JP2019026965A - Fiber structure and manufacturing method therefor - Google Patents

Abstract

To provide a fiber structure having water repellency and durability thereof equal to or more than these when existing fluorine compounds are used, by using a non-fluorine compound.SOLUTION: There is provided a fiber structure having a fiber substrate with a first main surface and a second main surface, and a first resin layer formed on a surface of at least the first main surface, in which the first resin layer contains an anionic compound (A) and a water repellent compound (B), the anionic compound has one or more anionic group in a molecule and weight average molecular weight thereof is 30,000 to 70,000, the water repellent compound (B) is a reaction product between a hydrocarbon compound (b1) and a compound (b2) which is at least one kind selected from a group consisting of bi- or higher functional isocyanate compound, bi- or higher functional methylol compound and derivatives thereof.SELECTED DRAWING: None

Description

  The present invention relates to a fiber structure having water repellency and a method for producing the same.

  Conventionally, as a method for imparting water repellency to a fiber structure, a method of fixing a fluorine compound to the surface of the fiber structure is generally used. According to this method, a fiber structure having high water repellency and excellent durability can be obtained.

  However, when fluorine compounds are discharged into the environment and decomposed, there is a possibility that perfluorooctanoic acid (PFOA) or perfluorooctanesulfonic acid (PFOS) is generated. PFOA and PFOS have been pointed out as concerns such as remaining in the environment and accumulation in ecology. Thus, there is a demand for water repellent processing technology and products that do not use fluorine compounds or their precursors.

  For example, Patent Documents 1 and 2 propose water-repellent fabrics treated with a silicone compound. Patent Document 3 proposes a method using an anionic dihalotriazine derivative.

International Publication No. 2015/083627 Pamphlet Japanese Patent Laying-Open No. 2015-165056 JP 2006-89316 A

  When imparting water repellency to a fiber structure using a non-fluorine compound as in Patent Documents 1 to 3, the water repellency at the initial stage and after washing cannot be sufficiently obtained as compared with the case of using a fluorine compound. According to Patent Document 3, an anionic dihalotriazine derivative is bonded to a fiber structure, and then a cationic water repellent is ionically bonded to an anionic group bonded to the fiber structure. Aqueous durability is improved. However, this method utilizes a reactive dye mechanism (covalent bond) for bonding an anionic dihalotriazine derivative to a fiber structure. Therefore, it cannot be applied to fibers having almost no reactive group such as polyester fiber, and lacks versatility.

  That is, the present condition is that the fluorine compound is used for the water-repellent processing for the fiber structure.

  An object of the present invention is to provide a fiber structure using a non-fluorine compound and having a water repellency equivalent to or higher than that when an existing fluorine compound is used, and having excellent durability.

  According to a first aspect of the present invention, (1) a fiber base having a first main surface and a second main surface opposite to the first main surface is formed on at least a surface of the first main surface. The first resin layer includes an anionic compound (A) and a water repellent compound (B), and the anionic compound (A) has an intramolecular structure. The anionic compound (A) has a weight average molecular weight of 30,000 to 70,000, and the water repellent compound (B) is a hydrocarbon compound (b1). The hydrocarbon compound (b1) is an alkyl urethane, ethylene urea, aliphatic carboxylic acid, its ester compound, aliphatic hydrocarbon, polyacrylic acid ester, polymethacrylic acid ester , Polyolefin, methylolamide And the compound (b2) is at least one selected from the group consisting of a bifunctional or higher functional isocyanate compound, a bifunctional or higher functional methylol compound, and derivatives thereof. It relates to a fiber structure which is a seed.

  This fiber structure has a water repellency equivalent to or higher than that when an existing fluorine compound is used, and is excellent in durability. Furthermore, since the first resin layer also has oil repellency, another resin layer can be easily formed on the surface thereof.

  (2) The compound (b2) is preferably at least one of a bifunctional or higher aliphatic isocyanate compound and a derivative thereof. Thereby, when forming a 2nd resin layer in the surface of a fiber structure, adhesiveness with a 2nd resin layer cannot fall easily.

  (3) The water repellency measured according to JIS L1092 of the first main surface is preferably 4th grade or more, and the water repellency after washing 20 times according to JIS L0217 103 is 3 It is preferable that it is a grade or more. In the case of having such a water repellency, the fiber structure is preferably used for outdoor use, sports use and the like.

  (4) The fiber structure further includes a second resin layer formed on at least a part of the surface of the first resin layer, and the second resin layer includes an acrylic resin, a urethane resin, a silicone resin, and a polyolefin. It is preferable to include at least one resin selected from the group consisting of resins. Thereby, various physical properties by a 2nd resin layer are provided to a fiber structure with water repellency. Therefore, the fiber structure can be used for, for example, windproof use, moisture permeable waterproof use, and the like.

  (5) The second resin layer preferably contains a urethane resin having a solidification value of 7 to 15% by mass. Thereby, the adhesiveness of the 1st resin layer and the 2nd resin layer increases. Further, since the hydrophilicity of the second resin layer is lowered, the water repellency of the resulting fiber structure is further improved.

(6) The fiber structure in which the second resin layer is formed has a water pressure resistance of 3,000 mmH ₂ O or more measured according to JIS L1092 A method, and measured according to JIS L1099 A-1 method and B-1 method. it is preferred moisture permeability is is 3,000g ^/ m ^2/24 hours or more.

  According to a second aspect of the present invention, (7) at least the first main surface of a fiber base including a first main surface and a second main surface opposite to the first main surface, A step of forming the resin layer, wherein the step of forming the first resin layer includes a first step of imparting an anionic compound (A) to at least the first main surface, and the anionic compound (A And at least the first main surface to which the hydrocarbon compound (b1) and the compound (b2) are imparted to at least the first main surface, wherein one or more anionic compounds (A) are present in the molecule. The anionic compound (A) has a weight average molecular weight of 30,000 to 70,000, and the hydrocarbon compound (b1) is an alkyl urethane, ethylene urea, or aliphatic carboxylic acid. , Its ester compounds, aliphatic hydrocarbons, The compound (b2) is at least one selected from the group consisting of oxalic acid ester, polymethacrylic acid ester, polyolefin, methylolamide, and derivatives thereof, and the compound (b2) is a bifunctional or higher functional isocyanate compound or a bifunctional or higher functional methylol compound And a method for producing a fiber structure, which is at least one selected from the group consisting of derivatives thereof.

  By this production method, it is possible to obtain a fiber structure having water repellency equivalent to or higher than that when using an existing fluorine compound and having excellent durability.

  (8) The first step is preferably performed under the conditions of pH 2-6. Thereby, sufficient quantity of anionic compound (A) can be made to adhere to the at least 1st main surface of a fiber base material.

  (9) After the step of forming the first resin layer, a step of forming a second resin layer on at least a part of the surface of the first resin layer may be performed. At this time, the second resin layer includes at least one resin selected from the group consisting of an acrylic resin, a urethane resin, a silicone resin, and a polyolefin resin. Such another resin layer (second resin layer) can be easily formed on the surface of the first resin layer.

  According to the present invention, it is possible to provide a fiber structure having a water repellency equivalent to or higher than that in the case of using an existing fluorine compound and having excellent durability. Furthermore, since this fiber structure also has oil repellency, another resin layer can be easily formed on the surface thereof.

  The fiber structure according to the present embodiment includes a fiber base including a first main surface and a second main surface opposite to the first main surface, and a first resin formed on the first main surface. A layer. The first resin layer includes an anionic compound (A) and a water repellent compound (B) that is a reaction product of the hydrocarbon compound (b1) and the compound (b2). The anionic compound (A) has one or more anionic groups in the molecule. The hydrocarbon compound (b1) is selected from the group consisting of alkyl urethane, ethylene urea, aliphatic carboxylic acid, its ester compound, aliphatic hydrocarbon, polyacrylic ester, polymethacrylic ester, polyolefin, methylolamide, and derivatives thereof. At least one selected. The compound (b2) is at least one selected from the group consisting of a bifunctional or higher functional isocyanate compound, a bifunctional or higher functional methylol compound, and derivatives thereof.

  The anionic compound (A) and the water-repellent compound (B) which is a reaction product of the hydrocarbon compound (b1) and the compound (b2) are attached to at least the first main surface of the fiber base material, and the first resin Forming a layer. Water repellency is exhibited mainly by the hydrocarbon compound (b1).

  An intermolecular interaction acts between the anionic compound (A) having a negative charge and the hydrocarbon compound (b1). A sufficient amount of the hydrocarbon compound (b1) is attached to the fiber substrate by the intermolecular interaction with the anionic compound (A). Therefore, the water repellency of the fiber structure including the fiber base material and the first resin layer is improved. The intermolecular interaction between the anionic compound (A) and the hydrocarbon compound (b1) depends on the structure of each compound. For example, electrostatic bonds and attractive forces such as ionic bonds and dipole interactions It is caused by intermolecular forces called van der Waals forces.

  The compound (b2) functions as a crosslinking agent (binder) for the hydrocarbon compound (b1). Therefore, a sufficient amount of the hydrocarbon compound (b1) is attached to the fiber base material in a state of being crosslinked by the compound (b2). A compound obtained by crosslinking the hydrocarbon compound (b1) with the compound (b2) is the water repellent compound (B). Therefore, the water repellency durability of the fiber structure is improved. That is, the fiber structure according to this embodiment has excellent water repellency and excellent durability even though a non-fluorine compound is used.

  By the way, non-fluorine compounds generally do not exhibit sufficient oil repellency. Therefore, a problem arises when a resin layer is formed on the surface of a resin layer formed of a non-fluorine compound using a resin compounding liquid containing an organic compound. For example, the resin compounded liquid penetrates into the inside of the fiber base material, and the texture of the fiber base material is cured, or the resin compounded liquid leaks back.

  Further, when a silicone compound is used as the water repellent, it is difficult to laminate a resin film or adhere a transfer label to the surface of the fiber structure by post-processing. This is because the silicone compound has high releasability.

  On the other hand, the fiber structure according to this embodiment exhibits excellent oil repellency because the first resin layer contains the hydrocarbon compound (b1). Therefore, an organic compound can be selected as a solvent or dispersant used for post-processing. That is, the hydrocarbon base (b1) can impart water repellency and oil repellency to the fiber substrate. Furthermore, the adhesion between the first resin layer and the second resin layer formed on the surface is improved. The compound (b2) further imparts durability to these properties without deteriorating the water repellency, oil repellency and adhesion properties expressed by the hydrocarbon compound (b1).

  That is, the fiber structure including the first resin layer is a material suitable for forming the second resin layer. Hereinafter, when the second resin layer is formed by coating, there is no permeation or back leakage of the resin compounding solution, and the first resin layer and the second resin layer formed on the surface thereof can be in close contact with each other. May be expressed as having excellent processability.

  It is preferable that the water repellency measured according to JIS L1092 (spray test) of the first main surface including the first resin layer is 4th or higher. Moreover, after washing a fiber structure provided with the first resin layer 20 times according to JIS L0217 103, the water repellency of the first main surface provided with the first resin layer measured according to JIS L1092 (spray test) is It is preferable that it is tertiary or higher.

  Furthermore, oil repellency (DMF repellency) to N, N-dimethylformamide (DMF) of the first main surface including the first resin layer is preferably 30 seconds or more, and more preferably 40 seconds or more. preferable. Here, the DMF repellency means that DMF, which is an organic solvent, is dropped on the surface of the first main surface including the first resin layer so that the diameter becomes 5 mm and completely penetrates into the fiber base material. This is a value obtained by measuring time. If the DMF repellency is within this range, the fiber structure is more suitable for coating with a resin compounding liquid containing an organic compound. If the DMF repellency is within the above range, the first resin layer can exhibit oil repellency with respect to other organic solvents.

[Fiber base]
The fiber substrate includes a first main surface and a second main surface opposite to the first main surface. Although it does not specifically limit as a form of a fiber base material, For example, a woven fabric, a knitted fabric, a nonwoven fabric etc. are mentioned. Further, the mass and thickness per unit of the fiber base material are not particularly limited, and are appropriately set according to the application. The fiber base material may be subjected to dyeing, softening processing, antistatic processing, flame retardant processing, calendar processing, and the like as necessary.

  The material of the fiber which comprises a fiber base material is not specifically limited, According to the use of a fiber structure, it selects suitably. Examples of materials include polyamides such as nylon 6 and nylon 66; polyesters such as polyethylene terephthalate and tripolymethylene terephthalate; synthetic fibers such as polyurethane and polyacrylic; natural fibers such as cotton, hemp, wool and silk; rayon and cupra Recycled fibers: semisynthetic fibers such as acetate and triacetate. These may be used alone or in combination of two or more.

[First resin layer]
The first resin layer includes an anionic compound (A) and a water repellent compound (B) that is a reaction product of the hydrocarbon compound (b1) and the compound (b2).

[Anionic compound (A)]
The anionic compound (A) is a compound having one or more anionic groups in the molecule. Examples of the anionic group include a sulfo group, a carboxyl group, a phosphate group, a hydroxyl group, and a mercapto group. The type of anionic group contained in the same molecule of the anionic compound (A) may be one type or two or more types.

  The anionic compound (A) preferably has a benzene ring. Thereby, the adhesiveness of an anionic compound (A) and a fiber base material and the adhesiveness of a hydrocarbon compound (b1) improve. In particular, the anionic compound (A) preferably has two or more benzene rings.

  Examples of the anionic compound (A) include a phenol compound and a thiophenol compound. More specifically, phenolsulfonic acid, dihydroxydiphenylsulfone, a copolymer of novolac type phenolic resin and methanesulfonic acid, benzylated phenolsulfonic acid, other compounds having a phenolic OH group, thiophenol, and these Examples thereof include metal chelate compounds or condensation products of these derivatives and formaldehyde. Specific examples of the condensation product include phenolsulfonic acid / formaldehyde condensate, bisphenol S / formaldehyde condensate, and thiophenol / formaldehyde condensate. These compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  Among these, a condensation product obtained by a condensation reaction of at least one of dihydroxydiphenylsulfone and its derivative and formaldehyde (hereinafter sometimes referred to as a dihydroxydiphenylsulfone compound) is preferable.

  The dihydroxydiphenylsulfone may be 4,4'-dihydroxydiphenylsulfone or 2,4'-dihydroxydiphenylsulfone. Examples of the derivatives of dihydroxydiphenylsulfone include alkylated dihydroxydiphenylsulfone, halogenated dihydroxydiphenylsulfone having a chlorine atom and the like, and mixtures thereof. Of these, 4,4'- or 2,4'-dihydroxydiphenylsulfone is preferable. The dihydroxydiphenylsulfone compound may be a compound obtained by subjecting dihydroxydiphenylsulfone and paraformaldehyde to a condensation reaction using paraformaldehyde as formaldehyde.

  The weight average molecular weight of the anionic compound (A) is 30,000 to 70,000. When the weight average molecular weight is within this range, the anionic compound (A) is suppressed from gelation and easily adsorbed physically to the fiber base material, and can adhere strongly. Moreover, even if an anionic compound (A) adheres, the texture of a fiber base material is hard to be impaired. The weight average molecular weight of the anionic compound (A) is preferably 30,000 to 50,000.

  It is preferable that the adhesion amount of an anionic compound (A) is 0.001-10 mass% with respect to a fiber base material. When the adhesion amount of the anionic compound (A) is within this range, the adhesion property of the hydrocarbon compound (b1) described later is improved, and the water repellency of the fiber structure provided with the fiber base material and the first resin layer is improved. improves. Moreover, even if an anionic compound (A) adheres, the texture of a fiber base material is hard to be impaired. Furthermore, since the oil repellency of the fiber structure is improved, the processability is also improved. The adhesion amount of the anionic compound (A) is preferably 0.1 to 5% by mass.

  The adhesion amount of the anionic compound (A) to the fiber substrate is calculated from, for example, a treatment liquid used when the anionic compound (A) is adhered to the fiber substrate. Specifically, the absorbance of the treatment liquid before and after the treatment is measured using a spectrophotometer, the amount of decrease in the anionic compound (A) in the treatment liquid is calculated from the peak intensity ratio, and the fiber base material Obtain the amount of adhesion to the surface. In addition, when the anionic compound (A) is applied to the fiber base material by the padding method, the product of the pickup rate (drawing rate) and the concentration of the anionic compound (A) in the treatment liquid is determined from the product to the fiber base material. Find the amount of adhesion.

  The anionic compound (A) is attached to the fiber substrate by ionic bonds or hydrogen bonds. For example, when the fiber base material contains polyimide and the anionic compound (A) contains a phenolsulfonic acid / formaldehyde condensate, it adheres by ionic bonding between the amino group of the polyimide and the sulfo group of the condensate. When the fiber base material contains polyester and / or cotton and the anionic compound (A) contains a compound having a phenolic OH group, it adheres by hydrogen bonding between the hydroxyl group of the polyester and / or cotton and the hydroxyl group of the above compound. It is thought that there is.

[Hydrocarbon compound (b1)]
The hydrocarbon compound (b1) is selected from the group consisting of alkyl urethane, ethylene urea, aliphatic carboxylic acid, its ester compound, aliphatic hydrocarbon, polyacrylic ester, polymethacrylic ester, polyolefin, methylolamide, and derivatives thereof. At least one selected.

  Specific examples of the hydrocarbon compound (b1) include alkyl urethanes such as N, N-ethylene lauryl urethane and N, N-ethylene stearyl urethane; ethylene ureas such as octadecyl ethylene urea; caprylic acid, capric acid and lauric acid. Aliphatic carboxylic acids such as myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, ricinolenic acid and ester compounds thereof; aliphatic hydrocarbons such as paraffinic hydrocarbons and olefinic hydrocarbons having 12 or more carbon atoms Lauryl acrylate, hexadecyl acrylate, stearyl acrylate, isostearyl acrylate, behenyl acrylate, lauryl methacrylate, hexadecyl methacrylate, stearyl methacrylate, isostearyl methacrylate , Polyacrylic acid ester and polymethacrylic acid ester compounds such as behenyl methacrylate with a monomer; methylol amide such as methylol stearamide; polyolefins such as polyethylene and polypropylene and derivatives thereof. These compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  Commercially available hydrocarbon compounds (b1) include “Neo Seed NR-90”, “Neo Seed NR-158” and “TH-44” (manufactured by Nikka Chemical Co., Ltd.), “Smarttrepel Hydro PM liq”. And “Smarttrepel Hydro CMD liq” (manufactured by Arkroma Japan Co., Ltd.), “Phobotex RSH” (manufactured by Huntsman Japan Co., Ltd.), “Mayshield P-300C” (manufactured by Meisei Chemical Industry Co., Ltd.), “ Unidyne XF-5001 "(manufactured by Daikin Industries, Ltd.)," Zelan R3 "(manufactured by Chemers Co., Ltd.) and the like can be used. These may be used alone or in combination of two or more.

  The ionicity of the hydrocarbon compound (b1) is not particularly limited, but is preferably cationic or nonionic, and more preferably cationic. This is because when the hydrocarbon compound (b1) is cationic, the intermolecular interaction with the anionic compound (A) works more strongly. When the hydrocarbon compound (b1) is used after being dispersed in water, the emulsifier used for dispersion is also preferably cationic.

  The hydrocarbon compound (b1) reacts with the compound (b2) and is crosslinked by the compound (b2), whereby the water repellent compound (B) is generated. This water repellent compound (B) is adhered to the fiber substrate. The adhesion amount of the structural portion derived from the hydrocarbon compound (b1) in the water repellent compound (B) to the fiber substrate is preferably 0.01 to 10% by mass. When the adhesion amount of the structural portion derived from the hydrocarbon compound (b1) is within this range, high water repellency is exhibited without impairing the texture of the fiber base material. In addition, oil repellency (DMF repellency) is also improved. If the texture of the fiber base material is maintained, when the second resin layer is formed, the adhesion between the first resin layer and the second resin layer tends to be higher. The adhesion amount of the structural part derived from the hydrocarbon compound (b1) is preferably 0.5 to 3% by mass.

  The adhesion amount of the structural part derived from the hydrocarbon compound (b1) is, for example, the absorbance of the treatment liquid used when the hydrocarbon compound (b1) is adhered to the fiber substrate, as in the case of the anionic compound (A), or , Using the product of the pickup rate and the concentration of the hydrocarbon compound (b1).

[Compound (b2)]
The compound (b2) is at least one compound selected from the group consisting of bifunctional or higher functional isocyanate compounds, bifunctional or higher functional methylol compounds, and derivatives thereof. These compounds are appropriately selected according to the type of the hydrocarbon compound (b1). These may be used alone or in combination of two or more.

  Examples of the bifunctional or higher isocyanate compounds and derivatives thereof include aromatics such as triresin diisoxylylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4- and / or 2,6-tolylene diisocyanate. Diisocyanates; aliphatic diisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; alicyclic diisocyanates such as tetramethylene diisocyanate, isophorone diisocyanate and hydrogenated MDI; and block isocyanates obtained by reacting these compounds with methyl ethyl ketone oxime, ε-caprolactam And group-containing compounds.

  Examples of bifunctional or higher functional methylol compounds and derivatives thereof include trimethylol melamine and hexamethylol melamine. The methylol compound may be used in combination with an organic amine compound as a catalyst, if necessary.

  Among these, at least one of a bifunctional or higher functional aliphatic isocyanate compound and a derivative thereof is preferable. This is because when the second resin layer is formed on the surface of the fiber structure, the adhesion between the first resin layer and the second resin layer is unlikely to decrease.

  The compound (b2) functions as a crosslinking agent for the hydrocarbon compound (b1), and is attached to the fiber substrate as the water repellent compound (B) together with the hydrocarbon compound (b1). Although the adhesion amount with respect to the fiber base material of the structure part derived from the compound (b2) in a water repellent compound (B) is not specifically limited, 100 mass with respect to the adhesion amount to the fiber base material of a hydrocarbon compound (b1). % Or less is preferable. When the adhesion amount of the compound (b2) is within this range, the adhesion of the hydrocarbon compound (b1) to the surface of the fiber substrate can be further improved without lowering the water repellency. In addition, the texture of the fiber structure is hardly damaged. Furthermore, when forming a 2nd resin layer in a fiber structure, the adhesiveness of a 1st resin layer and a 2nd resin layer becomes high. The adhesion amount of the structural part derived from the compound (b2) can be calculated, for example, by the same method as the method for measuring the adhesion amount of the structural part derived from the hydrocarbon compound (b1).

[Second resin layer]
A second resin layer may be formed on at least a part of the surface of the first resin layer. A fiber structure provided with a fiber base material and a first resin layer is excellent in processability. Thereby, other physical properties (water resistance, moisture permeability, etc.) can be further imparted to the fiber structure imparted with water repellency by the first resin layer. The second resin layer may be a single layer or may be formed of two or more layers having different components. The second resin layer may be formed on the entire surface of the first resin layer as long as it does not depart from the object of the present invention.

  The second resin layer preferably contains at least one resin selected from the group consisting of acrylic resins, urethane resins, silicone resins, and polyolefin resins. These resins may be used alone or in combination of two or more. Of these, acrylic resins and / or urethane resins are preferred, and urethane resins are particularly preferred from the viewpoints of film strength, texture, and adhesion to the first resin layer.

  In the second resin layer, in addition to the above resins, stabilizers such as antioxidants and light resistance improvers, organic fillers, inorganic fillers, crosslinking agents, non-solvents, lubricants, pigments, other additives, A function-imparting agent or the like can be added as appropriate.

  The second resin layer may be in a porous or non-porous state, and can be appropriately set according to the application and desired physical properties. In the case of imparting moisture permeability and waterproofness to the fiber structure, for example, the second resin layer is preferably a porous film formed by a wet coagulation method. In this case, the second resin layer preferably contains a urethane resin having a solidification value of 7 to 15% by mass. The solidification value of the urethane resin is more preferably 7.5 to 14% by mass. Thereby, the adhesiveness of the 1st resin layer and the 2nd resin layer increases. Further, since the hydrophilicity of the second resin layer is lowered, the water repellency (and further waterproofness) of the resulting fiber structure is further improved.

Here, the solidification value is a dripping amount (g) of water required until water, which is a poor solvent, is added dropwise to 25 g of urethane DMF solution having a concentration of 1% by mass while stirring, and the cloudiness of the solution does not disappear. Calculated from Specifically, the coagulation value is calculated by the following formula.
Solidification value = [Drop amount of water required until cloudy (g) / {25 (g) + Drop amount of water required until cloudy (g)}] × 100 (mass%)

  The thickness of the second resin layer is preferably 1 μm or more, and more preferably 5 μm or more. When the thickness is 1 μm or more, the physical properties of the second resin layer are easily exhibited.

  The peel strength between the first resin layer and the second resin layer is preferably 1 N / 2.54 cm or more, and more preferably 4 N / 2.54 cm or more.

  For measuring the peel strength, a sample is used in which a hot melt tape having a width of 25 mm is adhered to the surface of the second resin layer formed on the fiber structure with an iron at about 120 ° C. After the sample has cooled sufficiently, the second resin layer is peeled 10 mm from the end of the sample under the conditions of a gripping interval of 10 mm and a tensile speed of 100 mm / min, and the peel strength at this time is measured.

The fiber structure in which the second resin layer is formed preferably has a water pressure resistance measured according to JIS L1092 A method (low water pressure method) of 3,000 mmH ₂ O or more, and 5,000 mmH ₂ O or more. It is more preferable. If the water pressure resistance is within this range, the fiber structure can be preferably applied to windproof use, moisture permeable waterproof use, and the like.

Moisture permeability as measured according to JIS L1092 A-1 method and B-1 method of fiber structure where the second resin layer is formed is preferably at each 3,000 g ^/ m 2/24 hours or more, 5 , and more preferably 000g ^/ m ^2/24 hours or more. When the moisture permeability in the method A-1 is in this range, when the fiber structure is in contact with water vapor, the water vapor permeation performance is excellent. Moreover, when the water vapor transmission rate in the method B-1 is within this range, when moisture or the like adheres to the fiber structure due to sweat or the like, the water permeability is excellent. That is, when the moisture permeability of the fiber structure in both the A-1 method and the B-1 method is in the above ranges, the feeling of stuffiness when worn as clothes is suppressed, and a comfortable comfort is obtained.

  Such a fiber structure having water pressure resistance and moisture permeability is preferably applied to clothing, textile materials, etc. for casual, outdoor and sports applications.

[Method for producing fiber structure]
The manufacturing method of the fiber structure which concerns on this embodiment is equipped with the process of forming a 1st resin layer in the at least 1st main surface of a fiber base material. The step of forming the first resin layer includes a first step of applying the anionic compound (A), and a hydrocarbon compound (at least on the first main surface of the fiber substrate to which the anionic compound (A) has been applied. a second step of imparting b1) and compound (b2).

  Thus, an anionic compound (A) and a hydrocarbon compound are provided to a fiber base material first by giving an anionic compound (A) and then giving a hydrocarbon compound (b1) and a compound (b2). A first resin layer containing (b1) and a water-repellent compound (B) that is a reaction product of the compound (b2) is formed in a state of being strongly adhered to at least the first main surface.

Hereinafter, an example of this embodiment will be described for each process.
[First step: Application of anionic compound (A)]
The anionic compound (A) is applied to at least a first main surface of a fiber base material having a first main surface and a second main surface. For example, the anionic compound (A) is applied to at least the first main surface of the fiber base material in a state dissolved in a solvent. The solvent may be water or a mixture of a water-soluble organic compound such as ethanol or isopropyl alcohol and water. Of these, water is preferable in terms of handleability.

  Examples of the method for applying the anionic compound (A) to the fiber substrate include a padding method, a coating method, a gravure coating method, a spray method, a continuous application method such as a printing method, and a batch type application method such as an exhaust method. Means can be applied.

  In the case of the continuous application method, the concentration of the anionic compound (A) in the solution containing the anionic compound (A) (hereinafter referred to as an anionizing agent) is preferably 0.01 to 10% by mass. 1-3 mass% is more preferable. When the concentration of the anionic compound (A) is within this range, a sufficient amount of the anionic compound (A) is allowed to adhere to at least the first main surface of the fiber base material without impairing the texture of the fiber base material. Can do. Thereby, the adhesiveness of the hydrocarbon compound (b1) provided at a 2nd process and a fiber base material improves more.

  Among the continuous application methods, the padding method is preferable because it is simple. When using the padding method, the pickup rate is preferably 40 to 100%. When the pickup rate is within this range, a sufficient amount of the anionic compound (A) can be adhered to at least the first main surface of the fiber base material without unevenness.

  In the case of the batch application method, the concentration of the anionic compound (A) in the anionizing agent is preferably from 0.1 to 20% owf, more preferably from 0.5 to 10% owf. When the concentration of the anionic compound (A) is within this range, a sufficient amount of the anionic compound (A) is allowed to adhere to at least the first main surface of the fiber base material without impairing the texture of the fiber base material. Can do.

  In the case of the batch application method, the processing conditions are not particularly limited. Among them, the bath ratio, that is, the mass ratio of the fiber base material to the anionizing agent (fiber base material: anionizing agent) is preferably 1:10 to 1: 100, and 1:20 to 1:50. More preferably. When the bath ratio is within this range, a sufficient amount of the anionic compound (A) can be adhered to at least the first main surface of the fiber base material without unevenness. The treatment temperature may be about 40 to 135 ° C., and the treatment time may be about 10 to 60 minutes.

  In addition, in the case of the batch application method, it is preferable to remove the anionic compound (A) added excessively by washing with water after applying the anionic compound (A) to the fiber base material. By removing the excess anionic compound (A), when the hydrocarbon compound (b1) is imparted, aggregation and precipitation of the fine particles of the hydrocarbon compound (b1) in the treatment liquid are less likely to occur.

  In any of the continuous application method and the batch application method, the pH of the anionization treatment agent is preferably 2 to 6, and more preferably 3 to 5. When the pH of the anionizing agent is within this range, a sufficient amount of the anionic compound (A) can be attached to at least the first main surface of the fiber base material. For adjusting the pH of the anionizing agent, acetic acid, formic acid, ammonium sulfate and the like can be used.

  The fiber base material to which the anionic compound (A) has been applied is subjected to a drying treatment as necessary and is subjected to the second step. The drying conditions are not particularly limited, but the drying temperature may be about 100 to 180 ° C., and the drying time may be about 30 seconds to 5 minutes.

[Second Step: Application of Hydrocarbon Compound (b1) and Compound (b2)]
The said hydrocarbon compound (b1) and a compound (b2) are provided to the at least 1st main surface of the fiber base material provided with the anionic compound (A).

  The hydrocarbon compound (b1) and the compound (b2) may be attached to the fiber base material in one step, or may be attached in two steps. In the latter case, the order of attachment of the hydrocarbon compound (b1) and the compound (b2) is not particularly limited. After attaching the hydrocarbon compound (b1) to the fiber substrate first, the compound (b2) is attached. Alternatively, the hydrocarbon compound (b1) may be adhered after the compound (b2) is adhered to the fiber substrate.

  The hydrocarbon compound (b1) and the compound (b2) are applied to the fiber base material in a state of being dissolved in a solvent or dispersed in a dispersion medium, for example. The solvent or dispersion medium may be water or a mixture of a water-soluble organic compound such as ethanol or isopropyl alcohol and water. Of these, water is preferable in terms of handleability.

  Examples of the method for imparting the hydrocarbon compound (b1) and the compound (b2) to the fiber substrate include the same method as the method for imparting the anionic compound (A). Of these, the padding method is preferable because it is simple. When using the padding method, the pickup rate is preferably 40 to 100%. If the pickup rate is within this range, a sufficient amount of the hydrocarbon compound (b1) and the compound (b2) can be adhered to at least the first main surface of the fiber base material without unevenness.

  In the case of the continuous application method, a solution or dispersion containing the hydrocarbon compound (b1) (hereinafter referred to as the water repellent treatment agent B), or a solution or dispersion containing the hydrocarbon compound (b1) and the compound (b2). The concentration of the hydrocarbon compound (b1) in the liquid (hereinafter simply referred to as a water repellent agent) is preferably 1 to 25% by mass, and more preferably 3 to 15% by mass.

  In the case of the continuous application method, the concentration of the compound (b2) in the solution or dispersion containing the compound (b2) (hereinafter referred to as the water repellent treatment agent C) or the water repellent treatment agent is 0.01-10. % By mass is preferable, and 0.1 to 5% by mass is more preferable.

  When the concentration of the hydrocarbon compound (b1) and the compound (b2) is within this range, a sufficient amount of the hydrocarbon compound is formed on at least the first main surface of the fiber substrate without generating chalk marks or crack marks. (B1) and compound (b2) can be attached. As a result, the resulting fiber structure can exhibit excellent water and oil repellency. Further, the texture of the fiber base material is not easily damaged. Furthermore, when the second resin layer is formed, the adhesion between the first resin layer and the second resin layer tends to be high.

  For the water repellent treatment agent B and the water repellent treatment agent C, or the water repellent treatment agent, as necessary, a softener, a sewing improver, an antistatic agent, a pH adjuster, other additives, a function-imparting agent, etc. May be added.

  After applying the hydrocarbon compound (b1) and the compound (b2) to the fiber substrate, a drying treatment is performed. The conditions for the drying treatment are not particularly limited, and can be set as appropriate. The treatment temperature may be about 100 to 180 ° C., and the treatment time may be about 30 seconds to 5 minutes. During this drying treatment, the hydrocarbon compound (b1) and the compound (b2) react with each other by heat, and the water repellent compound (B) is generated to form the first resin layer. In order to sufficiently advance the reaction between the hydrocarbon compound (b1) and the compound (b2), if necessary, a heat treatment may be further performed after the drying treatment. Moreover, you may perform a coloring process and a calendar process as needed to the fiber base material in which the 1st resin layer was formed.

[Formation of second resin layer]
A second resin layer may be formed on the surface of the first resin layer. The second resin layer may be porous or nonporous.

  The second resin layer is formed in a film shape on the surface of the first resin layer by a method described later. The raw material resin for forming the second resin layer is used in a state where it is dissolved in a solvent or dispersed in a dispersion medium, or is thermally melted. As the solvent or dispersion medium, water, an organic compound, a mixture thereof, or the like is used.

  An example of a method for forming the second resin layer in the form of a film on the surface of the first resin layer is a coating method. In the coating method, for example, a resin compound solution containing a raw material resin is applied to the surface of the first resin layer by a known apparatus such as a knife coater, a comma coater, a roll coater, a die coater, or a lip coater. After the resin compounding liquid is applied, film formation is performed by a dry film formation method or a wet film formation method, and a film-like second resin layer is formed. Although content of raw material resin in a resin compounding liquid is not specifically limited, For example, it is 5-65 mass%.

  The porous second resin layer is formed by a wet film-forming method or a method of forming a pore by adding an additive such as a foaming agent to the resin compounding liquid. The nonporous second resin layer is formed by a dry film forming method or the like.

  The conditions for forming the porous second resin layer by the wet film forming method are not particularly limited. For example, when the raw material resin is a urethane resin, first, the surface of the first resin layer formed on the fiber base material is a resin compound solution obtained by dissolving the urethane resin in a polar solvent soluble in water (for example, DMF). Apply by coating method. Next, the fiber base material coated with the resin compounding solution is coagulated in water or an aqueous solution containing a polar solvent.

  Moreover, as a method of forming the second resin layer in a film shape on the surface of the first resin layer, there is a method in which a second resin layer formed separately is laminated on the first resin layer of the fiber structure. Can be mentioned. Examples of the lamination method include known methods such as a transfer method, thermal fusion, thermocompression bonding, and adhesion using an adhesive.

  When using an adhesive, the adhesive is preferably at least one selected from the group consisting of an acrylic resin, a urethane resin, a silicone resin, and a polyolefin resin. Especially, an acrylic resin and / or a urethane resin are more preferable from a viewpoint of film | membrane intensity | strength, a texture, and adhesiveness with a 1st resin layer.

  After the second resin layer is formed, the fiber structure may be subjected to various surface treatments, embossing, kneading, and the like as necessary.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by a following example.
In addition, evaluation of the performance in an Example followed the following method.

[Evaluation method]
(1) Adhesion amount of anionic compound adhered in the first step The absorbance of the anionizing agent before and after the treatment in the first step was measured using a spectrophotometer. The amount of decrease due to the treatment of the anionic compound in the anionization treatment agent was calculated from the peak intensity ratio before and after the treatment, and this was used to determine the amount of the anionic compound attached to the fiber substrate.

(2) Adhesion amount of each compound adhering in the second step Using the product of the concentration of each compound in the water repellent agent used in the second step and the pickup rate in the second step, The adhesion amount of each compound was determined.

(3) Water repellency According to the spray test of JIS L1092, the initial repellency of the fiber structure and water repellency after 20 washes were evaluated. Laundry was performed according to JIS L0217 103 method.

(4) DMF repellency DMF was dripped so that a diameter might be set to 5 mm to the main surface in which the 1st resin layer of the fiber structure was formed, and the time until it penetrate | infiltrated into a fiber base material completely was measured.

(5) Peel strength of second resin layer A 25 mm wide hot melt tape (manufactured by Sun Kasei Co., Ltd.) was adhered to the surface of the second resin layer of the fiber structure with an iron at about 120 ° C. Was made. After the sample had cooled sufficiently, the second resin layer was peeled 10 mm from the end, and the peel strength at this time was measured. Peeling was performed under the conditions of a grip interval of 10 mm and a tensile speed of 100 mm / min.

(6) Water pressure resistance JIS L1092 A method The water pressure resistance of the fiber structure was measured according to the low water pressure method.

(7) Moisture permeability According to JIS L1099 A-1 method and B-1 method, the moisture permeability of the fiber structure was measured.

(8) Back leakage After forming the second resin layer, the presence or absence of leakage of the resin compound liquid to the main surface opposite to the main surface on which the second resin layer of the fiber structure is formed, It was observed visually.

[Example 1]
(Preparation of fiber base material)
Nylon 6 taffeta (warp yarn: 44 dtex / 34f, weft yarn: 44 dtex / 34f) was scoured according to a conventional method. Next, taffeta was preset and dyed to obtain a fiber substrate.

(First step: application of anionic compound (A))
An anionic treatment agent 1 (pH is 4) containing an anionic compound (A) was applied to the fiber substrate by an exhaust method. The mass ratio (bath ratio) between the fiber substrate and the anionic compound (A) was 1:20. After exhausting for 15 minutes at a processing temperature of 80 ° C., drying was performed at 150 ° C. for 1 minute.

Anionizing agent 1
Anionic compound (A) (dihydroxydiphenylsulfone / formaldehyde condensate, weight average molecular weight 40,000, manufactured by OG Nagase Color Chemical Co., Ltd., SZ9904): 3% owf
Acetic acid (80% by mass aqueous solution): 0.5 mL / L

(Second step: provision of hydrocarbon compound (b1) and compound (b2))
The water repellent agent 1 containing the hydrocarbon compound (b1) and the compound (b2) was applied to the fiber substrate to which the anionic compound (A) was applied by a padding method (pickup rate: 60%). Next, after drying at 130 ° C. for 90 seconds, heat setting was performed at 170 ° C. for 60 seconds to form a first resin layer.

Water repellent treatment 1
Hydrocarbon compound (b1) ((meth) acrylic acid ester derivative, solid paraffin, manufactured by Nikka Chemical Co., Ltd., Neoseed NR-90): 6% by mass
Compound (b2) (N-methylol compound, Sumitomo Chemical Co., Ltd., Sumitex Resin M3): 0.5% by mass
Reaction catalyst (Sumitomo Chemical Co., Ltd., Sumitex Accelerator A): 0.1% by mass

  The adhesion amount of the anionic compound (A) to the fiber substrate and the adhesion amount of the structural portion derived from the hydrocarbon compound (b1) and the compound (b2) were measured according to the evaluation methods (1) and (2). In addition, (3) water repellency and (4) DMF repellency were evaluated. The evaluation results are shown in Table 1.

(Formation of second resin layer)
The surface of the formed first resin layer was calendered. Next, the resin compounding liquid 1 was applied to the surface of the first resin layer with a roll-on knife coater so that the thickness after drying was 50 μm and solidified in water for 2 minutes. Next, the fiber substrate having the coagulated film is immersed in warm water at 50 ° C. for 5 minutes for cleaning, and dried at 150 ° C. for 1 minute to form a second resin layer on the surface of the first resin layer. did.

Resin formulation 1
Polyurethane resin solution (solid content concentration 25% by mass, coagulation value 9.8% by mass, manufactured by Dainichi Seika Kogyo Co., Ltd., Resamine CU-4555): 100 parts Calcium carbonate / polyurethane resin solution (polyurethane resin concentration 16% by mass) , Manufactured by Dainichi Seika Kogyo Co., Ltd., MY-3657): 20 parts Isocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L): 1 part DMF: 40 parts

  The fiber structure on which the second resin layer was formed was evaluated for (5) peel strength, (6) water pressure resistance, (7) moisture permeability, and (8) back leakage. The results are shown in Table 1.

[Example 2]
Example, except that polyester taffeta (warp yarn: 56 dtex / 48f, weft yarn: 56 dtex / 48f) was used as the fiber substrate, and the water repellent agent 1 was applied by the padding method (pickup rate: 40%). A fiber structure was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 3]
A fiber structure was prepared and evaluated in the same manner as in Example 1 except that the water repellent agent 2 shown below was used instead of the water repellent agent 1. The results are shown in Table 1.

Water repellent 2
Hydrocarbon compound (b1) (alkyl urethane, manufactured by Chemers Co., Ltd., Zelan R3): 6% by mass
Compound (b2) (N-methylol compound, Sumitomo Chemical Co., Ltd., Sumitex Resin M3): 0.5% by mass
Reaction catalyst (Sumitex Accelerator A): 0.1% by mass

[Example 4]
A fiber structure was prepared and evaluated in the same manner as in Example 1 except that the water repellent agent 3 shown below was used instead of the water repellent agent 1. The results are shown in Table 1.

Water repellent 3
Hydrocarbon compound (b1) (Neo Seed NR-90): 6% by mass
Compound (b2) (aliphatic block isocyanate compound, manufactured by Nikka Chemical Co., Ltd., NK assist NY): 1% by mass
Reaction catalyst (Sumitex Accelerator A): 0.1% by mass

[Comparative Example 1]
A fiber structure was prepared and evaluated in the same manner as in Example 1 except that the first step was omitted, and the water repellent treatment agent 1 was used instead of the water repellent treatment agent 1 shown below. . The results are shown in Table 2.

Water repellent 4
Fluorine-based water and oil repellent (Asahi Guard AG-E700D manufactured by Asahi Glass Co., Ltd.): 6% by mass
N-methylol compound (Sumitex Resin M3): 0.5% by mass
Reaction catalyst (Sumitex Accelerator A): 0.1% by mass

[Comparative Example 2]
A fiber structure was prepared and evaluated in the same manner as in Example 1 except that the first step was omitted. The results are shown in Table 2.

[Comparative Example 3]
A fiber structure was prepared and evaluated in the same manner as in Example 2 except that the anionizing agent 2 shown below was used instead of the anionizing agent 1. The results are shown in Table 2.

Anionizing agent 2
Anionic compound (aromatic sulfonic acid derivative, weight average molecular weight 100, manufactured by Meisei Chemical Industry Co., Ltd., Mena 25): 3% owf
Acetic acid (80% by mass aqueous solution): 0.5 mL / L

[Comparative Example 4]
A fiber structure was prepared and evaluated in the same manner as in Example 1 except that the water repellent agent 5 shown below was used instead of the water repellent agent 1. The results are shown in Table 2.

Water repellent 5
Hydrocarbon compound (b1) (Neoseed NR-90): 65% by mass
Compound (b2) (N-methylol compound, Sumitomo Chemical Co., Ltd., Sumitex Resin M3): 0.5% by mass
Reaction catalyst (Sumitex Accelerator A): 0.1% by mass

[Comparative Example 5]
A fiber structure was prepared and evaluated in the same manner as in Example 1 except that the water repellent treatment agent 1 containing the following silicone compound was used instead of the water repellent treatment agent 1. The results are shown in Table 2.

Water repellent 6
Methyl hydrogen silicone (manufactured by Nikka Chemical Co., Ltd., Drypon 600E): 4% by mass
Compound (b2) (Sumitex Resin M3): 0.5% by mass
Reaction catalyst (manufactured by Nikka Chemical Co., Ltd., Drypon Z-7): 4% by mass

  As shown in Table 1, the fiber structures obtained in Examples 1 to 4 using the hydrocarbon compound (b1) are similar to the fiber structure obtained in Comparative Example 1 using a fluorine compound. It was water-based, suitable for processing and moisture-permeable and waterproof.

  On the other hand, as shown in Table 2, in Comparative Example 2, since the step of applying the anionic compound (A) was omitted, sufficient water repellency was not obtained, and since the DMF repellency was small, the second resin layer The back leakage of the resin compounded liquid occurred when forming the film. In Comparative Example 3, the molecular weight of the anionic compound (A) used was small, and the anionic compound (A) did not sufficiently adhere to the fiber structure surface. Therefore, as in Comparative Example 2, sufficient water repellency could not be obtained, and the back leakage of the resin compounded liquid occurred when the second resin layer was formed. In Comparative Example 4, since an excessive amount of the hydrocarbon compound (b1) was applied, the adhesion of the second resin layer was lowered, and sufficient peel strength was not obtained. Further, in Comparative Example 5, since a silicone compound was used as the water repellent agent, sufficient peel strength was not obtained due to its characteristics, and back leakage of the resin compounded liquid occurred when the second resin layer was formed. Furthermore, in Comparative Example 4 and Comparative Example 5, since the second resin layer was peeled off from the fiber structure during the measurement of the water pressure resistance, the water pressure resistance could not be measured accurately.

  Various embodiments and modifications can be made to the present invention without departing from the broad spirit and scope of the invention. Further, the above-described embodiments and examples are for explaining the present invention, and do not limit the scope of the present invention.

  The fiber structure of the present invention has high water repellency and its durability, and is excellent in processing suitability. Therefore, it can be used for clothing, textile materials, etc. such as casual, outdoor, and sports applications.

The anionic compound (A) is attached to the fiber substrate by ionic bonds or hydrogen bonds. For example, the fiber base material comprises a poly A bromide, deposited by ionic bonding with the sulfo group in the case, Ami de group and the condensation product of poly A bromide of anionic compounds (A) comprises a phenolsulfonic acid / formaldehyde condensate To do. When the fiber base material contains polyester and / or cotton and the anionic compound (A) contains a compound having a phenolic OH group, it adheres by hydrogen bonding between the hydroxyl group of the polyester and / or cotton and the hydroxyl group of the above compound. It is thought that there is.

Claims (9)

A fiber substrate comprising a first main surface and a second main surface opposite to the first main surface;
A first resin layer formed on at least the surface of the first main surface,
The first resin layer is
An anionic compound (A);
A water repellent compound (B),
The anionic compound (A) has one or more anionic groups in the molecule,
The anionic compound (A) has a weight average molecular weight of 30,000 to 70,000,
The water repellent compound (B) is a reaction product of a hydrocarbon compound (b1) and a compound (b2),
The hydrocarbon compound (b1) is a group consisting of alkyl urethane, ethylene urea, aliphatic carboxylic acid, its ester compound, aliphatic hydrocarbon, polyacrylic ester, polymethacrylic ester, polyolefin, methylolamide, and derivatives thereof. At least one selected from
The said compound (b2) is a fiber structure which is at least 1 sort (s) selected from the group which consists of a bifunctional or higher functional isocyanate compound, a bifunctional or higher functional methylol compound, and derivatives thereof.   The fiber structure according to claim 1, wherein the compound (b2) is at least one of a bifunctional or higher aliphatic isocyanate compound and a derivative thereof. The water repellency measured according to JIS L1092 of the first main surface is 4th or higher,
The fiber structure according to claim 1 or 2, wherein the water repellency after washing 20 times according to JIS L0217 103 is 3 or more. And a second resin layer formed on at least a part of the surface of the first resin layer,
The fiber structure according to any one of claims 1 to 3, wherein the second resin layer includes at least one resin selected from the group consisting of an acrylic resin, a urethane resin, a silicone resin, and a polyolefin resin. .   The fiber structure according to claim 4, wherein the second resin layer includes a urethane resin having a coagulation value of 7 to 15% by mass. The water pressure resistance measured according to JIS L1092 A method is 3,000 mmH ₂ O or more,
Moisture permeability as measured according to JIS L1099 A-1 method and B-1 method is respectively 3,000g ^/ m ^2/24 hours or more, the fiber structure of claim 4 or 5. A step of forming a first resin layer on at least the first main surface of a fiber base comprising a first main surface and a second main surface opposite to the first main surface;
Forming the first resin layer comprises:
A first step of applying an anionic compound (A) to at least the first main surface;
A second step of imparting a hydrocarbon compound (b1) and a compound (b2) to at least the first main surface to which the anionic compound (A) has been imparted,
The anionic compound (A) has one or more anionic groups in the molecule,
The anionic compound (A) has a weight average molecular weight of 30,000 to 70,000,
The hydrocarbon compound (b1) is a group consisting of alkyl urethane, ethylene urea, aliphatic carboxylic acid, its ester compound, aliphatic hydrocarbon, polyacrylic ester, polymethacrylic ester, polyolefin, methylolamide, and derivatives thereof. At least one selected from
The method for producing a fiber structure, wherein the compound (b2) is at least one selected from the group consisting of a bifunctional or higher functional isocyanate compound, a bifunctional or higher functional methylol compound, and derivatives thereof.   The manufacturing method of the fiber structure of Claim 7 with which the said 1st process is performed on the conditions of pH 2-6. After the step of forming the first resin layer, including a step of forming a second resin layer on at least a part of the surface of the first resin layer;
The method for producing a fiber structure according to claim 7 or 8, wherein the second resin layer includes at least one resin selected from the group consisting of an acrylic resin, a urethane resin, a silicone resin, and a polyolefin resin.