JP5523039B2 - Polyamide-based moisture-permeable and waterproof fabric and method for producing the same - Google Patents

Description

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

  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 obtaining a moisture-permeable waterproof fabric.

The present invention solves the above-described problems and has the following configuration.
(1) on the surface of the base fabric containing 0.03 to 2 wt% of the polyisocyanate compound with containing polyamide fibers, a hard Sen segment composition Gapo polyamide, polyether is a soft segment composition Gapo real sharp glycol A polyamide-based moisture-permeable and waterproof fabric, wherein a thermoplastic polyamide-based elastomer film containing a block amide copolymer is laminated by thermocompression bonding at 120 to 200 ° C.

(2) a base fabric containing polyamide fibers polyisocyanate compound content thereof was dried after having granted such that 0.03 to 2 wt%, a hard Sen segment composition Gapo polyamide, soft segment composition Gapo real sharp glycol is a polyether block amide copolymer containing polymeric thermoplastic polyamide elastomer film form extrusion, followed by thermocompression bonding and the base fabric and the extruded film at 120 to 200 [° C. A method for producing a polyamide-based moisture-permeable and waterproof fabric characterized by:

  The polyamide-based moisture-permeable and waterproof fabric of the present invention is simple in structure because the polyamide-based fiber base fabric and the thermoplastic polyamide-based elastomer film are laminated by thermocompression bonding without an adhesive layer. There is no feeling of thickness, and it is excellent in the feeling of wearing when it is used as clothing. Moreover, since it is not necessary to form an adhesive layer, it is advantageous in terms of cost and moisture permeability. Furthermore, it is recyclable because it is mainly composed of polyamide. 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 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 solution. On the other hand, when emphasizing the stability and pot life of the resin solution, use a block 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. After application by these methods, it is preferably 50 to 150 ° C., more preferably less than 130 ° C., and more preferably 100 ° C. or more and less than 130 ° C. in consideration of drying efficiency and isocyanate group reactivity. Dry under conditions of 3 minutes. 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 or resin used in combination is preferably smaller than the amount of the polyisocyanate compound used from the viewpoint of not increasing the thickness of the finally obtained fabric and making the texture hard.

  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.

  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.

  A thermoplastic polyamide-type elastomer film can be manufactured by a well-known manufacturing 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 produced by stretching both vertically and horizontally so as to have a predetermined film thickness.

  The thickness of the thermoplastic polyamide-based elastomer film 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 polyamide-based moisture-permeable and waterproof fabric is obtained by laminating the base fabric and the thermoplastic polyamide-based elastomer film of the composition by thermocompression bonding. The thermocompression bonding may be appropriately performed using a known laminating machine, a hot press machine, or the like at a pressure that allows the two to be in close contact with each other. The thermocompression bonding temperature needs to be 120 to 200 ° C, and preferably 130 to 190 ° C. If it is less than 120 ° C., it is difficult to obtain a good adhesive force.

  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 softening of the elastomer film is taken into account by selecting the heat treatment conditions that ensure that the block part of the polyisocyanate compound is thermally dissociated below the melting point of the elastomer film itself. As a result, the adhesive force can be improved.

  In the polyamide-based moisture-permeable waterproof fabric of the present invention, a water-repellent treatment may be performed after the base fabric and the elastomer film are laminated for the purpose of improving the water-repellent performance and the waterproof performance. 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. Among these, from the environmental viewpoint, it is more preferable to use one in which perfluorooctanoic acid does not easily remain in the fluorine-based water repellent or is difficult to generate with 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, “Unidyne” manufactured by Daikin Industries, Ltd. 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 fabric is immersed in a water repellent emulsion, the fabric is squeezed with a mangle, adjusted to a predetermined application amount, dried and cured to obtain a fabric with a water repellent finish throughout. It is done. In the gravure coating method, a water repellent finish is applied only to the surface by applying a water repellent emulsion only on the surface using a high mesh gravure roll, and drying and curing.

  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 moisture permeable waterproof performance after lamination, 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 waterproof fabric of the present invention has excellent moisture permeable performance and waterproof performance, and as well as materials for various clothing such as sports clothing and cold clothing that are environmentally friendly, mountaineering equipment such as tents, etc. It can also be used as a material. 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%). Then, a base fabric containing 0.05% by mass of a polyisocyanate compound was obtained by drying at 100 ° C. for 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, “Pebax MV3000”, melting point 158 ° C.) whose hard segment is nylon 12, nylon 11, etc. and whose soft segment is polyethylene glycol, etc. Was melt-extruded from a T-die at 190 ° C., and was stretched in the machine direction while cooling to obtain a thermoplastic polyamide elastomer film having a thickness of about 12 μm.

  Then, using a hot roll press machine, the base fabric and the elastomer film are bonded under the conditions of a temperature of 150 ° C., a gauge pressure of 0.5 MPa, and a speed of 3 m / min, and further subjected to aging at 40 ° C. for 3 days. Thus, a polyamide-based moisture-permeable waterproof fabric of Example 1 was obtained.

(Example 2)
Formulation 2 of Example 1 was changed to the following formulation 3. That is, the 1.25 mass% aqueous dispersion of the formulation 3 (the base fabric contains 0.5 mass% of a polyisocyanate compound) was used. The drying conditions were 100 ° C. × 2 minutes as in Example 1.

<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 weight Water 960 parts by weight Furthermore, the thickness of the thermoplastic polyamide-based elastomer film was changed to 15 μm as compared with Example 1, and the bonding conditions between the base fabric and the elastomer film were set at a temperature of 130 ° C., press The time was changed to 2 minutes. Then, a polyamide-based moisture-permeable and waterproof fabric of Example 2 was obtained in the same manner as in Example 1 except that.

(Example 3)
To the same base fabric used in Example 1, a 2.5% by mass aqueous dispersion of the following formulation 4 was applied by a padding method (pickup rate 40%). And the base fabric which contains 0.3 mass% of polyisocyanate type compounds by drying at 120 degreeC x 2 minutes was obtained.

<Prescription 4>
25 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 mass Water 965 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 MV1041”, melting point 170 ° C.) was melt-extruded from a T-die at 200 ° C., and was stretched in the machine direction while cooling to obtain a thermoplastic polyamide elastomer film having a thickness of about 15 μm.

  And the polyamide type moisture-permeable waterproof fabric of Example 3 was obtained by bonding a base fabric and an elastomer film on the same conditions as Example 1. FIG.

Example 4
The formulation 4 of Example 3 was changed to the following formulation 5. And the 8 mass% aqueous dispersion (The base fabric contains a polyisocyanate compound 0.96 mass%) of the prescription 5 was used. Furthermore, the drying conditions after padding the aqueous dispersion were set to 125 ° C. × 2 minutes, and the temperature during film bonding was set to 190 ° C. Otherwise, the polyamide-based moisture-permeable and waterproof fabric of Example 4 was obtained in the same manner as in Example 3.

<Prescription 5>
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

(Example 5)
The peel strength of the polyamide-based moisture permeable waterproof fabric of Example 3 was not necessarily excellent enough. Therefore, the reason is that the dissociation of the blocked isocyanate compound is insufficient, and the water repellent solution of the following prescription 6 is used as a high mesh in combination with the water repellent treatment and the dissociation treatment of the blocked isocyanate compound. This was applied to the surface of the fabric by a gravure coating method using a gravure roll. Thereafter, a heat treatment including drying at 150 ° C. for 2 minutes was performed with a tenter to obtain a polyamide-based moisture-permeable waterproof fabric of Example 5.

<Prescription 6>
Unidyne TG-5521 50 parts by mass (Daikin Kogyo Co., Ltd., fluorine-based water repellent emulsion, solid content 30% by mass)
Isopropyl alcohol 50 parts by weight Water 900 parts by weight

(Example 6)
For both warp and weft, weaving a plain fabric (weighing 63.8 g / m ² ) with a warp density of 110 yarns / 2.54 cm and a weft density of 90 yarns / 2.54 cm using nylon 11 multifilament 78 dtex / 34f. did. And under the conditions of the following prescription 7, scouring and dyeing were performed by a conventional method to obtain a base fabric.

<Prescription 7>
・ 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 degreeC x 1 minute Then, the 0.6 mass% aqueous dispersion of the following prescription 8 was provided to the base fabric by the padding method (pickup rate 40%). Then, a base fabric containing 0.24% by mass of a polyisocyanate compound was obtained by drying at 100 ° C. for 2 minutes.

<Prescription 8>
Aquanate 200 6 parts by mass (manufactured by Nippon Polyurethane Industry Co., Ltd., polyisocyanate compound, solid content 100% by mass)
Acetone 24 parts by mass Water 970 parts by mass Next, a polyamide-based moisture-permeable waterproof fabric of Example 6 was obtained by the same method as Example 1 except that the thickness of the thermoplastic polyamide-based elastomer film was about 10 μm. .

(Comparative Example 1)
The treatment of the polyisocyanate compound on the base fabric of Formulation 2 in Example 1 was omitted. Other than that, a polyamide-based moisture-permeable waterproof fabric of Comparative Example 1 was obtained in the same manner as in Example 1.

(Comparative Example 2)
The formulation 5 of Example 4 was replaced with the following formulation 9. And the 20 mass% aqueous dispersion of the polyisocyanate compound shown in Formula 9 was applied by the padding method (pickup rate 40%, polyisocyanate compound contained 2.4 mass%). Moreover, the temperature at the time of bonding was 150 degreeC. Other than that, a polyamide-based moisture-permeable waterproof fabric of Comparative Example 2 was obtained in exactly the same manner as in Example 4.

<Prescription 9>
200 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 790 parts by weight

(Comparative Example 3)
Compared with Example 2, the temperature at the time of film lamination was set to 100 ° C. Other than that, a polyamide-based moisture-permeable waterproof fabric of Comparative Example 3 was obtained in exactly the same manner as in Example 2.

(Comparative Example 4)
Compared with Example 3, the temperature at the time of film lamination was 210 ° C. Other than that, a polyamide-based moisture-permeable waterproof fabric of Comparative Example 4 was obtained in exactly the same manner as in Example 3.

(Comparative Example 5)
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 prescription 1 of Example 1 was replaced with the following prescription 10. And the moisture-permeable waterproof fabric of the comparative example 5 was obtained by the same method as Example 1 except it.

<Prescription 10>
・ 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 6)
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 Formula 6 of Example 5, 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 11 (solid content: 21%, viscosity: 15000 mPa · s / 25 ° C.) was applied in an amount of 100 g / m ² (a general application amount that expresses 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. A wet waterproof fabric was obtained.

<Prescription 11>
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 The performance of each moisture-permeable and waterproof fabric of Examples 1 to 6 and Comparative Examples 1 to 6 is shown in Table 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 of Examples 1 to 6 are excellent in moisture-permeable and waterproof performance, and, except for the dye adhesion in the dyeing process and the resin adhering component in the incidental processing, Since most of them are occupied by polyamide-based resins, the recyclability was also excellent. 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, the peel strength was extremely low because the polyisocyanate compound was not attached. In Comparative Example 2, since the content of polyisocyanate exceeded 2% by mass, the texture was hard, and therefore, it was assumed that it was disadvantageous in terms of wear when used as a garment. In Comparative Example 3, since the thermocompression bonding temperature at the time of film lamination was too low at 100 ° C., satisfactory thermocompression bonding could not be performed, and therefore sufficient peel strength could not be obtained. Since the thermocompression bonding temperature at the time of film bonding was as high as 210 degreeC, the comparative example 4 was inferior in texture compared with Examples 1-6. Comparative Example 5 has a problem that the base fabric is made of polyethylene terephthalate fiber without containing polyamide fiber, so that the contamination is severe and there is a high possibility of causing trouble in export or use by sea. Was. In Comparative Example 6, instead of a thermoplastic polyamide elastomer film containing a polyether block amide copolymer having a hard segment composition of polyamide and a soft segment composition of polyalkylene glycol, a polyurethane microporous membrane is used as the base fabric. Since it was laminated, it was assumed that it would be disadvantageous in terms of wearing when it was used as clothing.

Claims (2)

On the surface of the base fabric a polyisocyanate compound containing 0.03 to 2 wt% with containing polyamide fibers, a hard Sen segment composition Gapo polyamide, polyether block amide copolymer is a soft segment composition Gapo real sharp glycol A polyamide-based moisture-permeable and waterproof fabric, wherein a thermoplastic polyamide-based elastomer film containing a polymer is laminated by thermocompression bonding at 120 to 200 ° C. A base fabric containing polyamide fibers polyisocyanate compound content thereof was dried after having granted such that 0.03 to 2 wt%, a hard Sen segment composition Gapo polyamide, soft segment composition Gapo A thermoplastic polyamide-based elastomer containing a polyether block amide copolymer which is a realkylene glycol is extruded into a film shape, and then the extruded film and the base fabric are thermocompression bonded at 120 to 200 ° C. A method for producing a polyamide-based moisture-permeable and waterproof fabric.