonitrile-based crosslinked polymer obtained by introducing a crosslinked structure into an acrylonitrile-based polymer by treating with a hydrazine-based compound. The highly moisture-absorbing and desorbing fiber treatment agent according to claim 5, which has been converted to have a salt type carboxyl group of 1.0 mmol / g or more. 8. The amount of high moisture absorptive and desorptive organic fine particles (A), polyalkylene glycol (meth) acrylate (B) component and (meth) acrylic monomer (C) component contained in the solid content is A): 29 to 80 parts by mass, (B) component: 19 to 70 parts by mass, (C) component: 1 to 20 parts by mass, The highly hygroscopic fiber treating agent according to any one of claims 1 to 7. .