JPWO2015083627A1 - Fiber structure - Google Patents

Abstract

An object of the present invention is to provide a fiber structure exhibiting excellent water repellency and washing durability. The solution for that is that a resin film containing a hydrocarbon compound, a silicone compound and a melamine compound is fixed to the fiber surface, and the total amount of the silicone compound is 1 to 1 relative to the hydrocarbon-containing compound. It is a fiber structure having water repellency of 50% by mass. Examples of the hydrocarbon compounds include aliphatic hydrocarbons and polyolefins having 12 or more carbon atoms, aliphatic carboxylic acids having 12 or more carbon atoms and esterified products thereof, and hydrocarbon groups existing via ester bonds having 12 or more carbon atoms. A (meth) acrylic acid ester is preferred. The silicone compound is preferably selected from amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, methyl hydrogen silicone, and dimethyl silicone.

Description

  The present invention relates to a fiber structure having water repellency.

  Conventionally, in order to obtain a fiber structure with improved water repellency, means for fixing a fluorinated water repellent to the fiber surface is generally used, and various techniques have been proposed.

  In recent years, some of the fluorine-based water repellents may affect living environment and living organisms, such as perfluorooctanoic acid (hereinafter referred to as “PFOA”), perfluorooctanesulfonic acid (hereinafter referred to as “PFOS”). And the like, and there has been a demand for a fiber product using a fluorine-based water repellent that does not contain the substance or has as little content as possible.

  Furthermore, the generation of dioxins due to incineration of garbage has become a serious problem as an environmental measure, and the toxicity of halogenated dioxins other than chlorine is gradually becoming apparent.

  For this reason, it has become necessary to examine materials that can replace fluorine and technologies that impart water repellency using different methods.

   As such an environmentally conscious water repellent process, first, measures are taken to prevent PFOA from being included. Water- and oil-repellent durability and water-repellent and water-repellent properties that can suppress the release of PFOA to the environment, such as drainage, and the generation of PFOA from water- and oil-repellent fabrics in the manufacturing process of water- and oil-repellent fabrics. Attempts have been made to provide oily fabrics. A method of applying a PFOA-free fluorine-based water repellent and a crosslinking agent to a fiber fabric is disclosed (Patent Document 1). A fiber structure characterized in that a mixture of a fluorine-based water repellent and a water repellent compound not containing fluorine element is fixed on the fiber surface, and the concentration of PFOA and / or PFOS is extremely low. Have been proposed (Patent Document 2).

  Although these technologies are environmentally friendly, they use fluorine-containing water repellents, and the existence of environmental loads cannot be denied.

   As a water-repellent process that does not use a fluorine-based water repellent, there has been proposed a water-repellent fabric treated with a water-repellent treating agent composed of an organopolysiloxane having a reactive group at the molecular chain end (Patent Document 3). However, the water repellency is low, and even if only silicone is applied, the washing durability is low, and the slip between the threads is large, and there is a problem that the seam opens during use or wearing. .

  Although not intended for water repellency, a silicone synthetic resin is applied to a woven fabric in which polyamide synthetic fibers having a fineness of 5 to 30 dtex are arranged and the number of intersections between warps and wefts is 23,000 to 70000 pieces / (2.54 cm square) An applied thin fabric has been proposed (Patent Document 4).

  This is provided with a silicone resin for the purpose of improving the fact that a fine fabric and a high-density fabric have low tear strength. The silicone described in Patent Document 4 suppresses the stress at the time of tearing by sliding the thread, and there is no description regarding water repellency in the document.

  In addition, as a water-repellent process that does not use a fluorine-based water repellent, a hydrocarbon-based water repellent is a non-fluorine-based polymer containing an acrylic ester or methacrylic ester having 12 or more ester moieties as a monomer unit. There has been proposed a water-repellent fiber product in which a water-repellent agent is adhered to a fiber product (Patent Document 5). However, if the amount of the water repellent applied to the fiber and the amount of the crosslinking agent used are not suitable, sufficient water repellency for washing durability cannot be obtained, and the texture is hard when fixed to the fiber surface alone. However, when used in a thin fabric of ultrafine fibers, the present condition is that the rough feeling of the texture is remarkably manifested.

JP 2011-214216 A JP 2007-247091 A JP 2002-114972 A JP 2012-122188 A JP 2006-328624 A

  In view of the above problems, the present invention is intended to provide a fiber structure that takes into consideration environmental problems, does not require an elemental fluorine compound, and exhibits excellent water repellency and washing durability.

In order to solve the above problems, the present invention comprises the following fiber structure.
(1) A resin film containing a hydrocarbon compound, a silicone compound and a melamine compound is fixed to the fiber surface, and the total amount of the silicone compound is 1 to 50% by mass with respect to the hydrocarbon-containing compound. A certain fiber structure.
And as a preferable aspect of the said fiber structure, there exist the following fiber structures.
(2) The fiber structure, wherein the silicone compound is at least one selected from amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, methyl hydrogen silicone, and dimethyl silicone.
(3) The fiber structure according to any one of the above, wherein the hydrocarbon compound is at least one selected from aliphatic hydrocarbons having 12 or more carbon atoms and polyolefins.
(4) The fiber structure according to any one of the above, wherein the hydrocarbon compound is at least one selected from aliphatic carboxylic acids having 12 or more carbon atoms and esterified products thereof.
(5) The fiber structure according to any one of the above, wherein the hydrocarbon compound is a polymer of acrylic acid ester or methacrylic acid ester having 12 or more carbon atoms in a hydrocarbon group present via an ester bond.
(6) The fiber structure according to any one of the above, wherein the resin film further contains a urethane compound.
(7) The fiber structure according to any one of the above, wherein the fiber form is any one of a woven fabric, a knitted fabric, a nonwoven fabric, and a string.
(8) The fiber structure according to any one of the above, wherein the water repellency after 10 home washings is 3 or more.

In order to solve the above problems, the present invention comprises the following method for producing a fiber structure.
(9) A method for producing a fiber structure, comprising a step of bringing a coating composition containing a hydrocarbon group-containing compound, a silicone-based compound, and a melamine compound into contact with a fiber and attaching them to the surface of the fiber.

And as a preferable aspect of the manufacturing method of the said fiber structure, there exists the manufacturing method of the following fiber structures.
(10) The method for producing a fiber structure, wherein the silicone compound is at least one selected from amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, methyl hydrogen silicone, and dimethyl silicone.
(11) The method for producing any one of the fiber structures, wherein the hydrocarbon compound is at least one selected from aliphatic hydrocarbons having 12 or more carbon atoms and polyolefins.
(12) The method for producing any one of the fiber structures, wherein the hydrocarbon compound is at least one selected from aliphatic carboxylic acids having 12 or more carbon atoms and esterified products thereof.
(13) The fiber according to any one of the above, wherein the hydrocarbon compound contains, as an essential component, an acrylic ester or methacrylic ester polymer in which the hydrocarbon group present via an ester bond has 12 or more carbon atoms. Manufacturing method of structure.
(14) Any of the fiber structures having a step of attaching a compound having an anion group to a fiber before bringing the composition for a film containing a hydrocarbon group-containing compound, a silicone-based compound and a melamine compound into contact with the fiber. Manufacturing method.
(15) The method for producing a fiber structure, wherein the compound having an anion group is at least one selected from a sulfone group-containing compound and a polyhydric phenol compound.
(16) The method for producing a fiber structure according to any one of the above, wherein the calendering step is performed after the step of attaching the composition containing the hydrocarbon group-containing compound, the silicone compound and the melamine compound to the fiber.

  According to the present invention, a fiber structure exhibiting excellent water repellency can be obtained.

   If the word “sticking” is defined in the present invention, it means a state of being physically or chemically bonded. In this state, the treatment agent does not easily fall off due to washing or the like.

As the hydrocarbon group-containing compound of the present invention, Neoseed NR-90 (manufactured by Nikka Chemical Co., Ltd.), NR-158 (manufactured by Nikka Chemical Co., Ltd.), TH-44 (manufactured by Nikka Chemical Co., Ltd.) , PW-182 (manufactured by Yamato Chemical Co., Ltd.) Fobor RSH (manufactured by Huntsman Japan Co., Ltd.), palladium ECO-500 (manufactured by Ohara Paradium Chemical Co., Ltd.), NX018 (manufactured by Nanotex Co., Ltd.) and the like. Specifically, the following are exemplified.
Aliphatic hydrocarbons: For example, paraffinic hydrocarbons and olefinic hydrocarbons. The number of carbons is preferably 12 or more.
Aliphatic carboxylic acid: may be saturated or unsaturated, and preferably has 12 or more carbon atoms. It may be an esterified product of an aliphatic carboxylic acid.
Polyolefin: For example, polyethylene, polypropylene, ethylene-propylene copolymer.
Polyacrylic acid ester and polymethacrylic acid ester: The hydrocarbon group present via an ester bond preferably has 12 or more carbon atoms. On the other hand, the carbon number is preferably 24 or less. This hydrocarbon group may be linear or branched, may be saturated or unsaturated, and has an alicyclic or aromatic ring. You may do it. Among these, those that are linear are preferable, and those that are linear alkyl groups are more preferable. The monomer of acrylic acid ester or methacrylic acid ester in such a polymer is preferably 80 to 100% by mass with respect to the total amount of monomer units constituting the polymer. Moreover, it is preferable that the weight average molecular weight of this polymer is 500,000 or more. It may be a copolymer of acrylic acid ester and methacrylic acid ester.

  The silicone compound is polysiloxane and usually has a dimethylsiloxane structural unit. Polydimethylsiloxane is one in which dimethylsiloxane structural units are connected. This is also called dimethyl silicone. Those in which the methyl group of the siloxane structural unit is substituted with a phenyl group or those substituted with hydrogen, for example, a methylphenylsiloxane structural unit, a diphenylsiloxane structural unit, or a methylhydrogensiloxane structural unit can also be used.

  Examples of the amino-modified silicone include those having a structure in which an amino group is bonded to an organic group directly bonded to a silicon atom. The organic group may be an alkylene group or a divalent aromatic group. An alkylene group having 2 or more carbon atoms is preferred. As the divalent aromatic group, those having 6 or more carbon atoms are preferred. The amino group may be a primary amino group, a secondary amino group, or a tertiary amino group. Examples of the organic group to which the amino group is bonded include the following. 2-aminoethyl group, N-methyl-2-aminoethyl group, N, N-dimethyl-2-aminoethyl group, N-ethyl-2-aminoethyl group, N, N-diethyl-2-aminoethyl group, N, N-methylethyl-2-aminoethyl group, 3-aminopropyl group, N-methyl-3-aminopropyl group, N, N-dimethyl-3-aminopropyl group, N-ethyl-3-aminopropyl group N, N-diethyl-3-aminopropyl group, N, N-methylethyl-3-aminopropyl group. These functional groups may be in the side chain of the polysiloxane or at the terminal.

  Examples of the epoxy-modified silicone include those having a structure in which an epoxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be an alkylene group or a divalent aromatic group. Such a form is usually bonded to the organic group in the form of glycidyl ether. Examples of such a functional group include a 3-glycidoxypropyl group and a 2-glycidoxyethyl group. These functional groups may be in the side chain of the polysiloxane or at the terminal.

  Examples of the carboxy-modified silicone include those having a structure in which a carboxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be an alkylene group or a divalent aromatic group. An alkylene group having 2 or more carbon atoms is preferred. As the divalent aromatic group, those having 6 or more carbon atoms are preferred. Examples of such a functional group include a 3-carboxypropyl group and a 2-carboxyethyl group. These functional groups may be in the side chain of the polysiloxane or at the terminal.

Methyl hydrogen silicone is one in which a part of the side chain of polydiorganosiloxane is replaced with hydrogen and a hydrogen atom is directly connected to a silicon atom. In using methyl hydrogen silicone, a catalyst may be used to improve the reactivity. For example, zinc, tin, manganese, cobalt and iron based catalysts can be used. These catalysts are preferably organic acid metal salts, and the organic acid is preferably a fatty acid. From the viewpoint of safety, zinc stearate or the like can be used. The catalyst is preferably used in an amount of 10 to 40% based on methyl hydrogen silicone because the effect is easily exhibited.
Two or more kinds of amino-modified, epoxy-modified silicone, carboxy-modified silicone and methylhydrogen silicone may be mixed. Both are silicones having a reactive group, and are preferably silicones having film-forming properties. The film-forming property refers to forming a solid film rather than oil or gel after each silicone is adhered to the fiber surface in an emulsion state.

  In adhering to a fiber, it is preferable to contact the fiber with a coating composition containing a hydrocarbon compound, a silicone compound and a melamine compound. In such a composition, the silicone compound is preferably mixed in a proportion of 0.1 to 50% by mass with respect to the hydrocarbon compound. Furthermore, although any of the following compounds is essential, the total of amino-modified, epoxy-modified silicone, carboxy-modified silicone, dimethylsilicone and methylhydrogensilicone is preferably 0.1 to 50% by mass. More preferably, the ratio is 0.8 to 16% by mass. Thereby, durability can be further improved. A resin that is brittle with only a hydrocarbon-based compound becomes flexible by containing such silicone, and durability is improved by being fixed to the fiber surface.

  If the amount of silicone is too small relative to the hydrocarbon-based compound, the effect of improving the film property tends to decrease, and if it is too large, the water repellency tends to decrease.

Moreover, as a preferable aspect of the fiber structure of the present invention, the hydrocarbon group-containing compound is fixed in a proportion of 0.2 to 1.2% by mass with respect to the fiber mass.
If the amount is small, the ratio of covering the fiber surface tends to be small, and sufficient water repellency tends to be hardly obtained. Moreover, even if it is too much, the increased water repellency does not necessarily improve.

  The silicone compound is preferably 0.5 to 50% by mass with respect to the hydrocarbon compound, and if it is less than 0.5% by mass, the effect of improving washing durability is small. Is unfavorable because it inhibits water repellency and also increases the slipperiness of the yarn surface.

  As a preferred embodiment of the present invention, the coating composition further contains a melamine compound. The amount is preferably 15 to 100% by mass relative to the hydrocarbon group-containing compound.

By forming a resin film from a composition containing a melamine compound, it is considered that the orientation of the methyl group that develops the water repellency of hydrocarbon groups and silicone proceeds, and in addition to improving the water repellency immediately after processing, Adhesion with fibers is improved and washing durability is improved.
Examples of the melamine compound include trimethylol melamine and hexamethylol melamine. An organic amine catalyst may be added to the melamine compound.

  The coating composition preferably contains a urethane compound. As a result, the resin film contains a urethane compound.

  The urethane compound is preferably a urethane compound obtained by reacting an isocyanate group. There is no particular limitation as long as it is obtained from an organic compound having two or more isocyanate groups in the molecule. Examples of such an organic compound having an isocyanate group include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, triphenyl triisocyanate, xylene diisocyanate, dichloromethane methane diisocyanate, and the like. Furthermore, there are compounds that can regenerate isocyanate groups by heating to 70 to 200 ° C., such as trimethylolpropane tolylene diisocyanate adduct and frucrine tolylene diisocyanate adduct. Examples of such compounds include polyfunctional blocked isocyanate group-containing compounds obtained by reacting an isocyanate compound with phenol, malonic acid diethyl ester, methyl ethyl ketoxime, sodium bisulfite, ε-caprolactam, and the like.

   It is preferable that 0.03 to 0.15% by mass of the urethane compound is attached to the fiber. If the amount is too small, the effect as a binder may not be sufficiently exhibited. If the amount is too large, the texture as a fiber structure is impaired, and in addition to becoming hard, water repellency tends to be lowered. From the viewpoint of water repellency after processing and washing durability, 0.02 to 0.08% by mass is more preferable.

   The resin film of the fiber structure of the present invention may contain a temporary antistatic agent. As the temporary antistatic agent, it is preferable to use a material that does not hinder water repellency. Temporary antistatic agents include anionic surfactants such as higher alcohol sulfates, sulfated oils, sulfonates, phosphate esters, cations such as amine salt types, quaternary ammonium salts, and imidazoline type quaternary salts. Surfactants, non-ionic surfactants such as polyethylene glycol type and polyhydric alcohol ester type, amphoteric surfactants such as imidazoline type quaternary salt, alanine type and betaine type, and polymer compound types mentioned above. At least one kind of electropolymer, polyalkylamine and the like can be used.

  On the other hand, slipping between yarns and yarns may be increased by containing an antistatic agent, and preferably an antistatic agent composed of an organic salt of guanidine hydrochloride is preferable from the viewpoint that it is difficult to inhibit slippage and water repellency. .

   An antistatic agent exhibits an effect by containing 0.02-0.1 mass% with respect to a fiber structure, and there is also little inhibition to water repellency.

  The resin film of the present invention may contain fine particles. A preferred particle size is 10 μm or less. The particles may be either inorganic fine particles or organic fine particles, and may be mixed.

   Examples of the inorganic fine particles include aluminum oxide, silicon dioxide, 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 dioxide can be preferably used.

  The particle diameter of such particles is preferably 5 to 500 nm, more preferably 10 to 100 nm.

  Examples of the organic fine particles include particles made of acrylic resin, olefin resin, and melamine resin. Furthermore, composite particles obtained by coating the surface of organic particles with silica or alumina can also be used.

  The particle diameter of the particles is preferably 0.01 to 10 μm, more preferably 0.1 to 6 μm.

   The particle diameter referred to in the present invention is obtained by observing the fiber structure with an SEM (scanning electron microscope) and measuring the size of the particles.

   By containing the particles, there is an effect of suppressing slippage between the yarns caused by the silicone compound and the hydrocarbon compound adhering to the fiber surface.

   Moreover, since a fine unevenness | corrugation is formed in the fiber surface by containing particle | grains, a lotus leaf effect is acquired. Further, since the resin is easily fixed uniformly on the fiber surface and the adhesion to the fiber is improved, higher water repellency and durability can be obtained.

  Regarding the method for fixing the resin containing the hydrocarbon group-containing compound and the silicone compound to the fiber surface, the fiber structure is immersed in an emulsion solution, which is a film composition mixed with the compound, and then fixed in a spread state. A method of squeezing with pressure and drying at a high temperature is exemplified. A pad dry cure method of drying at 80 to 140 ° C. and then heat treatment at a temperature of 160 to 200 ° C., or a pad steam method in an atmosphere of 100 to 200 ° C. containing steam is preferable.

   Moreover, in manufacturing the fiber structure of the present invention, the coating composition may be contacted with the fiber and then calendered. Moreover, you may apply the temperature of the cold calender which does not apply temperature, and 130-200 degreeC. In these processes, the linear pressure is preferably 250 to 20000 N / cm. By performing the calendering process, an effect of further suppressing slippage between the fibers can be obtained.

  Normally, when a hydrocarbon compound or silicone compound is applied to the fiber surface, the surface of the thread becomes highly slippery, and when the sewing product is made of woven fabric, a phenomenon called seam misalignment that causes the seam of the sewing machine to open occurs. To do.

  The resin film of the present invention can suppress such stitch misalignment by using a melamine compound in combination, and the effect is improved by using inorganic particles in combination.

  The fiber structure of the present invention preferably has a seam misalignment of 3 mm or less at a load of 49 N when measured by JIS L 1096 “General Textile Test Method” (revised in 1999) by the sliding resistance method B method.

  As a preferred embodiment of the fiber structure of the present invention, after performing a pretreatment for adhering at least one selected from a sulfone group-containing compound having an anionic group and a polyhydric phenol compound on the fiber surface, a silicone compound is further added. It is preferable that the hydrocarbon group-containing compound and the melamine compound to be preferably added are attached.

  It is considered that the adhesion of the silicone-based compound and the hydrocarbon group-containing compound to be laminated is improved and the durability is improved by fixing the compound having an anion group on the fiber surface.

   As such a sulfone group-containing compound, a compound having affinity for the amino group of a polyamide fiber having a sulfone group in its molecular structure is preferable. For example, a salt of an α-olefin sulfonate, a sulfonate of a phenol formalin resin, or isophthalic acid. Examples include dimethyl sulfonic acid sodium salt. More preferred is a salt of an α-olefin sulfonate having an average carbon number of 12 to 30. Examples of the polyhydric phenol compound of the present invention include natural tannins and synthetic tannins represented by sulfonated phenol formalin resins such as novolac type and resol type.

  The method for fixing the sulfone group-containing compound and the polyhydric phenol compound to the fiber is not particularly limited, but preferably an aqueous solution containing the sulfone group-containing compound or polyhydric phenol compound (hereinafter referred to as “previous”). It is preferable to immerse the fiber structure in a “treatment liquid”. The sulfone group-containing compound and polyhydric phenol compound are preferably 1 to 10% by mass, more preferably about 2 to 5% by mass, based on the fiber. When the amount is small, the effect of further improving durability is not exhibited. When the amount is large, the texture of the fiber structure tends to be hard. It is preferable to adjust the pH of the pretreatment liquid to 2 to 6 in order to obtain the effect of improving the adhesiveness and durability. For pH adjustment, an acid such as acetic acid, maleic acid, hydrochloric acid, sulfuric acid, formic acid may be used, and there is no particular limitation.

   The bath ratio (mass ratio) between the fiber structure of the present invention and the pretreatment liquid is not particularly limited, but is preferably in the range of 10 to 50 of the pretreatment liquid with respect to the fiber structure 1.

    The pretreatment temperature is preferably 40 to 100 ° C, more preferably 50 to 90 ° C, and the treatment time is preferably 10 to 60 minutes.

  After such treatment, the silicone compound, the hydrocarbon group-containing compound and the melamine compound are laminated and fixed by the pad dry cure method described above or the pad steam method after washing with hot water and drying.

  The fibers used in the present invention are preferably synthetic fibers. Aromatic polyester fiber such as polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate Polyester fibers composed of aliphatic polyester fibers represented by lactic acid and a mixture of the above-mentioned polyesters; polyamide fibers such as nylon 6 and nylon 66; acrylic fibers represented by polyacrylonitrile; polyethylene Polyolefin fiber such as polypropylene and polypropylene, and polyvinyl chloride fiber are preferably used. A polyurethane elastic fiber may be combined with these fibers.

  In addition to synthetic fibers, semi-synthetic fibers such as acetate and rayon, and natural fibers such as cotton, hemp, silk, and wool may be used. 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 fiber structure of the present invention includes fabrics such as woven fabrics, knitted fabrics and nonwoven fabrics using the above-mentioned fibers, or string-like materials, and fabrics are preferred for the purpose of exhibiting a water-repellent effect.

  Since the fiber structure of the present invention exhibits excellent water repellency and flexible texture, it is particularly suitable for clothing and bedding called outerwear, specifically, down linings, coats, blousons, windbreakers, blouses, and dress shirts. , Skirts, slacks, gloves, hats, futon sides, futon covers, curtains or tents, etc., and are suitably used for textile products such as clothing and non-clothing products.

  Among them, applications for high water repellency include downsides and windbreakers. For these applications, a high-density fabric using ultrafine fibers is preferred because down-out and windbreakability are required. It is. When a high-density fabric using ultrafine fibers is used, it is preferable that the total fineness is 5 to 55 dtex and the single fiber fineness is 0.4 to 2.2 dtex.

  If the total fineness is too small, the strength is weak, and tearing is likely to occur when worn, and there is an undesirable occurrence of scuffing and thread breakage during papermaking. On the other hand, if the total fineness is too large, the texture of the woven fabric or product tends to be hard and wear comfort tends to be lost. The preferred range is 5-55 dtex, more preferably 7-44 dtex.

  In the case of a high-density woven fabric using ultrafine fibers, the single fiber fineness of the fibers is preferably 0.4 to 2.2 dtex. If the single fiber fineness is too small, a soft texture can be obtained, but the single yarn breaks and pilling tends to occur during wearing. On the other hand, if the single fiber yarn fineness is too large, the texture becomes hard and the windproof performance tends to be lowered. The single fiber fineness is a value obtained by dividing the total fineness by the number of filaments.

  EXAMPLES Hereinafter, although the fiber structure of this invention is demonstrated in detail by an Example, this invention is not limited by these Examples. Evaluation was performed by the following method.

(Washing method)
The method prescribed in 103 of Attached Table 1 of JIS L0217 “Display Symbols and Handling Methods for Textile Products” (1995) is washed by a simple method. Specifically, water of 40 ± 2 ° C is added to a household electric washing machine with a centrifugal dehydrator specified in JIS C 9606 so that the bath ratio (mass ratio) is 1:30, and a weak alkaline synthetic detergent is added. It was dissolved and washed for 25 minutes under strong conditions. Next, drainage and dehydration were carried out, and water was newly added so that the bath ratio became 1:30, followed by rinsing for 10 minutes. After draining and dewatering again, water was newly added so that the bath ratio became 1:30, and rinsing was performed for 10 minutes to drain and dewater. This process was carried out for 5 washings, and this was repeated twice to make a simple method of 10 home washings. And after washing, it was hung in a room under an environment of 20 ° C. × 65% RH and dried.

(Water repellency)
Evaluation was made by the spray test method according to the method prescribed in JIS L 1092 “Test method for waterproofness of textile products” (amended in 1998), and the grade was determined. For example, when water repellency of 4th grade or more and less than 5th grade is shown, it is set to 4-5 grade.

(Slip resistance)
It was measured at an initial load of 49 N according to JIS L 1096 “General Textile Test Method” (revised in 1999) by the sliding resistance method B method.

(Test fabric 1)
Nylon 6 yarn of 22 decitex and 20 filaments is used for both warp and weft, width: 165, 0 cm, warp yarn density: 185 yarns / 2.54 cm, weft yarn density: 155 yarns / 2.54 cm, and air jet Weaved in the room.

The obtained raw machine was scoured with an open soaper (90 ° C.), then intermediately set with a pin tenter (180 ° C. × 40 seconds), and dyed beige with a liquid dyeing machine. In Examples 2 to 11 and Comparative Examples 1 to 8, the same liquid flow dyeing machine was used, and the bath ratio was adjusted to 1:20 with the processing liquid shown below, and the temperature was changed from room temperature to 80 ° C. at 2 ° C./min. The temperature was raised and the treated fabric was treated in a bath for 30 minutes. Next, after the temperature was lowered to 50 ° C., the liquid was sequentially discharged, and the fabric was washed with water, dehydrated, and then dried at 140 ° C. using a pin tenter.
The chemical | medical agent used for Examples 2-11 and Comparative Examples 1-8 is a thing of the next description.

  Nylon fix 501 (manufactured by Senka Co., Ltd., polyhydric phenol condensate): 5% owf.

(Test fabric 2)
Use 33 decitex, 72 filament polyethylene terephthalate yarn for both warp and weft yarns, width: 165, 0 cm, warp yarn density: 175 yarns / 2.54 cm, weft yarn density: 149 yarns / 2.54 cm, and air jet Weaved with.

    The obtained raw machine was scoured with an open soaper (90 ° C.), then set with a pin tenter (180 ° C. × 40 seconds), dyed beige with a liquid dyeing machine, and dried. The obtained fabric was used as a test base fabric 2.

(Examples 1-11, Comparative Examples 1-8)
After immersing the test base cloth 1 in the emulsion solution shown in Table 1 and squeezing it with a mangle, it is dried at 130 ° C. for 2 minutes using a pin tenter, and then subjected to a dry heat treatment at 170 ° C. for 1 minute at a certain width using the pin tenter. went. The mangle squeezing rate was 40%.

(Examples 12-14, Comparative Examples 9-11)
In Examples 12 to 14 and Comparative Examples 9 to 11, the test base fabric 2 was used.
In Examples 13 and 14, as a pretreatment, after dyeing, the same flow dyeing machine was used to adjust the bath ratio to 1:20 with the processing liquid shown below, and the temperature was raised from room temperature to 80 ° C. at 2 ° C./min for 30 minutes. Treated in bath. Next, after the temperature was lowered to 50 ° C., the waste liquid, washed with water, and dehydrated were dried at 140 ° C. using a pin tenter. The obtained fabric was used.
The drugs used in Example 13 are as described below.
Nylon Fix 501 (Senka Co., Ltd. polyhydric phenol condensate): 5% owf
The drugs used in Example 14 are as described below.
Mena 25 (Maroise Chemical Co., Ltd. aromatic sulfonic acid derivative): 5% owf
Maleic acid: 2 g / L.

   Table 1 shows the results of measuring the water repellency and slip resistance of the test base fabrics obtained in Examples 1 to 14 and Comparative Examples 1 to 11 after 10 times of washing.

  About Examples 1-11, the high water repellency of the 4th grade or more of initial stage and the washing durability of the 3rd grade or more are shown even after 10 washings. Moreover, the slip-proof resistance was 3 mm or less, and a water-repellent fiber structure having good physical properties was obtained. On the other hand, Comparative Examples 1, 2 and 4 were low in water repellency from the beginning and very low from the viewpoint of washing durability. In Comparative Examples 5 and 7, although the initial water repellency is high, the washing durability is low. In Comparative Example 7, the water repellency is high both in the initial stage and after the washing, but the slip resistance is over 3 mm. When worn as a sewing product, the seam misalignment was large and the quality was poor.

  12 to 14 using the test base fabric 2 also show high water repellency at the initial grade 4 or higher and washing durability at the grade 3 or higher even after 10 washings. On the other hand, Comparative Examples 9 and 10 had high initial water repellency but low washing durability, and Comparative Example 11 had low water repellency from the beginning.

  Further, Example 10 was observed with a SEM (scanning electron microscope S-3500N (manufactured by Hitachi, Ltd.)) at a magnification of 5000, and it was confirmed that particles of 40 to 50 nm were adhered.

  The water repellency showed high durability of grade 3 or higher even after 10 home washings.

  Example 11 was observed using a SEM (scanning electron microscope S-3500N (manufactured by Hitachi, Ltd.)) at a magnification of 5000, and it was confirmed that particles having a particle diameter of 3 to 4 μm were adhered.

  Such particles act as an anti-slip effect on the yarn, and the slip-off resistance tends to be low.

In the table, "Light Tech", "Asahi Guard", "Snow Tech", "Opto Beads", and "Beccamin" are registered trademarks in Japan. “Neo Seed” is a registered trademark in Japan in Japanese characters.

   Since the fiber structure of the present invention has high water repellency, it can be used for clothing and textile materials.

  Among them, it can be preferably used for applications that require physical control such as down-out prevention in addition to water repellency and a soft texture such as the side of a down jacket.

Claims (16)

A fiber structure in which a resin film containing a hydrocarbon compound, a silicone compound and a melamine compound is fixed to the fiber surface, and the total amount of the silicone compound is 1 to 50% by mass with respect to the hydrocarbon-containing compound object. 2. The fiber structure according to claim 1, wherein the silicone compound is at least one selected from amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, methyl hydrogen silicone, and dimethyl silicone. The fiber structure according to claim 1 or 2, wherein the hydrocarbon compound is one or more selected from aliphatic hydrocarbons having 12 or more carbon atoms and polyolefins. The fiber structure according to claim 1 or 2, wherein the hydrocarbon compound is at least one selected from aliphatic carboxylic acids having 12 or more carbon atoms and esterified products thereof. 3. The fiber structure according to claim 1 or 2, wherein the hydrocarbon compound is a polymer of an acrylate ester or a methacrylate ester having 12 or more carbon atoms in a hydrocarbon group present via an ester bond. The fiber structure according to any one of claims 1 to 5, wherein the resin film further contains a urethane compound. The fiber structure according to any one of claims 1 to 6, wherein the form of the fiber is any one of a woven fabric, a knitted fabric, a nonwoven fabric and a string. The fiber structure according to any one of claims 1 to 7, wherein the water repellency after 10 home washings is 3 or more. The manufacturing method of the fiber structure which has the process which makes the composition for film | membrane containing a hydrocarbon group containing compound, a silicone type compound, and a melamine compound contact a fiber, and makes these adhere to the surface of a fiber. The method for producing a fiber structure according to claim 9, wherein the silicone compound is one or more selected from amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, methyl hydrogen silicone, and dimethyl silicone. The method for producing a fiber structure according to claim 9 or 10, wherein the hydrocarbon compound is at least one selected from aliphatic hydrocarbons having 12 or more carbon atoms and polyolefins. The method for producing a fiber structure according to claim 9 or 10, wherein the hydrocarbon compound is at least one selected from aliphatic carboxylic acids having 12 or more carbon atoms and esterified products thereof. The fiber according to claim 9 or 10, wherein the hydrocarbon-based compound contains, as an essential component, an acrylic ester or methacrylic ester polymer having a hydrocarbon group present through an ester bond and having 12 or more carbon atoms. Manufacturing method of structure. 14. The method according to claim 9, further comprising a step of attaching a compound having an anionic group to the fiber before bringing the coating composition containing the hydrocarbon group-containing compound, the silicone-based compound, and the melamine compound into contact with the fiber. A method for producing a fiber structure. The method for producing a fiber structure according to claim 14, wherein the compound having an anion group is at least one selected from a sulfone group-containing compound and a polyhydric phenol compound. The manufacturing method of the fiber structure in any one of Claims 9-15 which performs a calendering process after the process of attaching the composition containing a hydrocarbon group containing compound, a silicone type compound, and a melamine compound to a fiber.