JP7313124B2 - Antifouling woven or knitted fabric and method for producing the same - Google Patents

Description

The present invention relates to a woven or knitted fabric containing polyester fibers having antifouling properties, and particularly to a woven or knitted fabric suitable for clothing having excellent antifouling properties against powder stains such as mud and soil as pollution sources, antistatic properties, and water absorption. The present invention also relates to a method for producing the woven or knitted fabric.

Polyester fibers are used in a wide range of fields such as clothing and industrial materials because they are excellent in strength, color fastness, etc., and have high versatility in processing. However, it has the drawback of being easily soiled by contamination sources such as oily stains and powdery stains.

Various antifouling polyester fiber fabrics have been investigated to meet such demands. For example, Patent Literature 1 discloses that a fiber structure in which the entire single fiber surface is covered with a polyethylene glycol resin can have antistatic and antifouling properties.

In addition, Patent Document 2 discloses an ink-stain-resistant synthetic fiber in which an antifouling component containing a fluorine-based water- and oil-repellent agent having a hydrophilic segment, a hydrophilic polyester-based resin, a non-hydrophilic fluorine-based water- and oil-repellent agent, and a cross-linking agent blended in a specific ratio is attached to the fiber surface. Patent Document 3 discloses an antifouling polyester synthetic fiber containing a benzoxazole fluorescent whitening agent and having a zeta potential of −15 mV or less.

JP-A-62-162079 Japanese Patent No. 3800670 JP-A-3-174068

However, Patent Document 1 obtains antistatic and antifouling properties by hydrophilizing the fiber surface, and although it is effective against oily stains contained in perspiration, it is not effective against powder stains such as mud. Further, Patent Document 2 is SGR (Soil Guard & Release) processing containing a fluorine-based water and oil repellent, which rather adversely affects powder stains such as mud. On the other hand, Patent Document 3 is a fiber with a zeta potential of -15 mV or less on the fiber surface kneaded with a fluorescent brightening agent, which is intended to prevent recontamination during washing, and is insufficient for powder stains such as mud.

The present invention relates to a woven or knitted fabric having antifouling properties containing polyester fibers in view of the above-mentioned current situation, and in particular, it is an object of the present invention to provide a woven or knitted fabric having excellent antifouling properties against powder stains such as mud and soil as a contamination source, and further having excellent antistatic properties and water absorption, which is excellent in washing durability.

The present inventors arrived at the present invention as a result of intensive studies in order to solve the above problems.
That is, the present invention provides inventions according to the following aspects (1) to ( 8 ).
(1) A woven or knitted fabric containing polyester fibers,
On the surface of the polyester fiber, a coating containing a vinyl polymer obtained by polymerizing a bifunctional vinyl monomer containing polyoxyalkylene and a melamine component is included, and the bifunctional vinyl monomer does not contain a fluoroalkyl group,
Further, the vinyl polymer obtained by polymerizing 100 parts by mass of the difunctional vinyl monomer contains 133 to 250 parts by mass of the melamine component, and after industrial washing under the following conditions, the stain resistance according to the following measurement method is grade 4 or higher,
The B value (rigidity) measured by the KES method is 0.020 to 0.2000 gf·cm ² /cm for woven fabrics and 0.0020 to 0.0200 gf·cm ² /cm for knitted fabrics, and
A soil-resistant woven or knitted fabric having a 2HG5 value (shear angle 5° hysteresis) measured by the KES method of 4.5 to 9.0 gf/cm in the case of a woven fabric and 1.5 to 4.0 gf/cm in the case of a knitted fabric.
(Industrial washing conditions)
In the JIS L 1096: 2010 F -2 law (medium -temperature washer method), the washing and drying operation is washed once under the temperature of 60 ° C., 300 minutes of time, and then the hot water washing is 40 ° C. Changed to a condition of temperature 60 ° C and 30 minutes, and a total of 5 cycles of the washing and drying operation.
(Conditions for measurement of antifouling property)
Four test pieces of 10 cm long and 10 cm wide are prepared from the sample after industrial washing, and the weight of the four test pieces is measured. JIS Z 8901 test powder 1 (type 8 Kanto loam layer) was weighed in an amount of 1/10 of the total weight of four test pieces, and placed in a standard bag No. 16 (polyethylene bag of length 480 mm × width 340 mm, thickness 0.03 mm) is put into the bag at the same time as the test piece, then about 8600 mL of air is injected with an air pump, the mouth is twisted, and the twisted tip is closed with adhesive tape.
The bag is set in the rotating box of an ICI type pilling tester and operated at a speed of 60 ±2 rotations per minute for 60 minutes. After the operation, hold the four corners of the test piece and flick the center of the back surface of the test piece five times with fingers to remove excess dirt.
When flicking with fingers, use two fingers, rotate the test piece 90 degrees each time flicking, and flick five times in total.
The soiled test piece was washed by the method specified in No. 103 of Appendix 1 of JIS L 0217 [Testing methods by symbol - Washing method (washing with water)], and dried in a tumbler at 60°C for 30 minutes.
The color difference seen between the test piece before soiling and the test piece after washing is compared with the color difference of the staining gray scale specified in JIS L 0805 and judged. Judgment is represented by the average value of 4 test pieces.
(2) The antifouling woven or knitted fabric according to claim 1, characterized in that 0.5 to 5 parts by mass of the vinyl-based polymer obtained by polymerizing the bifunctional vinyl-based monomer is contained per 100 parts by mass of the total amount of constituent fibers of the woven or knitted fabric.
(3) The antifouling woven or knitted fabric according to (1) or (2) , characterized by containing 1 to 20 parts by mass of an oxazoline compound with respect to 100 parts by mass of the vinyl-based polymer polymerized with the bifunctional vinyl-based monomer.
(4) The antifouling woven or knitted fabric according to any one of (1) to ( 3 ), wherein the total fixation rate of the vinyl-based polymer polymerized with the bifunctional vinyl-based monomer, the melamine component, and the oxazoline compound is 1.0 to 5.0% by mass with respect to the total amount of the constituent fibers of the woven or knitted fabric.
(5) The antifouling woven or knitted fabric according to any one of (1) to ( 4 ), which has a triboelectrification voltage of 1000 V or less after industrial washing under the above conditions.
(Measurement condition of triboelectric charge voltage)
According to JIS L 1094: 2014 "Method for testing electrification of woven and knitted fabrics", the soil-resistant woven or knitted fabric according to any one of (1) to ( 5 ) is characterized by having a water absorbency of 10 seconds or less after industrial washing under the conditions of (6) above in an environment of 20 ° C. and 40% RH.
(Conditions for measuring water absorption)
A test piece with a length of 20 cm and a width of 20 cm is prepared, and the measurement is performed on this test piece according to the method specified in JIS L-1907:2010 "7.1.1 Drop method".
(7) The woven or knitted fabric containing polyester fibers is brought into contact with a treatment liquid containing 0.5 to 5% by mass of a difunctional vinyl monomer and 0.5 to 10 % by mass of a melamine component to carry out a radical polymerization step, followed by a hot water washing step by a high-speed liquid flow treatment without a drying step.
(8) The method for producing an antifouling woven or knitted fabric according to ( 7 ), wherein the treatment liquid further contains 0.05 to 5% by mass of an oxazoline compound.

The woven or knitted fabric of the present invention includes a film containing a bifunctional vinyl monomer containing polyoxyalkylene and a melamine component on the surface of the polyester fiber, and is preferably subjected to a high-speed liquid flow treatment. Therefore, the woven or knitted fabric of the present invention is particularly suitable as a material for clothing (a woven or knitted fabric for countermeasures against powdery dirt) that is worn when antifouling properties against powdery dirt such as mud are required.

4 is a photograph of the surface of the antifouling woven or knitted fabric obtained in Example 5, taken using an analytical scanning electron microscope (manufactured by JEOL Datum Co., Ltd.) (magnification: 100 times). 1 is a photograph of the surface of the woven or knitted fabric obtained in Comparative Example 1 taken using an analytical scanning electron microscope (manufactured by JEOL Datum Co., Ltd.) (magnification: 100 times).

The present invention will be described in detail below.
The present invention is an antifouling woven or knitted fabric containing polyester fibers. The surface of the polyester fiber contains a film containing a vinyl polymer obtained by polymerizing a bifunctional vinyl monomer containing polyoxyalkylene and a melamine component, and has an antifouling property against powder fouling having an antifouling property of grade 4 or higher according to the measurement method described later.

[Constituent thread]
The woven or knitted fabric of the present invention contains polyester fibers (multifilament yarns containing polyester single fibers) as constituent yarns.
The type of polyester resin constituting the polyester fiber is not particularly limited, but examples thereof include aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate; cationic dyeable polyesters, polylactic acid, and the like. Among these, aromatic polyesters are preferred, and polyethylene terephthalate is more preferred.

The single fiber fineness of the polyester fiber is not particularly limited, but is, for example, 0.1 to 10.0 dtex, preferably 0.3 to 8.0 dtex, more preferably 0.5 to 6.0 dtex. If the single filament fineness is 0.1 dtex or more, the yarn will have a springy feel and will be easy to wear when made into clothing. Also, if the single yarn fineness is 10.0 dtex or less, the yarn does not become too hard and the texture is good.

Also, the total fineness of the polyester fiber is not particularly limited, but is, for example, 30 to 300 dtex, preferably 50 to 250 dtex, more preferably 70 to 180 dtex. When the total fineness is 50 dtex or more, sufficient strength can be imparted to the woven or knitted fabric.

The number of filaments constituting the polyester fiber is determined according to the single fiber fineness and the total fineness of the single fiber used, and is, for example, 1 to 400, preferably 10 to 200, and further 20 to 100.

The cross-sectional shape of the monofilament of the polyester fiber is not particularly limited, and may be either a circular cross-section or an irregular cross-section.

In addition, the polyester fiber may contain titanium dioxide, silicon dioxide, pigment, etc., depending on the properties to be imparted.

The polyester fiber may be raw yarn that has not been subjected to false twisting, or may be false twisted yarn.

The woven or knitted fabric of the present invention may contain fibers other than the polyester fibers as constituent fibers as long as the effects of the present invention are not impaired. Examples of such other fibers include synthetic fibers such as nylon and acrylic; regenerated fibers such as rayon; semi-synthetic fibers such as acetate; and natural fibers such as cotton and wool.

In the woven or knitted fabric of the present invention, the mixing ratio of the polyester fiber is not particularly limited as long as the desired antifouling property, antistatic property, and water absorption can be expressed, but for example, it is 50% by mass or more, preferably 80% by mass or more, and more preferably 100% by mass.

[Texture and density of woven or knitted fabric]
When the woven or knitted fabric of the present invention is a woven fabric, polyester fibers may be used for at least one of the warp and weft, preferably both, and the warp and weft may be crossed to form a texture. When the woven or knitted fabric of the present invention is used as a woven fabric, the texture is not particularly limited, and examples thereof include plain, twill, satin, and variations of these textures.

In addition, when the woven or knitted fabric of the present invention is a knitted fabric, polyester fibers may be used to form a structure by continuous yarn loops. When the woven or knitted fabric of the present invention is made into a knitted fabric, the texture is not particularly limited, and may be either a warp knitted fabric or a weft knitted fabric. Examples of warp knitted fabrics include Denby knitting, cord knitting, and atlas knitting, and specific examples thereof include tricot half, tricot satin, and the like. Examples of weft knitted fabrics include plain knitted fabrics, rubber knitted fabrics, pearl knitted fabrics, and smooth knitted fabrics.

When the woven or knitted fabric of the present invention is a woven fabric, the weaving density may be appropriately set according to the use of the fabric. is 55 to 150 lines/2.54 cm.

In addition, when the woven or knitted fabric of the present invention is a knitted fabric, the knitting density may be appropriately set according to the use of the knitted fabric.

A woven or knitted fabric containing polyester fibers can be obtained by weaving or knitting using polyester fibers.

[Texture]
The texture referred to in the present invention means that the fabric has good firmness, stiffness, and swelling, and is suitable for clothing. Methods for evaluating the texture include, for example, the KES method (method using the KES-F system).

The KES method uses the "KESFB" system manufactured by Kato Tech Co., Ltd., and details thereof will be described later in Examples.

[Stain resistance]
The woven or knitted fabric of the present invention has remarkably excellent antifouling properties against powder stains such as soil or mud. Specifically, after industrial washing under the following conditions, the antifouling property measured by the following method is grade 4 or higher.
(Industrial washing conditions)
In the JIS L 1096: 2010 F -2 law (medium -temperature washer method), the washing and drying operation is washed once under the temperature of 60 ° C., 300 minutes of time, and then the hot water washing is 40 ° C. Changed to a condition of temperature 60 ° C and 30 minutes, and a total of 5 cycles of the washing and drying operation.
(Conditions for measurement of antifouling property)
Four test pieces of 10 cm long and 10 cm wide are prepared from the sample after industrial washing, and the weight of the four test pieces is measured. JIS Z 8901 test powder 1 (type 8 Kanto loam layer) was weighed in an amount of 1/10 of the total weight of four test pieces, and placed in a standard bag No. 16 (polyethylene bag of length 480 mm × width 340 mm, thickness 0.03 mm) is put into the bag at the same time as the test piece, then about 8600 mL of air is injected with an air pump, the mouth is twisted, and the twisted tip is closed with adhesive tape.
The bag is set in the rotating box of an ICI type pilling tester and operated at a speed of 60 ±2 rotations per minute for 60 minutes. After the operation, hold the four corners of the test piece and flick the center of the back surface of the test piece five times with fingers to remove excess dirt.
When flicking with fingers, use two fingers, rotate the test piece 90 degrees each time flicking, and flick five times in total.
The soiled test piece was washed by the method specified in No. 103 of Appendix 1 of JIS L 0217 [Testing methods by symbol - Washing method (washing with water)], and dried in a tumbler at 60°C for 30 minutes. The color difference seen between the test piece before soiling and the test piece after washing is compared with the color difference of the staining gray scale specified in JIS L 0805 and judged. Judgment is represented by the average value of 4 test pieces.

[Surface treatment with vinyl polymer]
In the woven or knitted fabric of the present invention, the surface of the polyester fibers, which are the constituent fibers, includes a film containing a vinyl polymer obtained by polymerizing a bifunctional vinyl monomer containing polyoxyalkylene and a melamine component. In this way, the polyester fiber is coated with a vinyl polymer and a melamine component having a specific structure, and is manufactured through a high-speed liquid flow treatment described later, so that it has excellent stain resistance, antistatic properties, and water absorption with excellent industrial washing durability. More preferably, it is possible to suppress processing unevenness and achieve good texture.

The number of carbon atoms in the alkylene group constituting the alkylene oxide contained in the bifunctional vinyl-based monomer is not particularly limited, but includes, for example, 2 to 5, preferably 2 or 3, more preferably 2. Further, when the alkylene group has 3 or more carbon atoms, the alkylene group may be linear or branched.

The number of added moles of the alkylene oxide contained in the bifunctional vinyl-based monomer is not particularly limited, but may be, for example, 3 to 30, preferably 6 to 26, more preferably 10 to 25. By satisfying the number of added moles of such an alkylene oxide, it becomes possible to more preferably impart antifouling properties, antistatic properties, and water absorbency excellent in durability to industrial washing.

Specific examples of bifunctional vinyl-based monomers containing polyoxyalkylene include compounds in which acrylic groups and/or methacrylic groups are linked to both ends of polyoxyalkylene. More specific examples include polyoxyalkylene-containing diacrylates, dimethacrylates, epoxydiacrylates, epoxydimethacrylates, and the like.

Preferred examples of bifunctional vinyl-based monomers containing polyoxyalkylene include compounds represented by the following general formula (1) or (2).

In general formula (1), R ¹ and R ² are the same or different and represent a hydrogen atom or a methyl group. R ¹ and R ² are preferably methyl groups.

In general formula (1), R ³ is an alkylene group having 2 to 5 carbon atoms. R ³ is preferably an alkylene group having 2 or 3 carbon atoms (ie methylene group or propylene group), more preferably an alkylene group having 2 carbon atoms (ie methylene group). When the alkylene group for R ³ has 3 to 5 carbon atoms, it may be linear or branched.

In general formula (1), n is an integer of 3-30. In the general formula (1), n is preferably 6 to 26, particularly preferably 10 to 25, from the viewpoint of more effectively suppressing uneven processing while more preferably imparting excellent antifouling properties, antistatic properties, and water absorbency with excellent durability to industrial washing.

In general formula (2), ^R4 and ^R5 are the same or different and are a hydrogen atom or a methyl group. R ¹ and R ² are preferably methyl groups.

In general formula (2), R ⁶ is an alkylene group having 2 to 5 carbon atoms. R ⁶ preferably includes an alkylene group having 2 or 3 carbon atoms (that is, a methylene group or a propylene group). When the alkylene group for R ⁶ has 3 to 5 carbon atoms, it may be linear or branched.

In general formula (2), n is an integer of 3-30. In the general formula (2), n is preferably 6 to 26, particularly preferably 10 to 25, from the viewpoint of more effectively suppressing processing unevenness while more preferably imparting excellent antifouling properties, antistatic properties, and water absorbency with excellent durability to industrial washing.

In the woven or knitted fabric of the present invention, the amount of the vinyl polymer relative to the total amount of the polyester fibers that are the constituent fibers may be appropriately set according to the degree of antifouling property, antistatic property, water absorbency, and suppression of processing unevenness to be imparted.

When the amount of the vinyl polymer is 0.5 parts by mass or more, the antifouling property, antistatic property, and water absorbency excellent in durability to industrial washing are further improved. On the other hand, when it is 5.0 parts by mass or less, the texture is further improved.

In the present invention, the coating contains a melamine component. Thereby, preferably, the melamine component is crosslinked to the vinyl-based polymer obtained by radically polymerizing the bifunctional vinyl-based monomer including polyoxyalkylene. This makes it possible to improve the antifouling property excellent in durability to industrial washing, and to further improve the antistatic property and water absorbency.

The melamine component may be a thermosetting resin obtained by condensation of a compound containing a triazine ring and having at least two polymerizable functional groups. Specific examples include trimethylolmelamine and hexamethylolmelamine. Examples of the melamine component include trimethylol melamine such as "RIKEN RESIN MM-3C", "RIKEN RESIN MM-35" (manufactured by Miki Riken Kogyo Co., Ltd.) and "Beckamine M-3" (manufactured by DIC Kitanihon Polymer Co., Ltd.); Commercially available products such as methylolmelamine can be used.

The content of the melamine component in the vinyl polymer is preferably 1 to 250 parts by mass, more preferably 5 to 240 parts by mass, and still more preferably 10 to 210 parts by mass per 100 parts by mass of the difunctional vinyl monomer used.

When the melamine component is 1 part by mass or more, the antifouling property against powder is further excellent.

In the present invention, the coating preferably contains an oxazoline compound. By cross-linking the vinyl-based polymer, the oxazoline compound has a synergistic effect with the melamine component, making it possible to further improve the effect of preventing redeposition of stains in the washing bath, and to impart remarkably excellent durability to restaining due to repeated industrial washing.

The oxazoline compound may be a water-soluble polymer containing an oxazoline group and a water-based cross-linking agent. As the oxazoline-containing polymer, for example, commercially available products such as "Epocross WS-300", "Epocross WS-500" and "Epocross WS-700" (manufactured by Nippon Shokubai Co., Ltd.) can be used.

The content of the oxazoline compound in the vinyl polymer is preferably 1 to 50 parts by mass, more preferably 1 to 40 parts by mass, and still more preferably 2 to 30 parts by mass per 100 parts by mass of the difunctional vinyl monomer used. When it is 1 part by mass or more, the durability to repeated industrial washing is further improved. On the other hand, when it is 50 parts by mass or less, the texture is further excellent.

In the woven or knitted fabric of the present invention, the film containing the vinyl polymer and the melamine component is preferably formed uniformly on each constituent fiber on the surface of the polyester fiber, which is the constituent fiber, by washing with hot water and rubbing in the high-speed liquid flow treatment described later. As a result, the texture, firmness, stiffness, and swelling are further improved, and stains such as powder are less likely to remain on the surface, and the antifouling property is further improved.

In the woven or knitted fabric of the present invention, the total fixing rate of the vinyl polymer, melamine component, and oxazoline compound is preferably 1.0 to 5.0% by mass, more preferably 2.0 to 4.0% by mass, based on the total amount of constituent fibers of the woven or knitted fabric. When it is 1.0% by mass or more, antifouling properties, antistatic properties, and water absorption excellent in industrial washing durability can be further exhibited, and when it is 5.0% by mass or less, unevenness in processing is suppressed and texture is further excellent.

Formation of a film on the surface of polyester fibers is carried out, for example, by attaching a bifunctional vinyl monomer and a melamine component to a woven or knitted fabric containing polyester fibers and radically polymerizing them, as will be described later. Therefore, in the woven or knitted fabric of the present invention, as the mode of attachment of the coating to the surface of the polyester fiber, (i) the vinyl polymer and the melamine component are chemically bonded to the surface of the polyester fiber, and (ii) the vinyl polymer and the melamine component are attached to the surface of the polyester fiber without chemical bonding.

The woven or knitted fabric of the present invention can be obtained, for example, by contacting the surface of the polyester fiber with a bifunctional vinyl monomer for radical polymerization, followed by high-speed liquid flow treatment to remove residual monomers and excess polymer adhering between fibers. In this way, by applying a high-speed liquid flow treatment after radical polymerization of the bifunctional vinyl monomer, a film containing the bifunctional vinyl monomer and the melamine component is uniformly formed on each of the constituent fibers, and it is possible to suppress uneven processing and improve the texture while imparting stain resistance, antistatic properties, and water absorption excellent in durability to industrial washing. In addition, the excess polymer adhering between the monomers and fibers is removed, and the surface becomes more uniform, making it more difficult for dirt such as mud to adhere, resulting in a more excellent antifouling property. As an index of the state in which the coating is uniformly formed, for example, the KES value described below is within the preferred range of the present invention.

In the woven or knitted fabric of the present invention, a method for forming a film containing the vinyl polymer and the melamine component on the surface of the polyester fiber will be described in detail below.
First, a woven or knitted fabric woven using polyester fibers is prepared. The woven or knitted fabric may be subjected to processing such as desizing, presetting, dyeing, etc., if necessary, before the vinyl-based polymer and the melamine component are adhered thereto.

Next, the prepared woven or knitted fabric is brought into contact with a bifunctional vinyl-based monomer and a melamine component. In order to bring the bifunctional vinyl monomer into contact with the woven or knitted fabric, the woven or knitted fabric may be impregnated with a treatment liquid containing the bifunctional vinyl monomer and the melamine component.

The treatment liquid is an aqueous solution in which a bifunctional vinyl-based monomer, a melamine component, and, if necessary, an oxazoline compound are dispersed or dissolved.

The concentration of the bifunctional vinyl-based monomer in the treatment liquid can be appropriately set according to the amount of the vinyl-based polymer contained in the film, the conditions of radical polymerization, etc. In the present invention, it is 0.5 to 5% by mass, preferably 1 to 5% by mass. Within this range, unevenness in processing can be easily suppressed, the texture becomes better, and the antistatic properties and water absorbency are further improved.

The concentration of the melamine component in the treatment liquid is 0.5 to 10% by mass, preferably 1 to 8% by mass. Within this range, unevenness in processing can be easily suppressed, the texture is better, and the antifouling property against powder stains is even more excellent.

The treatment liquid preferably contains an oxazoline compound in addition to the bifunctional vinyl-based monomer and the melamine component. The concentration of the oxazoline compound in the treatment liquid is preferably 0.05 to 5% by mass, more preferably 0.07 to 3% by mass. Within this range, unevenness in processing can be easily suppressed, the texture becomes better, and the durability to industrial washing is further improved.

In addition, the treatment liquid may contain a polymerization initiator in order to promote radical polymerization of the bifunctional vinyl monomer. Examples of the polymerization initiator include inorganic polymerization initiators such as ammonium persulfate, potassium persulfate, cerium ammonium nitrate and hydrogen peroxide; radical initiators such as organic radical initiators such as 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2′-azobis(N,N′-dimethyleneisobutyramidine) dihydrochloride, and 2-(carbamoirazo)isobutyronitrile. These polymerization initiators may be used singly or in combination of two or more. The concentration of the polymerization initiator in the treatment liquid is not particularly limited, and may be appropriately set according to the type of polymerization initiator to be used.

Moreover, the treatment liquid may contain a polymerization inhibitor, if necessary. When a polymerization inhibitor is contained, polymerization in a low temperature range can be suppressed, making it 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 tert-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 singly or in combination of two or more. The concentration of the polymerization inhibitor in the treatment liquid is not particularly limited, and may be appropriately set according to the type of polymerization inhibitor to be used.

Further, the treatment liquid may contain a redox initiator composed 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 reaction products of sodium sulfoxylate and formalin, hydrosulfite, and the like.

The amount of the woven or knitted fabric to be impregnated with the treatment liquid may be appropriately set according to the concentration of the bifunctional vinyl monomer in the treatment liquid, the amount of the vinyl polymer contained in the coating, the conditions of radical polymerization, etc. For example, the treatment liquid is 20 to 150 parts by mass, preferably 30 to 120 parts by mass, more preferably 50 to 100 parts by mass per 100 parts by mass of the woven or knitted fabric.

The method of impregnating the woven or knitted fabric with the treatment liquid is not particularly limited, and a known method such as a padding method, a spray method, a kiss roll coater method, a slit coater method, or the like may be used as appropriate.

After the woven or knitted fabric is impregnated with the treatment liquid, the bifunctional vinyl-based monomer and the melamine component are radically polymerized.
To radically polymerize the bifunctional vinyl-based monomer and the melamine component, for example, wet heat treatment (saturated steam treatment), exhaustion treatment, electron beam treatment, ultraviolet treatment, microwave treatment, etc. may be performed. The radical polymerization conditions may be appropriately selected according to the type of treatment to be employed, the concentration of the bifunctional vinyl monomer or melamine component in the treatment liquid, the amount of the vinyl polymer or melamine component, etc. For example, in the case of wet heat treatment, the treatment may be performed in the presence of steam at 80 to 180 ° C., preferably 98 to 150 ° C. for 1 to 30 minutes, preferably 3 to 10 minutes.

After radical polymerization of the bifunctional vinyl monomer and the melamine component, the resulting woven or knitted fabric (woven or knitted fabric in which a film is formed on the surface of the polyester fiber) is subjected to washing by high-speed liquid flow treatment without being subjected to a drying step. By applying the high-speed liquid flow treatment in this way, the remaining monomers and the excess polymer attached between the fibers are appropriately removed, and a coating containing the vinyl polymer is uniformly formed on the surface of the polyester fiber. Contamination such as powder tends to remain in areas where the film is uneven, but the woven or knitted fabric of the present invention has excellent antifouling properties because the film is formed uniformly, and it is possible to suppress uneven processing while having excellent antistatic properties and water absorbency that are excellent in durability to industrial washing. In addition, such a high-speed liquid flow treatment suppresses the texture of the woven or knitted fabric from becoming hard, and makes it possible to set the range of the KES value described later within a preferable range. The drying step is a step of evaporating water, for example, a step of drying at room temperature or higher.

In the present invention, the high-speed liquid flow treatment is a washing treatment in which a woven or knitted fabric is exposed to a washing liquid jetted at high speed.

As a suitable high-speed liquid flow treatment, there is a liquid flow washing process in which a woven or knitted fabric is passed through a washing liquid jetted at a high speed. The high-speed liquid flow treatment of this aspect will be described in detail below.

In the high-speed liquid flow treatment, the washing liquid may be sprayed from one direction to the passing woven or knitted fabric, but it is preferable to spray the washing liquid from all directions to the passing woven or knitted fabric using a filament nozzle or spun nozzle used for jet dyeing or the like. By injecting the washing liquid from all directions to the passing woven or knitted fabric in this way, it is possible to more efficiently remove the remaining monomers. 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 to the woven or knitted fabric passing through the internal space of the filament nozzle. In addition, the span nozzle is configured by combining hollow truncated conical members in one to three stages, and is configured so that the cleaning liquid can be sprayed from the gaps between the members to the woven or knitted 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 woven or knitted fabric may be appropriately set according to the time of the high-speed liquid flow treatment, the temperature of the cleaning liquid, etc. However, 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 woven or knitted fabric. By spraying the cleaning liquid at such an angle, it is possible to apply sufficient pressure to the woven or knitted fabric, remove the remaining monomers and the excess polymer attached between the fibers to the desired extent, and achieve excellent stain resistance, antistatic properties, water absorption, suppression of processing unevenness, and good texture that are excellent in 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 woven or knitted fabric.

In the high-speed liquid flow treatment, the speed at which the woven or knitted fabric is passed through the washing liquid jetted at high speed is not particularly limited, but is, 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 woven or knitted fabric is moved in one direction by the pressure of the jetted washing liquid, so there is no need to provide any special means for passing the woven or knitted fabric through the jetted washing liquid at high speed.

In the high-speed liquid flow treatment, the conditions for injecting the cleaning liquid are not particularly limited. For example, if a filament nozzle is used, the nozzle diameter (the diameter of the internal space of the filament nozzle; the diameter of the cross section in the direction perpendicular to the passing direction of the woven or knitted fabric) is 70 to 130 mm, the clearance for injecting the cleaning liquid is 2 to 6 mm, and the nozzle pressure when spraying the cleaning liquid is 0.15 to 0.5 Mpa, preferably 0.15 to 0.4 Mpa, more preferably. The pressure may be set to 0.15 to 0.3 MPa, and the flow rate of the cleaning liquid during spraying may be set to 800 to 1500 l/min, preferably 900 to 1400 l/min, more preferably 1000 to 1300 l/min.

In addition, in the high-speed liquid flow treatment, the number of times the woven or knitted fabric is passed through the sprayed washing liquid may be appropriately set within a range that allows the remaining monomers to be removed to a desired extent, and is, for example, 3 to 60 times, preferably 5 to 50 times, and more preferably 10 to 40 times. Here, the number of times that the woven or knitted fabric is passed through the jetted cleaning liquid is the number of times that one portion of the woven or knitted fabric is passed through the jetted cleaning liquid by the high-speed liquid flow treatment.

The high-speed liquid flow treatment of the woven or knitted fabric is desirably performed by connecting the ends of the woven or knitted fabric to a rope shape and circulating the rope-shaped woven or knitted fabric so that the woven or knitted fabric repeatedly passes through the sprayed cleaning liquid.

The cleaning liquid used in the high-speed liquid flow treatment may be water, but may be an aqueous solution to which a surfactant is added as necessary in order to increase the efficiency of removing the remaining monomers.

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

An apparatus for high-speed liquid flow treatment is not particularly limited, but a liquid jet dyeing machine used for dyeing fabrics can be suitably used. The liquid jet dyeing machine has a dyeing tank in which the fabric is retained, a transfer pipe connecting both ends of the dyeing tank, and an injection nozzle provided at the tip of the transfer pipe for injecting the treatment liquid (washing liquid in the present invention). The fabric connected in an endless loop is moved from the outlet of the dyeing tank to the transfer pipe, transferred in the transfer pipe together with the treatment liquid, and circulated back to the dyeing tank. By using a jet dyeing machine in which the conditions such as the angle of the injection nozzle are adjusted within the above range, the high-speed jet treatment in the present invention can be performed efficiently. As described above, a filament nozzle, a spun nozzle, or the like may be used as the injection nozzle provided in the jet dyeing machine, but the filament nozzle is preferable.

The woven or knitted fabric of the present invention can be obtained by performing a drying treatment after the high-speed liquid flow treatment. Further, the woven or knitted fabric of the present invention after the drying treatment may be processed such as wrinkle smoothing, if necessary.

The properties of the woven or knitted fabric of the present invention will be described. In terms of characteristics, it is excellent in durability to industrial washing, and the conditions for industrial washing are as follows.
(Conditions for industrial washing)
In the JIS L 1096: 2010 F -2 law (medium -temperature washer method), the washing and drying operation is washed once under the temperature of 60 ° C., 300 minutes of time, and then the hot water washing is 40 ° C. Changed to a condition of temperature 60 ° C and 30 minutes, and a total of 5 cycles of the washing and drying operation.

[Characteristic]
(Friction electrification voltage)
The woven or knitted fabric of the present invention has antistatic properties with excellent industrial laundering durability. As a suitable example of the antistatic property of the woven or knitted fabric of the present invention, the frictional electrification voltage measured by the following test method after industrial washing by the above method is preferably 1000 V or less in all directions of the woven or knitted fabric, more preferably 50 to 900 V.

<Test method>
(Measurement condition of triboelectric charge voltage)
JIS L 1094: Measure the frictional electrified voltage of the woven and knitted fabric after industrial washing in an environment of 20 ° C. and 40% RH in accordance with B method (method for measuring electrification property of woven and knitted fabrics).

(water absorption)
The woven or knitted fabric of the present invention has excellent water absorbency and durability to industrial washing. Suitable examples of the water absorbency of the woven or knitted fabric of the present invention include a water absorbency of 10 seconds or less, more preferably 5 seconds or less, and particularly preferably 3 seconds or less as measured by the following test method after industrial washing by the above method.

<Test method>
(Conditions for measuring water absorption)
A test piece measuring 20 cm long and 20 cm wide is prepared from the woven or knitted fabric after industrial washing. It is measured on a test piece by the method specified in JIS L-1907:2010 "7.1.1 Dropping method".

(Anti-fouling)
In the present invention, the antifouling property measured by the following measurement method is grade 4 or higher.
(Conditions for measurement of antifouling property)
Four test pieces of 10 cm long and 10 cm wide are prepared from the sample after industrial washing, and the weight of the four test pieces is measured. JIS Z 8901 test powder 1 (type 8 Kanto loam layer) was weighed in an amount of 1/10 of the total weight of four test pieces, and placed in a standard bag No. 16 (polyethylene bag of length 480 mm × width 340 mm, thickness 0.03 mm) is put into the bag at the same time as the test piece, then about 8600 mL of air is injected with an air pump, the mouth is twisted, and the twisted tip is closed with adhesive tape.
The bag is set in the rotating box of an ICI type pilling tester and operated at a speed of 60 ±2 rotations per minute for 60 minutes. After the operation, hold the four corners of the test piece and flick the center of the back surface of the test piece five times with fingers to remove excess dirt.
When flicking with fingers, use two fingers, rotate the test piece 90 degrees each time flicking, and flick five times in total.
The soiled test piece was washed by the method specified in No. 103 of Appendix 1 of JIS L 0217 [Testing methods by symbol - Washing method (washing with water)], and dried in a tumbler at 60°C for 30 minutes. The color difference seen between the test piece before soiling and the test piece after washing is compared with the color difference of the staining gray scale specified in JIS L 0805 and judged. Judgment is represented by the average value of 4 test pieces.

(texture)
The woven or knitted fabric of the present invention has firmness, stiffness, and bulging texture. As a preferred example of the texture of the woven or knitted fabric of the present invention, the KES value measured by the test method described in the examples below after the above industrial washing is preferably in the following range. Further, when the film is formed more uniformly on the surface of the woven or knitted fabric, the KES value tends to satisfy the following range.

<Bending properties>
The B value (rigidity), for example, is preferably 0.0200 to 0.2000 gf·cm ² /cm in the case of woven fabric, and preferably 0.0020 to 0.0200 gf·cm ² /cm in the case of knitted fabric. The 2HB value (resilience) is, for example, preferably 0.040 to 0.100 gf·cm ² /cm for woven fabrics, and preferably 0.0100 to 0.050 gf·cm ² /cm for knitted fabrics. When the flexural properties are within the above range, the fabric is not too soft and the resilience is not impaired, and the fabric is not too hard and comfortable to wear.

<Shear properties>
The G value (rigidity), for example, is preferably 1.01 to 2.00 gf·cm/deg in the case of woven fabrics, and preferably 0.50 to 1.00 gf·cm/deg in the case of knitted fabrics. The 2HG value (shear angle 0.5° hysteresis) is preferably 0.5 to 1.0 gf/cm for woven fabrics, and preferably 0.50 to 2.00 gf/cm for knitted fabrics. The 2HG5 value (shear angle 5° hysteresis), for example, is preferably 4.5 to 9.0 gf/cm for woven fabrics, and preferably 1.5 to 4.0 gf/cm for knitted fabrics. When the shear property is within the above range, the recoverability is further excellent, and the wearing comfort is improved.

<Surface properties>
The MIU value (coefficient of friction) is, for example, preferably 0.100 to 0.200 in the case of woven fabrics, and preferably 0.100 to 0.200 in the case of knitted fabrics. The MMD value (fluctuation of coefficient of friction), for example, is preferably 0.0700 to 0.900 in the case of woven fabrics, and preferably 0.010 to 0.020 in the case of knitted fabrics. The SMD value (fluctuation of surface roughness) is preferably 9.5 to 9.9 μm for woven fabrics, and preferably 2.000 to 3.000 μm for knitted fabrics. When the surface properties are within the above range, the fabric is more comfortable to wear without being too rough, and the fabric is soft to the touch.

In order to keep the KES value within the above range, for example, the conditions during radical polymerization or the composition of the treatment liquid may be appropriately adjusted, the fixation rate of the bifunctional vinyl monomer, melamine component, and oxazoline compound may be adjusted, or high-speed liquid flow treatment may be performed under appropriate conditions.

[Use]
The woven or knitted fabric of the present invention is excellent in durability against industrial laundering, antifouling properties, particularly against powder stains such as mud stains, and is preferably used as a woven or knitted fabric for countermeasures against powder stains. Furthermore, since it also has water absorption and antistatic properties, it is suitably used as a material for clothing that requires antistatic and electrifying properties. For example, pants, shirts, work clothes, etc. in the field of sports and uniforms, work clothes used in fields such as medical equipment, medicine, electronic industry, precision equipment, food processing; research laboratories, medical institutions, care institutions, etc. White coats used in the field.

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

1. Measurement and test methods Measurements and evaluations in the following examples and comparative examples were carried out according to the following methods.
(1) Measurement of total fixation rate of bifunctional vinyl-based monomer, melamine component, and oxazoline compound For each fabric, the fixation rate (%) was determined according to the following formula.
Sticking rate (%) = {(W1-W0)/W0} x 100
W0: Weight per unit area of the woven or knitted fabric before treatment with the treatment liquid W1: Weight per unit area of the woven or knitted fabric obtained after treatment with the treatment liquid and high-speed liquid flow treatment

(2) Industrial washing method According to the F-2 method (medium temperature washer method) specified in JIS L 1096: 2010, after washing once at a temperature of 60 ° C. for 300 minutes, hot water washing was performed twice at a temperature of 40 ° C. for 50 minutes and a temperature of 40 ° C. for 100 minutes. These operations were regarded as one cycle, and a total of 5 cycles were performed.

(3) Measurement of antistatic properties According to the B method (frictional electrification measurement method) specified in JIS L 1094:2014 "Method for testing the electrification of woven and knitted fabrics", the triboelectrification voltage of each woven or knitted fabric after industrial washing was measured in an environment of 20 ° C. and 40% RH.

(4) Measurement of Water Absorption A test piece measuring 20 cm long and 20 cm wide was prepared from each woven or knitted fabric after industrial washing. The test piece was measured by the method specified in JIS L-1907:2010 "7.1.1 Dropping method".

(5) Texture A test piece measuring 20 cm long and 20 cm wide was prepared from each woven or knitted fabric after industrial washing. The KES method (Kawabata evaluation method) was used to measure bending stiffness, shear resistance, and surface properties. See below for details.
(bending stiffness)
Using KESFB2-A (manufactured by Kato Tech Co., Ltd.), bending rigidity (B) and bending hysteresis width were determined.
(shearability)
Using KESFB1-A (manufactured by Kato Tech Co., Ltd.), the shear property (G) per 1 cm width, the shear hysteresis width (2HG) at a shear angle of φ0.5°, and the shear hysteresis width (2HG5) at a shear angle of φ5° were determined.
(Surface properties)
Using KESFB4-A (manufactured by Kato Tech Co., Ltd.), the average coefficient of friction (MIU), the variation of the coefficient of friction (MMD), and the variation of the unevenness of the surface (SMD, unit: μm) were determined.

(6) Antifouling property Four test pieces of 10 cm long x 10 cm wide are prepared from the sample after industrial washing, and the weight of the four test pieces is measured. JIS Z 8901 test powder 1 (type 8 Kanto loam layer) was weighed in an amount of 1/10 of the total weight of four test pieces, and placed in a standard bag No. 16 (polyethylene bag of length 480 mm × width 340 mm, thickness 0.03 mm) is put into the bag at the same time as the test piece, then about 8600 mL of air is injected with an air pump, the mouth is twisted, and the twisted tip is closed with adhesive tape.
The bag is set in the rotating box of an ICI type pilling tester and operated at a speed of 60 ±2 rotations per minute for 60 minutes. After the operation, hold the four corners of the test piece and flick the center of the back surface of the test piece five times with fingers to remove excess dirt.
When flicking with fingers, use two fingers, rotate the test piece 90 degrees each time flicking, and flick five times in total.
The soiled test piece was washed by the method specified in No. 103 of Appendix 1 of JIS L 0217 [Testing methods by symbol - Washing method (washing with water)], and dried in a tumbler at 60°C for 30 minutes. The color difference seen between the test piece before soiling and the test piece after washing is compared with the color difference of the staining gray scale specified in JIS L 0805 and judged. Judgment is represented by the average value of 4 test pieces.

2. Fabric production ( Reference Example 1 )
A 2/2 twill fabric with a warp density of 108/2.54 cm and a weft density of 59/2.54 cm was woven using polyester false twist yarns with a total fineness of 167 decitex/72 filaments as the warp and warp. The resulting twill fabric was scouring by a conventional method and preset at 190° C. for 30 seconds with a tenter (manufactured by Ichikin Kogyo Co., Ltd.). Next, using a jet dyeing machine ("Circular MF", manufactured by Hisaka Seisakusho Co., Ltd.), the fabric was dyed according to the following dyeing recipe at a temperature of 130°C for 30 minutes to obtain a white twill fabric with a basis weight of 180 g/ ^m2 .
<Dyeing formula>
- Fluorescent dye 1%o. m. f
・Acetic acid (48%) 0.2cc/l
- Water balance In addition, the fluorescent dye used "Hakkol STR" (made by Showa Chemical Industry Co., Ltd.).

Next, this twill fabric was immersed in a treatment solution shown in recipe 1 below, squeezed with a mangle at a drawing ratio of 70% by mass, and saturated steam treatment was performed at 103° C. for 5 minutes with a J box steamer (manufactured by Kyoto Kikai Co., Ltd.) without being subjected to a drying process, to radically polymerize the bifunctional vinyl monomer.
<Prescription 1>
・Bifunctional vinyl monomer A 3% by mass
・Ammonium persulfate 0.3% by mass
・Aqueous solution containing 80% by mass of trimethylolmelamine 3% by mass
・Aqueous solution containing 40% by mass of oxazoline compound 0.3% by mass
Water remainder The bifunctional vinyl-based monomer A is polyethylene glycol dimethacrylate (a compound in which R ¹ and R ² are methyl groups, R ³ is an ethylene group, and n is 23 in the general formula (1)) (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the aqueous solution containing 80% by weight of trimethylol melamine was "Beckamin M-3" (manufactured by Miki Riken Kogyo Co., Ltd.). In addition, "Epocross WS500" (manufactured by Nippon Shokubai Co., Ltd.) was used as an aqueous solution containing 40% by mass of an oxazoline compound. The same applies to the following examples and comparative examples.

After that, a high-speed liquid flow treatment was performed. Specifically, the high-speed jet treatment is performed using a jet dyeing machine ("Circular MF", manufactured by Hisaka Seisakusho Co., Ltd.), equipped with a filament nozzle (nozzle diameter: 90 mm, cleaning liquid jetting gap: 4 mm) having a cleaning liquid injection angle of 40° (washing water injection angle with respect to the direction of movement of the fabric), using water as the washing water, nozzle pressure: 0.2 Mpa, flow rate during injection of the washing liquid: 1200 l/min, cloth speed: 300 m/min, bath ratio: 1. : 10. The fabric (length (50 m/reverse x 6 reversals = 300 m) was made into an endless rope and circulated at 60°C for 5 minutes.

Then, the fabric was dried in a drum dryer at 120°C for 2 minutes and set in a tenter at 160°C for 1 minute to obtain a woven fabric. In the resulting woven fabric, the total fixation rate of the vinyl polymer, melamine component and oxazoline compound was 2.4%.

( Reference example 2 )
A woven fabric was obtained under the same conditions as in Reference Example 1, except that the treatment liquid of Formulation 2 below, in which the oxazoline compound was removed from the treatment liquid of Formulation 1, was used. The resulting woven fabric had a total fixation rate of the vinyl polymer and melamine component of 2.3%.
<Prescription 2>
・Bifunctional vinyl monomer A 3% by mass
・Ammonium persulfate 0.3% by mass
・Aqueous solution containing 80% by mass of trimethylolmelamine 3% by mass
・Remaining water

(Example 3)
A woven fabric was obtained under the same conditions as in Reference Example 2, except that the treatment liquid of Formulation 3 below was used instead of the treatment liquid of Formulation 2 . In the obtained fabric, the total fixation rate of the vinyl polymer and melamine component was 3.0%.
<Prescription 3>
・Bifunctional vinyl monomer A 3% by mass
・Ammonium persulfate 0.4% by mass
・Aqueous solution containing 80% by mass of trimethylolmelamine 5% by mass
・Remaining water

(Example 4)
A woven fabric was obtained under the same conditions as in Reference Example 2, except that the treatment liquid of Formulation 4 below was used instead of the treatment liquid of Formulation 2 . In the resulting woven fabric, the total fixation rate of the vinyl polymer and melamine component was 3.6%.
<Prescription 4>
・Bifunctional vinyl monomer A 3% by mass
・Ammonium persulfate 0.5% by mass
・Aqueous solution containing 80% by mass of trimethylolmelamine 7% by mass
・Remaining water

(Example 5)
A woven fabric was obtained under the same conditions as in Reference Example 2, except that the treatment liquid of Formulation 5 below was used instead of the treatment liquid of Formulation 2 . The resulting woven fabric had a total fixation rate of the vinyl polymer and melamine component of 2.3%.
<Prescription 5>
・Bifunctional vinyl monomer A 2% by mass
・Ammonium persulfate 0.35% by mass
・Aqueous solution containing 80% by mass of trimethylolmelamine 5% by mass
・Remaining water

(Comparative example 1)
Under the same conditions as in Reference Example 2 , the woven fabric (that is, the woven fabric that has been dyed) was immersed in the treatment liquid shown in Formula 2, then squeezed with a mangle at a squeezing rate of 70% by mass, dried in a tenter at 120 ° C. for 2 minutes, and further set at 160 ° C. for 1 minute (that is, saturated steam treatment and high-speed liquid flow treatment were not performed) to obtain a woven fabric. In the resulting woven fabric, the total fixation rate of the vinyl polymer and melamine component was 3.7%.

(Comparative example 2)
A woven fabric was obtained under the same conditions as in Comparative Example 1, except that the treatment liquid of Formulation 6 below was used instead of the treatment liquid of Formulation 2. The resulting fabric had a total fixation rate of the melamine component of 1.4%.
<Prescription 6>
・Aqueous solution containing 80% by mass of trimethylolmelamine 3% by mass
・Ammonium persulfate 0.15% by mass
・Remaining water

(Comparative Example 3)
A woven fabric was obtained under the same conditions as in Reference Example 1 , except that the treatment liquid of Formulation 6 was used. The total fixation rate of the melamine component in the resulting fabric was 0.6%.

( Reference example 6 )
A woven fabric was obtained under the same conditions as in Reference Example 1 , except that the treatment liquid of Formulation 7 below was used. The resulting woven fabric had a total fixation rate of the vinyl polymer and the melamine component of 9.7%.
<Prescription 7>
・Bifunctional vinyl monomer A 10% by mass
・Ammonium persulfate 0.5% by mass
・Aqueous solution containing 80% by mass of trimethylolmelamine 10% by mass
・Remaining water

(Comparative Example 4)
A woven fabric was obtained under the same conditions as in Reference Example 1 , except that the treatment liquid of Formulation 8 below was used. The resulting woven fabric had a total fixation rate of the vinyl polymer of 1.0%.
<Prescription 8>
・Bifunctional vinyl monomer A 3% by mass
・Ammonium persulfate 0.15% by mass
・Remaining water

(Comparative Example 5)
A woven fabric was obtained under the same conditions as in Reference Example 2 except that it was subjected to a drying process at 120° C. for 2 minutes in a drum dryer before the high-speed liquid flow treatment. The resulting woven fabric had a total fixation rate of the vinyl polymer of 3.5%.

( Reference example 7 )
Polyester false-twisted yarn (yarn A) with a total fineness of 84 decitex/72 filaments, polyester false-twisted yarn (yarn B) with a total fineness of 75 denier/36 filaments, and nylon false-twisted yarn (thread C) with a total fineness of 78 decitex/24 filaments are used. A mock rody knitted fabric was knitted at a knitting density of 4 cm. The obtained knitted fabric was scouring by a conventional method, and then, using a liquid jet dyeing machine ("Circular MF", manufactured by Hisaka Seisakusho Co., Ltd.), it was dyed according to the following dyeing recipe under the conditions of a temperature of 130 ° C. and a time of 30 minutes to obtain a white knitted fabric with a basis weight of 170 g / m ² .
A knitted fabric was obtained under the same conditions as in Reference Example 1 , except that the above knitted fabric was used. In the resulting knitted fabric, the total fixation rate of the vinyl polymer, melamine component and oxazoline compound was 2.3%.

( Reference example 8 )
A knitted fabric was obtained in the same manner as in Reference Example 7 , except that Formulation 2 was used instead of Formulation 1 of Reference Example 7 . In the resulting knitted fabric, the total fixation rate of the vinyl polymer and melamine component was 2.3%.

(Example 9)
A knitted fabric was obtained in the same manner as in Reference Example 7 , except that Formulation 3 was used instead of Formulation 1 of Reference Example 7 . In the resulting knitted fabric, the total fixation rate of the vinyl polymer and melamine component was 3.1%.

(Comparative Example 6)
Under the same conditions as in Reference Example 7 , the knitted fabric (i.e., the knitted fabric that had undergone dyeing treatment) was immersed in the treatment liquid shown in Formulation 2, then squeezed with a mangle at a squeezing rate of 70% by mass, dried in a tenter at 120 ° C. for 2 minutes, and further set at 160 ° C. for 1 minute (that is, saturated steam treatment and high-speed liquid flow treatment were not performed) to obtain a knitted fabric. In the resulting knitted fabric, the total fixation rate of the vinyl polymer and melamine component was 3.8%.

(Comparative Example 7)
A knitted fabric was obtained in the same manner as in Comparative Example 6, except that prescription 3 was used instead of prescription 2. In the obtained knitted fabric, the total fixation rate of the vinyl polymer and the melamine component was 4.1%.

In Table 1 and the steps in Table 1, A indicates that immersion, saturated steam treatment (103°C x 5 minutes), high-speed cleaning treatment (60°C x 5 minutes), drying (120°C x 2 minutes), and setting (160°C x 1 minute) are performed in this order. B indicates that immersion, drying (120° C.×2 minutes), and setting (160° C.×1 minute) are performed in this order. C indicates that immersion, saturated steam treatment (103°C x 5 minutes), drying (120°C x 2 minutes), high speed cleaning treatment (60°C x 5 minutes), and setting (160°C x 1 minute) are performed in this order.

Evaluation results are shown in Tables 1 and 2. As a result, the woven fabrics of Examples 3 to 5 and the knitted fabric of Example 9 had an antifouling property after industrial washing of grade 4 or higher, had a good texture, and were excellent in water absorption and antistatic properties. In addition, in Example 6, the texture was inferior, but the other performances were sufficient for practical use. On the other hand, the woven fabric of Comparative Example 1 and the knitted fabrics of Comparative Examples 6 and 7 used a bifunctional vinyl-based monomer, but were not subjected to high-speed liquid flow treatment. Comparative Example 2 was inferior in antifouling properties and antistatic properties because it was not subjected to high-speed liquid flow treatment and did not use a bifunctional vinyl monomer. Comparative Example 3 was subjected to high-speed liquid flow treatment, but was inferior in antifouling properties and antistatic properties because it did not use a bifunctional vinyl-based monomer. Comparative Example 4 was inferior in antifouling properties because no melamine component was used. Comparative Example 5 was inferior in antifouling properties because the drying process was performed before the high-speed liquid flow treatment.

FIG. 1 is a photograph of the surface of the antifouling woven or knitted fabric obtained in Example 5, taken using an analytical scanning electron microscope (manufactured by JEOL Datum Co., Ltd.) (magnification: 100 times). As can be seen from FIG. 1, in Example 5, which is excellent in antifouling properties, antistatic properties, water absorbency, and has a good texture, it is clear that a film containing a vinyl polymer obtained by polymerizing a bifunctional vinyl monomer and a melamine component is uniformly formed in each of the constituent fibers. FIG. 2 is a photograph of the surface of the woven or knitted fabric obtained in Comparative Example 1, taken using an analytical scanning electron microscope (manufactured by JEOL Datum Co., Ltd.) (magnification: 100 times). As can be understood from FIG. 2, in Comparative Example 1, in which the high-speed liquid flow treatment was not applied, the antifouling property was poor, and the KES value did not satisfy the preferred range of the present invention, it is clear that there were multiple locations where the film containing the vinyl-based polymer polymerized with the bifunctional vinyl-based monomer was excessively adhered between the constituent fibers, or where fine granular polymer remained.

From the above results, by subjecting the polyester fiber to a high-speed liquid flow treatment after polymerizing a bifunctional vinyl monomer containing a polyoxyalkylene containing a melamine component, it has good firmness, stiffness, and bulging texture, and it has become clear that it is possible to provide excellent antifouling properties, antistatic properties, and water absorbency that are excellent in durability to industrial washing.

Claims (8)

A woven or knitted fabric containing polyester fibers,
On the surface of the polyester fiber, a coating containing a vinyl polymer obtained by polymerizing a bifunctional vinyl monomer containing polyoxyalkylene and a melamine component is included, and the bifunctional vinyl monomer does not contain a fluoroalkyl group,
Further, the vinyl polymer obtained by polymerizing 100 parts by mass of the difunctional vinyl monomer contains 133 to 250 parts by mass of the melamine component, and after industrial washing under the following conditions, the stain resistance according to the following measurement method is grade 4 or higher ,
The B value (rigidity) measured by the KES method is 0.020 to 0.2000 gf·cm ² /cm for woven fabrics and 0.0020 to 0.0200 gf·cm ² /cm for knitted fabrics, and
A soil-resistant woven or knitted fabric having a 2HG5 value (shear angle 5° hysteresis) measured by the KES method of 4.5 to 9.0 gf/cm in the case of a woven fabric and 1.5 to 4.0 gf/cm in the case of a knitted fabric.
(Industrial washing conditions)
In the JIS L 1096: 2010 F -2 law (medium -temperature washer method), the washing and drying operation is washed once under the temperature of 60 ° C., 300 minutes of time, and then the hot water washing is 40 ° C. Changed to a condition of temperature 60 ° C and 30 minutes, and a total of 5 cycles of the washing and drying operation.
(Conditions for measurement of antifouling property)
Four test pieces of 10 cm long and 10 cm wide are prepared from the sample after industrial washing, and the weight of the four test pieces is measured. JIS Z 8901 test powder 1 (type 8 Kanto loam layer) was weighed in an amount of 1/10 of the total weight of four test pieces, and placed in a standard bag No. 16 (polyethylene bag of length 480 mm × width 340 mm, thickness 0.03 mm) is put into the bag at the same time as the test piece, then about 8600 mL of air is injected with an air pump, the mouth is twisted, and the twisted tip is closed with adhesive tape.
The bag is set in the rotating box of an ICI type pilling tester and operated at a speed of 60 ±2 rotations per minute for 60 minutes. After the operation, hold the four corners of the test piece and flick the center of the back surface of the test piece five times with fingers to remove excess dirt.
When flicking with fingers, use two fingers, rotate the test piece 90 degrees each time flicking, and flick five times in total.
The soiled test piece was washed by the method specified in No. 103 of Appendix 1 of JIS L 0217 [Testing methods by symbol - Washing method (washing with water)], and dried in a tumbler at 60°C for 30 minutes.
The color difference seen between the test piece before soiling and the test piece after washing is compared with the color difference of the staining gray scale specified in JIS L 0805 and judged. Judgment is represented by the average value of 4 test pieces. The antifouling woven or knitted fabric according to claim 1, wherein 0.5 to 5 parts by mass of the vinyl-based polymer obtained by polymerizing the bifunctional vinyl-based monomer is contained per 100 parts by mass of the total amount of constituent fibers of the woven or knitted fabric. The antifouling woven or knitted fabric according to claim 1 or 2 , characterized in that 1 to 20 parts by mass of an oxazoline compound is contained with respect to 100 parts by mass of the vinyl-based polymer polymerized with the bifunctional vinyl-based monomer. The stain-resistant woven or knitted fabric according to any one of claims 1 to 3 , wherein the total fixation rate of the vinyl-based polymer obtained by polymerizing the bifunctional vinyl-based monomer, the melamine component, and the oxazoline compound is 1.0 to 5.0% by mass with respect to the total amount of the constituent fibers of the woven or knitted fabric. The antifouling woven or knitted fabric according to any one of claims 1 to 4 , wherein the frictional electrification voltage is 1000 V or less after industrial washing under the above conditions.
(Measurement condition of triboelectric charge voltage)
JIS L 1094: 2014 "Method for testing the electrification property of woven and knitted fabrics" conforms to Method B (triboelectric charging method), and measures the triboelectric charging voltage of the fabric after industrial washing in an environment of 20 ° C. and 40% RH. The antifouling woven or knitted fabric according to any one of claims 1 to 5 , characterized in that the water absorption is 10 seconds or less after industrial washing under the above conditions.
(Conditions for measuring water absorption)
A test piece with a length of 20 cm and a width of 20 cm is prepared, and the measurement is performed on this test piece according to the method specified in JIS L-1907:2010 "7.1.1 Drop method". A woven or knitted fabric containing polyester fibers is brought into contact with a treatment liquid containing 0.5 to 5% by mass of a difunctional vinyl monomer and 0.5 to 10% by mass of a melamine component, and after performing a step of radical polymerization, the method for producing an antifouling woven or knitted fabric according to any one of claims 1 to 6 , wherein a hot water washing step is performed by high-speed liquid flow treatment without being subjected to a drying step. 8. The method for producing an antifouling woven or knitted fabric according to claim 7 , wherein the treatment liquid further contains 0.05 to 5% by mass of an oxazoline compound.