JP5865648B2 - Method for producing antifouling fabric - Google Patents

Description

The present invention relates to a process for preparing antifouling fabric 帛.

  Polyester fibers are excellent in strength, dyeing fastness and the like, and in addition, because they are excellent in processability, they are used in a wide range of applications such as clothing and industrial materials. However, polyester fiber is inferior in hydrophilicity as compared with cellulose fiber such as cotton. For this reason, there is a problem that oil and the like are easily contaminated, and various studies have been made to improve the antifouling property of a fabric made of polyester fiber (hereinafter sometimes referred to as “polyester fiber fabric”).

  The following techniques (1) to (3) have been studied as techniques for improving the antifouling properties of polyester fiber fabrics. In other words, (1) SG-based (Solid Guard) processing that makes it difficult for dirt to adhere to the polyester fiber fabric, and (2) If the dirt adheres to the polyester fiber cloth. However, SR (Solid Release) processing that can easily remove dirt by washing, (3) Dirt is difficult to adhere to the polyester fiber fabric, and dirt has adhered. Even if it is a case, performing the SGR property (Solid Guard Release) processing which can remove this dirt easily by washing is examined. Among these techniques for improving the antifouling property, imparting SGR property is a technology that is particularly excellent in antifouling property, and thus studies have been made in various fields.

  As a fabric to which the technique (1) is applied, for example, in Patent Document 1, a synthetic fiber fabric is treated with a water / oil repellent containing 50% by weight or more of fluorine, and then the surface of the fabric is further treated. There has been proposed a water-repellent antifouling fabric obtained by treatment with a polymer compound in which fluorine atoms are bonded to carbon of the main chain and the fluorine content is more than 20% by weight and less than 50% by weight.

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

  Furthermore, as a fabric to which the technique (3) is applied, Patent Document 3 discloses that a resin film containing a triazine ring is formed on the fiber surface, or a fluorine-based water / oil repellent resin and a triazine ring. A fiber structure is proposed in which a resin coating is formed, and the coating surface is coated with a resin comprising a fluorine-based water- and oil-repellent resin having a hydrophilic component and a non-hydrophilic fluorine-based water and oil-repellent resin. Has been. Furthermore, as a fabric to which the technique (3) is applied, Patent Document 4 discloses a fluorine-based water / oil repellent having a hydrophilic segment on a synthetic fiber fabric, a non-hydrophilic fluorine-based water / oil repellent, and An antifouling synthetic fiber fabric in which an antifouling coating layer containing a crosslinking agent is formed has been proposed.

JP-A-3-234870 JP-A-9-268472 JP 2008-303511 A Japanese Patent Laid-Open No. 10-317281

  However, the fabric disclosed in Patent Document 1 has a problem that once dirt is attached to the fabric, it cannot be easily removed by washing. In addition, the fabric disclosed in Patent Document 2 has a problem that the attached dirt is not sufficiently washed and removed.

  The fabrics disclosed in Patent Documents 3 and 4 have a problem that the water- and oil-repellent layer having a hydrophilic group and non-hydrophilic property on the fiber surface is not sufficiently fixed. Therefore, the present condition is that the deterioration of the antifouling property after washing is not suppressed, that is, sufficient SGR property is not obtained.

  An object of the present invention is to eliminate the drawbacks of the prior art as described above, and can suppress a decrease in the antifouling property after washing is performed (that is, an antifouling property excellent in washing resistance). It is to provide an antifouling fabric.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention.
That is, the present invention has the following contents.
(1) An aqueous solution containing a fluorine-based water repellent having a hydrophilic segment and a hydrophilic monomer is applied to the surface of a fabric made of polyester fiber, followed by drying, followed by low-temperature plasma treatment, and 130 A method for producing an antifouling fabric, which is subjected to a dry heat treatment at ˜190 ° C.
( 2 ) On the surface of the fabric made of polyester fiber, a film containing a fluorine-based water repellent having a hydrophilic segment and a hydrophilic polymer is formed , washed 30 times according to method 103 of JIS L 0217, and dried. a method of soil removal of the grades after being to produce antifouling fabric Ru der tertiary or higher, the surface of the fabric comprising a polyester fiber, a fluorine-based water-repellent agent having a hydrophilic segment and hydrophilic A method for producing an antifouling fabric, comprising: applying an aqueous solution containing a functional monomer; drying, then performing a low temperature plasma treatment, and then subjecting to a dry heat treatment at 130 to 190 ° C.
(3) the mass ratio of the fluorine-based solid and hydrophilic monomers of the water-repellent agent having a parent aqueous segment, and (fluorine-based water repellent solids) / (hydrophilic monomer) = 1 / 1-1 / 5, the total adhesion amount of the fluorine-based water repellent solids and hydrophilic polymers characterized that you and 0.5-10% by weight relative to the weight of fabric made of polyester fibers having a hydrophilic segment ( A method for producing an antifouling fabric of 1) or (2) .
(4) as the hydrophilic monomer, diacrylate monomer containing an alkylene oxide, and / or wherein Rukoto using dimethacrylate monomers containing alkylene oxide (1) to any of the antifouling fabric (3) Manufacturing method .

  In the antifouling fabric of the present invention, a film containing a fluorine-based water repellent having a hydrophilic segment and a hydrophilic polymer is formed on the surface of the fabric made of polyester fiber, and the hydrophilic polymer is a fiber as a graft polymer. Has been granted. In the present invention, it is considered that the fluorine-based water repellent is incorporated into a network of hydrophilic polymers. Further, in the coating, the hydrophobic group in the fluorine-based water repellent contained in the coating is oriented perpendicular to the polyester fiber, whereas the hydrophilic group in the fluorine-based water repellent is directed toward the polyester fiber. It is thought that it is arranged. That is, it is considered that the coating structure has a form as if the hydrophobic groups are partially arranged in the fiber vertical direction in the hydrophilic coating. In the antifouling fabric of the present invention, the antifouling property which is remarkably excellent in washing durability can be achieved although it is slightly inferior in water repellency due to such a structure. 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 and edible oil stains.

  And since the manufacturing method of the antifouling cloth of the present invention is dry heat-treated after applying low-temperature plasma processing without using a polymerization initiator or a binder resin, discoloration, fastness and deterioration in texture are suppressed. An antifouling fabric can be produced.

Hereinafter, the present invention will be described in detail.
The antifouling fabric of the present invention comprises a fluorine-based water repellent having hydrophilic segments on the surface of a fabric made of polyester fibers (in the present specification, sometimes referred to as “polyester fiber fabric”) and hydrophilic. A film containing a hydrophilic polymer is formed, and the hydrophilic polymer in the film is obtained by graft polymerization of a hydrophilic monomer on the surface of the polyester fiber. By having such a configuration, the antifouling fabric of the present invention satisfies the antifouling property excellent in washing durability.

  The polyester fiber fabric in the present invention is a fabric containing fibers (polyester fibers) obtained from a polyester resin 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 the present invention, the 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, bamboo; viscose rayon, copper ammonia rayon, solvent-spun cellulose fibers, etc. Regenerated fibers; semi-synthetic fibers such as acetate may be contained.

  Fibers other than these polyester fibers are contained in the fabric after being twisted, blended, blended, woven or knitted with the polyester fibers. The form of the polyester fiber fabric is not particularly limited, and examples thereof include woven fabrics, knitted fabrics, and nonwoven fabrics.

  As described above, in the antifouling fabric of the present invention, a film containing a fluorine-based water repellent having a hydrophilic segment and a hydrophilic polymer is formed on the surface of a polyester fiber fabric. And this hydrophilic polymer is obtained by graft-polymerizing a hydrophilic monomer in the polyester fiber surface. It is presumed that the fluorine-based water repellent contained in the film is taken into the hydrophilic polymer network by grafting the hydrophilic monomer. Thereby, the fluorine-based water repellent is more firmly attached to the polyester fiber fabric, and even if washing is repeated, the fluorine-based water repellent does not peel from the fabric, and thus the antifouling property does not decrease, That is, the effect of exhibiting antifouling properties excellent in washing durability is exhibited. When the hydrophilic monomer is not graft-polymerized on the surface of the polyester fiber, the film is merely coated on the surface of the polyester fiber fabric, and achieves antifouling property with excellent washing durability. I can't.

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

  The hydrophilic segment is a modification of an ethylenically unsaturated material such as acrylate, methacrylate, vinyl acetate, or vinyl chloride, and a hydrophilic group such as ethylene oxide, a hydroxyl group, a carboxyl group, or a sulfonic acid group. Is introduced. Among these, a hydrophilic segment obtained by reacting hydrogen sulfide with polyethylene glycol dimethacrylate is preferable from the viewpoint of improving stain removal and excellent antifouling properties.

  The fluorinated hydrophobic segment is preferably a fluoroalkyl acrylate containing a perfluoroalkyl group from the viewpoint of preventing the adhesion of dirt and having excellent antifouling properties.

  Specifically, a copolymer as shown in the following formula (1) is preferable. 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 to 10, a is preferably an integer of 1 to 10, and b is preferably an integer of 1 to 10. R represents a lower alkyl group, and an alkyl group having 1 to 3 carbon atoms is particularly preferable. Rf represents a perfluoroalkyl group, and among them, a perfluoroalkyl group having 4 to 10 carbon atoms is preferable.

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

  As such a fluorine-based water repellent, a commercially available product can be suitably used. Specific examples include Asahi Guard AG-E100 manufactured by Asahi Glass Co., Ltd.

  The hydrophilic polymer is a polymer containing a hydrophilic monomer as a constituent component. By using the hydrophilic polymer, it is possible to obtain an effect that dirt is easily removed by washing.

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

  Among the above hydrophilic monomers, from the viewpoint of reactivity with the polyester fiber fabric, a bifunctional vinyl monomer is preferable, and a diacrylate monomer containing alkylene oxide and / or a dimethacrylate monomer containing alkylene oxide is particularly preferable. .

  Specific examples of such hydrophilic monomer 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 23, and more preferably an integer of 14 to 23 from the viewpoint of easily removing dirt and being excellent in antifouling properties.

  In the above formula (3), n is preferably an integer of 1 to 23 and more preferably an integer of 14 to 23 from the viewpoint of easily removing dirt and being excellent in antifouling properties.

  In a film containing a hydrophilic water-repellent fluorine-based water repellent and a hydrophilic polymer, the mass ratio of the solid content of the water-soluble fluorine-containing water repellent and the hydrophilic monomer is (fluorine-based water repellent). / (Hydrophilic monomer) = 1/1 to 1/5 is preferable, and 1/1 to 1/3 is more preferable. If the amount of the hydrophilic monomer used is less than 1 times the solid content of the fluorine-based water repellent having a hydrophilic segment, the washability when soiling may be deteriorated. On the other hand, if the amount of the hydrophilic monomer used exceeds 5 times the solid content of the fluorinated water repellent having a hydrophilic segment, the antifouling property (antifouling property) may be lowered.

  The total of the solid content of the fluorine-based water repellent having a hydrophilic segment and the adhesion amount of the hydrophilic polymer is preferably 0.5 to 10% by mass, more preferably based on the total mass of the polyester fiber fabric. Is 1 to 5% by mass. Here, when the adhesion amount is less than 0.5% by mass, the antifouling property may not be exhibited. On the other hand, when the amount of adhesion exceeds 10% by mass, the resulting antifouling fabric may have a hard texture.

  The adhesion amount of the solid content of the fluorinated water repellent having a hydrophilic segment is preferably 0.25 to 5% by mass, more preferably 0.5 to 5% by mass with respect to the total mass of the polyester fiber fabric. 2% by mass. When the adhesion amount is less than 0.25% by mass, dirt may be easily attached, and when it exceeds 5% by mass, the removal property of the attached dirt may be deteriorated.

  The adhesion amount of the hydrophilic polymer is preferably 0.25 to 5% by mass, more preferably 0.5 to 4% by mass with respect to the total mass of the polyester fiber fabric. When the adhesion amount is less than 0.25% by mass, the stain removability is deteriorated and the antifouling property may be inferior, and when it exceeds 5% by mass, the texture may be cured.

The method for producing the antifouling fabric of the present invention will be described below.
In the production method of the present invention, an aqueous solution containing a fluorine-based water repellent having hydrophilic segments and a hydrophilic monomer is applied to the surface of a fabric made of polyester fiber, followed by drying, followed by low-temperature plasma treatment. After that, dry heat treatment is performed at 130 to 190 ° C.

  That is, first, an aqueous solution is obtained by dissolving a fluorine-based water repellent and a hydrophilic monomer having a hydrophilic segment as described above in an aqueous medium by a known method. Then, the obtained aqueous solution is applied to the surface of the polyester fiber fabric and dried. And after performing low-temperature plasma processing with respect to this polyester-type fiber fabric, the antifouling fabric of this invention can be obtained by performing dry heat processing at 130-190 degreeC.

  The aqueous medium in which the fluorine-based water repellent having a hydrophilic segment and the hydrophilic monomer are dissolved is not particularly limited, and examples thereof include water or a mixture of water and a known organic solvent.

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

  The polyester fiber fabric to which the aqueous solution is applied is preliminarily dried by air drying or heating for the purpose of uniformly attaching the aqueous solution. The conditions for the preliminary drying are usually preferably about 80 to 120 ° C. and about 120 to 300 seconds.

  And low-temperature plasma processing is performed with respect to the polyester-type fiber fabric to which aqueous solution was provided. As a result, the hydrophilic monomer is polymerized into a hydrophilic polymer, and the fluorine-based water repellent and the hydrophilic polymer can be firmly attached to the surface of the polyester fiber. The effect that it does not fall is produced.

  In the production method of the present invention, in order to graft polymerize the hydrophilic monomer on the surface of the polyester fiber, a graft polymerization method using a low temperature plasma treatment is used without using a polymerization initiator. When a polymerization initiator is used, problems such as discoloration, a decrease in fastness, and a hard texture appear. However, such problems can be avoided in the production method of the present invention.

  Low-temperature plasma is a discharge state obtained by applying electrical energy to a gas. Glow discharge under a reduced pressure containing negatively charged electrons, positively charged ions, and electrically neutral radicals. It is a state in a normal temperature range due to atmospheric pressure glow discharge, corona discharge or the like.

  The low temperature plasma treatment is usually performed as follows. That is, gas molecules are excited by applying high-frequency energy to a non-polymerizable gas in a reduced pressure state to generate a plasma state at a low temperature. Then, a polyester fiber fabric provided with an aqueous solution is allowed to stand in this low temperature plasma atmosphere for a certain period of time, and graft polymerization is performed by low temperature plasma.

  Examples of the non-polymerizable gas include oxygen, nitrogen, hydrogen, helium, argon, carbon dioxide gas and the like. Among these, oxygen is preferably used from the viewpoint of the polymerizability of the hydrophilic monomer on the polyester fiber surface.

  The frequency of the high-frequency energy is not particularly limited as long as it can generate low-temperature plasma, and can be used in the range of 1 to 3000 MHz, for example. In actual use, any one of 13.56 MHz, 27.12 MHz, 40.68 MHz, 915 MHz, and 2450 MHz is generally used according to regulations such as the Radio Law.

  The power of the high frequency energy (high frequency power) is preferably 0.1 to 15.0 kW, more preferably 0.3 to 10.0 kW, from the viewpoint of improving the kinetic energy of the generated plasma.

  From the viewpoint of maintaining a stable low-temperature plasma state, the degree of vacuum during the low-temperature plasma treatment is preferably 13 to 2670 Pa, and more preferably 40 to 1330 Pa.

  The time for the low-temperature plasma treatment is preferably in the range of 1 to 60 minutes, preferably 1 to 10 minutes from the viewpoint of firmly attaching the fluorine-based water repellent and the hydrophilic polymer to the polyester fiber surface. It is more preferable.

  In the production method of the present invention, it is necessary to perform a dry heat treatment after the low temperature plasma treatment is performed. By performing dry heat treatment, it is possible to more firmly attach the fluorinated water repellent to the polyester fiber, and to add a perfluoroalkyl group that is a fluorinated hydrophobic segment of the fluorinated water repellent. , Orienting in the direction perpendicular to the fiber surface, the surface tension of the fabric surface can be improved, and the water repellency can be further improved.

  Also, if dry heat treatment is performed before low temperature plasma treatment, graft polymerization of hydrophilic monomers by low temperature plasma treatment is hindered, soil removal due to washing or the like is reduced, and antifouling properties are poor.

  The dry heat treatment is preferably performed at a temperature of 130 to 190 ° C, and preferably 150 to 170 ° C. When the temperature is lower than 130 ° C., the perfluoroalkyl group or the like cannot be sufficiently oriented, and as a result, the water repellency is insufficiently improved, so that dirt is easily attached and the antifouling property is poor. There is. On the other hand, when the temperature exceeds 190 ° C., the coating film is deteriorated by heat, and the stain removability by washing or the like is lowered, which may be inferior in antifouling property.

  In addition, the time for performing the dry heat treatment is preferably 30 to 300 seconds from the viewpoint of the orientation of the perfluoroalkyl group.

  Further, soaping may be performed to remove unreacted hydrophilic monomer from the surface of the polyester fiber fabric. By performing the soaping, it is possible to suppress discoloration due to elution of the remaining unreacted substances, a decrease in dyeing fastness, and the like.

  The temperature at which soaping is performed is preferably 60 to 100 ° C. from the viewpoint of the removal efficiency of unreacted substances. Moreover, it is preferable that the time which performs soaping is 1 to 60 minutes from a viewpoint of the removal efficiency of an unreacted substance. In the case of soaping, a surfactant may be used in order to improve detergency and increase removal efficiency.

  The antifouling fabric obtained as described above has antifouling properties against oily dirt, and even when washing is performed, the deterioration of the antifouling property is remarkably suppressed. (That is, having antifouling property with excellent washing durability)

  The antifouling fabric of the present invention can be particularly suitably used in fields requiring antifouling properties with excellent washing durability, such as hospital lab coats and food factory uniforms.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to a following example.

Evaluation in Examples and Comparative Examples was performed by the following method.
1. Samples to be subjected to measurement, those washed 30 times using “Top Clear Liquid” manufactured by Lion in accordance with method 103 of JIS L 0217 (hereinafter sometimes referred to as “after 30 times of washing”) Two types were prepared, one before washing (hereinafter sometimes referred to as “finished processing”).

2. Dirt removal test 2-1. Dirt removal property for lipstick A 10 cm × 10 cm sample was collected. Then, 0.03 g of lipstick (manufactured by Kanebo Cosmetics) was uniformly applied on the film surface on which a circle having a diameter of 1.5 cm was drawn. Then, the sample was pressed against the surface of the film coated with lipstick with a rubber block from above for 10 seconds. Thereafter, washing was performed once in accordance with method 103 of JIS L 0217, and after drying, the degree of soiling was determined on a gray scale for contamination.
It was judged that those of grade 3 or higher can withstand actual use.

2-2. Dirt removal property to food oil A sample of 5 cm × 5 cm was collected. Then, 0.4 μL of food oil was weighed with a micropipette, adhered to the center of the sample, and left for 24 hours. Thereafter, washing was performed once in accordance with method 103 of JIS L 0217, and after drying, the degree of soiling was determined on a gray scale for contamination.
It was judged that those of grade 3 or higher can withstand actual use.

3. Recontamination prevention test A 10 cm x 10 cm sample was taken. Then, a solution in which 0.38 g / L of a surfactant is dissolved in 0.3 g / L of a mixture of A heavy oil and C heavy oil (A heavy oil: C heavy oil = 1: 1, mass ratio) is used as a bath for the sample. The ratio was adjusted to 1: 100. The sample was put into the heavy oil mixture, boiled and left for 10 minutes. The sample was taken out, washed with water and dried, and then the degree of soiling was determined on a gray scale for contamination.
It was judged that those of grade 3 or higher can withstand actual use.

4). Adhesion amount of fluorinated water repellent and hydrophilic polymer A 20 cm × 20 cm sample was taken from the fabric before and after forming the resin film, dried at 105 ° C. for 2 hours, and in an environment at a temperature of 25 ° C. and a humidity of 65%. After adjusting the humidity for 12 hours, the mass of each sample was measured, and the adhesion amount (%) was calculated by the following formula (4).
Adhesion amount (%) = {(mass after resin film formation−mass before resin film formation) / mass before resin film formation} × 100 (4)

(Examples 1-3, Comparative Examples 1-4)
Polyester multifilament processed yarn (167 dtex / 48f) is used as the warp, and polyester multifilament processed yarn (334 dtex / 96f) is used as the weft. 2.54 cm, basis weight: 200 g / cm ² ) was woven. This twill fabric was scoured and preset by a conventional method. Next, using the chemicals A to C shown below, the aqueous solutions shown in Formulas 1 to 7 were prepared, and the twill fabric was impregnated in each aqueous solution, and then squeezed with a mangle (squeezing rate: 80% by mass), 120 Pre-dried at 120 ° C. for 120 seconds.

Agent A: Asahi Guard AG-E100 (Asahi Glass Co., Ltd., fluorine water repellent with hydrophilic segment, solid content 30%)
B: Polyethylene glycol dimethacrylate monomer
C: Mynex SO (made by Meisei Chemical Co., Ltd., nonionic surfactant)

In Comparative Example 1, an aqueous solution having the following formulation 1 was used.
Formula 1
A 50g / L
B 10g / L
C 2g / L

In Example 1, an aqueous solution of the following formulation 2 was used.
Formula 2
A 50g / L
B 15g / L
C 2g / L

In Example 2, an aqueous solution of the following formulation 3 was used.
Formula 3
A 50g / L
B 20g / L
C 2g / L

In Example 3, an aqueous solution of the following formulation 4 was used.
Formula 4
A 50g / L
B 60g / L
C 2g / L

In Comparative Example 2, an aqueous solution of the following formulation 5 was used.
Formula 5
A 20g / L
B 40g / L
C 2g / L

In Comparative Example 3, an aqueous solution having the following formulation 6 was used.
Formula 6
A 5g / L
B 2g / L
C 2g / L

In Comparative Example 4, an aqueous solution of the following formulation 7 was used.
Formula 7
A 100g / L
B 90g / L
C 2g / L

Next, the pre-dried fabric was subjected to low-temperature plasma treatment under the conditions shown in Condition 1 below.
(Condition 1)
Gas type: Oxygen vacuum degree: 133 Pa
Frequency: 13.56MHz
High frequency power: 0.4 kW
Processing time: 1 minute

  Thereafter, the fabric subjected to the low temperature plasma treatment was subjected to a dry heat treatment at 170 ° C. for 1 minute. Next, soaping is performed for 10 minutes with warm water at a temperature of 60 ° C., and drying is performed for 2 minutes at 120 ° C. with a tenter to obtain an antifouling fabric of Examples 1 to 3 and a polyester fiber fabric of Comparative Examples 1 to 4. It was.

Example 4
In the warp and weft, spun yarn (60 count double yarn) containing polyester fiber and wool [mixing rate: (polyester) / (wool) = 50/50] was used, and plain fabric (warp density: 58/2. 54 cm, weft density: 51 yarns / 2.54 cm, 250 g / cm ² ). Then, this plain woven fabric was subjected to low temperature plasma treatment under the same conditions as in Example 1 except that scouring and setting out was performed by a normal method. Thereafter, curing was performed at 150 ° C. for 1 minute. Next, soaping was performed for 10 minutes with hot water at a temperature of 60 ° C., and drying was performed for 2 minutes at 120 ° C. with a tenter to obtain an antifouling fabric of Example 4.

(Example 5)
Using a polyester multifilament processed yarn (167 dtex / 48f), a circular knitted fabric (weight per unit area: 150 g / cm ² ) having a smooth structure was knitted with a 28 gauge circular knitting machine. And after carrying out the scouring width setting by this normal method with respect to this circular knitted fabric, the low temperature plasma process was performed on the same conditions as Example 1. FIG. Thereafter, curing was performed at 160 ° C. for 1 minute. Next, soaping was performed with warm water at a temperature of 60 ° C. for 10 minutes, and drying was performed at 120 ° C. for 2 minutes with a tenter to obtain an antifouling fabric of Example 5.

(Example 6)
In the warp and weft, a spun yarn (40 count double yarn) containing polyester fiber and wool [mixing rate: (polyester) / (wool) = 65/35] was used, and a twill woven fabric (warp density: 70/2. 54 cm, weft density: 52 yarns / 2.54 cm, basis weight: 300 g / cm ² ). This twill fabric was scoured and preset by a conventional method. Next, the twill fabric was impregnated with an aqueous solution shown in the following prescription 8, and then squeezed with mangle (squeezing rate: 80% by mass) and pre-dried at 120 ° C. for 120 seconds.

Formula 8
I-7240 (manufactured by Nikka Chemical Co., Ltd., fluorine water repellent having hydrophilic segment: solid content 20%) 50 g / L
Polyethylene glycol dimethacrylate monomer 20g / L
Mynex SO (made by Meisei Chemical Industry Co., Ltd., nonionic surfactant) 2g / L

  Next, the low temperature plasma treatment shown in the above condition 1 was performed. Thereafter, a dry heat treatment was performed at 150 ° C. for 1 minute. Next, soaping was performed for 10 minutes with warm water at a temperature of 60 ° C., and drying was performed for 2 minutes at 120 ° C. with a tenter to obtain an antifouling fabric of Example 6.

(Comparative Example 5)
The twill woven fabric obtained in Example 1 was impregnated with an aqueous solution shown in Formula 9 below, then squeezed with mangle (squeezing rate: 80% by mass), and pre-dried at 120 ° C. for 120 seconds. Then, a dry heat treatment was performed at 170 ° C. for 60 seconds to obtain a polyester fiber fabric of Comparative Example 5.

Formula 9
NK guard S-07 (manufactured by Nikka Chemical Co., Ltd., fluorine water repellent without hydrophilic segment) 50 g / L
NK Assist-NY (manufactured by Nikka Chemical Co., Ltd., blocked isocyanate) 10g / L

(Comparative Example 6)
The twill woven fabric obtained in Example 1 was impregnated with the aqueous solution shown in Formula 10 below, then squeezed with mangle (squeezing rate: 80% by mass), and pre-dried at 120 ° C. for 120 seconds. Then, a dry heat treatment was performed at 170 ° C. for 60 seconds to obtain a polyester fiber fabric.

Formula 10
Asahi Guard AG-E100 (manufactured by Asahi Glass Co., Ltd., fluorine water repellent with hydrophilic segment: solid content 30%) 50 g / L
Nice pole PR-99 (manufactured by Nikka Chemical Co., Ltd., polyester hydrophilizing agent, solid content 10% by mass)
20g / L
Mynex SO (made by Meisei Chemical Industry Co., Ltd., nonionic surfactant) 2g / L

(Comparative Example 7)
The same process as in Example 1 was performed until the fluorine-based water repellent having hydrophilic segments and the hydrophilic monomer were applied to the polyester fiber fabric, followed by a dry heat treatment at 170 ° C. for 1 minute. 1 was subjected to low-temperature plasma treatment, soaping and drying to obtain a polyester fiber fabric of Comparative Example 7.

(Comparative Examples 8 and 9)
Two points were prepared by applying exactly the same method as in Example 2 until the polyester fiber fabric was provided with a fluorine water repellent having hydrophilic segments and a hydrophilic monomer and subjected to low-temperature plasma treatment. One subjected to a dry heat treatment for 1 minute and one subjected to a dry heat treatment at 195 ° C. for 1 minute were prepared, and soaping and drying were performed under the same conditions as in Example 2 to obtain two polyester fiber fabrics. Comparative Example 8 was subjected to dry heat treatment at 120 ° C. for 1 minute, and Comparative Example 9 was subjected to dry heat treatment at 195 ° C. for 1 minute.

  Table 1 shows the results of performance evaluation of the antifouling fabrics obtained in Examples 1 to 6 and the polyester fiber fabrics obtained in Comparative Examples 1 to 9.

  As is clear from Table 1, the antifouling fabrics of Examples 1 to 6 were excellent in antifouling properties. In addition, it was excellent in antifouling property after 30 times of washing, that is, excellent in washing durability.

  In the polyester fiber fabrics obtained in Comparative Examples 1 and 2, the mass ratio of the fluorine-based water repellent solid content and the hydrophilic monomer deviated from the preferred range in the present invention. The grade did not become grade 3 or higher, and the soil resistance was poor.

  In the polyester fiber fabrics obtained in Comparative Examples 3 and 4, the total of the solid content of the fluorine-based water repellent having a hydrophilic segment and the adhesion amount of the hydrophilic polymer with respect to the mass of the fabric made of polyester fibers is the present invention. Therefore, the grade of soil removal after washing 30 times was not higher than the third grade, and the antifouling property was inferior. Furthermore, in Comparative Example 4, since the total amount of the above adhesion was excessive, the texture was hard.

  The polyester fiber fabric obtained in Comparative Example 5 was remarkably inferior in antifouling property because a fluorine-based water repellent having no hydrophilic segment was used.

  Since the polyester fiber fabrics obtained in Comparative Examples 6 and 10 were not subjected to low-temperature plasma treatment, the hydrophilic monomer did not undergo graft polymerization, and thus the adhesion of the fluorine-based water repellent did not become strong. As a result, the antifouling property after 30 times of washing was remarkably lowered, that is, the washing durability was inferior.

  Since the polyester fiber fabric obtained in Comparative Example 7 was subjected to a dry heat treatment before the low temperature plasma treatment, it was remarkably inferior in antifouling properties.

  In the polyester fiber fabrics obtained in Comparative Examples 8 and 9, the temperature at which the dry heat treatment was performed was out of the preferred range in the present invention. Therefore, the antifouling property was remarkably inferior.

Claims (4)

The surface of the fabric comprising a port Riesuteru fibers, dried after being applied an aqueous solution containing a fluorine-based water repellent and hydrophilic monomers having a hydrophilic segment, and then, after the low-temperature plasma treatment, 130 to 190 A method for producing an antifouling fabric, which is subjected to a dry heat treatment at 0 ° C. The surface of the fabric comprising a polyester fiber, a fluorine-based water-repellent agent having a hydrophilic segment and a coating comprising a hydrophilic polymer is formed, for 30 washes in accordance with 103 Method J IS L 0217, after drying a method of grade soil removal properties producing der Ru antifouling fabric tertiary or higher, the surface of the fabric comprising a polyester fiber, a fluorine-based water repellent and hydrophilic monomers having a hydrophilic segment A method for producing an antifouling fabric, comprising applying an aqueous solution to be contained and then drying, then performing a low-temperature plasma treatment, and then performing a dry heat treatment at 130 to 190 ° C. The mass ratio of the fluorine-based solid and hydrophilic monomers of the water-repellent agent having a parent aqueous segment, and (fluorine-based water repellent solids) / (hydrophilic monomer) = 1 / 1-1 / 5, the hydrophilic segment claim 1 or, characterized that you and 0.5-10% by weight relative to the weight of fabric made of polyester fibers the total adhesion amount of the fluorine-based water repellent solids and hydrophilic polymers having 2. A method for producing an antifouling fabric according to 2 . As the hydrophilic monomer, a manufacturing method of antifouling fabric according to any one of claims 1-3, characterized in Rukoto using dimethacrylate monomers containing diacrylate monomer containing an alkylene oxide, and / or an alkylene oxide.