WO2019000387A1 - Durable antistatic fiber product and manufacture method therefor - Google Patents

Abstract

A durable antistatic fiber product and a manufacture method therefor. The durable antistatic fiber product has a sufficient antistatic performance that is barely lowered after repeated washing by water. The durable antistatic fiber product comprises a component (A) in an amount of 0.01-10% on weight of fabric, and a component (B) in an amount of 0.01-10% on weight of fabric. The manufacture method for the durable antistatic fiber product comprises the step of treating a fiber product with the following component (A) and component (B), component (A) being polycarboxylic acid and/or a polycarboxylic acid derivative, and component (B) being an antistatic agent.

Description

Durable antistatic fiber product and method of manufacturing same Technical field

This invention relates to durable antistatic fibrous articles. Specifically, it relates to a durable antistatic fiber product excellent in durability which is less inferior in antistatic performance even when used for a long period of time, and a method for producing the same.

Background technique

Polyester fibers such as polyethylene terephthalate (hereinafter referred to as "PET fiber") are one of the materials widely used in clothing, and because of their hydrophobic structure, the water content is low and static electricity is likely to be generated. Therefore, in the case of using a polyester fiber such as PET fiber to form a clothing product, there is a problem that it is unpleasant to take, and in some special circumstances, there is a safety hazard such as a fire. In recent years, raised fabrics have become increasingly popular, and such raised fabrics are more likely to cause static electricity, so the need for antistatic processing is becoming more and more obvious from the perspective of wearing comfort.

In order to suppress the above-mentioned electrostatic troubles, antistatic agents have been generally developed and used. As these antistatic agents, an inorganic salt type, a surfactant type, and a polymer type are generally mentioned. Further, the polymer type usually has a hydrophilic group or a hydrophilic molecular chain, and examples of the hydrophilic group include a hydroxyl group, a phosphoric acid group, a sulfonic acid group, an ammonium group, a carboxylic acid group and the like. Further, as the hydrophilic molecular chain, a polyoxyalkylene chain can be exemplified. This type of polymer has a water solubility lower than that of an inorganic salt or the like, and can maintain a certain degree of water wash resistance. However, for these fiber products treated with the existing antistatic agent, the antistatic property is remarkably lowered after repeated washing with water, and the washing durability is not sufficient, especially for antistatic of raised fabrics and the like. The effect is weak. As described above, in the case where the comfort of taking care is highly valued, it is necessary to impart a durable antistatic property.

Patent Document 1 (JP2006-299434A) discloses a method for producing a polyester/cotton woven fabric and a processed product, wherein the following steps are sequentially performed: 1) providing water absorbing and antistatic monomers to the textile, and performing the reaction. And a step of curing; 2) a step of providing a durable water absorbing property and an antistatic polymer emulsion to the textile. However, in the technique disclosed in the comparative document 1, since the water absorbing property and the antistatic monomer are used, it is necessary to remove the uncured monomer and the initiator twice in a total of 10 minutes of the flow washing process, so the process is considered. The technology used in the time, etc., the technology is complicated to operate. And there is a problem of rising costs. More importantly, the antistatic effect of this technology is also insufficient (friction band voltage below 7500V).

A durable antistatic textile in which a yarn A containing an antistatic fiber is used on at least a part of the surface side of the textile and not on the outermost surface of the surface side of the textile is disclosed in Patent Document 2 (JP 2009-256858 A). Within the exposed range, the antistatic agent adheres in contact with at least a portion of the yarn A. However, in the technique disclosed in the comparative document 2, since the yarn A containing the conductive fiber is used, the color and the appearance of the fiber cause problems in the appearance and quality of the textile, and there is a problem that the cost rises and the like, so that it is practical. There will be restrictions on it.

Patent Document 1: JP2006-299434A

Patent Document 2: JP2009-256858A

Summary of the invention

Technical problem to be solved by the invention

The present invention has been made to solve the above problems, and an object thereof is to provide a durable antistatic fiber product which is relatively simple in processing, widely used, and capable of exhibiting an excellent durable antistatic effect, and capable of producing the durable antistatic fiber. A method of manufacturing a product (may also be referred to as "processing method of durable antistatic fiber product" or "processing method of durable antistatic fiber product").

Means for solving technical problems

In order to achieve the above object, the present invention provides the following technical solutions.

<1> A durable antistatic fiber product, wherein

Including: a component (A) a polycarboxylic acid and/or a derivative of a polycarboxylic acid, and a component (B) an antistatic agent,

The content of the component (A) is 0.01 to 10% o.w.f., and the content of the component (B) is 0.01 to 10% o.w.f.

<2> The durable antistatic fiber product described in the above <1>, wherein

The component (A) is one selected from the group consisting of oxalic acid, oxalic anhydride, a polyvalent carboxylic acid represented by the following formula (1), an acid anhydride thereof, an oxalic acid derivative, and a derivative of a polyvalent carboxylic acid represented by the formula (1). Or more than two compounds,

R-(COOH)n (1)

In the formula (1), R represents a residue of a hydrocarbon having 1 to 10 carbon atoms having a substituent or a substituent, and n represents an integer of 2 to 4,

Wherein the oxalic acid derivative is at least one carboxyl group in the oxalic acid and NH ₃ , an alkali metal hydroxide, an alkaline earth metal hydroxide, a lower alkylamine having 1 to 3 carbon atoms, or a lower alkane having 1 to 3 carbon atoms; a product produced by reacting an alkanolamine, and a product obtained by reacting a carboxyl group in oxalic acid with an alkanol having 1 to 3 carbon atoms;

Wherein the derivative of the polyvalent carboxylic acid represented by the formula (1) is at least one carboxyl group and NH ₃ , an alkali metal hydroxide, an alkaline earth metal hydroxide or a low carbon number of 1 to 3 in the formula (1). a product produced by reacting an alkylamine or a lower alkanolamine having 1 to 3 carbon atoms, and 1 to n-1 carboxyl groups in the formula (1) and an alkanol having 1 to 3 carbon atoms The product produced by the reaction.

<3> The durable antistatic fiber product according to the above <1> or <2>, wherein

In the above formula (1), R represents a residue of a chain-saturated or unsaturated hydrocarbon having 1 to 10 carbon atoms having a substituent or a substituent, and a carbon atom having a substituent or having no substituent A residue of a ring-shaped saturated or unsaturated hydrocarbon of 3 to 10 or a residue of an aromatic hydrocarbon having 6 to 10 carbon atoms having a substituent or a substituent.

The durable antistatic fiber product according to any one of the above-mentioned items, wherein

The component (A) is one or more selected from the group consisting of the following (A-1), (A-2), and (A-3),

(A-1) oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, citric acid, tartaric acid, itaconic acid, citraconic acid, and terephthalic acid, isophthalic acid, and Phthalate,

(A-2) the acid anhydride of the above (A-1),

(A-3) at least one carboxyl group in the above (A-1), and NH ₃ , an alkali metal hydroxide, an alkaline earth metal hydroxide, a lower alkylamine having 1 to 3 carbon atoms, or a carbon number of 1 to A product produced by the reaction of a lower alkanolamine of 3, and a product obtained by reacting a carboxyl group of (A-1) with an alkanol having 1 to 3 carbon atoms.

(5) The durable antistatic fiber product according to any one of the above-mentioned items, wherein

The component (B) is a polymer type antistatic agent having a hydrophilic group or a hydrophilic molecular chain.

<6> The durable antistatic fiber product according to the above <5>, wherein

The hydrophilic group is selected from the group consisting of a hydroxyl group, an ammonium group, a phosphate group and a salt thereof, a phosphonic acid group and a salt thereof, a sulfonic acid group and a salt thereof, a sulfate group and a salt thereof, and a carboxylic acid group and a salt thereof. Or more than 2 types,

The hydrophilic molecular chain is a polyoxyalkylene chain.

The durable antistatic fiber product according to any one of the above aspects, wherein

The component (B) is one or more selected from the group consisting of a polyester antistatic agent, a polyacrylic acid antistatic agent, and a polyurethane antistatic agent.

The durable antistatic fiber product according to any one of the above-mentioned items, wherein

The durable antistatic fiber product is obtained by a method for producing a durable antistatic fiber product, wherein the method for producing a durable antistatic fiber product comprises the step of treating the fiber product with the component (A) and the component (B) .

<9> The durable antistatic fiber product according to the above <8>, wherein

In the step of treating the fiber product with the component (A) and the component (B), the fiber product is treated with a mixture containing the component (A) and the component (B).

<10> The durable antistatic fiber product according to the above <8>, wherein

In the step of treating the fiber product with the component (A) and the component (B), the fiber product is treated with the component (A) and then treated with the component (B).

<11> A method for producing a durable antistatic fiber product, wherein

The process comprising treating a fibrous product with the following component (A) and component (B),

a component (A) a polycarboxylic acid and/or a derivative of a polycarboxylic acid,

Ingredient (B) antistatic agent.

Effect of the invention

According to the present invention, it is possible to provide a durable antistatic fiber product which is relatively simple in processing, has wide versatility, and has less reduction in antistatic property even after repeated water washing. Further, according to the production method of the present invention, it is possible to obtain a durable antistatic fiber product having an excellent durable antistatic effect even if the reduction in antistatic property is small even after repeated water washing. In particular, the durable antistatic fiber product obtained by the present invention can reliably improve the problem of poor durability of the antistatic fiber product in the prior art, and can practically greatly improve the durability of the antistatic fiber product.

Detailed ways

<ingredient (A)>

In the present invention, the component (A) is a derivative of a polyvalent carboxylic acid and/or a polyvalent carboxylic acid. In the present invention, as the component (A), not only a polyvalent carboxylic acid but also a derivative of a polyvalent carboxylic acid may be used alone, or a polybasic acid or a derivative of a polyvalent carboxylic acid may be used in combination.

Specific examples of the component (A) in the present invention include oxalic acid, oxalic anhydride, and oxalic acid derivatives, and a polyvalent carboxylic acid represented by the following formula (1), an acid anhydride thereof, and a derivative thereof. As the component (A), one type or two or more types of compounds selected from these can be used.

R-(COOH)n (1)

In the formula (1), R represents a residue of a hydrocarbon having 1 to 10 carbon atoms having a substituent or a substituent, and n represents an integer of 2 to 4.

In addition, examples of the oxalic acid derivative include at least one carboxyl group and NH ₃ , an alkali metal hydroxide, an alkaline earth metal hydroxide, a lower alkylamine having 1 to 3 carbon atoms, or a carbon number of 1 to 3 in oxalic acid. a product produced by the reaction of a lower alkanolamine, and a product obtained by reacting a carboxyl group of oxalic acid with an alkanol having 1 to 3 carbon atoms; a derivative of a polycarboxylic acid represented by the formula (1), The at least one carboxyl group in the formula (1) and NH ₃ , an alkali metal hydroxide, an alkaline earth metal hydroxide, a lower alkylamine having 1 to 3 carbon atoms, or a lower alkane having 1 to 3 carbon atoms may be mentioned. a product produced by reacting an alkanolamine, and a product obtained by reacting one to n-1 carboxyl groups in the formula (1) with an alkanol having 1 to 3 carbon atoms; wherein, regarding the alkali metal hydroxide Examples of the alkali metal in the material include lithium, sodium, potassium, rubidium, cesium, and the like; and examples of the alkaline earth metal in the alkaline earth metal hydroxide include calcium, magnesium, strontium, barium, and the like; and the alkyl group having 1 to 3 carbon atoms. The alcohol may, for example, be methanol, ethanol, propanol or isopropanol; Examples of the lower alkylamine having 1 to 3 subunits include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, etc.; Examples of the lower alkanolamine include methanolamine, ethanolamine, and propanolamine.

In the formula (1), R represents a residue of a hydrocarbon having 1 to 10 carbon atoms which has a substituent or a substituent. Here, the "residue of a hydrocarbon having 1 to 10 carbon atoms having a substituent or a substituent" is a residue indicating a "hydrocarbon having 1 to 10 carbon atoms having a substituent" and "having no substituent" The residue of a hydrocarbon having 1 to 10 carbon atoms. In addition, in the present invention, the so-called The "residue of a hydrocarbon having 1 to 10 carbon atoms having a substituent or having no substituent" means that the "hydrocarbon having 1 to 10 carbon atoms" has a substituent or has no substituent, and the "carbon atom" The number of hydrocarbons of 1 to 10 "residues after losing 2 to 4 hydrogens. Among them, examples of the substituent include a hydroxyl group and a halogen atom, and a hydroxyl group is preferred. Further, examples of the halogen atom include a fluorine atom F, a chlorine atom Cl, bromine Br, and iodine I. The number of the substituents is from 1 to 10, preferably from 1 to 6, more preferably from 1 to 4, still more preferably from 1 to 3, particularly preferably from 1 to 2. In the case of having a substituent, it is particularly preferred to have one hydroxyl group or two hydroxyl groups.

In addition, examples of the hydrocarbon having 1 to 10 carbon atoms include a chain saturated or unsaturated hydrocarbon having 1 to 10 carbon atoms, a cyclic saturated or unsaturated hydrocarbon having 3 to 10 carbon atoms, and a carbon number of 6 to 10 aromatic hydrocarbons, etc. Specific examples of the chain saturated or unsaturated hydrocarbon having 1 to 10 carbon atoms include methane, ethane, propane, isopropane, butane, isobutane, pentane, isopentane, neopentane, and hexane. Heptane, octane, decane, decane, ethylene, propylene, butene, pentene, hexene, heptene, octene, decene, decene, acetylene, propyne, 1,3-butadiene, 1,2-butadiene, isoprene, and the like. Examples of the cyclic saturated or unsaturated hydrocarbon having 3 to 10 carbon atoms include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, and cyclodecane. Examples of the aromatic hydrocarbon having 6 to 10 carbon atoms include benzene, toluene, xylene, and styrene. Further, the residue of the hydrocarbon having 1 to 10 carbon atoms means a group in which the hydrocarbons having 1 to 10 carbon atoms listed above lose 2 to 4 hydrogens. More specifically, examples of the residue of the hydrocarbon having 1 to 10 carbon atoms include a residue of a chain saturated hydrocarbon having 1 to 10 carbon atoms. Specific examples thereof include the loss of 2 hydrogens by methane. Subsequent -CH ₂ -, a group represented by -(CH ₂ ) _{1 to 10} - such as -(CH ₂ ) ₃ - after the loss of two hydrogens by propane.

In the present invention, the polycarboxylic acid represented by the formula (1) is preferably selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, citric acid, tartaric acid, itaconic acid, and citrine. One or more of an acid and terephthalic acid, phthalic acid, and isophthalic acid.

The acid anhydride of the polyvalent carboxylic acid represented by the formula (1) can be obtained by subjecting a polyvalent carboxylic acid represented by the formula (1) to a water molecule by a known method.

In the present invention, the component (A) is preferably one or more selected from the group consisting of the following (A-1), (A-2) and (A-3).

(A-1): oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, citric acid, tartaric acid, itaconic acid, citraconic acid, and terephthalic acid, phthalic acid and Isophthalic acid.

(A-2) The acid anhydride of the above (A-1), specifically, oxalic anhydride, malonic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, maleic anhydride, citric anhydride, tartaric anhydride, and clothing Coconic anhydride, citraconic anhydride, and phthalic anhydride.

(A-3) at least one carboxyl group in the above (A-1), and NH ₃ , an alkali metal hydroxide, an alkaline earth metal hydroxide, a lower alkylamine having 1 to 3 carbon atoms, or a carbon number of 1 to A product produced by the reaction of a lower alkanolamine of 3, and a product obtained by reacting a carboxyl group of (A-1) with an alkanol having 1 to 3 carbon atoms. Specifically, sodium oxalate, sodium malonate, sodium succinate, sodium glutarate, sodium adipate, sodium maleate, sodium citrate, sodium tartrate, sodium itaconate, citraconic acid can be exemplified. Sodium and sodium terephthalate, sodium isophthalate, sodium phthalate; potassium oxalate, potassium malonate, potassium succinate, potassium glutarate, potassium adipate, potassium maleate, potassium citrate, potassium tartrate , potassium itaconate, potassium citrate and potassium terephthalate, potassium isophthalate, potassium phthalate; calcium oxalate, calcium malonate, calcium succinate, calcium glutarate, calcium adipate , calcium maleate, calcium citrate, calcium tartrate, calcium itaconate, calcium citrate and calcium terephthalate; magnesium oxalate, magnesium malonate, magnesium succinate, magnesium glutarate, magnesium adipate , magnesium maleate, magnesium citrate, magnesium tartrate, magnesium itaconate, magnesium citrate and magnesium terephthalate, magnesium isophthalate, magnesium phthalate; ammonium oxalate, ammonium malonate, amber Ammonium acid, ammonium glutarate, ammonium adipate, ammonium maleate, ammonium citrate, ammonium tartrate, ammonium itaconate, ammonium citrate and terephthalic acid Ammonium, ammonium isophthalic acid, phthalic acid, ammonium and the like.

<ingredient (B)>

The component (B) in the present invention is an antistatic agent. As the component (B) antistatic agent, a polymer type antistatic agent which is generally used can be used, and a polymer type antistatic agent having a hydrophilic group or a hydrophilic molecular chain is preferably used.

In the polymer type antistatic agent having a hydrophilic group, examples of the hydrophilic group include a functional group having a general hydrophilicity, and a hydroxyl group, an ammonium group, a phosphoric acid group and a salt thereof, and a phosphonic acid group are preferable. Its salts, sulfonic acid groups and salts thereof, sulfate groups and salts thereof, and carboxylic acid groups and salts thereof. As a salt, an alkali metal salt is mentioned, for example. Further, examples of the alkali metal salt include a sodium salt, a potassium salt, a lithium salt, a phosphonium salt, and a phosphonium salt. A polymer type antistatic agent is obtained by having one or two or more selected from the group consisting of these hydrophilic groups in the molecular structure of the polymer.

Examples of the polymer type antistatic agent having a hydrophilic molecular chain include a polymer having a hydrophilic molecular chain in a main chain, and a block polymerization in which a part of the block chain is a hydrophilic molecular chain. Things and so on. Further, examples of the hydrophilic molecular chain include a polyoxyalkylene chain represented by the formula -(AO) _X -, and a polyoxyethylene chain is preferred. In the formula -(AO) _X -, x represents the average number of moles of addition of the alkylene oxide AO, and is a number from 10 to 250, preferably from 40 to 120. Further, in the polymer having a hydrophilic molecular chain, the content of the hydrophilic molecular chain is 20 to 98% by mass, preferably 70 to 90% by mass. As the polymer type antistatic agent having a hydrophilic molecular chain, a polymer containing 70 to 90% by mass of a polyoxyethylene chain represented by -(EO) _X - is particularly preferable, wherein x represents an average of ethylene oxide. The number of moles is 40 to 120.

Further, the component (B) antistatic agent may be classified into a polyester antistatic agent, a polyacrylic acid type antistatic agent, and a polyurethane type antistatic agent depending on the constituent unit thereof.

In addition, the polyester type antistatic agent is a polymer represented by the following general formula (3).

HO-(AO) _n1 -[OC-Ar-COO(AO) _n2 ] _m1 -OC-Ar-COO-(AO) _n3 H (3)

In the general formula (3), Ar represents an aromatic group or an aromatic group having a sulfonic acid group, and specific examples thereof include C ₆ H ₄ -, -C ₆ H ₃ -SO ₃ Na, and the like. AO represents an oxyalkylene group, and specific examples thereof include an oxyethylene group, an oxypropylene group, and an oxybutylene group. N1, n2, and n3 each independently represent the average number of moles of addition of the alkylene oxide AO, and are numbers of 10 to 250, and m1 is a number of 2 to 30.

In addition, the polyacrylic acid type antistatic agent is not particularly limited, and examples thereof include a polymer having a hydrophilic group or a hydrophilic molecular chain such as polyethylene oxide in a polymer structure, and an acrylate or methacrylate polymer. .

The polyurethane type antistatic agent is a general polyurethane resin, and is not particularly limited. For example, a water-soluble or water-dispersible polyurethane resin obtained by reacting a diisocyanate with a polyhydric alcohol can be used. Examples of the diisocyanate include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4-dicyclohexylmethane diisocyanate, and the like. An alicyclic diisocyanate, an aromatic diisocyanate such as xylene diisocyanate, phenyl phenylisocyanate or toluene diisocyanate, and a modified product of these diisocyanates (containing carbodiimide, uretdione, urea imine) Modified product, etc.). The polyhydric alcohol may, for example, be a diol such as polyethylene glycol or a polyoxyethylene-containing polyether.

In the present invention, as the component (B) antistatic agent, the above various antistatic agents may be used singly, and any two or more of them may be used in combination.

<Fiber Products>

In the specification of the present application, the term "fiber product" means a subject to be treated with the component (A) and the component (B) in the production method of the present invention.

In the present invention, the fiber component constituting the fiber product is not particularly limited, and chemical fibers such as polyester fiber, polyamide fiber, polypropylene fiber, polyacrylonitrile fiber, or rayon fiber may be used, and hemp and cotton may also be used. Natural fibers such as wool. Among them, polyester fibers are widely used for applications requiring durability, and are widely used, and therefore are preferable. Therefore, the fibrous product of the present invention is preferably an article containing a polyester fiber. Examples of the polyester fiber include polyethylene terephthalate (PET) fiber, polyethylene naphthalate (PEN) fiber, polytrimethylene terephthalate (PTT) fiber, and polyparaphenylene. Butylene formate (PBT) fiber and the like.

In the present invention, the form of the fiber product is not particularly limited, and examples thereof include a textile, a woven fabric, a raised fabric, and a nonwoven fabric.

<Durable antistatic fiber products>

The durable antistatic fiber product of the present invention is a product in which the fiber product contains the component (A) of 0.01 to 10% o.w.f. and the component (B) of 0.01 to 10% o.w.f. The product is preferably a product containing a component (A) of 0.2 to 8% owf and a component (B) of 0.2 to 5% owf, more preferably a component (A) having a content of 0.5 to 4% owf and a component (A) of 0.5 to 2% owf. Ingredient (B) product. Here, the fiber product in the present invention means a product before the component (A) and the component (B), that is, the product before the treatment with the component (A) and the component (B), unless otherwise specified. In the specification of the present application, "o.w.f." is an abbreviation of On weight of the fabric, and means the weight based on the weight of the fiber product. Specifically, "the component (A) having 0.01 to 10% by weight of the fiber product" means that the component (A) is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the fiber product. Similarly, "the component (B) containing 0.01 to 10% by weight of the fiber product" means that the component (B) is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the fiber product.

The durable antistatic fiber product of the present invention can be obtained by the method for producing a durable antistatic fiber product of the present invention.

<Method for producing durable antistatic fiber product>

The method for producing a durable antistatic fiber product of the present invention comprises the use of the component (A) and the component (B) A process of treating a fibrous product. The step of treating the fiber product with the component (A) and the component (B) in the present invention may include various embodiments. In this step, the treatment with the component (A) and the treatment with the component (B) may be carried out separately or simultaneously. Examples of the treatment performed by the component (A) and the treatment by the component (B) are as follows: (i) the fiber product is treated with the component (A) and then the component (B). (ii) For the fiber product, the component (B) is first treated, and then the component (A) is treated. Further, in the methods (i) and (ii), the "processing by the component (A)" and/or the "processing by the component (B)" may be performed only once, or may be repeated as necessary. The "treatment by the component (A)" and/or the "treatment with the component (B)" are carried out a plurality of times. Further, after the "treatment by the component (A)" and/or the "treatment with the component (B)" have been carried out, an appropriate subsequent treatment can be carried out as necessary, and as such a subsequent treatment, a drying treatment can be cited. Wait. This subsequent treatment, for example, drying treatment, can be carried out by a usual known method.

Further, when the treatment with the component (A) and the treatment with the component (B) are simultaneously carried out, a method of treating the fibrous product with a mixture containing the component (A) and the component (B) can be employed.

In the present invention, it is particularly preferable that (i-1) a fiber product is subjected to a treatment once with the component (A) and then with the component (B); and (iii) for the fiber product, A method in which the mixture of the component (A) and the component (B) is treated once.

Further, in the present invention, the "treatment of the fiber product with the component (A) and the component (B)" means the contact of the component (A) and the component (B) with the fiber product. The specific treatment method can be carried out by one or more selected from the group consisting of immersion, padding, spray, printing, and coating. In order to further improve the durability and antistatic performance, one or two or more kinds of treatments selected from the group consisting of immersion, padding, spray, printing, and coating may be repeated a plurality of times.

In the "treatment by the component (A)", specifically, one or more selected from the group consisting of dipping, padding, spraying, printing, and coating may be employed. Way to proceed. In the actual treatment, the concentration of various treatment liquids varies according to the processing method and equipment. The following is the most common padding processing in textile functional finishing. The treatment method is as follows: a processing liquid containing 0.01% by mass to 10% by mass of the component (A) is prepared by taking a 100% liquid passing rate as an example, and then the fiber product is padded with the processing liquid, and then dried. The content of the component (A) in the processing liquid is preferably 0.2% by mass to 8.0% by mass, and more preferably 0.5% by mass to 4.0% by mass.

In the "treatment by the component (B)", specifically, one or more selected from the group consisting of dipping, padding, spraying, printing, and coating may be employed. Way to proceed. The concentration of the actual treatment liquid varies according to the processing method and equipment. The following is still the most common padding processing in textile functional finishing as an example to illustrate the conventional treatment method: taking the 100% rolling solution as an example, the formulation contains 0.01% by mass to 10%. The processing liquid of the component (B) of the mass% is then padded with the processing liquid, and then dried. The content of the component (B) in the processing liquid is preferably 0.2% by mass to 5.0% by mass, and more preferably 0.3% by mass to 3.5% by mass.

Further, as described above, in the "step of treating the fiber product with the component (A) and the component (B)" of the present invention, the fiber product can be treated with a mixture containing the component (A) and the component (B). . In this case, as a specific treatment method, one or two or more types selected from the group consisting of immersion, padding, spray, printing, and coating may be employed. In this treatment mode, the amount of the agent in the actual treatment liquid can be appropriately adjusted according to the process and equipment. The following is a typical treatment method for the most common padding processing in the textile functional finishing: taking the 100% rolling rate as an example First, a processing liquid containing 0.01% by mass to 10% by mass of the component (A) and 0.01% by mass to 10% by mass of the component (B) is blended, and then the fiber product is padded with the processing liquid, and then dried. The processing liquid preferably contains 0.2% by mass to 8% by mass of the component (A) and 0.2% by mass to 5.0% by mass of the component (B), and more preferably 0.5% by mass to 4% by mass of the component (A) and 0.5% by weight of the component (B). Mass% to 2.0% by mass. Further, in the step of treating the fiber product with the component (A) and the component (B) of the present invention, the weight of the component (A) and/or the component (B) relative to the weight of the fiber product may be based on the constituent fiber. The properties of the fibers of the product and the properties of the component (A) and/or the component (B) are appropriately adjusted. For example, when the fibrous product is a product containing a polyester fiber, it may be based on the number of moles of the polyester in the fiber product 1 g, the number of moles of the carboxyl group in the component (A) 1 g, and the hydroxyl group in the component (B) 1 g. And/or the number of moles of a carboxyl group, etc., and the weight of the component (A) and / or component (B) with respect to the weight of a textile product is adjusted.

Example

Hereinafter, the durable antistatic fiber product of the present invention and a method for producing the same will be described in detail by way of examples.

The embodiments exemplified herein are merely preferred embodiments of the invention, and the invention is not limited to the embodiments. Modifications of the following embodiments can be easily conceived by those skilled in the art based on the disclosure of the present invention.

The evaluation conducted in the present invention is as follows.

(Evaluation of antistatic properties)

The triboelectric charging properties of unprocessed fiber products, processed fiber products, and washed fiber products are respectively measured by the standard JIS L1094:2008 friction band voltage measurement method and half-life measurement method (test environment conditions: 20±2 ° C 40±2% RH). The rubbing cloth used cotton or wool, and the friction band voltage thus obtained was recorded in the "cotton (V)" column and the "hair (V)" column of the following table, respectively.

The unprocessed products were the fiber products of Comparative Examples 1 to 3.

The initial performance data of the processed fiber product is a result of measurement of the fiber product obtained by the production method of the example or the comparative example without washing, and is referred to as "" in the following examples and comparative examples, respectively. The initial friction band voltage" is recorded in the "L0" column of the table below.

The performance data of the washed fiber product is a result of measurement of the fiber product obtained by washing the fiber product obtained by the production method of the example or the comparative example in accordance with the method of JIS L0217 103, in the following examples and comparative examples. They are referred to as "friction band voltage of L5", respectively, and are recorded in the "L5" column of the table below.

In the following examples and comparative examples, "%" means "% by mass" unless otherwise specified.

Specific information of each of the fiber products, reagents, and raw materials used in the following examples and comparative examples is as follows.

Single-sided fleece: 100% PET, 180g/m ²

Polyester antistatic agent: manufactured by Rihua Chemical Co., Ltd., NICEPOLE PR-913 (trade name), resin component 10%,

Red PET weave: 100% PET, 200g/m ² ,

Double-sided fleece: 100% PET, 220g/m ²

Polyurethane antistatic agent: manufactured by Rihua Chemical Co., Ltd., EVAFANOL AS-21 (trade name), non-volatile component 33%

Crosslinking agent: blocked isocyanate, manufactured by Nissin Chemical Co., Ltd., NK ASSIST FU (trade name), non-volatile component 40%

Example 1

Dissolve 0.5 g of malonic acid in 95.5 g of water, further add 4 g of a polyester antistatic agent (NICEPOLE PR-913), and stir until uniform, thereby obtaining an antistatic having 0.5% by mass of malonic acid and 4% by mass of polyester. The treatment solution of the agent. The single-side fleece was padded with the obtained treatment liquid (rolling rate: about 95%), and dried at 120 ° C for 5 minutes.

As a result of evaluation of the processed fiber product, the initial friction band voltage was 150 V (cotton), 80 V (hair), the half life was less than 1 s (indicated as "<1 s"), and the friction band voltage of L5 was 910 V (cotton), 1700 V. (hair), half-life is 2 seconds.

Comparative Example 1:

As a result of evaluation of the unprocessed single-faced fleece, the initial friction band voltage was 5,500 V (cotton), 4,800 V (hair), and the half life was 32 seconds.

Example 2

0.5 g of maleic acid was dissolved in 95.5 g of water, and 4 g of a polyester antistatic agent (NICEPOLE PR-913) was further added, and the mixture was stirred until uniform, thereby obtaining an antistatic having 0.5% by mass of maleic acid and 4% by mass of polyester. The treatment solution of the agent. The red PET woven fabric was padded with the obtained treatment liquid (rolling rate: about 80%), and dried at 120 ° C for 2 minutes.

As a result of evaluating the processed fiber product, the initial friction band voltage was 10 V (cotton), 49 V (hair), the half life was less than 1 second (indicated as "<1 s"), and the friction band voltage of L5 was 360 V (cotton). 410V (hair), half-life is 2 seconds.

Comparative Example 2:

As a result of evaluation of the unprocessed red PET woven fabric, the initial friction band voltage was 3000 V (cotton), 4700 V (hair), and the half life was more than 120 seconds (expressed as ">120 s").

Example 3

For double-sided fleece, firstly padded with a 1% by mass aqueous solution of malonic acid (rolling rate: about 90%), after drying at 120 ° C for 5 minutes, further using 4% by mass of a polyester antistatic agent. The treatment liquid was subjected to padding treatment (rolling rate: about 90%), and dried at 120 ° C for 5 minutes.

As a result of evaluating the processed fiber product, the initial friction band voltage was 120 V (cotton), 150 V (hair), the half life was less than 1 second (indicated as "<1 s"), and the friction band voltage of L5 was 890 V (cotton). 1750V (hair), half-life is 2 seconds.

Comparative example 3

As a result of evaluation of the unprocessed double-faced fleece, the initial friction band voltage was 5,500 V (cotton), 5,400 V (hair), and the half life was more than 120 seconds (expressed as ">120 s").

Comparative example 4

For double-sided fleece, firstly impregnated with a 1% by mass aqueous solution of propionic acid (a monocarboxylic acid) (rolling rate: about 90%), after drying at 120 ° C for 5 minutes, further using 4% by mass of polyester The aqueous solution of the type antistatic agent (NICEPOLE PR-913) was subjected to padding treatment (rolling rate: about 90%), and dried at 120 ° C for 5 minutes.

As a result of evaluation of the processed fiber product, the initial friction band voltage was 350 V (cotton), 280 V (hair), the half life was 1 second, and the friction band voltage of L5 was 5300 V (cotton), 3500 V (hair), and the half life was 48. second.

Example 4

For double-sided fleece, firstly padded with 2% by mass aqueous maleic acid solution (rolling rate: 100%), after drying at 120 ° C for 5 minutes, further using 4% by mass of polyester antistatic agent (NICEPOLE) The treatment liquid of PR-913) was subjected to padding treatment (rolling rate: 100%), and dried at 120 ° C for 5 minutes.

As a result of evaluating the processed fiber product, the initial friction band voltage was 100 V (cotton), 150 V (wool), the half life was less than 1 second (indicated as "<1 s"), and the friction band voltage of L5 was 920 V (cotton). 1700V (hair), half-life is 2 seconds.

Example 5

For double-sided fleece, firstly padded with a 2% by mass aqueous maleic anhydride solution (rolling rate: 100%), after drying at 120 ° C for 5 minutes, further using a treatment solution of 4% by mass of a polyester antistatic agent Paving treatment (rolling rate: 100%) was carried out and dried at 120 ° C for 5 minutes.

As a result of evaluating the processed fiber product, the initial friction band voltage was 65 V (cotton), 110 V (hair), the half life was less than 1 second (indicated as "<1 s"), and the friction band voltage of L5 was 950 V (cotton). 1800V (hair), half-life is 2 seconds.

Comparative Example 5

The treatment liquid of the 4% by mass polyester antistatic agent for single-sided fleece was subjected to padding treatment (rolling rate: 100%), and dried at 120 ° C for 5 minutes.

As a result of evaluating the processed fiber product, the initial friction band voltage was 300 V (cotton), 310 V (hair), the half life was less than 1 second (indicated as "<1 s"), and the friction band voltage of L5 was 4500 V (cotton). 3200V (hair), half-life is 44 seconds.

Example 6

In a 0.5% aqueous solution of malonic acid, half of the moles of malonic acid was neutralized with KOH, and this was used as a treatment liquid. The single-side fleece was padded with the treatment liquid (rolling rate: 100%), and after drying at 120 ° C for 5 minutes, the treatment liquid of 4% polyester antistatic agent (NICEPOLE PR-913) was further used. Paving treatment (rolling rate: 100%) was carried out and dried at 120 ° C for 5 minutes.

The pH of the extract of the processed product measured by the JIS L 1096 method was 5.2.

As a result of evaluating the processed fiber product, the initial friction band voltage was 240 V (cotton), 290 V (hair), the half life was less than 1 second (indicated as "<1 s"), and the friction band voltage of L5 was 1600 V (cotton). 2800V (hair), half-life is 4 seconds.

Example 7

Double-sided fleece was first padded with 2% maleic acid (cis-type) aqueous solution (rolling rate: about 90%), and after drying at 120 ° C for 5 minutes, further anti-static with 4% polyester type. The treatment liquid of the agent was subjected to padding treatment (rolling rate: about 90%), and dried at 120 ° C for 5 minutes.

As a result of evaluating the processed fiber product, the initial friction band voltage was 210 V (cotton), 190 V (hair), the half life was less than 1 second (indicated as "<1 s"), and the friction band voltage of L5 was 1480 V (cotton). 2500V (hair), half-life is 3 seconds.

Example 8

For double-sided fleece, firstly padded with 2% fumaric acid (trans-body) aqueous solution (rolling rate: about 90%), after drying at 120 ° C for 5 minutes, further use 4% polyester antistatic The treatment liquid of the agent was subjected to padding treatment (rolling rate: about 90%), and dried at 120 ° C for 5 minutes.

As a result of evaluating the processed fiber product, the initial friction band voltage was 270 V (cotton), 230 V (hair), the half life was less than 1 second (indicated as "<1 s"), and the friction band voltage of L5 was 1900 V (cotton). 2400V (hair), half-life is 4 seconds.

Example 9

For double-sided fleece, padding treatment with 2% aqueous citric acid solution (rolling rate: about 90%), after drying at 120 ° C for 5 minutes, further using 4% polyester antistatic agent (NICEPOLE PR-913) The treatment liquid was subjected to padding treatment (rolling rate: about 90%), and dried at 120 ° C for 5 minutes.

As a result of evaluating the processed fiber product, the initial friction band voltage was 180 V (cotton), 170 V (hair), the half life was less than 1 second (indicated as "<1 s"), and the friction band voltage of L5 was 1800 V (cotton). 2100V (hair), half-life is 3 seconds.

Example 10

For double-sided fleece, padding treatment with 2% aqueous solution of adipic acid (rolling rate: about 90%), after drying at 120 ° C for 5 minutes, further using 4% polyester antistatic agent (NICEPOLE PR- The treatment liquid of 913) was subjected to padding treatment (rolling rate: about 90%), and dried at 120 ° C for 5 minutes.

As a result of evaluating the processed fiber product, the initial friction band voltage was 300 V (cotton), 270 V (hair), the half life was less than 1 second (indicated as "<1 s"), and the friction band voltage of L5 was 2000 V (cotton). 2200V (hair), half-life is 4 seconds.

Example 11

According to the prior art (Liu Jixian et al., "Synthetic Fiber" 2008.02.25), methoxypolyethylene glycol monomethacrylate (H ₂ C=C(CH ₃ )OCO(CH ₂ CH ₂ O) was prepared in the same manner. ₂₃ CH ₃ ) a copolymer having a molar ratio of 1:1 to 2-hydroxyethyl acrylate, an emulsion of the copolymer (non-volatile component 10%) as an antistatic agent, and 4 masses in the emulsion 1% of maleic acid was dissolved in the % aqueous solution and used as a treatment liquid. The single-side fleece was padded with the treatment liquid (rolling rate: about 90%), and dried at 120 ° C for 5 minutes.

As a result of evaluating the processed fiber product, the initial friction band voltage was 210 V (cotton), 160 V (hair), the half life was less than 1 second (indicated as "<1 s"), and the friction band voltage of L5 was 3300 V (cotton). 2200V (hair), half-life is 10 seconds.

Comparative Example 6

According to the prior art (Liu Jixian et al., "Synthetic Fiber" 2008.02.25), methoxypolyethylene glycol monomethacrylate (H ₂ C=C(CH ₃ )OCO(CH ₂ CH ₂ O) was prepared in the same manner. ₂₃ CH ₃ ) a copolymer having a molar ratio of 1:1 to 2-hydroxyethyl acrylate, an emulsion of the copolymer (non-volatile component 10%) as an antistatic agent, and 4 masses of the emulsion The % aqueous solution is used as a treatment liquid. The single-side fleece was subjected to padding treatment (rolling rate: about 90%) with the treatment liquid, and dried at 120 ° C for 5 minutes.

As a result of evaluating the processed fiber product, the initial friction band voltage is 780V (cotton), 560V (hair), the half life is 2 seconds, and the friction band voltage of L5 is 5900V (cotton), 3100V (hair), and the half life is greater than 120. Seconds (expressed as ">120s").

Comparative Example 7

For single-sided fleece, firstly paddle with 1% acetic acid aqueous solution (rolling rate: about 90%), after drying at 120 ° C for 5 minutes, further use 4% polyester antistatic agent (NICEPOLE PR-913) The aqueous solution was subjected to padding treatment (rolling rate: about 90%) and dried at 120 ° C for 5 minutes.

As a result of evaluation of the processed fiber product, the initial friction band voltage was 380 V (cotton), 350 V (hair), the half life was 2 seconds, and the friction band voltage of L5 was 4200 V (cotton), 4500 V (hair), and the half life was 56. second.

Example 12

For single-sided fleece, padding treatment with 1% aqueous maleic acid solution (rolling rate: 90%), after drying at 120 ° C for 5 minutes, further using 10% polyurethane antistatic agent (EVAFANOL AS-21) The aqueous solution was padded (rolling rate: 90%) and dried at 120 ° C for 5 minutes.

As a result of evaluation of the processed fiber product, the initial friction band voltage was 380 V (cotton), 300 V (hair), the half life was 1 second, and the friction band voltage of L5 was 2700 V (cotton), 2500 V (hair), and the half life was 25 second.

Comparative Example 8

The single-side fleece was subjected to padding treatment (rolling rate: 90%) with an aqueous solution of a 10% polyurethane type antistatic agent (EVAFANOL AS-21), and dried at 120 ° C for 5 minutes.

As a result of evaluation of the processed fiber product, the initial friction band voltage was 560 V (cotton), 470 V (hair), the half life was 2 seconds, and the friction band voltage of L5 was 5200 V (cotton), 4800 V (hair), and the half life was 54. second.

Comparative Example 9

After double-layered fleece was subjected to padding treatment (rolling rate: 90%) by padding treatment (rolling rate: about 90%) of an aqueous solution of 4% polyester antistatic agent (NICEPOLE PR-913), Dry at 120 ° C for 5 minutes.

As a result of evaluating the processed fiber product, the initial friction band voltage was 320 V (cotton), 300 V (hair), the half life was less than 1 second (expressed as "<1 s"), and the friction band voltage of L5 was 5600 V (cotton). 5200V (hair), half-life greater than 120 seconds (expressed as ">120s").

Although the embodiments and the comparative examples have been described in detail above, the present invention is not limited thereto.

Table 1

*: "4% of PR-913" means an aqueous solution of 4% of a polyester type antistatic agent (NICEPOLE PR-913).

*: "10% of AS-21" means an aqueous solution of 10% of a polyurethane type antistatic agent (EVAFANOL AS-21).

Table 2

*: "4% of PR-913" means an aqueous solution of 4% of a polyester type antistatic agent (NICEPOLE PR-913).

*: "10% of AS-21" means an aqueous solution of 10% of a polyurethane type antistatic agent (EVAFANOL AS-21).

From the comparison of Example 1 with Comparative Example 1, the comparison of Example 2 with Comparative Example 2, and the comparison of Example 3 with Comparative Example 3, it is understood that the fiber product obtained by the production method of the present invention has sufficient antistatic property. Further, it has a durable antistatic property which is small in resistance to reduction in antistatic property even after repeated washing, and a durable antistatic fiber product can be obtained.

From the comparison between Example 1, Example 3, Comparative Example 4, and Comparative Example 7, it was found that in Comparative Example 4 and Comparative Example 7, the component (A) was not used, but a monocarboxylic acid was used, and as a result, The initial antistatic property was confirmed, but the friction band voltage of L5 was remarkably higher than that of Example 1 and Example 3, and no durable antistatic effect was confirmed.

From the comparison of Examples 1 to 10 with Comparative Example 5 and Comparative Example 9, it is understood that in the case of the treatment with the same component (B), in Examples 1 to 10, the components (A) and (B) were used. The treatment was carried out, and the L5 friction band voltage was remarkably lowered as compared with Comparative Example 5 and Comparative Example 9 which were only treated with the component (B), whereby a good durable antistatic effect was confirmed.

From the comparison between Example 11 and Comparative Example 6, and the comparison between Example 12 and Comparative Example 8, it is understood that in the case of treatment with different components (B), in Examples 11 and 12, the components were used. (A) and (B) were treated, and the L5 friction band voltage was remarkably lowered as compared with Comparative Example 6 and Comparative Example 8 which were treated only with the component (B), whereby a good durable antistatic effect was confirmed.

[Possibility of industrial use]

The present invention provides a durable antistatic fiber product which is relatively simple in processing, widely used, and which exhibits an excellent durable antistatic effect, and a manufacturing method capable of producing the durable antistatic fiber product. According to the present invention, it is possible to provide a durable antistatic fiber product which has sufficient antistatic properties and which has less reduction in antistatic property after repeated water washing.

The invention can be widely applied to the fields of clothing materials and industrial materials which require durable antistatic fiber products.

Claims (11)

1. A durable antistatic fiber product, wherein

   Including: a component (A) a polycarboxylic acid and/or a derivative of a polycarboxylic acid, and a component (B) an antistatic agent,

   The content of the component (A) is 0.01 to 10% o.w.f., and the content of the component (B) is 0.01 to 10% o.w.f.
2. The durable antistatic fiber product according to claim 1, wherein

   The component (A) is one selected from the group consisting of oxalic acid, oxalic anhydride, a polyvalent carboxylic acid represented by the following formula (1), an acid anhydride thereof, an oxalic acid derivative, and a derivative of a polyvalent carboxylic acid represented by the formula (1). Or more than two compounds,

   R-(COOH)n (1)

   In the formula (1), R represents a residue of a hydrocarbon having 1 to 10 carbon atoms having a substituent or a substituent, and n represents an integer of 2 to 4,

   Wherein the oxalic acid derivative is at least one carboxyl group in the oxalic acid and NH ₃ , an alkali metal hydroxide, an alkaline earth metal hydroxide, a lower alkylamine having 1 to 3 carbon atoms, or a lower alkane having 1 to 3 carbon atoms; a product produced by reacting an alkanolamine, and a product obtained by reacting a carboxyl group in oxalic acid with an alkanol having 1 to 3 carbon atoms;

   Wherein the derivative of the polyvalent carboxylic acid represented by the formula (1) is at least one carboxyl group and NH ₃ , an alkali metal hydroxide, an alkaline earth metal hydroxide or a low carbon number of 1 to 3 in the formula (1). a product produced by reacting an alkylamine or a lower alkanolamine having 1 to 3 carbon atoms, and 1 to n-1 carboxyl groups in the formula (1) and an alkanol having 1 to 3 carbon atoms The product produced by the reaction.
3. The durable antistatic fiber product according to claim 1 or 2, wherein

   In the above formula (1), R represents a residue of a chain-saturated or unsaturated hydrocarbon having 1 to 10 carbon atoms having a substituent or a substituent, and a carbon atom having a substituent or having no substituent A residue of a ring-shaped saturated or unsaturated hydrocarbon of 3 to 10 or a residue of an aromatic hydrocarbon having 6 to 10 carbon atoms having a substituent or a substituent.
4. The durable antistatic fiber product according to any one of claims 1 to 3, wherein

   The component (A) is one or more selected from the group consisting of the following (A-1), (A-2), and (A-3),

   (A-1) oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, citric acid, tartaric acid, itaconic acid, citraconic acid, and terephthalic acid, phthalic acid and Phthalic acid,

   (A-2) the acid anhydride of the above (A-1),

   (A-3) at least one carboxyl group in the above (A-1), and NH ₃ , an alkali metal hydroxide, an alkaline earth metal hydroxide, a lower alkylamine having 1 to 3 carbon atoms, or a carbon number of 1 to A product produced by the reaction of a lower alkanolamine of 3, and a product obtained by reacting a carboxyl group of (A-1) with an alkanol having 1 to 3 carbon atoms.
5. The durable antistatic fiber product according to any one of claims 1 to 4, wherein

   The component (B) is a polymer type antistatic agent having a hydrophilic group or a hydrophilic molecular chain.
6. The durable antistatic fiber product according to claim 5, wherein

   The hydrophilic group is selected from the group consisting of a hydroxyl group, an ammonium group, a phosphate group and a salt thereof, a phosphonic acid group and a salt thereof, a sulfonic acid group and a salt thereof, a sulfate group and a salt thereof, and a carboxylic acid group and a salt thereof. Or more than 2 types,

   The hydrophilic molecular chain is a polyoxyalkylene chain.
7. The durable antistatic fiber product according to any one of claims 1 to 6, wherein

   The component (B) is one or more selected from the group consisting of a polyester antistatic agent, a polyacrylic acid antistatic agent, and a polyurethane antistatic agent.
8. The durable antistatic fiber product according to any one of claims 1 to 7, wherein

   The durable antistatic fiber product is obtained by a method for producing a durable antistatic fiber product, wherein the method for producing a durable antistatic fiber product comprises the step of treating the fiber product with the component (A) and the component (B) .
9. The durable antistatic fiber product according to claim 8, wherein

   In the step of treating the fiber product with the component (A) and the component (B), the fiber product is treated with a mixture containing the component (A) and the component (B).
10. The durable antistatic fiber product according to claim 8, wherein

    In the step of treating the fiber product with the component (A) and the component (B), the fiber product is treated with the component (A) and then treated with the component (B).
11. A method for manufacturing a durable antistatic fiber product, wherein

    The process comprising treating a fibrous product with the following component (A) and component (B),

    a component (A) a polycarboxylic acid and/or a derivative of a polycarboxylic acid,

    Ingredient (B) antistatic agent.