JP2012202009A - Method for producing moisture permeable waterproof fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a moisture permeable waterproof fabric that can effectively reduce occurrence of curling.SOLUTION: There is provided a method for producing a moisture permeable waterproof fabric which is obtained by laminating a microporous film mainly comprising polyurethane resin on one surface of a polyamide-based fabric whose surface is rendered water repellent. The method includes: applying a resin composition for forming the microporous film including the polyurethane resin and a crosslinking agent on one surface of the polyamide-based fabric that is rendered water repellent; and then, during or after coagulating and coating a resin component of the resin composition for forming the microporous film to form a resin film for forming the microporous film, widening the polyamide-based fabric with the resin film for forming the microporous film in a width direction of the fabric within a range of 3 to 10%.

Description

  The present invention relates to a method for producing a moisture-permeable and waterproof fabric.

  In applications such as sports clothing and cold clothing, moisture permeability that releases water vapor from sweat from the body to the outside of the clothing and waterproofness that prevents rainwater from entering the clothing are required. A fabric is used.

  Such a moisture-permeable and waterproof fabric generally has a configuration in which a microporous film is formed on the fabric surface. As a resin composition for forming a microporous film (resin composition for forming a microporous film), a resin composition containing a polyurethane resin as a main component is used from the viewpoint of versatility, cost performance, and high moisture permeability. It has been. That is, the moisture-permeable and waterproof fabric is obtained by applying the resin composition for forming a microporous film on the surface of the fabric, followed by drying and solidifying to form a microporous film (so-called dry film forming method). Alternatively, after applying the resin composition for forming a microporous film on the surface of the fabric, it is immersed in water to wet-coagulate the composition, and then dried to form a microporous film (so-called wet film formation). Method), a moisture-permeable waterproof fabric is obtained.

  On the other hand, as a base material used for the fabric, polyamide fibers such as nylon 6 and nylon 66 and polyester fibers are used in terms of cost and strength.

  However, when a microporous membrane is formed on the fabric surface, the thickness of the membrane generally tends to be increased for the purpose of expressing high waterproof performance. Therefore, when the obtained moisture permeable waterproof fabric is cut or sewn, extreme curling occurs from the end of the fabric due to the hygroscopic difference between the polyamide fiber and the microporous film formed thereon. It may appear, and it is regarded as a problem that it interferes with work.

  Various attempts have been made to solve the above curling problem. For example, in Patent Document 1, a method for producing a coated fabric excellent in water resistance and moisture permeability is obtained by coating the surface of a fabric with a solution obtained by mixing a fine powder in a polyurethane solution containing an acrylic compound, and then wet coagulating. Is disclosed. Furthermore, Patent Document 1 discloses that a hydrophilic anionic or hydrophobic nonionic surfactant is added to improve the smoothness of the film surface and curling.

  Patent Document 2 discloses that curling is suppressed by coating the fabric surface with a hygroscopic polyurethane polymer composition containing a magnesium salt.

JP-A 61-160480 JP-A-5-271432

  However, in the case of Patent Document 1, the effect of improving curling was insufficient. In Patent Document 2, as described in Example 4, when obtaining a fabric that achieves a low water pressure of about 2000 mm (19.6 kPa), a polyurethane containing a magnesium salt as a hygroscopic agent A polymer composition is used. However, for example, when a high water pressure of 50 kPa or more is obtained, if a polyurethane polymer composition containing a magnesium salt that is a hygroscopic agent is used, curling is improved, but water resistance is lowered, so that a waterproof fabric is obtained. It may be difficult to apply

  Therefore, in view of these problems, an object of the present invention is a process for forming a microporous membrane when producing a moisture-permeable and waterproof fabric in which a microporous membrane is formed on a fabric. It is an object of the present invention to provide a method for producing a moisture-permeable and waterproof fabric capable of effectively reducing the occurrence of curling due to the difference in resin shrinkage and the moisture absorption performance that occurs during solidification with water or the like.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a moisture-permeable and waterproof fabric that can effectively reduce curling due to hygroscopicity and a method for producing the fabric, and have reached the present invention.
That is, the gist of the present invention is as follows.
(1) A method for producing a moisture-permeable and waterproof fabric in which a microporous membrane mainly composed of a polyurethane resin is laminated on one surface of a polyamide-based fabric having a surface imparted with water repellency. A resin composition for forming a microporous film containing a polyurethane resin and a cross-linking agent is applied to one side of the polyamide-based fabric, and then the resin component of the resin composition for forming a microporous film is formed into a solidified film. While forming the resin film for forming a porous film, or after forming the resin film for forming a microporous film by forming a solidified film, the polyamide-based fabric is combined with the resin film for forming the microporous film in the width direction of the fabric. A method for producing a moisture-permeable and waterproof fabric, characterized by widening in a range of -10%.
(2) The method for producing a moisture-permeable and waterproof fabric according to (1), wherein the polyamide-based fabric is mainly composed of nylon 11 fibers or nylon 12 fibers.
(3) The method for producing a moisture-permeable and waterproof fabric according to (1) or (2), wherein a fluorine-based water repellent, a crosslinking agent, and a penetrating agent are used as a method for imparting water repellency.

  According to the present invention, when obtaining a moisture-permeable and waterproof fabric in which a microporous film is formed on the fabric, a moisture-permeable and waterproof fabric in which curling is greatly reduced can be obtained. Further, since the microporous membrane is cross-linked, dimensional stabilization is achieved, and curling can be more effectively reduced. Furthermore, curling can be more effectively reduced when the polyamide-based fabric is mainly composed of nylon 11 fibers and nylon 12 fibers.

It is the schematic which shows the method of measuring the curling angle in this invention.

Hereinafter, the present invention will be specifically described.
The present invention is a method for producing a moisture-permeable and waterproof fabric in which a microporous membrane mainly composed of a polyurethane resin is laminated on one side of a polyamide-based fabric having a water-repellent surface. In the production method, a resin composition for forming a microporous film containing a polyurethane resin and a crosslinking agent is applied to one side of a polyamide-based fabric imparted with water repellency, and then the resin composition for forming a microporous film is used. While forming a resin film for forming a microporous film by forming a resin component into a solidified film, or after forming a resin film for forming a microporous film by forming a solidified film, the polyamide-based fabric is converted into a resin for forming a microporous film. It is indispensable to carry out a process of widening in the range of 3 to 10% in the width direction of the fabric together with the film.

  The polyamide-based fabric used in the present invention is a fabric mainly composed of polyamide fibers, and examples thereof include woven fabrics, knitted fabrics, and nonwoven fabrics made of conventionally known polyamide fibers. Polyamide fibers have the advantage of being excellent in strength and cost.

  Specific examples of polyamide fiber include nylon 6 fiber synthesized by polycondensation reaction of ε-caprolactam; nylon 11 fiber obtained from undecane lactam, nylon 12 fiber obtained from lauryl lactam; co-condensation of hexamethylenediamine and adipic acid Nylon 66 fiber synthesized by polymerization reaction; nylon 46 fiber obtained from tetramethylenediamine and adipic acid; nylon 66 fiber or nylon 56 fiber synthesized by co-condensation polymerization reaction of hexamethylenediamine and sebacic acid; nylon 5,10 Fiber, aliphatic polyamide fiber such as nylon 6,10 fiber; nylon 6T fiber and nylon 9T fiber obtained from diamine and terephthalic acid; aromatic polyamide fiber such as nylon 6I fiber obtained from hexamethylenediamine and isophthalic acid; aromatic The system Aramide fibers synthesized by copolycondensation reaction of Min and dicarboxylic acids.

  Among these, nylon 6 fiber or nylon 66 fiber is preferable from the viewpoint of cost and versatility. In addition, nylon 11 fiber or nylon 12 fiber is preferable from the viewpoint of low density and light weight, and low hygroscopicity and water absorption. If the hygroscopicity is low, curling can be reduced more effectively. Furthermore, when the water absorption is low, when a microporous film made of an aqueous polyurethane resin is formed on the fabric surface, the film is easily formed.

  In particular, nylon 11 is obtained by synthesizing 11 aminoundecanoic acid using castor oil extracted from castor seeds as a starting material. Therefore, since it is used suitably as what is called biomass material which uses a plant as a raw material, it is still more preferable from an environmental viewpoint.

  The polyamide-based fabric may contain fibers other than the polyamide fibers. Other fibers include polyester-based synthetic fibers such as polyethylene terephthalate; polyacrylonitrile-based synthetic fibers; synthetic fibers such as polyvinyl alcohol-based synthetic fibers; semi-synthetic fibers such as triacetate; and natural fibers such as cotton and wool. . The content of other fibers is preferably 30% by mass or less with respect to the entire polyamide-based fabric.

  The polyamide-based fabric needs to have water repellency. In order to impart water repellency, a conventionally known water repellent can be used. Examples of the water repellent include a fluorine water repellent, a polysiloxane water repellent, and a paraffin water repellent. These water repellents may be used in the form of an emulsion. Especially, it is preferable to use a fluorine-type water repellent from a durable viewpoint at the time of wear or washing.

  The water repellency of the polyamide-based fabric referred to in the present invention is grade 3 or higher according to the measurement method (water repellency measurement) by JIS L-1092 spray method, and grade 4 by the measurement method (oil repellency measurement) by AATCC-TM118. That means the above. In the present invention, by satisfying these water repellency performances, the moisture permeable waterproof fabric obtained can have sufficient water repellency.

  The amount of the water repellent used is preferably 0.1 to 3% by mass and more preferably 0.3 to 2% by mass in terms of solid content with respect to the polyamide-based fabric. If the amount used is less than 0.1% by mass, sufficient water repellency may not be imparted to the fabric body. On the other hand, if it exceeds 3% by mass, the texture of the moisture-permeable and waterproof fabric obtained is easily cured, the adhesion between the polyamide-based fabric and the microporous membrane formed later is reduced, or the permeability of the microporous membrane is reduced. May adversely affect wetness.

  The method of imparting water repellency to the polyamide-based fabric preferably uses a fluorine-based water repellent, a crosslinking agent, and a penetrating agent from the viewpoint of improving water repellency durability. By using a crosslinking agent, there is an advantage that durability at the time of wearing or washing can be easily obtained. The penetrant plays a role of allowing a fluorine-based water repellent to penetrate into a polyamide-based fabric. By using the penetrant, there is an advantage that the durability of the obtained moisture-permeable and waterproof fabric is further improved. Further, when a penetrant is used for a polyamide-based fabric having a low water absorption, such as the above-described nylon 11 fiber or nylon 12 fiber, there is an advantage that the adhesion of the water repellent to the polyamide-based fabric is improved.

  As the fluorine-based water repellent agent, a perfluorooctanoic acid-free fluorine-based water repellent agent mainly containing a perfluoroalkyl group having 1 to 6 carbon atoms is particularly preferable from the environmental viewpoint.

  In addition, the perfluorooctanoic acid-free fluorine-based water repellent in the present invention means the following water repellent. That is, it means a water repellent that does not contain perfluorooctanoic acid and its related substances or precursor substances thereof. Alternatively, it means a water repellent which cannot qualify perfluorooctanoic acid and its related substances or precursor substances when measured by a high performance liquid chromatograph mass spectrometer.

  As the fluorine-based water repellent containing no perfluorooctanoic acid, a commercially available product can be suitably used. For example, “Asahi Guard AG-E061 (trade name)”, “Asahi Guard AG-E082” (product) manufactured by Asahi Glass Co., Ltd. Name) ”,“ Asahi Guard AG-E500D (trade name) ”;“ Unidyne TG-5521 (trade name) ”,“ Unidyne TG-5541 (trade name) ”, Unidyne TG-5601 (trade name) manufactured by Daikin Industries, Ltd. “NUVA N2114 LIQ (trade name)”, “NUVA N2116 LIQ (trade name)” manufactured by Clariant Japan, and the like.

  Examples of the crosslinking agent include isocyanate compounds and triazine compounds. As the isocyanate compound, from the viewpoint of pot life and processing stability of a resin solution (that is, a solution prepared from a fluorine-based water repellent, a crosslinking agent, and a penetrant), the isocyanate group may be acetoxime, phenol, caprolactam, etc. Preferable examples include blocked thermal dissociation type blocked isocyanate compounds. As the isocyanate compound, a commercially available product can be suitably used. Specific examples include “Meikanate FM-1 (trade name)”, “Meikanate TP-10 (trade name)”, and “Meikanate” manufactured by Meisei Chemical Industry Co., Ltd. WEB (trade name) ".

  Commercially available products of the triazine-based compounds can also be suitably used. Specific examples include “Beccamin M-3 (trade name)” manufactured by DIC.

  As a usage-amount of a crosslinking agent, about 10 mass parts-50 mass parts are preferable with respect to 100 mass parts of said water repellent solid content. Moreover, it is preferable that it is 0.01-0.5 mass% in conversion of solid content with respect to a polyamide-type fabric, and it is more preferable that it is 0.03-0.3 mass%. When the amount is less than the above-mentioned use amount, the durability improving effect may not be exhibited. On the other hand, if it exceeds the above range, it is not preferable because it adversely affects the texture and fastness of the resulting moisture-permeable and waterproof fabric.

  The penetrant is not particularly limited as long as it improves the permeability of the water repellent to the polyamide-based fabric, and representative examples include a surfactant or an organic solvent.

  Examples of the surfactant include nonionic surfactants such as polyoxyalkylene monoalkyl ethers; cationic surfactants such as alkyltrimethylammonium salts; amphoteric surfactants such as alkylamine oxides and alkylbetaines. It is preferable that the usage-amount of surfactant is 0.005-0.5 mass% with respect to the amount of resin solutions to be used, More preferably, it is 0.01-0.3 mass%. If it is less than 0.005% by mass, the permeation effect of the water repellent will be poor, and uneven adhesion of the water repellent may occur. On the other hand, if it exceeds 0.5% by mass, the permeability of the water repellent is improved, but the stability of the water repellent is lowered, and the water repellency may be lowered.

  Further, the organic solvent is not particularly limited, and examples thereof include general-purpose and less toxic ethyl alcohol and isopropyl alcohol. The content of the organic solvent is preferably 0.3 to 10% by mass, more preferably 0.5 to 8% by mass with respect to the polyamide-based fabric. If it is less than 0.3% by mass, the water repellent penetration effect may be poor, and uneven adhesion of the water repellent may occur. On the other hand, when it exceeds 10% by mass, the permeability of the water repellent improves, but the stability of the water repellent may decrease.

  In order to impart water repellency to the polyamide-based fabric, a conventionally known method can be employed. For example, a method of immersing a polyamide fabric in a resin solution containing a water repellent (padding method), a method of applying a resin solution containing a water repellent to the surface of a polyamide fabric (coating method, gravure coating method) , Spray method) and the like.

  The following describes how to impart water repellency to the polyamide-based fabric by the padding method. That is, after immersing a polyamide-based fabric in a resin solution containing a water repellent agent, the polyamide fabric is taken out and adjusted to a predetermined application amount by squeezing with a mangle. After drying at a temperature of 80 to 150 ° C., 150 to 180 ° C. Curing for 30 seconds to 3 minutes at temperature. As a result, a fabric having a water repellent finish is obtained.

  The following description will be given to imparting water repellency to the polyamide-based fabric by the gravure coating method. That is, using a high mesh gravure roll, a resin solution containing a water repellent agent is attached to only one side of a polyamide-based fabric. Then, after drying at a temperature of 80 to 150 ° C., curing is performed at a temperature of 150 to 180 ° C. for 30 seconds to 3 minutes. As a result, a fabric having a water repellent finish only on one side of the fabric is obtained.

  In addition, after performing said drying and curing on the surface of a polyamide-type fabric, it is preferable to perform a crushing process using the calendar processing machine which comprises a mirror surface roll. Thus, as described later, when a resin composition for forming a microporous film is applied to one side of a polyamide-based fabric, the composition is prevented from penetrating deeply into the fabric body, and the moisture-permeable and waterproofing obtained The effect that it can prevent that the texture of a property cloth becomes hard is show | played.

In moisture-permeable waterproof fabric obtained in the production method of the present invention, on one side of the polyamide fabric, wherein water repellency is granted, a microporous film composed mainly of a polyurethane resin is laminated. Polyurethane resin has high versatility, is excellent in cost, and can impart high moisture permeability and waterproofness. A conventionally well-known thing can be used for a polyurethane resin, For example, the polyurethane resin obtained by making a polyisocyanate component and a polyol component react is mentioned. In the present invention, the main component means that 70% by mass or more of the polyurethane resin is contained with respect to the entire microporous film to be formed.

  Examples of the polyisocyanate component include aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate. Specific examples include tolylene-2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, or 1,4-cyclohexane diisocyanate. A tri- or higher functional polyisocyanate may be used. These may be used alone or in combination of two or more.

  Examples of the polyol component include polyether polyol and polyester polyol. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetraethylene glycol. Examples of the polyester polyol include a reaction product of a diol such as ethylene glycol or propylene glycol and a dibasic acid such as adipic acid or sebacic acid, or a ring-opening polymer such as caprolactone. Further, an oxyacid monomer or a polymer of a prepolymer thereof can also be used.

  In the production method of the present invention, it is necessary that the above-mentioned microporous membrane contains a crosslinking agent, that is, the microporous membrane is crosslinked. The advantages of crosslinking the microporous membrane are described below. An uncrosslinked microporous membrane is easy to deform, and a crosslinked microporous membrane is difficult to deform. Therefore, a film before widening treatment (hereinafter referred to as a microporous film-forming resin film) for forming a microporous film on a polyamide-based fabric is formed, and before or after the microporous film-forming resin film is cross-linked However, the dimensional stabilization of the microporous membrane obtained by extending the polyamide-based fabric by applying a strong tension in the lateral direction is improved. As a result, the occurrence of curling in the microporous membrane can be greatly reduced.

  Examples of the crosslinking agent for crosslinking the microporous membrane include carbodiimide compounds, aziridine compounds, and isocyanate compounds. Among them, it is preferable to use an isocyanate compound. Usually, the isocyanate compound is used for the purpose of crosslinking the polyurethane resin to improve the strength of the microporous membrane or improving the adhesive force between the microporous membrane and the polyamide-based fabric. However, in the present invention, a crosslinking agent such as an isocyanate compound is contained for the purpose of reducing curling.

  The amount of the crosslinking agent that crosslinks the microporous membrane is selected from the viewpoint of effectively preventing curling, from the viewpoint of effectively preventing curling (ie, a resin composition containing a urethane resin as a main component and other substances). ) Is preferably 1 to 10% by mass, more preferably 2 to 8% by mass. When the amount of the crosslinking agent used is less than 1% by mass, the strength of the microporous membrane and the adhesive force between the microporous membrane and the polyamide-based fabric may be insufficient. On the other hand, if it exceeds 10% by mass, the texture of the microporous membrane may be hardened or the water pressure resistance may be reduced.

  Examples of the crosslinkable isocyanate compound include tolylene 2,4-diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and the like. Further, triisocyanates obtained by an addition reaction between 3 mol of these diisocyanates and 1 mol of a compound containing active hydrogen may be used. In addition, as a compound containing active hydrogen, a trimethylol propane, glycerol, etc. are mentioned, for example.

  In the present invention, a resin other than the polyurethane resin may be added to the microporous membrane. The amount added is, for example, about 20% by mass or less in the solid content of the microporous membrane. As such a resin, for example, a polymer or copolymer such as polyacrylic acid, polyvinyl chloride, polystyrene, polybutadiene, polyamino acid, and polycarbonate is used. In addition, those obtained by modifying these polymers or copolymers with fluorine or silicon can also be used.

  In order to give an antibacterial function to the microporous membrane, if necessary, a filler such as titanium oxide, calcium carbonate, silicon oxide, a moisture permeability improver, or a moisture permeable waterproof fabric, as long as the effects of the present invention are not impaired. Additives such as an antibacterial agent, a deodorizing agent for imparting a deodorizing effect to the moisture permeable waterproof fabric, and a flame retardant for imparting a flame retardant effect to the moisture permeable waterproof fabric may be added.

  The thickness of the microporous film is not particularly limited, but is usually about 10 to 70 μm regardless of the film formation method. When the thickness of the microporous membrane is less than 10 μm, the water pressure resistance may be lowered. On the other hand, if it exceeds 70 μm, moisture permeability may be reduced, the texture may be cured, and the curling degree may be increased.

  The method for forming the resin film for forming a microporous film is not particularly limited as long as it can form a microporous film having moisture permeability and waterproofness, and a conventionally known method can be adopted. For example, a resin solution for forming a microporous film such as a polyurethane resin solution is applied to a polyamide-based fabric, and then immersed in a coagulation bath containing water as a main component to form a coagulated film of the resin component, followed by washing with hot water and drying. A method of forming a film by applying a resin solution for forming a microporous film such as a polyurethane resin solution composed of water and / or an organic solvent to a polyamide-based fabric and then forming a dry film. A method (so-called dry film-forming method).

  In the present invention, it is necessary to perform a widening treatment during or after the formation of the microporous film-forming resin film. The widening process is a process of extending (expanding) in the width direction (TD direction: Transverse Direction) in a pin tenter type dryer or the like. Usually, the widening process is performed in order to finely adjust the heat set of the finally obtained product and the width of the final product to be within the standard value range. When performing the widening process for such a purpose, the widening ratio is usually less than 2%. However, in the present invention, a remarkable effect that curling can be effectively reduced is achieved by performing the widening process at a rate that greatly exceeds the normal widening rate. Note that the normal widening process of about 0 to 1% for finely adjusting the width of the final product to be within the range of the standard value as described above is generally referred to as a wide width process.

  When a resin film for forming a microporous film is formed on a polyamide-based fabric using a wet film-forming method, a moisture-permeable waterproof fabric can be obtained in one step, and crosslinking and widening can be performed efficiently. From the viewpoint of achieving this, it is preferable to perform a widening process during drying after solidification and hot water washing. On the other hand, when forming a resin film for forming a microporous film by a dry film forming method, from the viewpoint that a permeable waterproof fabric can be obtained in one step and that crosslinking and widening can be performed efficiently. It is preferable to perform a widening process during film formation.

  The widening ratio is preferably 3 to 10% and more preferably 5 to 10% with respect to the entire width direction. If it is less than 3%, the curling reduction effect may be poor. On the other hand, if it exceeds 10%, although it depends on the strength and stretchability of the microporous film to be formed, it is not preferable because there is a fear that the water pressure resistance at the edge of the microporous film may be lowered.

  The widening treatment may be performed simultaneously with drying for volatilizing water from the resin film for forming a microporous film, may be performed after volatilizing water, or may be performed separately in an oven or the like. May be dried and immediately after drying using a pin tenter or the like.

  An example of manufacturing the moisture-permeable and waterproof fabric of the present invention using the wet film forming method will be described below. First, the polyurethane resin is made into a resin composition for forming a microporous film mainly composed of a polar solvent that can be easily replaced with water such as N, N-dimethylformamide, N-methylpyrrolidone and the like. The resin composition for forming a microporous film is preferably adjusted to a solid content concentration of about 15 to 35% and a viscosity of 5000 to 30000 mPa · s (25 ° C.). When the solid content concentration and the viscosity are too high, the leveling property and the desolvation property may be lowered. If the solid content concentration or viscosity is too low, the resin composition for forming a microporous film penetrates into the interior of the polyamide-based fabric body and easily leaks to the opposite surface, so that the moisture-permeable waterproof fabric obtained has a hard texture. Or it may be difficult to adjust the thickness of the predetermined microporous membrane.

  Examples of the method for forming a solidified film after applying the resin composition for forming a microporous film include the following methods. That is, elution of N, N-dimethylformamide in a coagulation bath for 0.5 to 5 minutes at 5 to 30 ° C. using water or mixed water containing N, N-dimethylformamide having a concentration of 30% by mass or less. Followed by hot water washing for the purpose of removing residual N, N-dimethylformamide at 30 to 80 ° C. for about 1 to 10 minutes, followed by drying.

  The widening treatment may be performed simultaneously with the formation of the solidified film or may be performed after the formation of the solidified film. Further, the widening process may be performed using a pin tenter or the like during or immediately after drying.

  Two methods will be described below for forming a microporous film-forming resin film using a dry film forming method. As a first method, a small amount of an emulsifier and / or a hydrophilic polyurethane resin is added to a hydrophobic emulsion in which polyurethane fine particles having a size of 0.1 to 5 μm are dispersed in an organic solvent such as methyl ethyl ketone and toluene. To give a W / O type (water-in-oil type) polyurethane emulsion, and a crosslinking agent is further added to obtain a resin composition for forming a microporous film. And the resin composition for microporous film formation is formed by apply | coating this resin composition for microporous film formation to a polyamide-type fabric, and drying for 0.5 to 5 minutes at 80-150 degreeC after that, for example. The widening treatment may be performed simultaneously with the volatilization of moisture, may be performed after volatilizing the moisture, or may be performed using a pin tenter or the like immediately after drying the resin solution in an oven or the like.

  As a second method, an O / W type (oil-in-water type) polyurethane emulsion as a main agent and a water-based polyurethane resin such as a self-emulsifying polyurethane emulsion in which polyurethane fine particles are dispersed in water, and an auxiliary agent as A resin composition for forming a microporous film is prepared by mixing a crosslinking agent with an aqueous solution or a water-soluble polyurethane resin such as a paste or starch that can be an elution component under normal temperature to 100 ° C. warm water. Then, the resin composition for forming a microporous film is applied to a polyamide-based fabric, and then dried to form a film, and an auxiliary agent that becomes an elution component later is used in a home washing machine, an industrial washing machine, or a dyeing machine. Then, the resin film for forming a microporous film is formed by performing soaping for about 5 to 15 minutes at a temperature at which elution is easy and elution. The widening process may be performed at the time of dry film formation or the drying process after soaping.

  As other means, a gas foaming agent or the like is mixed to form a dry film, or a surfactant, foaming agent, etc. is used to generate a large number of fine bubbles in the resin composition for forming a microporous film, and then applied. And a means for forming a dry film. Also in this regard, a widening process similar to that described above may be performed at the time of dry film formation or after dry film formation.

  The dryer used for forming the microporous film-forming resin film is preferably one that easily applies tension in the width direction, and for example, a pin tenter type processing machine or the like is preferably used. And 3-10% of widening process should just be performed simultaneously, making it dry at 80-150 degreeC for 0.5-5 minutes. If the temperature is less than 80 ° C., the stretchability of the base fabric may be poor and the widening process may be difficult. If the tension exceeds 150 ° C. until a microporous film is formed, a polyamide-based fabric It is not preferable because the cell form is deformed in the cross section, and the moisture permeable waterproof performance is likely to be adversely affected.

  In addition, what is necessary is just to perform application | coating of the resin composition for microporous film formation so that it may become predetermined thickness on the single side | surface of a polyamide-type fabric using a conventionally well-known comma coater, a knife coater, etc.

  When the surface of the polyamide fabric is uneven, there may be a problem that the peel strength of the microporous membrane is low or the resin composition for forming the microporous membrane leaks to the opposite surface of the polyamide fabric. is there. In such a case, the resin film for forming a microporous film may be formed in two steps to form a two-layer form. In the case of a two-layer configuration, it is preferable that the first layer (layer formed on the surface of the polyamide-based fabric) is made thinner than the second layer from the viewpoint of the peel strength and moisture permeability of the microporous membrane.

Water pressure resistance can be used as an index of waterproofness of the moisture permeable waterproof fabric of the present invention. In the present invention, the water pressure resistance is preferably 50 kPa or more. Further, moisture permeability can be used as an indicator of moisture permeability of the moisture-permeable and waterproof fabric of the present invention. In the present invention, the moisture permeability is preferably 5000 g / m ² · 24 hrs or more. The water pressure resistance is measured according to JIS L1092 (high water pressure method), and the moisture permeability is measured according to JIS L1099 (A-1 method).

  The moisture-permeable and waterproof fabric of the present invention has curling reduced when forming a microporous film on a polyamide-based fabric imparted with water repellency, or by a widening treatment after formation, and is 120 ° or less. It has a curling angle. A method for obtaining the curling angle will be described below with reference to FIG. That is, the moisture-permeable waterproof fabric 3 of the present invention in which the microporous membrane 1 is formed on the polyamide-based fabric 2 is cut into a size of 20 cm × 20 cm to obtain a sample. The sample is allowed to stand on a flat table 4 with the surface on which the microporous membrane 1 is formed facing up, and is left for 24 hours in an environment of a temperature of 20 ° C. and a humidity of 65% RH. Next, a tangent line 6 is drawn at a point 5 curled to the maximum on the side in the horizontal direction, and an angle on the table by the tangent line 6 is set as a curling angle 7.

  Furthermore, when a polyamide-based fabric mainly composed of nylon 11 fiber or nylon 12 fiber having low hygroscopicity is used, curling is further suppressed, so that the curling angle can be 90 degrees or less.

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
In addition, the measurement of the performance of the fabric in an Example and a comparative example and evaluation were performed with the following method.
(1) Water pressure resistance Measured according to JIS L-1092 (high water pressure method).

(2) Moisture permeability It was measured according to JIS L-1099 A-1 method (calcium chloride method).

(3) Curling angle The moisture permeable waterproof fabric of the present invention was cut into a size of 20 cm × 20 cm to prepare a sample. The sample was allowed to stand on a flat surface with the surface on which the microporous film was formed facing up, and was allowed to stand for 24 hours in an environment of a temperature of 20 ° C. and a humidity of 65% RH. Next, a tangent line was drawn at the point curled maximum on the side in the horizontal direction, and the angle on the table by the tangent line was defined as the curling angle.

(4) Water repellency measured according to JIS L-1092 (spray method).
(5) Oil repellency measured according to AATCC-TM118 method.

(6) Peel strength According to JIS L-1089 method, the longitudinal peel strength between the polyamide-based fabric and the microporous membrane or the resin membrane and the backing fabric was measured.

(7) Washing durability (durability)
(7-1) Water pressure resistance retention rate According to JIS L-0217 (Method 103), after washing was performed 50 times continuously, tumbler drying was performed at 60 ° C. for 20 minutes, and the water pressure resistance was determined according to the method of (1) above. Asked. The water pressure resistance retention was calculated according to the following formula.
(Water pressure retention rate) = [(Water pressure after washing 50 times) / (Water pressure before washing)] × 100

(7-2) Water repellency after washing 50 times According to JIS L-0217 (Method 103), after washing 50 times continuously, tumbler drying is performed at 60 ° C. for 20 minutes, and the water repellency is It calculated | required according to the method of 4).

Example 1
Nylon 6 multifilament (78 dtex / 68f) is used for both warp and weft, and a plain fabric with a warp density of 115 / 2.54 cm and a weft density of 95 / 2.54 cm is woven to obtain a polyamide fabric. It was. The obtained polyamide-based fabric is scoured with 1 g / L of a scouring agent (Sunmall FL (manufactured by Nikka Chemical Co., Ltd.)), and then an acid dye ("Kayanol Blue N2G", Nippon Kayaku Co., Ltd.) 1.0% omf Thereafter, a 5% aqueous dispersion of the following formulation 1 was applied to the polyamide-based fabric by a padding method (pickup rate: 40%) and dried at 110 ° C. for 1 minute, Heat treatment was performed at 170 ° C. for 40 seconds to impart water repellency, followed by crushing using a calender machine having a mirror roll at a temperature of 170 ° C., a pressure of 300 kPa, and a speed of 30 m / min. A water crushing processed fabric was obtained.

<Prescription 1>
Fluorine-based water repellent emulsion 50 parts by weight ("AG-E500D" manufactured by Asahi Glass Co., Ltd., solid content 30% by weight)
950 parts by weight of water A resin composition for forming a microporous film of the following formulation 2 (resin solid content: 15%, viscosity: 8500 mPa · s / 25 ° C.) is used on a crushed surface of the water-repellent crushed fabric by a comma coater. And 180 g / m ² . Then, using a pin tenter type dryer, a 5% widening treatment was performed in the width direction while drying at 130 ° C. under drying conditions for 3 minutes to form a microporous film. Subsequently, heat setting was performed at 170 ° C. for 1 minute to obtain a moisture-permeable and waterproof fabric of Example 1.

<Prescription 2>
100 parts by weight of W / O type polyurethane resin (Haimen ATX-10, solid content: 26% by mass, manufactured by Dainichi Seika Kogyo Co., Ltd.)
2 parts by mass of isocyanate compound (Rezamin X, manufactured by Dainichi Seika Kogyo Co., Ltd.)
Methyl ethyl ketone 20 parts by mass Toluene 20 parts by mass Water 40 parts by mass Asahi Guard AG-E082 2 parts by mass (manufactured by Asahi Glass Co., Ltd., fluorine-based water repellent emulsion having a solid content of 20% by mass)

(Example 2)
A resin composition for forming a microporous film of the following formulation 3 (resin solid content: 22%, viscosity: 11000 mPa · s / 25 ° C.) on the crushed surface of the water-repellent crushed fabric obtained in Example 1 using a comma coater. ) At a coating amount of 100 g / m ² . The resin was solidified by immersing in a 20 ° C. water bath for 2 minutes, then washed with hot water at 50 ° C. for 5 minutes, and then squeezed with mangle. Subsequently, a 6% widening treatment in the width direction was performed while drying at 130 ° C. for 3 minutes using a pin tenter type dryer. Subsequently, it heat-set at 170 degreeC for 1 minute, and the moisture-permeable waterproof fabric of Example 2 was obtained.

<Prescription 3>
100 parts by mass of ester type polyurethane resin solution
(Daiichi Seika Kogyo Co., Ltd., Rezamin CU4555, solid content 27% by mass)
Isocyanate compound 2 parts by mass (manufactured by Dainichi Seika Kogyo Co., Ltd., Rezamin X crosslinking agent)
N, N-dimethylformamide 30 parts by mass

(Example 3)
A moisture-permeable waterproof fabric of Example 3 was obtained in the same manner as in Example 2, except that the widening ratio was 10%.

Example 4
On the crushed surface of the water-repellent crushed fabric obtained in Example 1, a resin composition for forming a microporous film (resin solid content: 27%, viscosity: 9500 mPa · s / 25 ° C.) of the following formulation 4 was used as a comma coater. The coating amount was 120 g / m ² . Then, using a pin tenter type dryer, a 5% widening treatment was performed in the width direction while drying at 130 ° C. for 3 minutes, thereby forming a dry film. Next, heat setting was performed at 170 ° C. for 2 minutes. Subsequently, the following paramillion AF50 was eluted by soaping using a liquid dyeing machine at 60 ° C. for 10 minutes to obtain a microporous membrane. Next, rinsing with normal temperature water for 5 minutes, and using a pin tenter type dryer, drying for 3 minutes at 150 ° C. while performing a 3% widening treatment in the width direction. A fabric was obtained.

<Prescription 4>
80 parts by mass of aqueous polycarbonate urethane emulsion (Parasol PNA-120, solid content: 30% by mass, manufactured by Ohara Palladium Chemical Co., Ltd.)
20 parts by mass of water-soluble polyurethane resin (Paramilion AF50, solid content: 50% by mass, manufactured by Ohara Palladium Chemical Co., Ltd.)
Block isocyanate 5 parts by mass (Ohara Palladium Chemical Co., Ltd. Paracat PGW-4)
Isopropyl alcohol 5 parts by weight Water 20 parts by weight

(Example 5)
In both warp and weft, a nylon-based multifilament (78 dtex / 34f) is used to obtain a polyamide-based fabric, and a moisture-permeable waterproof fabric in which the microporous membrane of Example 5 is formed by the same method as Example 2. Got.

(Example 6)
A moisture-permeable waterproof fabric with a microporous film of Example 6 was obtained by the same method as Example 5 except that the water-repellent processing of Example 5 was changed from Formulation 1 to Formula 5 below.

<Prescription 5>
Fluorine-based water repellent emulsion 50 parts by mass (Asahi Glass AG-E500D, solid content: 30% by mass)
10 parts by mass of block type isocyanate (Maysei Chemical Industries, Ltd. Meikanate FM-1)
Isopropyl alcohol 50 parts by mass Water 890 parts by mass Subsequently, a moisture-permeable and waterproof fabric on which the microporous membrane of Example 5 was formed was obtained by the same method as Example 2.

(Comparative Example 1)
A moisture-permeable waterproof fabric for Comparative Example 1 was obtained in the same manner as in Example 1 except that the widening treatment was replaced with the wide width treatment (ratio: 0.5%).

(Comparative Example 2)
A moisture-permeable waterproof fabric of Comparative Example 2 was obtained in the same manner as in Example 1 except that the widening treatment was 12%.

(Comparative Example 3)
A moisture-permeable waterproof fabric of Comparative Example 3 was obtained in the same manner as in Example 2 except that the widening process was replaced with the widening process (ratio: 0.5%).

(Comparative Example 4)
A moisture-permeable waterproof fabric of Comparative Example 4 was obtained in the same manner as in Example 4 except that the widening process was replaced with the widening process (ratio: 0.5%).

  The performance of each fabric obtained in Examples 1 to 6 and Comparative Examples 1 to 4 is shown in Table 1 below.

  As is apparent from the results in Table 1, the moisture permeable waterproof fabric of the present invention can effectively reduce curling without affecting physical properties such as water pressure resistance, moisture permeability, water repellency, and peel strength. Met.

  In particular, in Examples 5 and 6, a polyamide-based fabric was obtained using nylon 11 fibers, and in addition, water repellency was imparted using a water repellent, a crosslinking agent, and a penetrating agent in combination. Therefore, curling was remarkably reduced and the curling angle was 90 degrees or less. In addition, it was excellent in water repellency.

  On the other hand, in Comparative Examples 1, 3, and 4 in which the wide width process was performed without performing the widening process, the curling angle exceeded 120 degrees, and the curling was not reduced. Further, in Comparative Example 2 in which the widening treatment exceeds 10%, although the curling is reduced, the water pressure resistance is inferior.

DESCRIPTION OF SYMBOLS 1 Microporous film 2 Polyamide-type fabric 3 Moisture-permeable waterproof fabric 4 Plane base 5 Point curled to the maximum 6 Tangent 7 Curling angle

Claims (3)

  A method for producing a moisture-permeable and waterproof fabric in which a microporous membrane mainly composed of a polyurethane resin is laminated on one side of a polyamide-based fabric having a water-repellent surface, the polyamide having a water-repellent property A microporous film-forming resin composition containing a polyurethane resin and a crosslinking agent is applied to one side of the base fabric, and then the resin component of the microporous film-forming resin composition is solidified to form a microporous film. After forming the resin film for forming or forming the resin film for forming the microporous film by forming a coagulated film, the polyamide-based fabric together with the resin film for forming the microporous film is 3 to 10% in the width direction of the fabric. The manufacturing method of the moisture-permeable waterproof fabric characterized by expanding in the range of.   The method for producing a moisture-permeable and waterproof fabric according to claim 1, wherein the polyamide-based fabric comprises nylon 11 fibers and nylon 12 fibers as main components. The method for producing a moisture-permeable and waterproof fabric according to claim 1 or 2, wherein a fluorine-based water repellent, a crosslinking agent, and a penetrating agent are used as a method for imparting water repellency.

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