JP2011073222A - Method for producing moisture-permeable waterproof polyamide cloth - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce a moisture-permeable waterproof polyamide cloth which can solve a problem of a conventional technology, has no feeling of thickness, is excellent in the feeling of wear when used as clothing, and is advantageous in terms of cost and permeability performance. <P>SOLUTION: A polyisocyanate compound is added into a base cloth containing polyamide fibers to make its content 0.03-2 mass%. After that, a thermoplastic polyamide elastomer film containing a polyether block amide copolymer in which a hard segment composition is polyamide such as nylon 6, nylon 11, or nylon 12, and a soft segment composition is polyalkylene glycol such as ethylene glycol or propylene glycol is extruded directly on the base cloth added with the polyisocyanate compound to be brought into a laminated state. In addition, the film in a laminated state and the base cloth are unified by hot pressing. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a polyamide-based moisture-permeable and waterproof fabric mainly composed of a polyamide-based material and mainly used for cold clothing, sports clothing, casual clothing and the like.

  Moisture-permeable and waterproof material that combines moisture permeability and waterproofness has the function of releasing water vapor from sweat from the body to the outside of clothes and the function of preventing rain from entering the clothes. It is suitably used for sports clothing.

  Such moisture permeable and waterproof materials include those in which a resin layer is laminated on a fiber fabric, and this form is preferable in fields requiring high waterproof performance such as rain clothing, mountain use, marine use, etc. It is used.

  As the base material for the moisture-permeable and waterproof material, fabrics made of polyamide-based synthetic fibers such as nylon 6 and polyester-based synthetic fibers such as polyethylene terephthalate are widely used in terms of versatility, cost, or strength. . As the resin layer, a resin system such as polyurethane, polyester, or polytetrafluoroethylene is frequently used because it easily imparts moisture permeability. Thus, what formed the resin layer directly or indirectly on the single side | surface of the fabric by the coating method or the lamination method has comprised the mainstream of the moisture-permeable waterproof material.

  However, these configurations have many problems in terms of environment or physical properties. For example, in the polyurethane coating fabric of Patent Document 1, excellent moisture permeability and waterproof performance can be obtained by the microporous membrane, but since the microporous membrane unique to polyurethane is formed, the resin layer is thick. Therefore, it cannot be said that there is no risk of causing a difficulty in wearing or increasing the amount of incinerated materials at the time of disposal. The hydrophobic porous membrane laminate fabric of Patent Document 2 can similarly obtain excellent moisture permeability and waterproof performance. For example, the formed porous membrane is a typical polytetrafluoroethylene membrane. In this case, there is a possibility of inducing toxic gas when trying to incinerate it, which still involves many environmental problems.

  A technique described in Patent Document 3 is cited as an excellent environmental measure. That is, Patent Document 3 describes a waterproof and moisture-permeable garment having an improved recycling rate by laminating a polyester film on a woven or knitted fabric containing 90% or more polyester multifilament. However, when dyeing the resulting woven or knitted fabric, it is unavoidable to use a disperse dye to develop a dark color in practical use. Even if a polyester film is used as a transparent film, the disperse dye is applied to the film layer. There is a problem that the transition occurs and it is easy to cause a disadvantage in terms of application and fastness.

JP 05-078984 JP 2001-315236 A JP 2007-296798 A

  Accordingly, the present invention solves the problems of the prior art as described above, and further has a feeling of thickness, is excellent in wearing feeling when used as clothing, and is advantageous in terms of cost and moisture permeability. It aims at enabling manufacture of a moisture-permeable waterproof fabric.

The present invention solves the above-described problems and has the following configuration.
(1) A polyisocyanate compound is applied to a base fabric containing polyamide fibers so that the content thereof is 0.03 to 2% by mass, and then hardened to the base fabric provided with the polyisocyanate compound. A thermoplastic polyamide-based elastomer film containing a polyether block amide copolymer whose polyamide composition is a polyamide such as nylon 6, nylon 11 or nylon 12 and whose soft segment composition is a polyalkylene glycol such as ethylene glycol or propylene glycol. A method for producing a polyamide-based moisture-permeable and waterproof fabric, characterized by directly extruding into a laminated form and further integrating the laminated film and the base fabric by thermocompression bonding.

  (2) The method for producing a polyamide-based moisture-permeable and waterproof fabric according to (1), wherein the polyisocyanate-based compound is dried at less than 150 ° C. when the polyisocyanate compound is applied to the base fabric containing the polyamide fiber.

  (3) The method for producing a polyamide-based moisture-permeable and waterproof fabric according to (1) or (2), wherein the laminated film and base fabric integrated by thermocompression are heat-treated at 130 to 180 ° C. .

  (4) Manufacture of a polyamide-based moisture-permeable and waterproof fabric according to any one of (1) to (3), wherein a water-repellent treatment is applied to a laminated film and base fabric integrated by thermocompression bonding. Method.

  According to the method for producing a polyamide-based moisture-permeable and waterproof fabric of the present invention, the polyamide-based fiber base fabric and the thermoplastic polyamide-based elastomer film are laminated by thermocompression bonding without an adhesive layer, It is possible to produce a fabric that is structurally simple and does not have a feeling of thickness, and is excellent in a feeling of wearing when used as a garment. In addition, there is no need to form an adhesive layer, and a thermoplastic polyamide-based elastomer film as a moisture-permeable and waterproof film is directly extruded onto a base fabric with a polyisocyanate-based compound. However, it is also advantageous in terms of moisture permeability. Furthermore, since the fabric obtained by the manufacturing method is mainly composed of polyamide, it has recyclability. If the base fabric contains, for example, naturally derived nylon 11 at a high rate, it is further excellent from the viewpoint of biomass.

Examples of the base fabric used in the method for producing the polyamide-based moisture-permeable and waterproof fabric of the present invention include woven fabrics, knitted fabrics and nonwoven fabrics made of conventionally known polyamide fibers.
Specific examples of the 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, and a combination of hexamethylenediamine and adipic acid. Nylon 66 fiber synthesized by condensation polymerization reaction, nylon 46 fiber obtained from tetramethylenediamine and adipic acid, nylon 66 fiber synthesized by co-condensation polymerization reaction of hexamethylenediamine and sebacic acid or nylon 56 fiber, nylon 5, Aliphatic polyamide fibers such as 10 fibers and nylon 6,10 fibers can be mentioned. Other examples include aromatic polyamide fibers such as nylon 6T fiber and nylon 9T fiber obtained from diamine and terephthalic acid, and nylon 6I fiber obtained from hexamethylenediamine and isophthalic acid. Furthermore, the aramid fiber synthesize | combined by the copolycondensation reaction of aromatic diamine and dicarboxylic acid is mentioned.

  In the present invention, any polyamide fiber can be used, but nylon 6 or nylon 66 is preferably used from the viewpoint of cost and versatility. From the environmental point of view, so-called biomass materials made from plants that are friendly to the global environment are preferably used. For example, nylon 11 obtained by synthesizing after producing 11 aminoundecanoic acid based on castor oil extracted from castor seeds has a smaller density and lighter weight than nylon 6 and nylon 66, and is resistant to resistance. It is more preferable because it is excellent in wear resistance, chemical resistance, bending fatigue resistance, and the like.

  For the base fabric, polyester fibers such as polyethylene terephthalate, synthetic fibers such as polyacrylonitrile synthetic fibers and polyvinyl alcohol synthetic fibers, semi-synthetic fibers such as triacetate, cotton, etc., other than polyamide fibers Natural fibers such as wool may be included.

  In the present invention, a polyisocyanate compound is applied to a base fabric mainly composed of polyamide fibers. This is because required adhesiveness is exhibited with the thermoplastic polyamide-based elastomer film.

  The polyisocyanate compound referred to in the present invention may be any compound mainly composed of an isocyanate compound used as a general known crosslinking agent. For example, aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate; 1,3-cyclopentane diisocyanate, 1,3 or 1,4-cyclohexane diisocyanate, Finger ring diisocyanates such as methyl 2,4-cyclohexane diisocyanate; aromatic diisocyanates such as 2,4 or 2,6-tolylene diisocyanate, 2,2 ′ or 4,4′-diphenylmethane diisocyanate; and triphenylmethane-4 , 4 ', 4 "-triisocyanate, 1,3,5-triisocyanatebenzene and the like; 4,4'-diphenyldimethylmethane-2,2'-5,5'-te Organic tetraisocyanate monomers such as laisocyanate, dimers, trimers, burettes, allophanates derived from the above polyisocyanate monomers, etc. These may be used alone or in combination of two or more. Can do.

  In the present invention, the polyisocyanate compound may be dissolved or dispersed in water and / or an organic solvent and applied to the base fabric. In this case, when importance is attached to the adhesiveness to the elastomer film described later, a material having a relatively high isocyanate content may be used depending on the solid content of the resin liquid. On the other hand, when emphasizing the stability and pot life of the resin liquid, use a blocked isocyanate in which an additional block body is formed with phenol, lactam, methyl ketoxime, etc., which is dissociated by heat treatment. Is preferred.

  The amount of the polyisocyanate compound applied to the base fabric needs to be 0.03 to 2% by mass. It is preferable that it is 0.05-1 mass%. If it is less than 0.03% by mass, the adhesive strength with the elastomer film described later is poor, and if it exceeds 2% by mass, the texture of the base fabric tends to be hard and the adhesive strength of the surface of the base fabric tends to be too strong. .

  Examples of the imparting means include known and commonly applied padding methods, printing methods, coating methods, and spraying methods. What is necessary is just to dry after provision by these methods. The drying conditions are preferably 50 to 150 ° C., more preferably less than 130 ° C., more preferably 100 ° C. or more and less than 130 ° C. for 1 to 3 minutes in consideration of drying efficiency and isocyanate group reactivity. . When it is dried at 150 ° C. or higher, there is a possibility that the isocyanate group of the polyisocyanate compound reacts depending on the time.

  In the present invention, before or after applying the polyisocyanate compound, the surface of the base fabric may be crushed using a calendar processing machine equipped with a mirror roll. This is performed in the sense of imparting smoothness as a base fabric in order to favor the adhesiveness when the thermoplastic polyamide-based elastomer film is thermocompression bonded later. In particular, the effect is exhibited when the base fabric has unevenness.

  In the present invention, in the sense of imparting smoothness to the base fabric, or in the sense of improving the adhesion between the base fabric and the elastomer film, the polyisocyanate compound and other adhesives and resins to the extent that the moisture permeability is not impaired. May be used in combination. For example, an adhesive such as acrylic, polyester, polyamide, polyurethane, or a resin may be used in combination. In that case, the amount of the adhesive and resin used in combination is the use of the polyisocyanate compound from the viewpoint of efficiency at the time of recycling, the thickness of the finally obtained fabric is not increased, and the texture is not hardened. The smaller the amount, the better.

  Next, the thermoplastic polyamide-based elastomer film will be described. This film is mainly composed of a polyether block amide copolymer having a hard segment composition of polyamide such as nylon 6, nylon 11 or nylon 12 and a soft segment composition of polyalkylene glycol such as ethylene glycol or propylene glycol. Is. This film is directly extruded onto the base fabric to which the above-mentioned polyisocyanate compound is applied to form a laminated form.

  Specifically, the thermoplastic polyamide-based elastomer film is synthesized from one or more of caprolactam, aminoundecanoic acid, lauryl lactam, such as nylon 6, nylon 11, nylon 12, nylon 6, 12, nylon 11, 12, etc. The composition is mainly composed of a copolymer having a polyamide block and a polyether block synthesized from one or more of ethylene glycol, propylene glycol, tetramethylene glycol and the like.

  Any copolymer having a polyamide block and a polyether block may be obtained by polycondensation of a known polyamide block having a reactive end group and a polyether block having a reactive end group. Examples thereof include those composed of a polyamide unit having a diamine chain end group and a polyoxyalkylene unit having a dicarboxylic chain end group, or a polycondensation of a polyamide unit having a dicarboxylic chain end group and a polyether diol.

  From the viewpoint of moisture permeability, the content of the soft segment in the polyether block amide copolymer is preferably about 5 to 70% by mass, and preferably 10 to 50% by mass. If the content of the soft segment is less than 5% by mass, the effect of improving the moisture permeability is poor, and if it exceeds 70% by mass, the water swellability when used as an elastomer film becomes too large, and sweat, rainwater when worn It is easy to be influenced by this, and it is easy to become inferior to washing durability.

  The hard segment depends on the soft segment content, but using nylon 11 or nylon 12 is less sensitive to humidity than nylon 6 and has excellent impact properties at low temperatures. Therefore, it is preferable.

  In addition to the polyamide-based elastomer composition, as the third component, other components may be contained in a small amount, for example, about 20% by mass or less in the total solid content. As such a resin, those having affinity for polyamide elastomer and improving flexibility are preferable. For example, a polyester resin having a graft group, a polyolefin resin having a functional group introduced therein, or a plasticizer such as butylbenzenesulfoamide can be used. In addition, as a third component, a lubricant such as silicon dioxide, a pigment, a heat stabilizer, an antioxidant, a weathering agent, a flame retardant, and the like may be included as long as the film characteristics are not significantly impaired.

  The thermoplastic polyamide-based elastomer can be formed into a film by a known method. For example, the composition is melt-mixed with a single screw extruder or a twin screw extruder, extruded into a sheet shape with a thickness considering the draw ratio using a T die or the like, and then sequentially biaxially stretched or simultaneously. By biaxial stretching, the film can be formed by stretching both vertically and horizontally so as to have a predetermined film thickness.

  The thickness of the thermoplastic polyamide-based elastomer film laminated on the base fabric is preferably about 3 to 25 μm, and preferably 6 to 20 μm. When the thickness is less than 3 μm, the waterproof performance tends to be unstable and the workability tends to be poor. On the other hand, when the thickness exceeds 25 μm, it is a non-porous film, so that extreme moisture permeability is likely to be deteriorated, and the texture is liable to be disadvantageous.

  In the present invention, a film-like thermoplastic polyamide-based elastomer film extruded using the composition is directly laminated on a base fabric, and then immediately, preferably continuously in a lamination step, and subjected to thermocompression bonding. Thereby, a polyamide-type moisture-permeable waterproof fabric is obtained. What is necessary is just to perform a thermocompression bonding suitably with the pressure which can closely_contact | adhere a base fabric and a film at the temperature of 150-200 degreeC using a well-known laminating machine. If it is less than 150 degreeC, it will be hard to exhibit required adhesive force. When the temperature exceeds 200 ° C., the melting point of the thermoplastic polyamide-based elastomer film is generally lower than 200 ° C., so that even if the pressure bonding is instantaneous, laminating wrinkles are likely to occur and the workability is poor. Or the appearance of the base fabric is likely to change.

  The thermoplastic polyamide-based elastomer generally has a melting point of about 150 to 200 ° C. as described above from the viewpoint of composition or practical use. For this reason, the normal extrusion temperature at the die portion is 170 to 250 ° C. Degree. In the present invention, the residual heat at the time of extrusion, the heat at the time of pressure bonding, and the reaction of the polyisocyanate compound can contribute to favorably bond the base fabric and the film.

  When the adhesive strength is insufficient after thermocompression bonding, specifically when it is less than 5N / 2.54cm, it tends to cause problems in durability when used as clothing or during washing, etc. May be added as appropriate to improve the adhesive strength. For example, if the polyisocyanate compound is a non-block type, it is possible to improve the adhesive force by aging for 1 to 4 days in an environment of about 40 ° C. Furthermore, if processing conditions that are lower than the melting point of the polyamide-based elastomer film and approximate to the melting point are selected and heat treatment is performed using an oven, a tenter, etc., softening of the elastomer film improves adhesion between the base fabric and the elastomer film. Contributing and further improving the adhesion. In addition, if the polyisocyanate compound is a block type, the elastomer is selected by selecting a heat treatment condition of 130 to 180 ° C. that ensures the thermal dissociation of the block portion of the polyisocyanate compound below the melting point of the elastomer film itself. The softening of the film can be taken into account and the adhesive force can be improved.

  As described above, heat treatment is not an indispensable condition in the present invention. However, when this heat treatment is performed, a temperature condition of 180 ° C. or lower is considered in consideration of the melting point of the elastomer film and the dissociation temperature of the block type polyisocyanate compound. Is necessary. When it exceeds 180 ° C., discoloration, texture hardening, etc. of the elastomer film and the base fabric are caused.

  In the production method of the present invention, for the purpose of improving water repellency and waterproof performance, water repellency treatment may be performed after the base fabric and the elastomer film are laminated. The water repellent treatment may be performed using a known water repellent emulsion. As the water repellent emulsion, conventionally known fluorine water repellent emulsion, polysiloxane water repellent emulsion, paraffin water repellent emulsion and the like can be used. Especially, it is preferable to use a fluorine-type water repellent emulsion from a durable viewpoint. Furthermore, from the environmental viewpoint, it is more preferable to use a perfluorooctanoic acid that does not easily remain in the fluorine-based water repellent or that does not easily form over time. This is because perfluorooctanoic acid is difficult to decompose and remains in the environment, which is undesirable for the global environment. A typical example of such a fluorine-based water repellent is one obtained by polymerizing an acrylate compound having a C 1-6 perfluoroalkyl group in the side chain. Specifically, "Asahi Guard AG-E061 (trade name)", "Asahi Guard AG-E092 (trade name)", "Asahi Guard AG-E081 (trade name)" manufactured by Asahi Glass Co., Ltd., "Unidyne" manufactured by Daikin Industries TG-5521 (product name) "," Unidyne TG-5601 (product name) "and the like.

  A conventionally known method may be adopted as a method of water-repellent finishing the fabric. Specifically, means such as a padding method, a coating method, a gravure coating method, and a spray method can be employed. For example, in the padding method, after a laminated fabric is dipped in a water repellent emulsion, it is squeezed with a mangle, adjusted to a predetermined application amount, dried, and cured, so that the entire laminated fabric is water repellent. Processing can be performed. The gravure coating method uses a high mesh gravure roll to attach a water repellent emulsion only to the surface, and then drying and curing to obtain a laminated fabric with water repellent finish only on the surface. It is done.

  Therefore, drying may be performed at 80 to 150 ° C. for about 30 seconds to 5 minutes, and curing may be performed at 150 to 180 ° C. for about 30 seconds to 3 minutes. Alternatively, the heat treatment step described above and the water repellent drying and curing step may be performed simultaneously, and in that case, the manufacturing cost is very advantageous.

As the performance of the produced moisture-permeable waterproof fabric, the water pressure resistance, which is an index of waterproof performance, is preferably 50 kPa or more, and more preferably 100 kPa or more. Index serving moisture permeability of the moisture permeation performance, preferably 4000g ^/ m 2 · 24hrs or more, 6000g ^/ m 2 · 24hrs or more is more preferable. The water pressure resistance here is measured according to JIS L1092 (high water pressure method), and the water vapor transmission rate here is measured according to JIS L1099 (A-1 method, B-1 method).

  The moisture-permeable and waterproof fabric obtained by the production method of the present invention is a tent of course as a material for various clothing such as sports clothing and cold clothing that is environmentally friendly while having excellent moisture permeability and waterproof performance. It can also be used as a material for mountain climbing equipment. Furthermore, it can be used as a material for various products that require moisture permeability and waterproofness.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, the measurement of the performance of the fabric in a following 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) Water vapor permeability Measured according to JIS L-1099 A-1 method (calcium chloride method) and B-1 method (potassium acetate method).

(3) Peel strength According to JIS L-1089 method, the peel strength between the base fabric in the warp direction and the elastomer film was measured.

(4) Texture The following four stages were evaluated by handling.
◎: Very soft 〇: Soft △: Normal ×: Hard

(5) Fastness test Using a thermo-hygrostat, suspend the product so that it does not come into contact with other samples under the condition of 60 ° C. × 90% RH (free state). The change was observed and evaluated in the following three stages.

○: Little change in appearance △: Partial stain occurs ×: Overall stain of base fabric color occurs

Example 1
Nylon 6 high multifilament 78dtex / 68f is used for both the warp and the weft, and a plain fabric (weighing 70.7 g / m ² ) having a warp density of 110 / 2.54 cm and a weft density of 90 / 2.54 cm is used. Weaved. And it refined and dye | stained by the conventional method on the conditions of the following prescription 1.

<Prescription 1>
・ Scouring: 80 ° C. × 20 minutes {Scouring agent (“Sun Mall FL” 1 g / L, manufactured by Nikka Chemical Co., Ltd.)}
Dyeing: 100 ° C. × 20 minutes {Acid dye (“Kayanol Milling Blue 2RW” manufactured by Nippon Kayaku Co., Ltd.) 1% omf, leveling agent (“Leberan NKD” manufactured by Maruhishi Oil Chemical Co., Ltd.) 2% omf, acetic acid (48 %): 0.2 ml / L}
Fix: 80 ° C. × 20 minutes {fix agent (“Sun Life E-37” manufactured by Nikka Chemical Co., Ltd.) 1% omf}
・ Final set: 170 ℃ × 1min

  Then, 0.125 mass% aqueous dispersion of the following prescription 2 was applied to the base fabric by the padding method (pickup rate 40%). And the base fabric containing 0.05 mass% of polyisocyanate type compounds was obtained by drying at 110 degreeC x 2 minutes.

<Prescription 2>
Aquanate 140 1.25 parts by mass (manufactured by Nippon Polyurethane Industry Co., Ltd., polyisocyanate compound, solid content 100% by mass)
Acetone 8.75 parts by mass Water 990 parts by mass Next, using a twin screw extruder, a polyether block amide copolymer (manufactured by Arkema Co., Ltd.) whose hard segment is nylon 12, nylon 11, etc. and soft segment is polyethylene glycol, etc. , “Pebax MV3000”, melting point 158 ° C.) was melt-extruded from a T-die at 190 ° C. and simultaneously biaxially stretched at 150 ° C. to obtain a film-like thermoplastic polyamide elastomer having a thickness of about 12 μm.

  The film-like elastomer was directly laminated on the base fabric by interlocking the film-like thermoplastic polyamide-based elastomer with the base fabric prepared below in advance. Then, after this lamination position, a polyamide-based moisture-permeable and waterproof fabric is formed by thermocompression bonding using a laminating machine at 150 ° C., a gauge pressure of 0.5 MPa, and a feed rate of 3 m / min. Got.

(Example 2)
Formulation 2 of Example 1 was changed to the following formulation 3. That is, a 1.25% by mass aqueous dispersion of Formulation 3 (the base fabric contained 0.5% by mass of a polyisocyanate compound) was used, and the drying conditions were 120 ° C. × 2 minutes.

<Prescription 3>
Aquanate 200 12.5 parts by mass (manufactured by Nippon Polyurethane Industry Co., Ltd., polyisocyanate compound, solid content 100% by mass)
Acetone 27.5 parts by mass Water 960 parts by mass Further, compared to Example 1, the thickness of the thermoplastic polyamide-based elastomer film was changed to 15 μm. Other than that, a polyamide-based moisture-permeable waterproof fabric was obtained in the same manner as in Example 1.

(Example 3)
To the same base fabric used in Example 1, an 8% by mass aqueous dispersion of the following formulation 4 was applied by the padding method (pickup rate 40%). Then, a base fabric containing 0.96% by mass of a polyisocyanate compound was obtained by drying at 130 ° C. for 2 minutes.

<Prescription 4>
80 parts by mass of NBP-211 (manufactured by Meisei Chemical Industry Co., Ltd., block type polyisocyanate compound, solid content: 30% by mass)
Isopropyl alcohol 10 parts by weight Water 910 parts by weight Next, using a twin-screw extruder, a polyether block amide copolymer (manufactured by Arkema, whose hard segment is nylon 12, nylon 11, etc. and whose soft segment is polyethylene glycol, etc. “Pebax MV1041”, melting point 170 ° C.) was melt-extruded from a T-die at 200 ° C. and simultaneously biaxially stretched at 150 ° C. to obtain a film-like thermoplastic polyamide elastomer having a thickness of about 12 μm.

  The film-like thermoplastic polyamide-based elastomer was directly laminated on the base fabric by interlocking the feeding of the film-like thermoplastic polyamide-based elastomer and the base fabric prepared in advance below the film-like thermoplastic polyamide-based elastomer. Subsequently, at the rear of this lamination position, a polyamide-based moisture-permeable and waterproof fabric is obtained by thermocompression bonding at 170 ° C., a gauge pressure of 0.5 MPa, and a feed rate of 3 m / min using a laminating machine. Got.

Example 4
In addition to the method for producing the moisture-permeable waterproof fabric of Example 2, a polyamide-based moisture-permeable waterproof fabric of Example 4 was obtained by performing a heat treatment at 140 ° C. for 2 minutes using a tenter.

(Example 5)
In addition to the method for producing the polyamide-based moisture-permeable and waterproof fabric of Example 2, a heat treatment also serving as a water repellent treatment was performed. Specifically, a water repellent solution of the following formulation 5 was applied to the surface of the fabric by a gravure coating method using a high mesh gravure roll. Thereafter, heat treatment including drying was performed at 165 ° C. for 1 minute using a tenter to obtain a polyamide-based moisture-permeable and waterproof fabric of Example 5.

<Prescription 5>
Unidyne TG-5521 50 parts by mass (Daikin Kogyo Co., Ltd., fluorine-based water repellent emulsion, solid content 30% by mass)
Isopropyl alcohol 30 parts by weight Water 920 parts by weight

(Example 6)
For both warp and weft, nylon 11 multifilament 78dtex / 34f is used to weave a plain fabric (weighing 63.8 g / m ² ) with a warp density of 110 / 2.54 cm and a weft density of 90 / 2.54 cm. Then, under the conditions of the following prescription 6, scouring and dyeing were performed by a conventional method to obtain a base fabric.

<Prescription 6>
・ Scouring: 80 ° C. × 20 minutes {Scouring agent (“Sun Mall FL” 1 g / L, manufactured by Nikka Chemical Co., Ltd.)}
Dyeing: 130 ° C. × 30 minutes {Acid dye (Sumitomo Chemical “Suminol Milling Red RS (125%)” 1% omf, leveling agent (Marebishi Oil Chemical Co., Ltd. “Leberan NKD”) 2% omf, acetic acid (48%): 0.2 ml / L}
Fix: 80 ° C. × 20 minutes {fix agent (“Sun Life E-37” manufactured by Nikka Chemical Co., Ltd.) 1% omf}
Final set: 160 ° C. × 1 minute Subsequently, a polyamide-based moisture-permeable waterproof fabric was obtained in the same manner as in Example 1 except that the above-described base fabric was used.

(Comparative Example 1)
The treatment of the polyisocyanate compound on the base fabric of Formulation 2 in Example 1 was omitted. Other than that, an attempt was made to produce a polyamide-based moisture-permeable and waterproof fabric by the same method as in Example 1. However, the adhesiveness at the time of lamination was insufficient, and for this reason, wrinkles entered during thermocompression bonding, and a good product could not be manufactured.

(Comparative Example 2)
Formulation 3 in Example 2 was changed to a padding method of an aqueous dispersion of 6% by mass of a polyisocyanate compound shown in the following formulation 7 (pickup rate 40%, containing polyisocyanate compound 2.4% by mass).

<Prescription 7>
Aquanate 200 60 parts by mass (manufactured by Nippon Polyurethane Industry Co., Ltd., polyisocyanate compound, solid content 100% by mass)
Acetone 60 parts by mass Water 880 parts by mass Further, compared to Example 2, the thickness of the thermoplastic polyamide-based elastomer film was changed to 12 μm.

  Other than that, a polyamide-based moisture-permeable and waterproof fabric was obtained in exactly the same manner as in Example 2.

(Comparative Example 3)
The nylon 6 high multifilament 78 dtex / 68f used for both the warp and weft of Example 1 was changed to polyethylene terephthalate high multifilament 83 dtex / 72f. Furthermore, the formulation 1 of Example 1 was changed to the following formulation 8. Other than that, a moisture-permeable and waterproof fabric was obtained in the same manner as in Example 1.

<Prescription 8>
・ Scouring: 80 ° C. × 20 minutes {Scouring agent (“Sun Mall FL” 1 g / L, manufactured by Nikka Chemical Co., Ltd.)}
Dyeing: 130 ° C. × 30 minutes {Disperse dye (“Kayalon Microester Blue AQ-LE” manufactured by Nippon Kayaku Co., Ltd.) 1% omf, Dispersant (“Nikka Sun Salt SN130” manufactured by Nikka Chemical Co., Ltd.) 2% omf, Acetic acid (48%): 0.2 ml / L}
・ Reduction cleaning: 80 ° C. × 20 minutes (“Bisnol P-55” manufactured by one company) 5 g / L
・ Final set: 170 ℃ × 1min

(Comparative Example 4)
In order to prevent resin leakage to the surface using the dyed base fabric of Example 1, water repellent treatment was performed in the same manner as Formulation 3 of Example 1, and then the temperature was set at 170 ° C. with a calendar machine. The crushing process was performed under the conditions of a gauge pressure of 0.5 Mpa and a speed of 20 m / min. Subsequently, a polyurethane microporous film-forming resin solution having the following formulation 9 (solid content: 21%, viscosity: 15000 mPa · s / 25 ° C.) is an application amount of 100 g / m ² (a general application amount that develops water pressure resistance). The film thickness at this time was about 50 μm). Thereafter, it is solidified with water at 20 ° C. for 1 minute, followed by washing with hot water at 40 ° C. for 5 minutes, drying at 120 ° C. for 2 minutes, and then curing at 170 ° C. for 1 minute to provide a moisture-permeable waterproof fabric. Got.

<Prescription 9>
100 parts by mass of rack skin UJ8517 (manufactured by Seiko Kasei Co., Ltd., polyurethane resin for wet film formation, solid content 27%)
30 parts by mass of rack skin UJ8518M (manufactured by Seiko Kasei Co., Ltd., silica-containing polyurethane resin for improving moisture permeability, solid content 21%)
Rezamin X 1 part by mass (Daiichi Seika Kogyo Co., Ltd., isocyanate compound)
N, N-dimethylformamide 25 parts by mass

(Reference Example 1)
Compared to Example 3, the drying conditions after adding the polyisocyanate compound were changed to 190 ° C. × 20 seconds. Other than that, a polyamide-based moisture-permeable and waterproof fabric was obtained in exactly the same manner as in Example 3.

  Table 1 shows the performance of the moisture-permeable and waterproof fabrics obtained by the production methods of Examples 1 to 6, Comparative Examples 2 to 4, and Reference Example 1. For reference, the thickness of each moisture permeable waterproof fabric was measured with a thickness gauge.

  As is apparent from the results in Table 1, the moisture-permeable and waterproof fabrics obtained by the production methods of Examples 1 to 6 are excellent in moisture-permeable and waterproof performance, and the resin adheres in the dyeing process and incidental processing. Except for the part, since most of it was occupied by polyamide-based resin, it was excellent in recyclability. The moisture-permeable and waterproof fabric obtained by the production method of Example 6 was advantageous from the viewpoint of biomass because nylon 11 was used for the base fabric.

  On the other hand, in Comparative Example 1, since the base fabric was not subjected to an auxiliary processing of the polyisocyanate compound, the peel strength was extremely low, and thus the intended fabric could not be obtained. In Comparative Example 2, since the content of the polyisocyanate exceeded 2% by mass, the texture of the fabric was hard, and it was assumed that this fabric was disadvantageous in terms of wear when used as a garment. In Comparative Example 3, since a fabric composed of polyethylene terephthalate fiber not containing polyamide fiber was used as the base fabric, the obtained fabric was severely contaminated, and there was a possibility of hindering export or use by sea. It had the problem of being large. In Comparative Example 4, a polyurethane microporous membrane was used instead of the thermoplastic polyamide-based elastomer film containing a polyether block amide copolymer having a hard segment composition of polyamide and a soft segment composition of polyalkylene glycol. The manufactured fabric was supposed to be disadvantageous in terms of wear when used as clothing.

  The fabric of Reference Example 1 exhibited a slightly dull blue color compared to the fabric of Example 3 because the drying temperature after applying the polyisocyanate compound was too high, which was not preferable in terms of quality.

Claims (4)

  A polyisocyanate compound is applied to a base fabric containing polyamide fibers so that the content thereof is 0.03 to 2% by mass, and then a hard segment composition is applied to the base fabric provided with the polyisocyanate compound. A thermoplastic polyamide-based elastomer film containing a polyether block amide copolymer which is a polyamide such as nylon 6, nylon 11 or nylon 12 and whose soft segment composition is a polyalkylene glycol such as ethylene glycol or propylene glycol is directly extruded. A method for producing a polyamide-based moisture-permeable and waterproof fabric, characterized in that the laminated film and the base fabric are integrated by thermocompression bonding.   2. The method for producing a polyamide-based moisture-permeable and waterproof fabric according to claim 1, wherein when the polyisocyanate-based compound is applied to the base fabric containing the polyamide fiber, the polyamide-based moisture-permeable waterproof fabric is dried at less than 150 ° C.   The method for producing a polyamide-based moisture-permeable and waterproof fabric according to claim 1 or 2, wherein the laminated film and base fabric integrated by thermocompression are heat-treated at 130 to 180 ° C.   The method for producing a polyamide-based moisture-permeable and waterproof fabric according to any one of claims 1 to 3, wherein a water repellent treatment is applied to the laminated film and the base fabric integrated by thermocompression bonding.