JP7313802B2 - Antifouling fabric and manufacturing method thereof - Google Patents

Description

The present invention relates to stain resistant fabrics and methods of making the same.

Polyester fibers are excellent in terms of strength, easy care, drying speed, color fastness, etc., and are also excellent in workability, so they are used in a wide range of applications such as uniforms and sports applications. However, polyester fibers are less hydrophilic than cellulose fibers such as cotton. Therefore, there is a problem that it is easily soiled, and various studies have been made to improve the antifouling property of fabrics made of polyester fibers (hereinafter sometimes referred to as "polyester fiber fabrics").

Techniques such as the following (1) to (3) have been studied as techniques for improving the antifouling property of polyester fiber fabrics. That is, (1) the polyester fiber fabric is subjected to SG (Solid Guard) processing that makes it difficult for dirt to adhere, (2) the polyester fiber fabric is subjected to SR (Solid Release) processing that enables easy removal of dirt by washing even when dirt adheres, (3) the polyester fiber fabric is difficult to adhere to dirt, and even if dirt adheres, the dirt can be easily removed by washing. SGR (Solid Guard Release) processing that can be removed is being studied. Among these techniques for improving antifouling properties, imparting SGR properties is a technique that is particularly excellent in antifouling properties, and has therefore been studied in various fields.

As a fabric to which the above technique (1) is applied, for example, Patent Document 1 proposes a water-repellent and stain-resistant fabric obtained by treating a synthetic fiber fabric with a water and oil repellent agent containing 50% by mass or more of fluorine, and then further treating the surface of the fabric with a polymer compound having a fluorine atom bonded to the carbon of the main chain and having a fluorine content of more than 20% by mass and less than 50% by mass.

As a fabric to which the technique (2) is applied, Patent Document 2 proposes an antifouling polyester fiber fabric in which a block copolymer obtained by copolymerizing polyalkylene glycol, an aromatic dicarboxylic acid, and an alkylene glycol, a modified organosilicate, and an aminoplast resin are attached to the surface of a polyester fiber fabric.

Furthermore, as a fabric to which the above technique (3) is applied, Patent Document 3 proposes a fiber structure in which a resin film containing a triazine ring is formed on the fiber surface, or a resin film containing a fluorine-based water- and oil-repellent resin and a triazine ring is formed, and the film surface is coated with a resin composed of a fluorine-based water- and oil-repellent resin having a hydrophilic component and a non-hydrophilic fluorine-based water- and oil-repellent resin. Furthermore, as a fabric to which the above technique (3) is applied, Patent Document 4 proposes an antifouling synthetic fiber fabric in which an antifouling coating layer containing a fluorine-based water and oil repellent agent having a hydrophilic segment, a non-hydrophilic fluorine-based water and oil repellent agent, and a cross-linking agent is formed on a synthetic fiber fabric.

JP-A-3-234870 JP-A-9-268472 JP 2008-303511 A JP-A-10-317281

However, the fabric disclosed in Patent Literature 1 has a problem that once dirt adheres to the fabric, it cannot be easily removed by washing. In addition, the fabric disclosed in Patent Document 2 has a problem that the removability of adhering stains by washing is insufficient.

The fabrics disclosed in Patent Documents 3 and 4 have a problem that the water- and oil-repellent layer having hydrophilic groups and non-hydrophilicity adheres insufficiently to the fiber surface. Therefore, it is not possible to suppress the deterioration of antifouling property after washing, that is, the present situation is that sufficient SGR property is not obtained.

An object of the present invention is to solve the above-described drawbacks of the prior art, and to provide an antifouling fabric that can suppress the deterioration of antifouling properties after washing (that is, has antifouling properties with excellent washing resistance).

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 (5).
(1) On the surface of a fabric made of polyester fiber, a coating made of a resin composition containing a fluorine-based water repellent agent having a hydrophilic segment and a hydrophilic polymer obtained by polymerizing a hydrophilic monomer ,
The mass ratio of the solid content of the fluorine-based water repellent agent to the hydrophilic polymer in the coating is (solid content of the fluorine-based water repellent agent)/(hydrophilic polymer) = 1/5 to 1/30,
The coating contains trimethylolmelamine,
Washed 30 times according to the F-2 method of JIS L 1096, and the dirt removal grade after drying is grade 3 or higher,
An antifouling fabric characterized by having a water absorbency of 110 seconds or less according to the JIS L1907 dropping method.
(2) The antifouling fabric according to (1), wherein the total amount of the solid content of the fluorine-based water repellent and the adhesion amount of the hydrophilic polymer is 0.5 to 10% by mass with respect to the mass of the fabric made of the polyester fiber.
(3) The antifouling fabric according to any one of (1) or (2), wherein the hydrophilic polymer is a polymer mainly composed of a bifunctional vinyl-based monomer as a structural unit.
(4) A method for producing the antifouling fabric according to (1) to (3),
After contacting the surface of the fabric made of polyester fiber with an aqueous solution containing a fluorine-based water repellent agent having a hydrophilic segment, a hydrophilic monomer, trimethylol melamine, and a polymerization initiator, steam heat treatment is performed, followed by washing with a high-speed liquid flow treatment with a liquid jet dyeing machine.
The high-speed liquid flow treatment is
a dyeing tank in which the fabric is retained;
a transfer pipe connecting both ends of the dyeing tank;
A method for producing an antifouling fabric using a jet dyeing machine having a filament nozzle that is provided at the tip of the transfer pipe and that sprays the washing liquid from all directions onto the passing woven or knitted fabric, and the fabric connected in an endless loop is transferred from the outlet of the dyeing tank to the transfer pipe, transferred in the transfer pipe together with the washing liquid, and returned to the dyeing tank dyeing tank.
(5) The method for producing an antifouling fabric according to (4), wherein the mass ratio of the solid content of the fluorine-based water repellent agent to the hydrophilic monomer in the aqueous solution is (solid content of the fluorine-based water repellent agent)/(hydrophilic monomer) = 1/5 to 1/30.

Since the antifouling fabric of the present invention includes a film containing a fluorine-based water repellent agent having a hydrophilic segment and a hydrophilic polymer, it is possible to achieve antifouling properties remarkably excellent in washing durability. The antifouling fabric of the present invention is particularly effective because it can achieve antifouling properties that are remarkably excellent in washing durability against lipstick stains, food oil stains, and machine oil stains.

In addition, in the method for producing the stain-resistant fabric of the present invention, after the steam heat treatment is performed using the polymerization initiator, the fabric is washed with a jet dyeing machine. Therefore, it is possible to produce not only the stain-resistant washing durability but also the stain-resistant fabric excellent in fastness. In addition, since the excess water repellent agent is removed, it is possible to produce a stain resistant fabric with even better water absorption.

The present invention will be described in detail below.
The antifouling fabric of the present invention includes a coating containing a fluorine-based water repellent agent having a hydrophilic segment and a hydrophilic polymer on the surface of a fabric made of polyester fiber (herein sometimes referred to as "polyester fiber fabric"). The hydrophilic polymer in the coating is obtained by polymerizing a hydrophilic monomer on the polyester fiber surface. By having such a configuration, the antifouling fabric of the present invention satisfies antifouling properties with excellent washing durability.

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, more preferably 80% by mass or more, of polyester fiber in the fabric. In addition, the fineness of the polyester fiber, the number of filaments, etc. are not particularly limited, and can be appropriately selected according to the application.

In the present invention, the above 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;

These fibers other than polyester fibers are mixed, mixed, mixed, mixed, woven or knitted with polyester fibers and contained in the fabric. The form of the polyester fiber fabric is not particularly limited, and examples thereof include woven fabrics, knitted fabrics, and non-woven fabrics.

As described above, the antifouling fabric of the present invention has the following effects by including a film containing a fluorine-based water repellent agent having a hydrophilic segment and a hydrophilic polymer on the surface of the polyester fiber fabric. That is, the hydrophilic polymer is obtained by polymerizing a hydrophilic monomer on the surface of the polyester fiber. It is presumed that the hydrophilic polymer is imparted to the fiber as a polymer by adding the fluorine-based water repellent in the polymerization stage of the hydrophilic monomer and polymerizing the hydrophilic monomer, and the fluorine-based water repellent contained in the film is incorporated into the network of the hydrophilic polymer. In the coating, the hydrophobic groups of the fluorine-based water repellent contained in the coating are oriented perpendicularly to the polyester fibers, whereas the hydrophilic groups of the fluorine-based water repellent are thought to be directed toward the polyester fibers. That is, it is considered that the coating structure has a form as if the hydrophobic groups were partially arranged in the direction perpendicular to the fibers in the hydrophilic coating.

Owing to such a structure, the stain-resistant fabric of the present invention can achieve stain-resistant properties remarkably excellent in washing durability. Specifically, the fluorine-based water repellent adheres more firmly to the polyester fiber fabric, and since the hydrophobic group covers the surface, dirt cannot penetrate into the interior of the fiber, and even if the fabric is washed repeatedly, the fluorine-based water repellent does not separate from the fabric. In addition, since the hydrophilic polymer swells and covers the surface during washing, dirt can be lifted and removed, so that the dirt removal property is also excellent. If the hydrophilic monomer is not polymerized on the surface of the polyester fiber, the film is simply coated on the surface of the polyester fiber fabric, and antifouling properties with excellent washing durability cannot be achieved. In addition, even when the hydrophilic polymer and the fluorine-based water repellent are simply mixed, the film structure described above (hydrophobic groups are partially arranged in the hydrophilic film in the direction perpendicular to the fiber) is not obtained, so it is not possible to achieve excellent antifouling properties with excellent washing durability.

A fluorine-based water repellent having a hydrophilic segment includes a copolymer obtained by copolymerizing a hydrophilic segment and a fluorinated hydrophobic segment. If a water repellent other than a fluorine-based water repellent is used, the water repellency is poor, so the antifouling property is lowered, and the effect of the present invention, that is, the antifouling property having excellent durability cannot be obtained.

The hydrophilic segment is obtained by modifying ethylenically unsaturated substances such as acrylate, methacrylate, vinyl acetate, and vinyl chloride, and introducing hydrophilic groups such as ethylene oxide, hydroxyl groups, carboxyl groups, and sulfonic acid groups into these modified products. Among them, a hydrophilic segment obtained by reacting hydrogen sulfide and polyethylene glycol dimethacrylate is preferable from the viewpoint of improving the stain removability and excellent antifouling property.

Moreover, as the fluorinated hydrophobic segment, a fluoroalkyl acrylate containing a perfluoroalkyl group is preferable from the viewpoint of preventing adhesion of dirt and having excellent antifouling properties.

Specifically, copolymers represented by the following formula (1) are preferred. This is a copolymer obtained by copolymerizing a hydrophilic segment obtained by reacting hydrogen sulfide with polyethylene glycol dimethacrylate and a fluoroalkyl acrylate as a fluorinated hydrophobic segment.

In the above formula, n is preferably an integer of 2-10, a is preferably an integer of 1-10, and b is preferably an integer of 1-10. R represents a lower alkyl group, preferably an alkyl group having 1 to 3 carbon atoms. Rf represents a perfluoroalkyl group, preferably a perfluoroalkyl group having 4 to 10 carbon atoms, more preferably 4 to 6 carbon atoms from the viewpoint of the natural environment.

The above water repellent agent may contain a component other than a copolymer obtained by copolymerizing a hydrophilic segment and a fluorinated hydrophobic segment.

Commercially available products can be suitably used as such a fluorine-based water repellent, and specific examples include Ohara Palladium Chemical Co., Ltd., trade name "Paraguard SRF6000" (solid content: 20% by mass). "Paraguard SRF6000" is a fluorine-based water repellent in which Rf is a perfluoroalkyl group having 6 carbon atoms in the above formula (1).

Hydrophilic polymers are polymers containing hydrophilic monomers as constituents. By using a hydrophilic polymer, it is possible to achieve the effect of easily removing stains by washing.

Examples of hydrophilic monomers constituting the hydrophilic polymer include alkylene oxide-containing acrylates, alkylene oxide-containing methacrylates, alkylene oxide-containing epoxy acrylates, and alkylene oxide-containing epoxy methacrylates.

Among the above hydrophilic monomers, bifunctional vinyl monomers are preferred from the viewpoint of reactivity with polyester fiber fabrics, and diacrylate monomers containing alkylene oxide and/or dimethacrylate monomers containing alkylene oxide are particularly preferred.

Specific examples of such hydrophilic monomers include polyethylene glycol diacrylate represented by the following formula (2), polyethylene glycol dimethacrylate represented by the following formula (3), and the like.

In the above formula (2), n is preferably an integer of 1 to 30, more preferably 10 to 25, and even more preferably an integer of 14 to 23, from the viewpoint of easy removal of stains and excellent antifouling properties.

In the above formula (3), n is preferably an integer of 1 to 30, more preferably 10 to 25, and even more preferably an integer of 14 to 23, from the viewpoint of easy removal of stains and excellent antifouling properties.

In the amount of use containing a fluorine-based water repellent having a hydrophilic segment and a hydrophilic polymer, the mass ratio of the solid content of the fluorine-based water repellent having a hydrophilic segment and the hydrophilic polymer is (fluorine-based water repellent) / (hydrophilic polymer) = 1/1 to 1/30, more preferably 1/5 to 1/30, more preferably 1/10 to 1/30, particularly preferably 1/15 to 1/25 from the viewpoint of water absorption.

When the solid content of the fluorine-based water repellent agent having a hydrophilic segment and the mass ratio of the hydrophilic polymer are within the above range, the water repellent segment does not become too dominant, and the water absorbability is further improved, and the stain adhesion prevention property (stain resistance) is further improved.

The total amount of the solid content of the fluorine-based water repellent and the adhesion amount of the hydrophilic polymer is preferably 0.5 to 10% by mass, preferably 1.0 to 5.0% by mass, more preferably 2.0 to 3.0% by mass, relative to the mass of the fabric made of the polyester fiber. When the solid content of the fluorine-based water repellent and the adherence amount of the hydrophilic polymer are within the above ranges, the balance between the antifouling property and the water absorbency is further improved, and the processing cost and color fastness are further improved.

Moreover, in the present invention, the film may contain a melamine resin, if necessary. The melamine resin may be a thermosetting resin obtained by condensing a compound containing a triazine ring and having at least two polymerizable functional groups, and specific examples thereof include trimethylolmelamine and hexamethylolmelamine. Examples of the melamine resin include trimethylol melamine such as "Riken Resin MM-3C", "Riken Resin MM-35" (manufactured by Miki Riken Kogyo Co., Ltd.), "Beckamine M-3" (manufactured by DIC Kitanihon Polymer Co., Ltd.); Commercially available products such as methylolmelamine can be used.

The method for producing the antifouling fabric of the present invention will be described below.
In the production method of the present invention, the surface of a fabric made of polyester fiber is brought into contact with an aqueous solution containing a fluorine-based water repellent agent having a hydrophilic segment, a hydrophilic monomer, and a polymerization initiator, followed by steam heating treatment, and then washing treatment with a jet dyeing machine.

Before attaching the hydrophilic monomer, the fabric made of polyester fiber may be subjected to processing such as desizing, presetting, dyeing, etc., if necessary.

The aqueous medium in which the hydrophilic segment-containing fluorine-based water repellent and the hydrophilic monomer are dissolved is not particularly limited, and examples thereof include water and mixtures of water and known organic solvents.

In the present invention, a polymerization initiator may be used to promote radical polymerization of hydrophilic monomers. 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 aqueous solution is not particularly limited, and may be appropriately set according to the type of polymerization initiator to be used.

In the aqueous solution, the mass ratio of the solid content of the fluorine-based water repellent agent to the hydrophilic monomer is preferably (solid content of the fluorine-based water repellent agent)/(hydrophilic monomer) = 1/1 to 1/30, more preferably 1/5 to 1/30, further preferably 1/10 to 1/30, and particularly preferably 1/15 to 1/25. When the mass ratio is within this range, the balance between water absorption and antifouling properties is even more excellent.

Moreover, the aqueous solution may contain a polymerization inhibitor. 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 aqueous solution is not particularly limited, and may be appropriately set according to the type of polymerization inhibitor to be used.

Furthermore, the aqueous solution may, if necessary, contain a redox initiator consisting of a peroxide and a reducing substance in order to increase the efficiency of polymerization. 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 method of bringing the aqueous solution into contact with the polyester fiber fabric and imparting 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 impregnated with the aqueous solution, a steam heat treatment is performed to polymerize the hydrophilic monomer. That is, so-called radical polymerization proceeds. The steam heat treatment temperature is 80 to 180° C., preferably 98 to 150° C., in the presence of steam for 1 to 30 minutes, preferably 3 to 15 minutes. In order to further improve the polymerization efficiency, it is preferable not to perform the drying step before the steam heat treatment. In addition to steam heat treatment, methods of polymerization include exhaust treatment, electron beam treatment, ultraviolet treatment, microwave treatment, etc. In the present invention, steam heat treatment is essential from the viewpoint of versatility of equipment and production efficiency (polymerization efficiency).

In the present invention, after the radical polymerization of the hydrophilic monomer, the resulting fabric (fabric in which the vinyl-based polymer is attached to the surface of the polyester-based fiber) is subjected to washing by high-speed liquid flow treatment. By applying the high-speed liquid flow treatment in this way, the remaining monomers and excess water repellent adhering between fibers are appropriately removed, and a coating containing a hydrophilic polymer and a fluorine-based water repellent having a hydrophilic segment is uniformly formed on the surface of each of the constituent fibers on the surface of the polyester fiber. As a result, in the stain resistant fabric of the present invention, it is possible to suppress processing unevenness while providing excellent stain removability without making the fiber surface hydrophobic. In addition, such a high-speed liquid flow treatment suppresses the stain resistant fabric from becoming hard and further suppresses discoloration and deterioration of color fastness due to elution of the remaining monomer.

In the present invention, the high-speed liquid flow treatment is a washing treatment in which the 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 the cloth 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 on the passing fabric, but it is preferable to spray the washing liquid from all directions on the passing fabric using a filament nozzle or spun nozzle used for jet dyeing or the like. By spraying the washing liquid from all directions onto the passing fabric in this way, it is possible to more efficiently remove the remaining monomer. 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 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 fabric passing through the internal space of the span nozzle.

In the high-speed liquid flow treatment, the angle at which the cleaning liquid is sprayed onto the 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 fabric. By spraying the cleaning liquid at such an angle, it is possible to apply sufficient pressure to the fabric, remove the remaining monomer and excess polymer attached between the fibers to the desired extent, and achieve excellent antistatic properties and water absorption, suppression of uneven processing, and good texture. 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 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 cloth is moved in one direction by the pressure of the sprayed cleaning liquid, so there is no need to provide any special means for passing the cleaning liquid sprayed at high speed through the cloth.

In the high-speed liquid flow treatment, the conditions for spraying the cleaning liquid are not particularly limited. For example, in the case of using a filament nozzle, the nozzle diameter (the diameter of the internal space of the filament nozzle; the diameter of the cross section perpendicular to the passing direction of the fabric) is 70 to 130 mm and the gap for spraying 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 fabric is passed through the sprayed cleaning liquid may be appropriately set within a range in which the remaining monomer can be removed to the desired extent. Here, the number of times the cloth is passed through the jetted cleaning liquid is the number of times the jetted cleaning liquid is passed through one portion of the fabric by the high-speed liquid flow treatment.

The high-speed liquid flow treatment of the fabric is preferably performed by connecting the ends of the fabric into a rope shape and circulating the rope-shaped 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 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.

After the high-speed liquid flow treatment, dry heat treatment is performed to obtain the antifouling fabric of the present invention. The dry heat treatment is preferably performed at a temperature of 130 to 190°C, preferably 150 to 170°C. If the temperature is less than 130°C, the hydrophobic groups such as perfluoroalkyl groups cannot be sufficiently arranged in the direction perpendicular to the fiber as described above, and as a result, the improvement in water repellency is insufficient, so that stains easily adhere, and the antifouling property may be inferior. On the other hand, when the temperature exceeds 190° C., the film is deteriorated by heat, and the stain removability by washing or the like is lowered, and the antifouling property may be inferior.

The antifouling fabric obtained as described above has antifouling properties against oily stains, lipstick, foundation, etc., and even when washed, the deterioration of antifouling properties is remarkably suppressed (that is, it has antifouling properties with excellent washing durability).

In addition, by subjecting the fabric to the high-speed liquid flow treatment, excess fluorine-based water repellent can be removed, and since the fabric surface is not completely covered with the fluorine-based water repellent, it is easier to exhibit appropriate water absorption and is excellent in wearing comfort.

The antifouling fabric of the present invention, for example, white coats of hospitals, factory work clothes and kitchen clothes represented by food factory uniforms, women's blouses such as office shirts and blouses, work clothes such as cleaning staff, golf shirts, sports shirts, etc. Can be particularly suitably used in the field of sportswear in general.

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. Samples As samples to be subjected to measurement, according to the F-2 method of JIS L 1096, two types were prepared: one that was washed 30 times (hereinafter sometimes referred to as "after washing 30 times") and the one before the washing (hereinafter sometimes referred to as "after processing"). These two types of samples were evaluated.

2. Stain Removability Test 2-1. Stain Removability for Lipstick A 10 cm x 10 cm sample was taken. A circle with a diameter of 1.5 cm was drawn on the surface of the polyethylene film, and 0.03 g of lipstick (manufactured by Kanebo Cosmetics Co., Ltd.) was evenly applied in the circle. A rubber block (diameter: 24 mm, mass: 26.4 g) was placed on the lipstick-applied film surface and pressed with a finger for 10 seconds with a pressure of 7 kg. After that, the fabric was washed once according to JIS L 0217, Method 103, dried, and then the degree of staining was determined using a staining gray scale.
Those rated at grade 3 or higher were judged to be suitable for practical use.

2-2. Stain Removability Against Food Oil A sample measuring 5 cm long and 5 cm wide was taken. Then, 0.4 μL of food oil was weighed out with a micropipette, adhered to the center of the sample, and left for 24 hours. After that, the fabric was washed once according to JIS L 0217, Method 103, dried, and then the degree of staining was determined using a staining gray scale.
Those rated at grade 3 or higher were judged to be suitable for practical use.

2-3 Stain Removability by Grease A sample measuring 9 cm long and 9 cm wide was taken. Also, a contamination source was prepared by kneading a Kanto loam layer in an amount of 5% by mass with respect to the mass of the grease. Then, after weighing out 0.1 g of the contamination source, spread it over the sample with the pad of your finger. After leaving it for 2 hours, it was washed once with the home washing method 103 (bath ratio 1:100), dried, and then the degree of staining was judged by the staining gray scale.
Those rated at grade 3 or higher were judged to be suitable for practical use.

3. Water absorption A test piece measuring 20 cm long and 20 cm wide was taken. The test piece was measured by the method specified in JIS L-1907:2010, "7.1.1 Dropping method".

4. Adhesion Amount For the fabrics obtained in Examples and Comparative Examples, the adhesion rate (%) of the solid content of the fluorine-based water repellent and the adhesion amount of the hydrophilic polymer was determined according to the following equations.
Adhesion rate (%) = {(W1-W0)/W0} x 100
W0: Mass per unit area of fabric before treatment with aqueous solution W1: Mass per unit area of fabric obtained by treatment with aqueous solution and high-speed liquid flow treatment

Examples 1 to 3, Reference Example 4, Comparative Example 1
A twill fabric (warp density: 128/2.54 cm, weft density: 58/2.54 cm, basis weight: 200 g/cm ² ) was woven using polyester multifilament textured yarn (167 dtex/48f) as the warp and polyester multifilament textured yarn (334 dtex/96f) as the weft. This 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, after immersing this twill fabric in an aqueous solution having the composition shown in Table 1, it was 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 drying, to radically polymerize the hydrophilic monomer. In addition, in the composition of the aqueous solution shown in Table 1, the remainder is water.

The hydrophilic monomer used was polyethylene glycol dimethacrylate (a compound in which R1 and R2 are methyl groups, R3 is an ethylene group, and n is 23 in the above general formula (1)) (manufactured by Shin-Nakamura Chemical Co., Ltd.). As the melamine resin, an aqueous solution containing 80% by weight of trimethylolmelamine "Beckamine M-3" (manufactured by Miki Riken Kogyo Co., Ltd.) was used. As the fluorine-based water repellent, the trade name "Paraguard SRF6000" (solid content: 20% by mass) manufactured by Ohara Palladium Chemical Co., Ltd. was used. As an oxazoline compound, an aqueous solution containing 40% by mass of an oxazoline compound "Epocross WS500" (manufactured by Nippon Shokubai Co., Ltd.) was used.

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/roll x 6 rolls = 300 m) was circulated in the form of an endless rope at a temperature of 60°C for 5 minutes.

Then, it was dried in a drum dryer at 120°C for 2 minutes and set in a tenter at 170°C for 1 minute to obtain fabrics of Examples 1 to 3, Reference Example 4, and Comparative Example 1.

Table 1 shows the performance evaluation results of the fabrics obtained in Examples and Comparative Examples.

As is clear from Table 1, the antifouling fabrics of Examples 1 to 3 were excellent in antifouling properties. In addition, it was also excellent in antifouling property after washing 30 times, that is, it was excellent in washing durability. Furthermore, it was excellent also in water absorption. In Examples 1 to 3, since the mass ratio of the hydrophilic polymer to the solid content of the water repellent agent is preferable, the balance between water repellency and water absorbency is remarkably excellent, and not only the antifouling property but also the water absorbency is excellent. Since Comparative Example 1 did not use a fluorine-based water repellent agent, it was inferior not only in the antifouling property after washing but also in the initial antifouling property.

Claims (5)

On the surface of a fabric made of polyester fiber, a coating made of a resin composition containing a fluorine-based water repellent agent having a hydrophilic segment and a hydrophilic polymer obtained by polymerizing a hydrophilic monomer ,
The mass ratio of the solid content of the fluorine-based water repellent agent to the hydrophilic polymer in the coating is (solid content of the fluorine-based water repellent agent)/(hydrophilic polymer) = 1/5 to 1/30,
The coating contains trimethylolmelamine,
Washed 30 times according to the F-2 method of JIS L 1096, and the dirt removal grade after drying is grade 3 or higher,
An antifouling fabric characterized by having a water absorbency of 110 seconds or less according to the JIS L1907 dropping method. The antifouling fabric according to claim 1, wherein the total amount of the solid content of the fluorine-based water repellent and the adhesion amount of the hydrophilic polymer is 0.5 to 10% by mass with respect to the mass of the fabric made of the polyester fiber. The antifouling fabric according to claim 1 or 2, wherein the hydrophilic polymer is a polymer mainly composed of a bifunctional vinyl-based monomer as a structural unit. A method for producing the antifouling fabric according to claims 1 to 3,
After contacting the surface of the fabric made of polyester fiber with an aqueous solution containing a fluorine-based water repellent agent having a hydrophilic segment, a hydrophilic monomer, trimethylol melamine, and a polymerization initiator, steam heat treatment is performed, followed by washing with a high-speed liquid flow treatment with a liquid jet dyeing machine.
The high-speed liquid flow treatment is
a dyeing tank in which the fabric is retained;
a transfer pipe connecting both ends of the dyeing tank;
A method for producing an antifouling fabric using a jet dyeing machine having a filament nozzle that is provided at the tip of the transfer pipe and that sprays the washing liquid from all directions onto the passing woven or knitted fabric, and the fabric connected in an endless loop is transferred from the outlet of the dyeing tank to the transfer pipe, transferred in the transfer pipe together with the washing liquid, and returned to the dyeing tank dyeing tank. The mass ratio of the solid content of the fluorine-based water repellent agent to the hydrophilic monomer in the aqueous solution is (solid content of the fluorine-based water repellent agent) / (hydrophilic monomer) = 1/5 to 1/30. The method for producing an antifouling fabric according to claim 4.