JP2008163476A - Fiber structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber structure which has excellent washing-resistant, water-repelling and anti-staining properties. <P>SOLUTION: This fiber structure has a resin coating film containing a triazine ring-containing polymerizable monomer as a polymerization component, on the surface of a single fiber, contains a fluorine-based, water-repelling, oil-repelling agent, in the coating film, and has the water-repelling degree of the fourth grade or more. The water-repelling degree of the fiber structure is the third grade or more, after washed ten times. The triazine ring-containing polymerizable monomer is a compound containing a triazine ring and having at least two polymerizable functional groups. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a fiber structure having durable water repellency and antifouling properties, specifically pollen adhesion prevention and mud antifouling properties.

  In recent years, pollen scattered in the early spring causes symptoms in the nose, eyes, etc., and the number of so-called hay fever is increasing, and hay fever is said to be a national disease. There is no established treatment method for hay fever, and as a precautionary measure, people mask it, make it difficult to get pollen on the clothes, or make it easier to fall off by hand and bring it into the house. Various fiber fabrics have been proposed from the viewpoint of avoiding them.

For example, those using a compound having a sulfonate, carboxylate, phosphate, etc. (Patent Document 1) are those that chemically adsorb allergen substances in pollen, making it difficult to attach to clothes or making it easier to fall off. It has no function and will bring pollen into the house. Also,
A method for uniformly attaching colloidal silica fine particles to the surface of the fabric (Patent Document 2)
Although it has some performance that pollen is difficult to adhere and is easy to fall off, there is a problem that it lacks washing durability.
In addition, demand for sports uniforms such as baseball and soccer, uniforms for infants and students, and gymnastics for mud removal is increasing year by year. Although one has been proposed (see Patent Documents 3 and 4), the surface is made hydrophilic, and there is no water / oil repellency and its use is limited.
JP-A-6-158494 JP 2004-3046 A JP2003-227072A JP 2004-137617 A

  In view of the background of the prior art, the present invention is to provide a fiber structure having both water repellency and antifouling properties excellent in washing durability, in particular, pollen adhesion preventing property and mud antifouling property. .

In order to solve the above problems, the present invention employs the following means.
(1) The surface of a single fiber has a resin film containing a triazine ring-containing polymerizable monomer as a polymerizable component, and the film contains a fluorine-based water and oil repellent, and has a water repellency. Is a grade 4 or higher fiber structure.
(2) The fiber structure as described in 1 above, wherein the water repellency after 10 washings is 3 or more.
(3) The fiber structure according to 1 or 2, wherein the fluorine-based water / oil repellent is at least one of organic fluorine-based compounds represented by the following general formula 1.

(4) The fiber structure according to any one of the above items 1 to 3, wherein the coating contains inorganic fine particles and / or organic fine particles.
(5) The fiber structure as described in 4 above, wherein the inorganic fine particles are silicon oxide.
(6) The fiber structure according to any one of the above 1 to 5, which is a fabric having a number of pseudo pollens adhering to the fiber structure surface of 250 or less as measured by the following measurement method.
(Measuring method)
Thirty pieces of 7 × 7 cm fiber fabrics are left in an environment of 20 ° C. × 65% RH for 24 hours, placed in a polyethylene bag together with 1 g of artificial pollen, and about 20 liters in air at 20 ° C. × 65% RH. Inflate and bind mouth. The polyethylene bag was tied at a speed of 1 sec / sec and shaken up and down 100 times with respect to the mouth, and then the fiber fabric was taken out, and three photographs of the fiber fabric surface magnified 50 times were taken. Count the number of x10 cm pseudo-pollen and calculate the average of the three locations.
(7) The fiber structure according to any one of 1 to 5, wherein the antifouling property when measured by the following measurement method is 4th or higher.
(Measuring method)
Red jade soil / black soil / water is collected at a 1/1/1 weight ratio, placed in a mortar and pulverized and mixed to prepare a mud for contamination. 20 g of the stain is applied to a 10 cm × 10 cm fabric surface with a knife coater and left for 24 hours, and then the stain is struck by hand, washed by the method prescribed in the JIS L0217-103 method, and contaminated. The grade is determined with a gray scale for contamination.
(8) A clothing application product using the fiber structure according to any one of 1 to 7 above.

  ADVANTAGE OF THE INVENTION According to this invention, the fiber structure which has water repellency and antifouling property of washing durability, specifically pollen adhesion prevention property and mud antifouling property, can be supplied stably.

  The present invention, as a result of intensive investigations on the above-mentioned problem, that is, imparting pollen adhesion preventing property excellent in washing durability, resulted in a polymer of a triazine ring-containing monomer and a fluorine-based water and oil repellent agent on the surface of a single fiber. It has been sought to solve such problems at once by forming a film in which fine particles are mixed.

  The triazine ring-containing compound of the present invention is a compound containing a triazine ring and having at least two polymerizable functional groups, and examples thereof include those represented by the following general formula 2.

In the present invention, in addition to those represented by the above general formula, ethylene urea copolymer compounds, dimethylol urea copolymer compounds, dimethylol thiourea copolymer compounds, acid colloid compounds, and the like of the above compounds can also be used.

  As the fluorine-based water and oil repellent of the present invention, those having a water repellency of 4 or more are used. For example, a polymer essentially including a polymer unit of (meth) acrylic acid ester having a fluoroalkyl group is preferably used, and may be a copolymer. The polymer having a polymerization unit of (meth) acrylic acid ester having a fluoroalkyl group as an essential component is a compound in which a fluoroalkyl group is present in the alcohol residue part of (meth) acrylic acid ester. Such a fluoroalkyl group refers to a group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms. 1-20 are preferable and, as for carbon number of a fluoroalkyl group, 6-16 are especially preferable. The fluoroalkyl group is preferably a linear or branched group. In the case of a branched group, the branched portion is preferably present at the terminal portion of the fluoroalkyl group and is a short chain having about 1 to 4 carbon atoms. Further, the fluoroalkyl group is preferably a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (that is, a perfluoroalkyl group) or a group having a perfluoroalkyl group at the terminal portion. In the case of a perfluoroalkyl group, the number of carbon atoms is particularly preferably 4-16. When the number of carbon atoms is less than 4, the water repellency of the processing agent composition tends to be lowered. When the number is more than 16, the copolymer becomes solid at room temperature, has high sublimation properties, and is difficult to handle. There is a fear. The polymer essentially including a polymer unit of (meth) acrylic acid ester having such a fluoroalkyl group may contain one or more of such polymer units. In addition, a compound having a hydrophilic group such as OH group, COOH group, NH2 group or the like or a compound having a polyalkylene glycol segment may be contained in the molecule as long as the effect of the present invention is not inhibited. Specific examples of the fluorine-based water / oil repellent of the present invention include compounds represented by the following general formula 1.

In the present invention, the solid weight mixing ratio of the resin comprising the triazine ring-containing polymerizable monomer as a polymerization component and the fluorine-based water / oil repellent is preferably from 5 to 80/3 to 30 per fiber weight. It is preferable to deposit 5 to 5% by weight.

In the present invention, it is preferable that inorganic fine particles and / or organic fine particles are contained in the resin film from the viewpoints of uniform film formation and improved film strength.
Examples of the inorganic fine particles include aluminum oxide, silicon oxide, titanium oxide, kaolin, bentonite, talc, calcium carbonate, calcium silicate, magnesium oxide and the like, and these can be used alone or in combination of two or more. It is preferably used as an aqueous dispersion. Of these, silicon oxide is preferably used. The number average particle diameter of the particles is preferably 5 to 500 nm, more preferably 10 to 100 nm.
The organic fine particles are particles made of an olefin resin, an acrylic resin, or a urethane resin, and the number average particle diameter of the particles is preferably 0.01 to 5 μm, more preferably 0.1 to 2 μm. It is.
Moreover, the composite particle | grains which coat | covered the surface of the organic type particle | grains with the silica or the alumina can also be used. By blending the particles, fine irregularities are formed in the film, so that it is possible to enhance the function of preventing pollen from being easily removed. Further, the film formability is improved, and the film becomes a tough film, and the durability can be enhanced.

  In the present invention, in the case of containing fine particles, the solid content weight ratio of the resin having a polymerizable monomer as a polymerization component, the fluorine-based water / oil repellent and the fine particles is 8 to 80/3 to 30/1. 10 and preferably 0.5 to 5% by weight per fiber weight.

  In the present invention, an aqueous solution in which a polymerizable monomer and a fluorine-based water / oil repellent are mixed is applied onto a fiber, and then heat treatment is performed to form a polymer film. Examples of such catalysts include acetic acid, formic acid, acrylic acid, malic acid, tartaric acid, maleic acid, phthalic acid, sulfuric acid, persulfuric acid, hydrochloric acid, phosphoric acid and the like, and ammonium salts, sodium salts, potassium salts, magnesium salts thereof and the like. Yes, one or more of these can be used. Of these, ammonium persulfate and potassium persulfate can be preferably used. Such a catalyst is preferably used in a proportion of 0.1 to 20% by weight based on the amount of the polymerizable monomer used.

  The heat treatment for the polymerization is preferably dry heat treatment or steam heat treatment at a temperature of 50 to 180 ° C. for 0.1 to 30 minutes. Steaming heat treatment makes it easier to form a uniform film on the fiber surface, and the film strength is higher, and the resulting fabric has a softer texture. For steaming, saturated steam or superheated steam at 80 to 160 ° C. is preferably used. More preferable saturated water vapor is 90 to 130 ° C., and superheated water vapor is 110 to 160 ° C., both of which perform the treatment for several seconds to several minutes. After such steaming and heat treatment, in order to remove unreacted monomers and catalysts, and to ensure dyeing fastness, washing with hot water at a temperature of 50 to 95 ° C., nonionic surfactant, sodium carbonate, hydrosal It is preferable to perform cleaning using a fight or the like.

  The resin film of the present invention preferably has a thickness of 5 to 100 nm when observed using a transmission electron microscope (TEM) at a magnification of 100000 times.

The resin film of the present invention may contain a polyfunctional isocyanate compound. The polyfunctional isocyanate-based compound is not particularly limited as long as it is an organic compound containing two or more isocyanate functional groups in the molecule. Tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diisocyanate. Examples include phenyl methane diisocyanate, triphenyl triisocyanate, xylene diisocyanate, and dichloromethane diisocyanate. In addition, phenol and diethyl malonate, which are blocking compounds (compounds that regenerate isocyanate groups by heating to 70 to 200 ° C. together with isocyanate adducts) such as trimethylolpropane tolylene diisocyanate adducts and fryserin tolylene diisocyanate adducts Mention may be made of a polyfunctional block isocyanate urethane resin in which an ester, methyl ethyl ketoxime, sodium bisulfite, ε-caprolactam or the like is reacted. As the dissociation catalyst used for promoting the improvement of the thermal separation rate of the blocked isocyanate and the reduction of the thermal dissociation temperature, dibutyltin dioleate, dibutyltin stearate, stearyl zinc and organic amine compounds are preferred. The mixing of such a mixture has an effect of enhancing the durability of the fluorine-based water / oil repellent, and if mixed with a polymerizable monomer and a fluorine-based water / oil repellent compounding treatment solution at a concentration of 0.01 to 1%. Good.
The fiber structure of the present invention also has durable pollen adhesion preventing performance. When pollen adhesion prevention performance is evaluated using pseudo pollen, it is preferable to have the following performance. Pseudo-pollen refers to a natural product similar to the particle size of pollen called Ishimatsuko (manufactured by Tsuda Shoten). Ishimatsuko is a spore of a fern family genus Kazura with a particle size of 30 to 40 μm and has a particle size and shape close to that of pollen. It is possible to confirm the prevention of pollen adhesion by using this Ishimatsuko as a pseudo pollen. The method for measuring the pollen adhesion preventing performance is carried out by the following method. That is, 30 pieces of 7 × 7 cm fiber fabrics were allowed to stand in an environment of 20 ° C. × 65% RH for 24 hours, placed in a polyethylene bag together with 1 g of artificial pollen, and about 20 ° C. × 65% RH in air. Inflate to 20 liters and bind mouth. After tying such a polyethylene bag at a speed of 1 sec / sec and shaking it up and down 100 times based on the mouth, take out the fiber fabric and take three photos of the fiber fabric surface magnified 50 times. Count the number of pseudo-pollens within the range of 7.5 × 10 cm and calculate the average of the three locations.

The fiber structure of the present invention preferably has a pollen adhesion preventing performance by the measuring method such that the average number of three positions is 250 or less. When the number of deposits exceeds 250, pollen adhesion is clearly confirmed when the fabric surface is viewed with the naked eye, and it is difficult to say that pollen is difficult to adhere. In the present invention, the number of adhering pseudo pollens can be reduced to 250 or less due to the releasing effect of the fluorine-based water repellent and the unevenness effect of the film by the fine particles.
The fiber structure of the present invention has a mud antifouling performance in addition to durable antistatic and water / oil repellency. The effects of the present invention preferably have the following performance when evaluated by the following method. Using red jade earth and black earth, red jade earth / black earth / water is collected at a 1/1/1 weight ratio, placed in a mortar and pulverized and mixed to create a mud for contamination, and on the fabric surface of 10 cm × 10 cm, 20 g of this contaminant is applied with a knife coater and allowed to stand for 24 hours, and then washed according to the method defined in the JIS L0217-103 method. Preferably, it is quaternary or higher. It is hard to say that the anti-contamination property is good below the third grade. In the present invention, due to the releasing effect of the fluorine-based water repellent, the above mud antifouling property can be made to be 4th or higher.
The fiber material used in the fiber structure of the present invention is not particularly limited, but is an aromatic polyester fiber such as polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate, and a third component such as isophthalic acid, isophthalic acid. Aromatic polyester fiber copolymerized or blended with acid sulfonate, adipic acid and polyethylene glycol, aliphatic polyester fiber represented by L-lactic acid as a main component, polyamide fiber such as nylon 6 and nylon 66 , Acrylic fibers based on polyacrylonitrile, polyolefin fibers such as polyethylene and polypropylene, synthetic fibers such as polyvinyl chloride fibers, semi-synthetic fibers such as acetate and rayon, cotton, hemp, silk and And natural fibers such as wool, and the like. In the present invention, these fibers can be used singly or as a mixture of two or more. However, fibers mainly composed of polyester fibers and polyamide fibers are preferably used.

  The fibers used in the present invention may be flat yarns such as false twisted yarns, strong twisted yarns, taslan yarns, thick yarns and mixed yarns in addition to ordinary flat yarns, and staple fibers, tows, or spinning yarns. Various forms of fibers such as yarn may be used.

  The fiber structure of the present invention includes a knitted fabric using the fibers, a fabric-like material such as a woven fabric or a non-woven fabric, or a string-like material.

  Since the fiber structure of the present invention has durable pollen adhesion preventing property, it is particularly clothes and bedding called outer, specifically coats, blousons, windbreakers, blouses, dress shirts, skirts, slacks, Gloves, hats, futon sides, futon drying covers, curtains, tents, and the like are suitably used for applications such as apparel products and non-apparel products.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Moreover, the quality evaluation in an Example was implemented with the following method.

(Water repellency)
Evaluation was made by the spray method according to the method specified in JIS L 1092 “Test method for waterproofness of textile products” (1998), and the grade was determined.

(Pollen adhesion prevention)
Thirty pieces of 7 × 7 cm fiber fabrics are left in an environment of 20 ° C. × 65% RH for 24 hours, then placed in a polyethylene bag together with 1 g of artificial pollen, and about 20 liters with 20 ° C. × 65% RH air. Inflate and bind mouth. After tying such a polyethylene bag at a speed of 1 sec / sec and shaking it up and down 100 times based on the mouth, take out the fiber fabric and take three photos of the fiber fabric surface magnified 50 times. Count the number of pseudo-pollens within the range of 7.5 × 10 cm and calculate the average of the three locations.

(Mud antifouling property)
Using red jade earth and black earth, red jade earth / black earth / water is collected at a weight ratio of 1/1/1, put into a mortar and pulverized and mixed to prepare mud for contamination. 20 g of the stain is applied to a 10 cm × 10 cm fabric surface with a knife coater and left for 24 hours, and then washed according to the method defined in the JIS L0217-103 method. Grade).

(Washing durability)
A weak alkaline synthetic detergent specified in JIS K337 is dissolved in an automatic inversion swirl electric washing machine to a concentration of 0.2% by weight, and a strong bath is used at a temperature of 40 ± 2 ° C. at a bath ratio of 1:50. Washing was carried out for 10 minutes under the conditions, and then the process of draining and washing with overflowing water for 10 minutes × 2 times was repeated 10 times, and then air-dried.

(Examples 1-7, Comparative Examples 1-6)
After weaving a plain fabric using 84 dtex, 72 filament false twisted yarn made of polyethylene terephthalate as warp yarn and weft yarn, the fabric is scoured at a temperature of 95 ° C. according to a conventional method using a continuous scourer. It was washed with water, then dried at 130 ° C. and pinter set at 180 ° C. Next, using a flow dyeing machine, dyed fluorescent white at a temperature of 130 ° C., washed with hot water, dried, and pintenter set at 170 ° C., dyed black for evaluation of mud antifouling properties. What was subjected to reduction washing, washing with hot water, drying and setting a pin tenter at 170 ° C. was used for pollen antifouling evaluation. The fabric density for both the white and black fabrics was 140/88 vertical / 2.54 cm.

  Table 1 shows the results of treating the white and black fabrics by the following method and evaluating the performance. All of them had durable antistatic property, water repellency, pollen adhesion prevention property, mud antifouling property and soft texture.

  The processing method is shown below. The following A to E are mixed at the ratio of the treatment liquid composition shown in Table 1 to adjust the treatment liquid, the fabric is dipped in the treatment liquid, squeezed with a mangle, and the treatment liquid adhesion amount is 90% by weight. After adjusting so that it might become, it processed for 5 minutes in 105 degreeC saturated water vapor | steam atmosphere.

Subsequently, it was washed for 1 minute in a 60 ° C. aqueous solution containing 1 g / L of a nonionic surfactant and 1 g / L of sodium carbonate, washed with water, dried at 130 ° C., and pinter set at 170 ° C.
(Polymerizable monomer)
A: Becamine M3 (Dainippon Ink Co., Ltd., trimethylol melamine, solid content 80%)
(Fluorine-based water and oil repellent)
B: F470 (manufactured by Kyo Silk Chemical Co., Ltd., fluorine-based water and oil repellent, solid content 20%)
C: F200 (manufactured by Kyo Silk Chemical Co., Ltd., fluorine-based water and oil repellent, solid content 20%)
(Inorganic fine particles)
D: Snowtex AK (manufactured by Nissan Chemical Industries, Ltd., silicon oxide, solid content 20%, particle size 10-20 nm)
(Organic fine particles)
E: Chemipearl S-120 (manufactured by Sumitomo Chemical Co., Ltd., olefin resin, solid content 30%, particle size 20-30 nm)

Claims (8)

It has a resin film containing a triazine ring-containing polymerizable monomer as a polymerization component on the surface of a single fiber, the film contains a fluorine-based water and oil repellent, and has a water repellency of 4 or more. The fiber structure characterized by being. The fiber structure according to claim 1, wherein the water repellency after 10 washings is 3 or more. The fiber structure according to claim 1 or 2, wherein the fluorine-based water / oil repellent is at least one of organic fluorine-based compounds represented by the following general formula 1.

The fiber structure according to any one of claims 1 to 3, wherein the coating contains inorganic fine particles and / or organic fine particles. The fiber structure according to claim 4, wherein the inorganic fine particles are silicon oxide. The fiber structure according to any one of claims 1 to 5, wherein the fiber structure is a cloth having 250 or less pseudo pollen adhered to the surface of the fiber structure as measured by the following measurement method.
(Measuring method)
Thirty pieces of 7 × 7 cm fiber fabrics are left in an environment of 20 ° C. × 65% RH for 24 hours, placed in a polyethylene bag together with 1 g of artificial pollen, and about 20 liters in air at 20 ° C. × 65% RH. Inflate and bind mouth. The polyethylene bag was tied at a speed of 1 sec / sec and shaken up and down 100 times with respect to the mouth, and then the fiber fabric was taken out, and three photographs of the fiber fabric surface magnified 50 times were taken. Count the number of x10 cm pseudo-pollen and calculate the average of the three locations. The fiber structure according to any one of claims 1 to 5, which has a mud antifouling property of 4th grade or higher when measured by the following measurement method.
(Measuring method)
Red jade soil / black soil / water is collected at a 1/1/1 weight ratio, placed in a mortar and pulverized and mixed to prepare a mud for contamination. 20 g of the stain is applied to a 10 cm × 10 cm fabric surface with a knife coater and left for 24 hours, and then washed according to the method defined in the JIS L0217-103 method. Grade). The clothing which uses the fiber structure in any one of Claims 1-7.