JP7486985B2 - Woven and knitted fabrics and their manufacturing method - Google Patents

Description

The present invention relates to a woven or knitted fabric that has excellent antistatic properties and water and oil repellency, and a method for producing the same.

Polyester fibers are excellent in terms of strength, ease of care, drying speed, and color fastness, and are also easy to process, making them useful in a wide range of applications, including uniforms and sportswear.

Various methods for imparting water and oil repellency to polyester fibers have been investigated in order to improve the stain resistance and other properties of the fibers. For example, Patent Document 1 proposes a fiber structure in which a resin coating containing a triazine ring is formed on the fiber surface, or a resin coating containing a fluorine-based water and oil repellent resin and a triazine ring is formed, and the coating surface is covered with a resin consisting of a fluorine-based water and oil repellent resin having a hydrophilic component and a non-hydrophilic fluorine-based water and oil repellent resin.

Patent Document 2 also proposes a stain-resistant synthetic fiber fabric in which a stain-resistant coating layer containing a fluorine-based water- and oil-repellent agent having hydrophilic segments, a non-hydrophilic fluorine-based water- and oil-repellent agent, and a crosslinking agent is formed on a synthetic fiber fabric.

JP 2008-303511 A Japanese Patent Application Laid-Open No. 10-317281

However, the fabrics disclosed in Patent Documents 1 and 2 have a problem in that the water- and oil-repellent layer having hydrophilic and non-hydrophilic groups is not sufficiently fixed to the fiber surface, resulting in poor washing durability of the water- and oil-repellent properties. In addition, the fiber surface to which water- and oil-repellent properties have been imparted has a problem in that it has poor antistatic properties.

The objective of the present invention is to overcome the drawbacks of the prior art and to obtain a woven or knitted fabric that is excellent in both water and oil repellency and antistatic properties after washing.

［一般式（１）中、Ｒ^１及びＲ^２は同一又は異なる水素原子又はメチル基を示し、Ｒ^３は 炭素数２～５のアルキレン基を示し、ｎは１０以上の整数を示す。］
下記（Ｉ）～（ＩＩＩ）を満足する、織編物。
（Ｉ）ＪＩＳ Ｌ １０９６のＧ法に従って３０回洗濯を行い、ＪＩＳ Ｌ１０９２スプレー法にて測定された撥水性が２級以上である。
（ＩＩ）ＪＩＳ Ｌ １０９６のＧ法に従って３０回洗濯を行い、ＡＡＴＣＣ１１８法に 従って測定された撥油性が２．５級以上である。
（ＩＩＩ）ＪＩＳ Ｌ １０９６のＧ法に従って３０回洗濯を行い、ＪＩＳ Ｌ１０９４ 摩擦帯電圧法に従って測定された制電性が、タテ方向およびヨコ方向の何れについても２ ０００Ｖ以下である。
（ｉｉ）前記ビニル系化合物の分子量が６００以上である、（ｉ）の織編物。
（ｉｉｉ）織編物の構成繊維の質量に対して、前記ビニル系ポリマーが０．５～５質量％ 含まれる、（ｉ）または（ｉｉ）の織編物。
（ｉｖ）織編物の構成繊維の質量に対して、前記炭素数が６以下のパーフルオロアルキル 基を含む共重合体又はアクリル系ポリマーが０．２～２．０質量％含まれる、（ｉ）～（ ｉｉｉ）の何れかの織編物。
（ｖ）（ｉ）～（ｉｖ）の何れかの織編物の製造方法であって、ポリエステル系繊維布帛の少なくとも一方の表面に、上記一般式（１）に示すビニル系 化合物、および重合開始剤を含む水溶液を接触させ、次いで蒸気加熱処理を行い、炭素数が６以下のパーフルオロアルキル基を含む共重合体又はアクリル系ポリマーおよ び架橋剤を含む水溶液を浸漬させる、織編物の製造方法。
（ｖｉ）前記蒸気加熱処理を行った後、かつ炭素数が６以下のパーフルオロアルキル基を 含む共重合体および架橋剤を含む水溶液を浸漬させる前に、高速液流処理を行う、（ｖ）の織編物の製造方法。
The present inventors conducted extensive research to solve the above problems and arrived at the present invention.
That is, the present invention relates to the following (i) to (vi).
(i) A woven or knitted fabric comprising a polyester fiber fabric and a coating film A made of a vinyl polymer obtained by polymerizing a vinyl compound represented by the following general formula (1) and a coating film B containing a copolymer or an acrylic polymer containing a perfluoroalkyl group having a carbon number of 6 or less and a crosslinking agent laminated in this order on at least one surface thereof,

[In general formula (1), ^R1 and ^R2 are the same or different and each represents a hydrogen atom or a methyl group, ^R3 represents an alkylene group having 2 to 5 carbon atoms, and n represents an integer of 10 or more.]
A woven or knitted fabric that satisfies the following (I) to (III).
(I) After washing 30 times according to JIS L 1096 G method, the water repellency measured by JIS L 1092 spray method is grade 2 or higher.
(II) After washing 30 times according to JIS L 1096 G method, the oil repellency measured according to AATCC 118 method is grade 2.5 or higher.
(III) After washing 30 times according to JIS L 1096 G method, the antistatic properties measured according to JIS L 1094 friction electrification voltage method are 2000 V or less in both the warp and weft directions.
(ii) The woven or knitted fabric of (i), wherein the molecular weight of the vinyl compound is 600 or more.
(iii) The woven or knitted fabric according to (i) or (ii), wherein the vinyl polymer is contained in an amount of 0.5 to 5% by mass relative to the mass of the constituent fibers of the woven or knitted fabric.
(iv) A woven or knitted fabric according to any one of (i) to (iii), wherein the copolymer or acrylic polymer containing a perfluoroalkyl group having 6 or less carbon atoms is contained in an amount of 0.2 to 2.0 mass% relative to the mass of the constituent fibers of the woven or knitted fabric.
(v) A method for producing a woven or knitted fabric according to any one of (i) to (iv), comprising contacting at least one surface of a polyester fiber fabric with an aqueous solution containing the vinyl compound represented by the general formula (1) and a polymerization initiator, followed by steam heating treatment, and then immersing the fabric in an aqueous solution containing a copolymer containing a perfluoroalkyl group having 6 or less carbon atoms or an acrylic polymer and a crosslinking agent.
(vi) The method for producing the woven or knitted fabric of (v), further comprising the step of subjecting the woven or knitted fabric to a high-velocity liquid flow treatment after the steam heating treatment and before the immersion in the aqueous solution containing a copolymer containing a perfluoroalkyl group having 6 or less carbon atoms and a crosslinking agent.

The woven or knitted fabric of the present invention exhibits a crosslinked structure in coating B by a copolymer or acrylic polymer containing a perfluoroalkyl group having 6 or less carbon atoms and a crosslinking agent, and further exhibits a crosslinked structure in which the vinyl polymer formed by radical polymerization of the vinyl compound in coating A is firmly bound to the crosslinking agent in coating B, resulting in a configuration that is incorporated into coating B, thereby achieving water/oil repellency and antistatic properties with outstanding washing durability. Therefore, the woven or knitted fabric of the present invention can be suitably used in fields where stain resistance and antistatic properties due to excellent water/oil repellency are required, such as hospital lab coats, doctor's coats, factory work clothes and kitchen clothes typified by food factory uniforms, women's blouses such as office shirts and blouses, work clothes for cleaners, golf shirts, sports shirts, windbreakers, and other sportswear in general.

According to the method for producing a woven or knitted fabric of the present invention, by polymerizing the vinyl compound represented by the above general formula (1) and then performing steam heating treatment, as described above, coating B exhibits a crosslinked structure, and further, the vinyl polymer formed by radical polymerization of the vinyl compound in coating A exhibits a crosslinked structure firmly bound to the crosslinking agent in coating B, and is incorporated into coating B, thereby achieving water/oil repellency and antistatic properties with outstanding washing durability. In addition, when high-speed liquid flow treatment is performed after the above heat treatment, processing unevenness of the vinyl polymer can be suppressed. As a result, excessive hydrophilization by the vinyl polymer can be suppressed, and the uniform formation of coating B can further improve water/oil repellency. Furthermore, a woven or knitted fabric with excellent texture and fastness can be produced.

［一般式（１）中、Ｒ^１及びＲ^２は同一又は異なる水素原子又はメチル基を示し、Ｒ^３は 炭素数２～５のアルキレン基を示し、ｎは１０以上の整数を示す。］
このような構成を有することにより、本発明の織編物は、洗濯耐久性に優れた撥水撥油性 、制電性を満足するものとなる。 The present invention will be described in detail below.
The woven or knitted fabric of the present invention is formed by laminating, in this order, on at least one surface of a fabric made of polyester fibers (referred to as a "polyester fiber fabric" in this specification), a coating A made of a vinyl polymer obtained by polymerizing a vinyl compound represented by the following general formula (1), and a coating B containing a copolymer or an acrylic polymer containing a perfluoroalkyl group having 6 or less carbon atoms and a crosslinking agent.

[In general formula (1), ^R1 and ^R2 are the same or different and each represents a hydrogen atom or a methyl group, ^R3 represents an alkylene group having 2 to 5 carbon atoms, and n represents an integer of 10 or more.]
By virtue of this constitution, the woven or knitted fabric of the present invention is able to satisfy the requirements of water and oil repellency, antistatic properties and excellent washing durability.

(Polyester fiber fabric)
The polyester fiber fabric in the present invention is a fabric containing fibers (polyester fibers) obtained from polyester resins such as polyethylene terephthalate, polylactic acid, polybutylene terephthalate, and polypropylene terephthalate. From the viewpoint of washing durability, the polyester fiber fabric preferably contains 50% by mass or more of polyester fibers in the fabric, more preferably 80% by mass or more. In addition, the fineness, number of filaments, cross-sectional shape, etc. of the polyester fiber are not particularly limited and can be appropriately selected depending on the application, etc.

In the present invention, the above-mentioned fabric may contain fibers other than polyester fibers. For example, polyamide fibers such as nylon 6 and nylon 66; acrylic fibers; polyurethane fibers; natural fibers such as cotton, animal hair fibers, silk, hemp, and bamboo; regenerated fibers such as viscose rayon, cuprammonium rayon, and solvent-spun cellulose fibers; and semi-synthetic fibers such as acetate.

These fibers other than polyester fibers are twisted, blended, interwoven, interknitted with polyester fibers and contained in the fabric. The form of the polyester fiber fabric is not particularly limited, and examples include woven fabrics and knitted fabrics. There are also no particular limitations on the structure, weaving density, knitting density, etc., but woven fabrics are preferred, and twill fabrics are particularly preferred.

The surface of the polyester fiber, which is a constituent fiber, may be surface-treated with a resin other than the vinyl polymer described below or a crosslinking agent, if necessary. Examples of such resins and crosslinking agents include resins having reactive functional groups, such as melamine resins, glyoxal resins, and epoxy resins; and crosslinking agents such as imine crosslinking agents.

(Coating A)
The coating A is made of a vinyl polymer, and the vinyl polymer is obtained by polymerizing the vinyl compound represented by the above general formula (1). By laminating the coating A made of a vinyl polymer, the surface of the fabric is made hydrophilic, and antistatic properties can be imparted to the woven or knitted fabric of the present invention.

In the general formula (1), ^R1 and ^R2 are the same or different and each is a hydrogen atom or a methyl group. ^R1 and ^R2 are preferably a methyl group.

In general formula (1), ^R3 is an alkylene group having 2 to 5 carbon atoms. ^R3 is preferably an alkylene group having 2 or 3 carbon atoms (i.e., a methylene group or a propylene group), and more preferably an alkylene group having 2 carbon atoms (i.e., a methylene group). When the alkylene group of ^R3 has 3 to 5 carbon atoms, it may be either linear or branched.

In the general formula (1), n is the number of moles of alkylene oxide added, and is an integer of 10 or more. In this way, by using a vinyl polymer obtained by radical polymerization of a vinyl compound having a large number of moles of alkylene oxide added, it is possible to maintain water and oil repellency, provide excellent antistatic properties, and suppress the deterioration of water and oil repellency and antistatic properties even after repeated washing. If a vinyl polymer obtained by radical polymerization of a vinyl compound having n smaller than 10 in the general formula (1) is used, the coating formed does not have the above-mentioned characteristic values, and the water and oil repellency and antistatic properties are reduced. Furthermore, repeated washing tends to reduce the water and oil repellency and antistatic properties. From the viewpoint of further improving the water and oil repellency and antistatic properties while more effectively suppressing the deterioration of the water and oil repellency and antistatic properties after washing, n in the general formula (1) is preferably 10 to 30, more preferably 12 to 24.

The molecular weight of the vinyl compound is preferably 600 or more. When the molecular weight of the vinyl compound is 600 or more, it is possible to maintain the water/oil repellency and provide excellent antistatic properties while suppressing the decrease in water/oil repellency and antistatic properties even after repeated washing. From the viewpoint of further improving the water/oil repellency and antistatic properties while more effectively suppressing the decrease in water/oil repellency and antistatic properties after washing, a molecular weight of 700 to 1200 is more preferable.

To laminate the coating A made of the vinyl polymer on the surface of the polyester fiber fabric, as described below, the surface of the polyester fiber fabric is brought into contact with an aqueous solution containing a vinyl compound represented by the general formula (1) and a polymerization initiator, and radical polymerization is carried out. Therefore, in the woven or knitted fabric of the present invention, the lamination mode of the vinyl polymer on the surface of the polyester fiber fabric is assumed to be either one of the following modes or a combination of both modes: (i) the vinyl polymer is attached to the entire surface of the polyester fiber fabric by chemical bonding, or (ii) the vinyl polymer is attached to the entire surface of the polyester fiber fabric without chemical bonding.

The amount of vinyl polymer attached to the woven or knitted fabric of the present invention may be appropriately set depending on the water/oil repellency and antistatic properties to be imparted, but is preferably 0.5 to 5 mass%, more preferably 0.5 to 4.5 mass%, and even more preferably 0.5 to 3 mass% relative to the mass of the constituent fibers of the woven or knitted fabric. If it is less than 0.5 mass%, the antistatic properties may be poor, while if it exceeds 5 mass%, the water/oil repellency may be poor. Here, the amount of vinyl polymer attached is the ratio of the vinyl polymer attached to 100 mass% of the constituent fibers before the vinyl polymer is attached.

The thickness of the coating A made of a vinyl polymer in the woven or knitted fabric of the present invention is not particularly limited, but may be, for example, 50 to 200 nm, and preferably 70 to 180 nm. In the present invention, the thickness is a value measured using, for example, a field emission scanning electron microscope.

(Coating B-1)
As described above, the coating B contains a copolymer containing a perfluoroalkyl group having 6 or less carbon atoms and a crosslinking agent.

Specifically, the copolymer containing a perfluoroalkyl group having 6 or less carbon atoms is preferably a copolymer represented by the following general formula (2).

This is a copolymer formed by copolymerizing a hydrophilic segment obtained by reacting hydrogen sulfide with polyethylene glycol dimethacrylate and a fluoroalkyl acrylate as a fluorinated hydrophobic segment. By including such a copolymer in coating B, it is possible to develop water and oil repellency.

In the above formula, n is preferably an integer from 2 to 10, a is preferably an integer from 1 to 10, and b is preferably an integer from 1 to 10. R represents a lower alkyl group, and preferably an alkyl group having 1 to 3 carbon atoms. Rf represents a perfluoroalkyl group having 6 or less carbon atoms. Having such a perfluoroalkyl group is preferable from the viewpoint of the natural environment.

In addition, in the present invention, by using a copolymer having a fluorinated hydrophobic segment, the water- and oil-repellency has excellent washing durability, and therefore, it is possible to achieve the effect of exhibiting water- and oil-repellency and antistatic properties that are excellent in washing durability.

Hydrophilic segments are formed by modifying ethylenically unsaturated compounds such as acrylates, methacrylates, vinyl acetate, and vinyl chloride, and introducing hydrophilic groups such as ethylene oxide, hydroxyl groups, carboxyl groups, and sulfonic acid groups into these modified compounds. Among these, fluoroalkyl acrylates containing perfluoroalkyl groups are preferred from the viewpoint of excellent water and oil repellency.

As such copolymers, commercially available products dissolved in a solvent can be suitably used. Specific examples of such commercially available products include "Paraguard SRF6000" (solid content concentration 20% by mass) manufactured by Ohara Palladium Chemical Co., Ltd. and "NK Guard S-09" (solid content concentration 20% by mass) manufactured by Nicca Chemical Co., Ltd. "Paraguard SRF6000" is a fluorine-based water repellent agent in which Rf in the above formula (2) is a perfluoroalkyl group having 6 carbon atoms.

The above copolymer may contain components other than the copolymer in which the hydrophilic segment and the fluorinated hydrophobic segment are copolymerized, as long as the effect of the copolymer is not impaired.

(Coating B-2)
Coating B contains an acrylic polymer and a crosslinking agent as described above.
As the acrylic monomer, a non-fluorine-based one not containing a perfluoroalkyl group is preferable, and among them, the following general formula (3) can be mentioned.

A1: H, CH3
A2: a non-fluorine-containing acrylic segment containing a repeating unit derived from a non-fluorine-containing monomer represented by a linear or branched alkyl group having 1 to 30 carbon atoms.

In particular, the coating B in the present invention is preferably made of a non-fluorine-based polymer containing, as a monomer unit, A2, a (meth)acrylic acid ester having 12 to 24 carbon atoms.
Here, the term "(meth)acrylic acid ester" means an "acrylic acid ester" or the corresponding "methacrylic acid ester", and has the same meaning as "(meth)acrylic acid", "(meth)acrylamide", etc.

As described above, the (meth)acrylic acid ester monomer used in the present invention preferably has an ester portion having 12 to 24 carbon atoms, and this ester portion is preferably a hydrocarbon group. This hydrocarbon group may be linear or branched, may be a saturated or unsaturated hydrocarbon, and may further have an alicyclic or aromatic ring. Among these, linear groups are preferred, and linear alkyl groups are more preferred. In this case, water repellency is more excellent. The number of carbon atoms in the ester portion is more preferably 12 to 21. When the number of carbon atoms is within this range, water repellency and feel are particularly excellent. A linear alkyl group having 12 to 18 carbon atoms is particularly preferred as the ester portion.

Specific examples of the acrylic polymers that can be used include Daikin's Unidyne XF series (XF-4001, XF-5001, XF-5003, XF-5005) and Nicca Chemical's NR-7080, NR-7400, NR-7500, etc.

In the coating B, the copolymer or acrylic polymer containing a perfluoroalkyl group having 6 or less carbon atoms is preferably contained in an amount of 0.2 to 2.0% by mass, more preferably 0.5 to 1.5% by mass, based on the mass of the constituent fibers of the woven or knitted fabric. If it is less than 0.2% by mass, the water and oil repellency may not be fully expressed, while if it exceeds 2.0% by mass, the antistatic properties may be poor. The amount of the copolymer or acrylic polymer containing a perfluoroalkyl group having 6 or less carbon atoms is calculated using the solid content (mass %) of the copolymer or acrylic polymer in the solvent, the amount used for processing (g/L), and the mangle squeezing rate (%). For example, if the solid content of the copolymer in the solvent is 20% by mass, the amount used for processing is 50 g/L, and the mangle squeezing rate is 60%, the amount is 0.2 x 0.05 x 0.6 x 100 = 0.6 (mass %).

In addition, in the present invention, a crosslinking agent is contained in coating B. By using a crosslinking agent in coating B, the vinyl polymer is firmly bound to the crosslinking agent, resulting in a structure in which it is incorporated into coating B. Due to this structure, coating B, which is the outermost layer, exhibits water and oil repellency, and the vinyl polymer incorporated into coating B can exhibit antistatic properties, thereby achieving water and oil repellency and antistatic properties that are remarkably excellent in washing durability.

As the crosslinking agent, melamine resin is preferable. The melamine resin may be a thermosetting resin obtained by condensation of a compound containing a triazine ring and having at least two polymerizable functional groups, and specific examples thereof include trimethylol melamine and hexamethylol melamine. As the melamine resin, for example, commercially available products such as trimethylol melamine such as "RIKEN RESIN MM-3C" and "RIKEN RESIN MM-35" (both manufactured by Miki Riken Kogyo Co., Ltd.) and "BECKAMINE M-3" (manufactured by DIC Kitanihon Polymer Co., Ltd.) and hexamethylol melamine such as "RIKEN RESIN MM-601" and "RIKEN RESIN MM-630" (both manufactured by Miki Riken Kogyo Co., Ltd.) (both manufactured by Miki Riken Kogyo Co., Ltd.) can be used.

In the coating B, the crosslinking agent is preferably contained in an amount of 0.05 to 1.0 mass %, and more preferably 0.1 to 0.5 mass %, relative to the mass of the constituent fibers of the woven or knitted fabric. If it is less than 0.05 mass %, the durability against washing may not be fully exhibited, while if it exceeds 1.0 mass %, the feel as a garment may be poor. The amount of the crosslinking agent is calculated using the solid content (mass %) of the crosslinking agent, the amount used for processing (g/L), and the mangle squeeze rate (%).
For example, when the solid content of the crosslinking agent is 80% by mass, the amount used in processing is 0.3 g/L, and the mangle squeezing rate is 60%, the formula is 0.8×0.003×0.6×100=0.14 (% by mass).

The woven or knitted fabric of the present invention satisfies the following (I) to (III).
(I) The water repellency evaluated by the JIS L1092 spray method after washing 30 times according to the JIS L1096 G method is at least grade 2, and preferably at least grade 3. This is an index of excellent washing durability of water repellency.
(II) The oil repellency evaluated according to AATCC118 method after washing 30 times according to JIS L 1096 G method is at least grade 2.5, and preferably at least grade 3. This is an index of excellent washing durability of oil repellency.
(III) The antistatic property evaluated according to the JIS L 1094 friction electrification voltage method after washing 30 times according to the JIS L 1096 G method is 2000 V or less, and preferably 1000 V or less. This is an index of excellent washing durability of the antistatic property.

The method for producing the woven or knitted fabric of the present invention will be described below.
The production method of the present invention includes contacting at least one surface of a polyester fiber fabric with an aqueous solution containing a vinyl compound represented by the above general formula (1) and a polymerization initiator,
Then, a steam heating treatment is performed.
The substrate is immersed in an aqueous solution containing a copolymer or an acrylic polymer containing a perfluoroalkyl group having 6 or less carbon atoms and a crosslinking agent.

Before contacting the polyester fiber or fabric with the aqueous solution, it may be subjected to processing such as desizing, scouring, presetting, and dyeing, as necessary.

The aqueous medium in which the vinyl compound represented by the above general formula (1) and the polymerization initiator are dissolved can be water or a mixture of water and a known organic solvent.

In the present invention, a polymerization initiator is used to promote the radical polymerization of vinyl compounds. Examples of the polymerization initiator include inorganic polymerization initiators such as ammonium persulfate, potassium persulfate, cerium ammonium nitrate, and hydrogen peroxide; and organic radical initiators such as 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis(N,N'-dimethyleneisobutyramide) dihydrochloride, and 2-(carbamoirazo)isobutyronitrile.

These polymerization initiators may be used alone or in combination of two or more. The concentration of the polymerization initiator in the aqueous solution is not particularly limited and may be set appropriately depending on the type of polymerization initiator used, but examples of the concentration include 0.1 to 20 parts by mass, preferably 0.3 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass of the polymerization initiator per 100 parts by mass of the vinyl compound.

The aqueous solution may contain a redox initiator consisting of a peroxide and a reducing substance, if necessary, in order to increase the polymerization efficiency. Examples of peroxides used in redox initiators include ammonium persulfate and potassium persulfate, and examples of reducing substances used in redox initiators include the reaction product of sodium sulfoxylate and formalin, hydrosulfite, etc.

Furthermore, the aqueous solution may contain a polymerization inhibitor. When a polymerization inhibitor is contained, polymerization in a low temperature range can be suppressed, and it becomes easier to obtain a vinyl polymer having a desired degree of polymerization. Examples of polymerization inhibitors include quinones such as benzoquinone, hydroquinone, and methoxyphenol; polyoxy compounds such as tertiary butylcatechol; organic sulfur compounds such as sodium dimethyldithiocarbamate and diethylhydroxylamine; nitro compounds; and amino compounds such as diethylhydroxylamine and isopropylhydroxylamine. These polymerization inhibitors may be used alone or in combination of two or more. The concentration of the polymerization inhibitor in the aqueous solution is not particularly limited and may be appropriately set depending on the type of polymerization inhibitor used, but for example, the polymerization inhibitor may be 0.01 to 2 parts by mass, preferably 0.015 to 1.5 parts by mass, and more preferably 0.02 to 1 part by mass per 100 parts by mass of the vinyl compound.

The method for contacting the polyester fiber fabric with the aqueous solution is not particularly limited, and examples thereof include the following methods. That is, the aqueous solution may be applied to the polyester fiber fabric by a known method such as a padding method, a spray method, a kiss roll method, or a slit coater method.

After the polyester fabric is contacted with the aqueous solution, a steam heating treatment is performed to polymerize the vinyl compound. In other words, so-called radical polymerization proceeds. The temperature of the steam heating treatment is 80 to 180°C, preferably 98 to 150°C, and the treatment is performed in the presence of steam for 1 to 30 minutes, preferably 3 to 15 minutes. In order to achieve even better polymerization efficiency, it is preferable not to perform a drying process before the steam heating treatment. In addition to steam heating treatment, other polymerization methods include exhaustion treatment, electron beam treatment, ultraviolet treatment, and microwave treatment, but in the present invention, steam heating treatment is essential from the viewpoint of versatility of equipment and production efficiency (polymerization efficiency). In the present invention, as described above, this treatment results in a crosslinked structure in coating B consisting of a copolymer or acrylic monomer containing a perfluoroalkyl group having 6 or less carbon atoms and a crosslinking agent, and further, the vinyl polymer formed by radical polymerization of the vinyl compound in coating A forms a crosslinked structure that is firmly bound to the crosslinking agent in coating B, and is incorporated into coating B. This is believed to achieve water/oil repellency and antistatic properties with outstanding washing durability.

In the present invention, after the radical polymerization of the vinyl compound, it is preferable to subject the obtained fabric (a polyester fiber fabric having a surface on which a coating A made of a vinyl polymer is laminated) to washing by high-speed liquid flow treatment. By subjecting the fabric to high-speed liquid flow treatment in this manner, the remaining monomer (vinyl compound) and excess vinyl polymer adhering between the fibers are appropriately removed, and the vinyl polymer is uniformly formed on the surface of each of the constituent fibers on the surface of the polyester fiber. This makes it possible for the woven or knitted fabric of the present invention to have even better water and oil repellency and antistatic properties while suppressing processing unevenness. In addition, such high-speed liquid flow treatment makes it possible to suppress the woven or knitted fabric from becoming stiff in texture, and further suppresses discoloration and deterioration of color fastness caused by the elution of the remaining monomer.

In the present invention, high-speed liquid flow treatment is a cleaning process in which the fabric is exposed to cleaning liquid that is sprayed at high speed.

A suitable example of a high-speed liquid flow treatment is a liquid flow cleaning process in which the fabric is passed through a cleaning liquid sprayed at high speed. This type of high-speed liquid flow treatment is described in detail below.

In the high-speed liquid flow treatment, the cleaning liquid may be sprayed from one direction onto the passing fabric, but it is preferable to spray the cleaning liquid from all directions onto the passing fabric using a filament nozzle or span nozzle used in liquid flow dyeing, etc. In this way, spraying the cleaning liquid from all directions onto the passing fabric makes it possible to more efficiently remove remaining monomers or excess polymers attached between the fibers. The filament nozzle is configured by combining a nozzle pipe and an outer ring (nozzle boss), and is configured so that the cleaning liquid can be sprayed from the gap between the nozzle pipe and the nozzle boss onto the fabric passing through the internal space of the filament nozzle. In addition, the span nozzle is configured by combining hollow truncated cone-shaped members in one to three stages, and is configured so that the cleaning liquid can be sprayed from the gap between the members onto the fabric passing through the internal space of the span nozzle.

In addition, in the high-speed liquid flow treatment, the angle at which the cleaning liquid is sprayed onto the fabric may be set appropriately depending on the time of the high-speed liquid flow treatment, the temperature of the cleaning liquid, etc., but it is usually important to spray the cleaning liquid at an angle of 10° or more with respect to the traveling direction of the passing fabric. By spraying the cleaning liquid at such an angle, sufficient pressure is applied to the fabric, and the remaining monomer and excess polymer adhering between the fibers are removed to the desired extent, making it possible to achieve water and oil repellency, antistatic properties, suppression of processing unevenness, and good texture with excellent industrial washing durability. The angle at which the cleaning liquid is sprayed is preferably 10 to 40°, more preferably 15 to 40° with respect to the traveling direction of the passing fabric.

In the high-speed liquid flow treatment, the speed at which the fabric is passed through the cleaning liquid being sprayed at high speed is not particularly limited, but may be, for example, 50 to 600 m/min, preferably 100 to 500 m/min, and more preferably 200 to 400 m/min. In the high-speed liquid flow treatment, the fabric moves in one direction due to the pressure of the sprayed cleaning liquid, so there is no need to provide any special means for passing the fabric through the cleaning liquid being sprayed at high speed.

In the high-speed liquid flow treatment, the spraying conditions for the cleaning liquid are not particularly limited, but for example, when using a filament nozzle, a filament nozzle with a nozzle diameter (diameter of the internal space of the filament nozzle; diameter of the cross section perpendicular to the direction of passage of the fabric) of 70 to 130 mm and a gap for spraying the cleaning liquid of 2 to 6 mm is used, the nozzle pressure when spraying the cleaning liquid is set to 0.15 to 0.5 MPa, preferably 0.15 to 0.4 MPa, and more preferably 0.15 to 0.3 MPa, and the flow rate when spraying the cleaning liquid is set to 800 to 1500 L/min, preferably 900 to 1400 L/min, and more preferably 1000 to 1300 L/min.

In the high-speed liquid flow treatment, the number of times the fabric is passed through the sprayed cleaning liquid may be set appropriately within a range that allows the remaining monomer to be removed to the desired extent, for example, 3 to 60 times, preferably 5 to 50 times, and more preferably 10 to 40 times. Here, the number of times the fabric is passed through the sprayed cleaning liquid refers to the number of times the fabric passes through the sprayed cleaning liquid per location by the high-speed liquid flow treatment.

It is desirable to subject the fabric to high-velocity liquid flow treatment by tying the fabric into a rope with its ends connected together and circulating the rope-like fabric so that the fabric repeatedly passes through the sprayed cleaning liquid.

The cleaning liquid used in the high-speed liquid flow treatment may be water, but may also be an aqueous solution containing a surfactant if necessary to increase the efficiency of removing the remaining monomer.

In the high-speed liquid flow treatment, the temperature of the cleaning liquid is not particularly limited, but may be, for example, 40 to 100°C, preferably 50 to 90°C, and more preferably 60 to 80°C. By using a cleaning liquid at such a temperature, the remaining monomer and excess polymer adhering between the fibers can be efficiently removed.

The device for performing the high-speed liquid flow treatment is not particularly limited, but a liquid flow dyeing machine used for dyeing fabrics can be suitably used. The liquid flow dyeing machine has a dyeing tank for retaining the fabric, a transfer pipe connecting both ends of the dyeing tank, and a spray nozzle installed at the tip of the transfer pipe for spraying a treatment liquid (cleaning liquid in the present invention). The device is configured so that the fabric connected in an endless loop moves from the outlet of the dyeing tank to the transfer pipe, is transported inside the transfer pipe together with the treatment liquid, and circulates back to the dyeing tank. By using a liquid flow dyeing machine in which the conditions such as the angle of the spray nozzle are adjusted to the above range, the high-speed liquid flow treatment in the present invention can be performed efficiently. As described above, the spray nozzle installed in the liquid flow dyeing machine may be a filament nozzle or a span nozzle, but is preferably a filament nozzle.

After the steam heating treatment or high-speed liquid flow treatment as described above, the fabric is immersed in an aqueous solution containing a copolymer or acrylic polymer containing a perfluoroalkyl group having 6 or less carbon atoms and a crosslinking agent. The immersion method is not particularly limited, and examples include the following methods. That is, the aqueous solution is applied to the polyester fiber fabric by a known method such as a padding method, a spray method, a kiss roll method, or a slit coater method. At this time, it is preferable to adjust a squeeze roller such as a mangle so that the mass of the copolymer is 0.2 to 1 mass% relative to the mass of the constituent fibers of the woven or knitted fabric. If it is less than 0.2 mass%, the water and oil repellency may be poor. If it exceeds 1 mass%, the antistatic performance may be poor.

After immersion in an aqueous solution containing a copolymer containing a perfluoroalkyl group having 6 or less carbon atoms and a crosslinking agent or an acrylic polymer and a crosslinking agent, it is preferable to perform a dry heat treatment. The dry heat treatment is preferably performed at a temperature of 100 to 190°C, and more preferably at 150 to 170°C. If the temperature is less than 100°C, the hydrophobic groups such as perfluoroalkyl groups cannot be sufficiently arranged in the direction perpendicular to the fibers as described above, and as a result, the improvement in water repellency may be insufficient. On the other hand, if the temperature exceeds 190°C, the coating (coating B described above) may deteriorate due to heat, resulting in poor water and oil repellency.

The woven or knitted fabric of the present invention can be particularly suitably used in fields such as hospital gowns, doctor's coats, factory work clothes such as food factory uniforms, kitchen clothes, women's blouses such as office shirts and blouses, work clothes for cleaners, golf shirts, sports shirts, windbreakers, and other sportswear in general.

The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the following examples.

Measurements and evaluations in the following examples and comparative examples were carried out according to the following methods.
1. Samples Two types of samples were prepared for the measurement: one washed 30 times according to the G method of JIS L 1096 (hereinafter, sometimes referred to as "HL30") and one before the washing (hereinafter, sometimes referred to as "initial"). These two types of samples were evaluated.

2. Water repellency: The fabric was washed 30 times according to the G method of JIS L 1096, and evaluated according to the spray method of JIS L1092.

3. Oil repellency: The fabric was washed 30 times according to JIS L 1096 G method and evaluated according to AATCC 118 method.

4. Antistatic Property The fabric was washed 30 times according to the G method of JIS L 1096, and evaluated according to the friction electrification voltage method of JIS L1094.

5. Adhesion amount of vinyl polymer Adhesion amount of vinyl polymer (mass%)={(W1-W0)/W0}×100
W0: mass per unit area of polyester fiber fabric W1: mass per unit area of polyester fiber fabric to which vinyl polymer is attached 6. Adhesion amount of perfluoroalkyl group-containing copolymer or acrylic polymer Adhesion amount of perfluoroalkyl group-containing copolymer or acrylic polymer (mass%)={(W2-W0)/W0}×100×(W3/1000)×(W4/100)
W0: Mass per unit area of polyester fiber fabric W2: Mass per unit area of polyester fiber fabric to which perfluoroalkyl group-containing copolymer or acrylic polymer is attached W3: Amount of perfluoroalkyl group-containing copolymer or acrylic polymer used W4: Solid content of perfluoroalkyl group-containing copolymer or acrylic polymer

Example 1
A twill fabric (warp density: 128/2.54 cm, weft density: 58/2.54 cm, basis weight: 180 g/ ^cm2 ) was woven using polyester multifilament textured yarn (167 dtex/48 f) as the warp yarn and polyester multifilament textured yarn (334 dtex/96 f) as the weft yarn. The twill fabric was scoured in a conventional manner and pre-set at 190°C for 30 seconds using a tenter (manufactured by Ichikin Kogyo Co., Ltd.). Next, the fabric was dyed using a liquid flow dyeing machine ("Circular MF", manufactured by Hisaka Seisakusho Co., Ltd.) at a temperature of 130°C and a time of 30 minutes according to the dyeing recipe below, to obtain a white twill fabric with a basis weight of 220 g/ ^m2 .
<Dyeing recipe>
Fluorescent dye 1% o.m.f
Acetic acid (48%) 0.2 cc/l
Water Balance: The fluorescent dye used was "Hakkol STR" (manufactured by Showa Chemical Industry Co., Ltd.).

Next, this twill fabric was immersed in an aqueous solution having the composition shown in Recipe 1, and then squeezed with a mangle at a squeezing rate of 70% by mass. Without drying, it was subjected to saturated steam treatment at 103°C for 5 minutes in a J Box Steamer (manufactured by Kyoto Machinery Co., Ltd.) to carry out radical polymerization of a vinyl compound.
<Formulation 1>
NK Ester 14G (manufactured by Shin-Nakamura Chemical Co., Ltd., vinyl compound represented by the above general formula (1), n=14, molecular weight 736, R1=CH ₃ , R2=CH ₃ , R3=CH ₂ CH ₂ ): 10 g/L
Polymerization initiator (ammonium persulfate): 0.5 g/L
Water: Remainder

After that, high-speed liquid flow treatment was performed. Specifically, high-speed liquid flow treatment was performed by using a liquid flow dyeing machine ("Circular MF", manufactured by Hisaka Works) equipped with a filament nozzle (nozzle diameter 90 mm, gap for spraying cleaning liquid 4 mm) with a cleaning liquid spray angle (spray angle of cleaning water with respect to the direction of travel of the fabric) of 40°, and circulating the fabric (length (50 m/reel x 6 reels = 300 m)) in the shape of an endless rope under the following conditions: nozzle pressure 0.2 MPa, flow rate when spraying cleaning liquid 1200 l/min, fabric speed 300 m/min, bath ratio 1:10, temperature 60°C for 5 minutes.

Further, the fabric was immersed in an aqueous solution having the composition shown in Formulation 2 below using a padding method to achieve a mangle squeeze rate of 70%.
<Formulation 2>
Aqueous solution containing a copolymer having a perfluoroalkyl group having 6 carbon atoms and represented by the above general formula (2): NK Guard S-09 (manufactured by Nicca Chemical Co., Ltd., solid content concentration 20% by mass), 50 g/L
Crosslinking agent: Beckamin M-3 (manufactured by Dainippon Ink Co., Ltd., N-methylolmelamine: active ingredient concentration (solid content concentration) 80% by mass), 0.3 g/L
Catalyst: Catalyst ACX (manufactured by Dainippon Ink Co., Ltd., amino alcohol hydrochloride: active ingredient concentration 35% by mass) 0.1 g/L
Water: Remainder

Then, the fabric was dried in a drum dryer at 120°C for 2 minutes, and then set in a tenter at 170°C for 1 minute (dry heat treatment) to obtain the woven or knitted fabric of Example 1.

Example 2
The same procedure as in Example 1 was carried out, except that the aqueous solution of Formulation 1 in Example 1 was changed to the composition of Formulation 3 below.
<Formulation 3>
NK Ester 14G (manufactured by Shin-Nakamura Chemical Co., Ltd., vinyl compound represented by the above general formula (1), n=14, molecular weight 736): 20 g/L
Polymerization initiator (ammonium persulfate): 1.0 g/L
Water: Remainder

Example 3
The same procedure as in Example 1 was carried out, except that the aqueous solution of Formulation 1 in Example 1 was changed to the composition of Formulation 4 below.
<Formulation 4>
NK Ester 23G (manufactured by Shin-Nakamura Chemical Co., Ltd., vinyl compound represented by the above general formula (1), n=23, molecular weight 1136, R1=CH ₃ , R2=CH ₃ , R3=CH ₂ CH ₂ ): 10 g/L
Polymerization initiator (ammonium persulfate): 0.5 g/L
Water: Remainder

Example 4
The same procedure as in Example 1 was carried out, except that the aqueous solution of formulation 1 in Example 1 was changed to the composition of formulation 5 below, and the aqueous solution of formulation 2 was changed to formulation 6 below.
<Formulation 5>
NK Ester 14G (manufactured by Shin-Nakamura Chemical Co., Ltd., vinyl compound represented by the above general formula (1), n=14, molecular weight 736): 40 g/L
Polymerization initiator (ammonium persulfate): 2.0 g/L
Water: balance <Formulation 6>
Aqueous solution containing a copolymer having a perfluoroalkyl group having 6 carbon atoms and represented by the above general formula (2): NK Guard S-09 (manufactured by Nicca Chemical Co., Ltd., solid content concentration 20% by mass) 60 g/L
Crosslinking agent: Beckamin M-3 (manufactured by Dainippon Ink Co., Ltd., N-methylol melamine: active ingredient concentration (solid content concentration) 80% by mass), 0.3 g/L
Catalyst: Catalyst ACX (manufactured by Dainippon Ink Co., Ltd., amino alcohol hydrochloride: active ingredient concentration 35% by mass) 0.1 g/L
Water: Remainder

Example 5
The same procedure as in Example 1 was carried out, except that the aqueous solution of Formulation 2 in Example 1 was changed to the composition of Formulation 7 below.
<Formulation 7>
Aqueous solution containing a copolymer having a perfluoroalkyl group having 6 carbon atoms and represented by the above general formula (2): NK Guard S-09 (manufactured by Nicca Chemical Co., Ltd., solid content concentration 20% by mass) 70 g/L
Crosslinking agent: Beckamin M-3 (manufactured by Dainippon Ink Co., Ltd., N-methylol melamine: active ingredient concentration (solid content concentration) 80% by mass), 0.4 g/L
Catalyst: Catalyst ACX (manufactured by Dainippon Ink Co., Ltd., amino alcohol hydrochloride: active ingredient concentration 35% by mass) 0.1 g/L
Water: Remainder

Example 6
The same procedure as in Example 1 was repeated, except that after radical polymerization of the aqueous solution of Formulation 1 in Example 1, washing was performed using a rope washer (manufactured by Kimura Iron Works) instead of the high-speed liquid flow treatment.

Example 7
The same procedure as in Example 1 was carried out, except that the aqueous solution of Formulation 2 in Example 1 was changed to the composition of Formulation 8 below.
<Formulation 8>
Aqueous solution containing an acrylic polymer: Unidyne XF-5003 (manufactured by Daikin Industries, Ltd., solid content concentration 30% by mass), 50 g/L
Crosslinking agent: Beckamin M-3 (manufactured by Dainippon Ink Co., Ltd., N-methylol melamine: active ingredient concentration (solid content concentration) 80% by mass), 0.3 g/L
Catalyst: Catalyst ACX (manufactured by Dainippon Ink Co., Ltd., amino alcohol hydrochloride: active ingredient concentration 35% by mass) 0.1 g/L
Water: Remainder

Example 8
The same procedure as in Example 2 was carried out, except that the aqueous solution of Formulation 2 in Example 2 was changed to the composition of Formulation 9 below.
<Formulation 9>
Aqueous solution containing an acrylic polymer: Unidyne XF-5003 (manufactured by Daikin Industries, Ltd., solid content concentration 30% by mass) 70 g/L
Crosslinking agent: Beckamin M-3 (manufactured by Dainippon Ink Co., Ltd., N-methylol melamine: active ingredient concentration (solid content concentration) 80% by mass), 0.3 g/L
Catalyst: Catalyst ACX (manufactured by Dainippon Ink Co., Ltd., amino alcohol hydrochloride: active ingredient concentration 35% by mass) 0.1 g/L
Water: Remainder

Comparative Example 1
The same procedure as in Example 1 was carried out, except that the aqueous solution of Formulation 1 in Example 1 was changed to the composition of Formulation 10 below.
<Formulation 10>
NK Ester 9G (manufactured by Shin-Nakamura Chemical Co., Ltd., vinyl compound represented by the above general formula (1), n=9, molecular weight 536, R1=CH ₃ , R2=CH ₃ , R3=CH ₂ CH ₂ ): 10 g/L
Polymerization initiator (ammonium persulfate): 0.5 g/L
Water: Remainder

Comparative Example 2
The same procedure as in Example 1 was carried out, except that the aqueous solution of Formulation 2 in Example 1 was changed to the composition of Formulation 11 below.
<Formulation 11>
Aqueous solution containing a copolymer having a perfluoroalkyl group having 6 carbon atoms and represented by the above general formula (2): NK Guard S-09 (manufactured by Nicca Chemical Co., Ltd., solid content concentration 20% by mass), 50 g/L
Water: Remainder

Comparative Example 3
The same procedure as in Example 1 was carried out except that the aqueous solution of Formulation 1 in Example 1 was not subjected to the steam heating treatment after radical polymerization.

The evaluation results of the examples and comparative examples are summarized in Tables 1 to 3.

As is clear from Tables 1 to 3, the woven and knitted fabrics of Examples 1 to 8 were excellent in both water and oil repellency and antistatic properties after washing. Furthermore, the feel was also good.
In contrast, the woven or knitted fabric of Comparative Example 1 was inferior in both water and oil repellency and antistatic properties because the vinyl compound represented by the above general formula (1) in which n = 9 was used.
In the woven or knitted fabric of Comparative Example 2, since no crosslinking agent was used in Coating B, the water and oil repellency was poor.
In the woven or knitted fabric of Comparative Example 3, the steam heating treatment was not carried out after the radical polymerization of the vinyl compound, and therefore the antistatic property was poor.

Claims (6)

At least one surface of the polyester fiber fabric is
A woven or knitted fabric comprising a coating film A made of a vinyl polymer obtained by polymerizing a vinyl compound represented by the following general formula (1) and a coating film B containing a copolymer or an acrylic polymer containing a perfluoroalkyl group having 6 or less carbon atoms and a crosslinking agent, laminated in this order:

[In general formula (1), R ¹ and R ² are the same or different and represent a hydrogen atom or a methyl group, R ³ represents an alkylene group having 2 to 5 carbon atoms, and n represents an integer of 10 or more.]
A woven or knitted fabric that satisfies the following (I) to (III).
(I) After washing 30 times according to JIS L 1096 G method, the water repellency measured by JIS L 1092 spray method is grade 2 or higher.
(II) After washing 30 times according to JIS L 1096 G method, the oil repellency measured according to AATCC 118 method is grade 2.5 or higher.
(III) After washing 30 times according to JIS L 1096 G method, the antistatic properties measured according to JIS L1094 friction electrification voltage method are 2000 V or less in both the warp and weft directions. The woven or knitted fabric according to claim 1, wherein the molecular weight of the vinyl compound is 600 or more. The woven or knitted fabric according to claim 1 or 2, wherein the vinyl polymer is contained in an amount of 0.5 to 5 mass% relative to the mass of the constituent fibers of the woven or knitted fabric. The woven or knitted fabric according to any one of claims 1 to 3, wherein the copolymer or acrylic polymer containing the perfluoroalkyl group having 6 or less carbon atoms is contained in an amount of 0.2 to 2.0 mass% relative to the mass of the constituent fibers of the woven or knitted fabric. A method for producing the woven or knitted fabric according to any one of claims 1 to 4, comprising contacting at least one surface of a polyester fiber fabric with an aqueous solution containing a vinyl compound represented by the general formula (1) and a polymerization initiator, followed by steam heating treatment;
A method for producing a woven or knitted fabric, comprising immersing the fabric in an aqueous solution containing a copolymer or an acrylic polymer containing a perfluoroalkyl group having 6 or less carbon atoms and a crosslinking agent. The method for producing a woven or knitted fabric according to claim 5, further comprising: performing a high-velocity liquid flow treatment after the steam heating treatment and before the fabric is immersed in an aqueous solution containing a copolymer or an acrylic polymer containing a perfluoroalkyl group having 6 or less carbon atoms and a crosslinking agent.