JP5087862B2 - Fiber structure - Google Patents

Description

  The present invention relates to an excellent fiber structure that has both a durable antistatic property and water repellency, both of which have been difficult to achieve together, and also has a function of antifouling property and prevention of pollen adhesion. .

  The fiber fabric has antistatic properties as an essential function required when it is worn not only during sewing but also as clothing. If the garment is an outer garment such as a coat or a blouson, the garment may get wet due to rain, snow, etc., and functions such as water repellency and antifouling properties are required. In addition, these outer garments are often worn in early spring, and due to the increase in the number of hay fever patients over the past few years, even the ability to adhere to pollen is required.

  However, satisfying both the antistatic property obtained by hydrophilizing the fiber and the performance that dirt is easily removed by washing, and the water repellency obtained by hydrophobizing the fiber and the performance that is difficult to get dirty. Is very difficult, and it is very difficult to make it more durable in addition to such performance. In addition, it was even more difficult to obtain a fiber structure that also had pollen adhesion prevention performance.

  As an antistatic and water-repellent finishing method for fiber structures, the surface of the fiber fabric is covered with a film having two or more acrylic or methacrylic groups at the end of the main chain or the side chain of the main chain mainly composed of polyalkylene oxide segments. The coated fabric has a polyfluoroalkyl group-containing acrylic copolymer, and further has at least one of a reaction product of an aminoplast resin and a polyfunctional blocked isocyanate-containing urethane resin. A water repellent and antistatic fabric (see Patent Document 1), a fabric mainly composed of polyester fibers to which an antistatic polymer having no water repellent is fixed, and at least a part of the antistatic polymer Is a water-repellent polyester fabric with improved antistatic durability coated with a water-repellent polymer (see Patent Document 2), water-repellent agent and graft polymer Fiber fabric having a Li Cheng coating or the above polymerization film is known further manufacturing method (see Patent Document 3) of fiber fabric to be treated with solvent-based treatment solution containing a water repellent agent or the like.

  For preventing pollen adhesion, the fiber structure fabric is treated with a processing agent containing colloidal silica fine particles, and the colloidal silica fine particles are uniformly adhered to the surface of the fabric (see Patent Document 4). Etc. have been proposed.

  However, in order to obtain high water repellency, as described in Patent Document 1, it is covered with a film having two or more acrylic or methacrylic groups at the end of the main chain or the side chain of the main chain mainly composed of polyalkylene oxide segments. And a fiber fabric to which a fluoroalkyl group-containing acrylic copolymer is fixed, or a fiber cloth to which an antistatic polymer having no water repellent as shown in Patent Document 2 is fixed, and at least one of the antistatic polymers The part coated with a water-repellent polymer is a film having the opposite characteristics of a hydrophilic film and a water-repellent resin film, so the adhesion of both films is poor and it is difficult to obtain durability. there were.

  Moreover, it is difficult to make it compatible with the performance which has the characteristic which conflicts in one film called the fiber fabric which has a film which consists of a water repellent and a graft polymer like patent document 3, and the durability of a film is inferior. Similarly, in the method for producing a fiber fabric in which the polymer coating is further treated with a solvent-based treatment liquid containing a water repellent, the durability of the polymer coating is also inferior, and the polymer coating itself has water repellency. For this reason, the water repellent agent to be further applied needs to be treated with a solvent-based treatment liquid. For example, the workability is very poor, and the adhesion between the two layers is poor and it is difficult to obtain durability.

In addition, as described in Patent Document 4 proposed for preventing pollen adhesion, a material in which fine particles of colloidal silica are uniformly adhered to the surface of the cloth has a performance that it is difficult to adhere pollen and is easy to fall off, but is durable against washing. In addition to the lack of anti-static performance, pollen adsorption was likely to occur due to static electricity.
Japanese Patent Laid-Open No. 9-132872 Japanese Patent No. 3133227 Japanese Patent No. 3615827 JP 2004-3046 A

  In view of the background of such prior art, the present invention is to provide an excellent multifunctional fiber structure having antistatic properties, water repellency, and a function of preventing pollen adhesion. .

In order to solve the above problems, the present invention employs the following means. That is, the fiber structure of the present invention has the following configurations (1) to ( 7 ).
(1) Both a main chain mainly containing a polyalkylene glycol polyester block copolymer, a polyalkylene glycol polyester block copolymer, a polyalkylene glycol polyurethane block copolymer containing a water repellent and inorganic fine particles on the fiber surface. end or one end or the resin coating the polymerizable monomer to have a antistatic polymerized with at least one functional group selected from the two or more acrylic groups and methacrylic groups as side chains of the main chain is formed Further, at least a part of the coating is coated with a fluorine-based water repellent, and is fixed in a layer form, and the water-repellent contained in the antistatic resin contains a polyalkylene glycol. A fiber structure characterized by being a water repellent.
( 2 ) A polymerizable monomer having two or more methacryl groups as both ends of the main chain mainly composed of a polyalkylene oxide segment or one terminal or a side chain of the main chain and a water repellent on the fiber surface Is formed by polymerizing a composition containing 1: 0.01 to 1: 1.0, and at least one part of the coating is coated with a water repellent and fixed in a layered manner. The fiber structure according to (1) , wherein
( 3 ) Polymerization of (meth) acrylic acid ester in which both of the fluorine-based water repellent contained in the antistatic resin and the fluorine-based water repellent fixed in a layer form have a fluoroalkyl group The fiber structure according to claim 1 or 2, wherein the fiber structure is a copolymer having an essential unit.
(4) water repellent is coated to layered, characterized in that it is obtained by forming a resin to be film with any of the aminoplast resin or aminoplast resin and a polyfunctional isocyanate group-containing urethane resin ( The fiber structure according to any one of 1) to ( 3 ).
( 5 ) The fiber structure according to any one of (1) to ( 4 ), wherein the resin film having antistatic properties contains inorganic fine particles.
( 6 ) The fiber structure according to any one of (1) to ( 5 ), wherein the inorganic fine particles are silicon oxide.
( 7 ) The fiber structure according to any one of (1) to ( 6 ), wherein the number of pseudo pollens attached to the surface of the fiber structure is 250 or less when measured by the following measurement method object.
(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.
( 8 ) It is used for any of coats, blousons, windbreakers, blouses, dress shirts, skirts, slacks, gloves, hats, futon sides, futon drying covers or curtains (1) to ( 7 ) The fiber structure in any one of.

ADVANTAGE OF THE INVENTION According to this invention, while having the antistatic property and water repellency with washing durability which are the essential functions as a fiber structure, the fiber structure which also has pollen adhesion prevention performance can be provided.

  As a result of intensive studies on the above-mentioned problem, that is, a fiber structure having antistatic properties, water repellency, and pollen adhesion preventing properties with durability to washing, when forming a resin coating having antistatic properties on the fiber surface, It has been clarified that by admixing a water repellent and further coating at least a part of the coating with a water repellent, the adhesion between the coating and the water repellent is significantly improved, and this problem can be solved all at once. It is.

  Hereinafter, the present invention will be described in detail.

The resin having antistatic properties in the present invention, those containing hydrophilic groups, specifically, the polyester block copolymer of a polyalkylene glycol, a polyurethane block copolymer of a polyalkylene glycol, or polyalkylene oxide segment the means a polymer by a monomer having both ends or one end or main chain at least one functional group selected from the two or more acrylic groups and methacrylic groups as side chains of the main chain mainly.

Such a polyester block copolymer of polyalkylene glycol is obtained by block copolymerization of polyalkylene glycol with a polyester using an aromatic dicarboxylic acid and an alkylene glycol. The polyalkylene glycol as used herein refers to one having a main chain of —C _n H _2n O— (n = 2 to 4) in the molecule, preferably having a molecular weight in the range of 300 to 40,000. Is in the range of 1000-10000. As such a polyalkylene glycol, for example, polyethylene glycol, polypropylene glycol, or a block polymer thereof can be used. When the molecular weight is less than 300, the durability tends to be insufficient, and when the molecular weight exceeds 40000, the dispersibility tends to decrease.

Next, the polyalkylene glycol polyurethane block copolymer is a polymer or prepolymer having a polyalkylene glycol as a functional group, and preferably a thermal reaction having an isocyanate group blocked with a blocking agent that dissociates by heat. A polyalkylene glycol blocked product of type prepolymer is preferred. A dissociation catalyst may be used to promote dissociation, and dibutyltin thiolate, dibutyltin tearate, stearyl zinc, and organic amine compounds are preferable. Copolymerized water-soluble polyalkylene glycol, terephthalic acid and ethylene glycol, urethane resin containing polyalkylene glycol, or both ends of the main chain mainly composed of polyalkylene oxide segments or as one end or side chain of the main chain Examples thereof include a polymer of a monomer having at least one functional group selected from an acrylic group and a methacryl group.

In the present invention, it is particularly preferable that at least one functional group selected from two or more acrylic groups and methacrylic groups as both ends or one end of the main chain mainly composed of a polyalkylene oxide segment or a side chain of the main chain. The polymerizable monomer having the polymerization is polymerized on the fiber surface. Monomer having at least one functional group selected from two or more acrylic groups and methacrylic groups as both ends of one or the other end of the main chain or a side chain of the main chain mainly comprising the polyalkylene oxide segment in the present invention As, for example, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol-polypropylene glycol dimethacrylate, polyethylene glycol-polypropylene glycol diacrylate, ethylene oxide adduct dimethacrylate of bisphenol A, ethylene oxide adduct diacrylate of bisphenol A, Propylene oxide adduct dimethacrylate of bisphenol A, propylene oxide adduct diacrylate of bisphenol A, etc. These can be used alone or as a mixture of two or more.

    In the present invention, a water repellent is mixed with such a resin.

  In the present invention, it is preferable that the weight mixing ratio of the water repellent to the resin having antistatic properties is 0.001: 1 to 1: 1.

  If the water repellent is less than 0.001, the resin coating having antistatic properties has a strong hydrophilic property, so that even if the water repellent adheres in layers to the coating, sufficient water repellency cannot be obtained. . On the other hand, if it is more than 1, the resin coating having antistatic properties shows a strong water-repellent tendency, and the adhesiveness with the water-repellent agent fixed in a layered manner on the coating is lowered, making it difficult to obtain washing durability. Is.

  Furthermore, it is preferable that it is 0.01: 1-1.0: 1 at the point which makes compatible the function of antistatic and water repellency with sufficient durability.

The water repellent of the present invention is a fluorine water repellent . The fluorine-based water repellent is preferably a copolymer having a polymerization unit of a (meth) acrylic acid ester having a fluoroalkyl group as an essential component, and the alcohol residue part of the (meth) acrylic acid ester is a fluoroalkyl group More preferred are compounds present in

  Such a fluoroalkyl group refers to a group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms. 2-20 are preferable and, as for carbon number of a fluoroalkyl group, 6-16 are especially preferable. The fluoroalkyl group is a linear or branched group, and when it is a branched group, the branched portion is present at the terminal portion of the fluoroalkyl group and has about 1 to 4 carbon atoms. Short chains are preferred. 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 carbon number is preferably 1-20, and particularly preferably 4-16. When the number of carbon atoms is less than 4, the water repellency of the processing agent composition tends to decrease. 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 copolymer essentially including a polymer unit of (meth) acrylic acid ester having a fluoroalkyl group may contain one or two or more of such polymer units.

The copolymer containing, as essential polymerized units of (meth) acrylic acid ester having a fluoroalkyl group of the present invention, the polyalkylene glycol is Dressings containing. Such a polyalkylene glycol is preferably polyethylene glycol or polypropylene glycol. By including such a hydrophilic component, compatibility with the resin having antistatic properties is improved, and affinity when a film is formed on the fiber. As well as improving the adhesion to the water repellent that adheres in layers to the coating.

  Such a resin may contain a water repellent alone or may be contained together with at least one of an aminoplast resin and a polyfunctional isocyanate group-containing urethane resin.

  By being contained together with an aminoplast resin or a polyfunctional isocyanate group-containing urethane resin, the resin strength is increased and the durability is improved.

  In order to further improve the adhesion between the resin coating and the water repellent that is fixed in a layered manner, the polymer coating is preferably subjected to plasma treatment or electron beam treatment.

  The method for forming a film on the fiber with the antistatic resin of the present invention is not particularly limited, but after applying the fiber structure to the treatment liquid by padding or spraying after immersion, There are a method of dry heat treatment or wet heat treatment, a method of adsorbing in a bath of such treatment liquid, and the like.

Particularly preferably in the present invention, at least one functional group selected from two or more acrylic and methacrylic groups as both ends of one or the other end of the main chain mainly composed of a polyalkylene oxide segment or a side chain of the main chain. Although the polymerizable monomer is polymerized on the fiber surface, as a polymerization initiator for polymerizing the polymerizable monomer on the fiber surface, ammonium persulfate, potassium persulfate, azobisisobutyronitrile, A general vinyl polymerization initiator such as ammonium sulfate is used.

  Such a polymer resin film is obtained by immersing a fiber structure in a mixed solution of a polymerizable monomer, a fluorine-based water repellent, and a polymerization catalyst, and squeezing with a constant squeeze rate in a mangle, and a saturated steam or supersaturated steam atmosphere at 80 to 160 ° C. A continuous or discontinuous film can be formed on the fiber surface by treating for 0.5 to 10 minutes.

The water repellent coating layered onto polymer film in the present invention, it is an fluorine-based water repellent agent to maintain high Ibachi aqueous.

  The fluorine-based water repellent is preferably fixed together with at least one of an aminoplast resin and a polyfunctional isocyanate group-containing urethane resin to constitute a resin composition.

  As aminoplast resin, it is possible to use melamine resins such as trimethylol melamine and hexamethylol melamine, urea resins such as dimethylol propylene urea, dimethylol ethylene urea and dimethylol hydroxy urea, and uron resins such as dimethylol uron. it can. Among them, hexamethylol melamine and trimethylol melamine are preferable.

  The polyfunctional isocyanate group-containing urethane resin is not particularly limited as long as it is an organic compound containing two or more isocyanate functional groups in the molecule. Specific examples include tolylene diisocyanate, hexamethylene diisocyanate, diphenyl methane diisocyanate, hydrogenated diphenyl methane diisocyanate, triphenyl triisocyanate, xylene resin isocyanate, dichloromethane methane diisocyanate, trimethylolpropane tolylene diisocyanate adduct, fryserylene tolylene diene. Phenol, malonic acid diethyl ester, methyl ethyl ketoxime, sodium bisulfite, ε-caprolactam, and the like were reacted as a blocking compound that can be dissociated upon heating at 70 to 200 ° C. to an isocyanate adduct and regenerate active isocyanate groups. A polyfunctional block isocyanate urethane resin can be mentioned. 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 diolate, dibutyltin stearate, stearyl zinc and organic amine compounds are preferred.

  Moreover, it is preferable that the water repellent fixed in the form of a layer is a solvent-type water repellent. If a solvent-type water repellent is used, the adhesiveness is improved when the solvent-type water repellent is fixed in layers on the antistatic resin film containing the water repellent.

  The water-repellent agent only needs to be fixed in a layered manner on at least a part of the resin coating having antistatic properties, but it is more preferable that the water-repellent agent is entirely covered.

  The fluorine-based water repellent is preferably fixed at 0.04 to 3% by weight with respect to the fiber weight. If it is less than 0.04% by weight, water repellency cannot be obtained, and if it exceeds 3% by weight, the film thickness becomes large and the texture hardens, and it adheres in a block shape and has durability and prevention of pollen adhesion. It may be difficult to obtain.

As a method for providing such a water repellent, a treatment liquid in which at least one selected from an aminoplast resin and a polyfunctional isocyanate group-containing urethane resin is added to the water repellent is attached to the fiber structure and then heat treated. Is preferred. As a method for applying the treatment liquid, it is preferable that the fiber structure is applied to the treatment liquid after immersion by a padding method or a spray method. The heat treatment is either a dry heat treatment or a wet heat treatment, preferably a dry heat treatment at 100 to 200 ° C. When the temperature is less than 100 ° C, the washing durability is insufficient, and when the temperature exceeds 200 ° C, the fiber tends to yellow or become brittle.

Further, the present invention is a resin film having such antistatic properties are those which contain inorganic fine particles.

  In general, when forming a resin film, it is easy to cause migration at the time of heat treatment or polymerization by applying only the resin and heat treatment, or by polymerizing only the monomer. Although it is difficult to form a uniform film, it is possible to form a uniform film on a single fiber by mixing inorganic fine particles, and this uniform film formation improves washing durability. Is. The coating is uniformly formed, but the term “uniform” as used herein does not mean that the surface is completely smooth but means that the surface is evenly coated.

  Specific 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. These may be used alone or in combination of two or more. Can do. The average particle diameter of the particles is preferably 5 to 500 nm, more preferably 10 to 300 nm. If it is smaller than 5 nm, it will be buried in the resin, and the effect of preventing migration will be small. If it exceeds 500 nm, continuous film formation tends to be insufficient at the time of resin formation. Although it is preferable that the inner diameter is within the range, it is acceptable that a particle having a particle size outside the particle size range is included to the extent that the film formation is not affected.

  In the present invention, the weight mixing ratio between the antistatic resin and the inorganic fine particles is preferably in the range of 0.04 to 1.0 with respect to the resin or the polymerizable monomer 1.

  When the inorganic fine particle is less than 0.04, the migration preventing effect is small and the surface unevenness is small. When the inorganic fine particle is more than 1.0, the film-forming property is deteriorated and the washing durability tends to be hardly obtained.

  Since the fiber structure of the present invention has durable antistatic properties, it has pollen adhesion preventing performance in addition to antistatic and water repellency.

  In the fiber structure of the present invention, pollen adhesion prevention performance is evaluated using simulated pollen. The simulated pollen referred to in the present invention is a particle size of pollen called Ishimatsuko (manufactured by Tsuda Shoten). Refers to natural products close to. Ishimatsuko is a spore of 30-40 μm fern family, 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 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, put 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.

  Examples of the fiber structure of the present invention include polyester fibers, polyethylene fibers, polypropylene fibers, polyamide fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyacrylonitrile fibers and other synthetic fibers, rayon, acetate and the like. Natural fibers such as semi-synthetic fibers, cotton, hemp, silk, wool can be used, and these can be used alone or in combination of two or more, and can be either long fibers or short fibers. You may mix and use. As the structure of the fiber fabric of the present invention, woven fabrics, knitted fabrics, nonwoven fabrics and the like made of the above-mentioned fibers can be used.

  Examples of the polyester fiber include a polyester fiber containing an aromatic component and an aliphatic polyester fiber. Examples of polyester fibers containing an aromatic component include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, or those and third components such as isophthalic acid, isophthalic acid sulfonate, adipic acid, and polyethylene glycol. can do. Examples of the aliphatic polyester fiber include poly L lactic acid, poly D lactic acid and poly D, homopolymer composed of L lactic acid, polylactic acid-glycolic acid copolymer, and the like.

  The polyester fiber may contain various commonly used additives in order to improve productivity and characteristics in the production process and processing process of the raw yarn. For example, additives such as heat stabilizers, antioxidants, light stabilizers, UV absorbers, antistatic agents, colorants, smoothing agents, plasticizers, antibacterial agents, fungicides, and deodorants are added to polyester fibers. It can be included.

  Since the fiber structure of the present invention has antistatic properties, water repellency, and pollen adhesion preventing property, it is particularly clothes and bedding called outerwear, specifically coats, blousons, windbreakers, blouses, dress shirts, It is suitably used for applications such as skirts, slacks, gloves, hats, futon sides, futon drying covers or curtains.

  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.

(Antistatic)
In accordance with JIS L 1094 method “Charging test method for woven and knitted fabrics. Established 1980.03.01”, in a 20 ° C. × 40% RH atmosphere, the friction resistance is measured using cotton as the target fabric. V). The smaller the value, the better the antistatic property.

(Water repellency)
Evaluation was made by the spray method according to JIS L 1092 “Test method for waterproofness of textile products. Establishment 1977.3.1”, and the grade was determined.

Grade 5: No wetting or water droplets on the surface. Grade 4: No wetting on the surface but showing small water droplets. Grade 3: Showing small individual water droplets on the surface. Grade 2: Half of the surface. Indicating wetness, indicating that individual small wetness penetrates the cloth. Grade 1: Indicating wetting on the entire surface, or indicating wetting on the entire surface and backside (prevention of pollen)
Thirty pieces of 7 × 7 cm fiber fabrics are allowed to stand in an environment of 20 ° C. × 65% RH for 24 hours, placed in a polyethylene bag with 1 g of artificial pollen, and about 20 liters in air of 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. Count the number of pseudo pollen within the range of 5 × 10 cm and calculate the average of 3 places.

(Washing durability)
A weak alkaline synthetic detergent specified in JIS K 3371 “Laundry Synthetic Detergent. Established 1972.8.1” is dissolved in an automatic inversion swirl electric washing machine to a concentration of 0.2%, and the bath ratio is 1:50. The process of washing for 25 minutes under strong conditions at a temperature of 40 ± 2 ° C., then draining and washing with overflow water for 10 minutes × 2 times was repeated twice and then air-dried. The antistatic property, water repellency and pollen adhesion preventing property after washing were evaluated after washing by the washing method.

(Examples 1 and 2 )
After weaving a plain fabric using 84 dtex, 72 filament false twisted yarn made of polyethylene terephthalate as warp and weft yarn, the fabric is scoured and washed in hot water at a temperature of 95 ° C. according to a conventional method. Then, it was dried at 130 ° C. and pinter set at 180 ° C. Subsequently, it was dyed with a liquid dyeing machine, dried at 130 ° C., and pintter set at 170 ° C. to obtain a scarlet woven fabric having a warp / width of 140/88 / 2.54 cm.

The dyed fabric was treated by the following method, and the performance was evaluated. All of them had durable antistatic properties, water repellency, and pollen adhesion preventing properties.
<First stage processing>
(Antistatic resin or monomer)
A. Pararesin U-300E (Ohara Palladium Chemical Co., Ltd., reactive urethane resin, solid content 30%)
B. TO-SR-1 (manufactured by Takamatsu Yushi Co., Ltd., polyester resin, solid content 10%)
C. Polyethylene glycol dimethacrylate with a polyalkylene oxide segment of molecular weight 1000 (solid content 100%)
(Water repellent)
D. NK Guard SR-108 (manufactured by Nikka Chemical Co., Ltd., fluorinated water repellent, solid content 20%)
E. F-470 (manufactured by Kyo Silk Kasei Co., Ltd., fluorine water repellent, active ingredient 20%)
(Inorganic fine particles)
Silicon oxide having the following particle size was used as an aqueous dispersion.

F. Snowtex OL (manufactured by Nissan Chemical Industries, solid content 20%, particle size 40-50nm)
(Aminoplast resin)
Sumitses Resin M-3 (manufactured by Sumitomo Chemical Co., Ltd., solid content 80%)
(Polyfunctional block isocyanate-containing urethane resin)
Super Fresh JB-7200 (manufactured by Kyo Silk Chemical Co., Ltd., 40% active ingredient)
The antistatic resin A, B or monomer C, water repellents D, E, and inorganic fine particles F are mixed in the ratios shown in Table 1, and then the dyed cloth is immersed in the treatment liquid. The film was squeezed with mangles so as to be 100%, and A and B were dried with a dryer at 130 ° C. and subjected to a dry heat treatment at 170 ° C. for 1 minute. For C, 2 g / l of ammonium persulfate was used as a catalyst in the treatment solution, and after squeezing with mangle, the treatment was carried out in a saturated steam atmosphere at 105 ° C. for 3 minutes, and then 1 g / L of nonionic surfactant. It was washed for 1 minute in an aqueous solution of sodium carbonate 1 g / L at 60 ° C., washed with water, and dried at 130 ° C.
<Second stage processing>
Next, it was immersed in the processing liquid which mixed the following, and was squeezed with the mangle so that the squeezing rate of the processing liquid might be 100%. Then, it dried with the 130 degreeC dryer and performed the heat processing for 1 minute at 170 degreeC.
(Water repellent)
F-470 (manufactured by Kyo Silk Chemical Co., Ltd., fluorine-based water repellent, solid content 20%) 50 g / l
(Aminoplast resin and catalyst)
Sumitses Resin M-3 (manufactured by Sumitomo Chemical Co., Ltd., solid content 80%) 3 g / l
Sumitex Resin Accelerator ACX (Sumitomo Chemical Co., Ltd., solid content 35%)
0.5g / l
(Polyfunctional block isocyanate-containing urethane resin)
Super Fresh JB-7200 (manufactured by Kyokin Kasei Co., Ltd., 40% active ingredient) 5g / l
(Comparative Example 1)
The same treatment as in Example 1 was performed except that the treatment was not performed with the second-stage fluorine-based water repellent-containing treatment liquid. The results of evaluating the performance are shown in Table 1.

  Although the antistatic property and the pollen adhesion preventing property can be obtained, the water repellency cannot be obtained, and when applied to a coat or the like, basically the required functions are not provided.

(Comparative Example 2)
The same treatment as in Example 6 was performed except that the treatment was not performed with the second-stage fluorine-based water repellent-containing treatment liquid. The results of evaluating the performance are shown in Table 1.

  Although the antistatic property and the pollen adhesion preventing property can be obtained, the water repellency cannot be obtained, and when applied to a coat or the like, basically the required functions are not provided.

(Comparative Example 3)
The same treatment as in Example 1 was performed except that the water repellent was not mixed with the first-stage antistatic resin. The results of evaluating the performance are shown in Table 1. Although the durability of the frictional voltage was obtained, the durability of the water repellency was low.

(Comparative Example 4)
The same treatment as in Example 7 was performed except that the water repellent was not mixed with the first-stage polymerizable monomer. The results of evaluating the performance are shown in Table 1. Although the durability of the frictional voltage was obtained, the durability of the water repellency was low.

(Comparative Example 5)
The same treatment as in Example 1 was performed, except that the treatment was not performed with the treatment liquid with the first-stage antistatic resin. The results of evaluating the performance are shown in Table 1. Since the durability of water repellency is not sufficient and there is no antistatic property, pollen adheres due to static electricity and is unpreferable for clothing.

Claims (7)

Containing water repellent , inorganic fine particles on the fiber surface, polyalkylene glycol polyester block copolymer, polyalkylene glycol polyurethane block copolymer, or both ends of the main chain mainly composed of polyalkylene oxide segments are terminal or resin coating the polymerizable monomer to have a antistatic polymerized with at least one functional group selected from the two or more acrylic groups and methacrylic groups as side chains of the main chain is formed Further, at least a part of the coating film is coated with a fluorine-based water repellent and fixed in layers, and the water-repellent agent contained in the antistatic resin contains a polyalkylene glycol. The fiber structure characterized by being. On the fiber surface, a polymerizable monomer having two or more methacryl groups as both ends of one of the main chains mainly composed of a polyalkylene oxide segment or one of the main chains or a side chain of the main chain and a water repellent 1: A film formed by polymerizing a composition containing 0.01 to 1: 1.0 is formed, and at least a part of the film is coated with a water repellent and fixed in a layered manner. fiber structure of claim 1, wherein the. Both of the fluorine-based water repellent contained in the resin having antistatic properties and the fluorine-based water repellent fixed in a layer form must have a polymer unit of (meth) acrylic acid ester having a fluoroalkyl group. fiber structure according to claim 1 or 2, characterized in that a copolymer to be. Water repellent is coated on the layer shape, claim 1, characterized in that is obtained by forming a resin to be film with any of the aminoplast resin or aminoplast resin and a polyfunctional isocyanate group-containing urethane resin 4. The fiber structure according to any one of 3 . The fiber structure according to any one of claims 1 to 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 has 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. Coat, jackets, windbreaker, blouses, dress shirts, skirts, slacks, gloves, hats, futon side ground, according to any one of claims 1 to 6, characterized in that for use in any of the duvet dry cover or curtain Fiber structure.