JP5147252B2 - Moisture permeable waterproof fabric - Google Patents

Description

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

Moisture permeable waterproof fabrics that prevent moisture from entering, such as rain, are used for various things, including moisture, such as wings, ski wear, windbreakers, tents, shoe materials, and gloves.
Such a moisture-permeable waterproof fabric is coated with a urethane resin solution on a fiber fabric and then dried, or coated with a urethane resin solution on a release paper and then dried, and the resulting urethane resin film is passed through an adhesive. One having a nonporous urethane resin film produced by bonding to a fiber fabric is known.

As another example, a moisture-permeable waterproof fabric having a porous urethane resin film manufactured by applying a urethane resin solution to a fiber fabric and then immersing it in water is known.
The solvent of the urethane resin solution used in these is an organic solvent such as dimethylformamide, toluene, and methyl ethyl ketone, which are good solvents for the urethane resin. As a result of the release of this solvent, there are concerns about problems in work environment sanitation during production and air pollution.
Therefore, a moisture-permeable waterproof fabric obtained by using a polyurethane emulsion and water-soluble polyurethane (Patent Document 1) is known as a moisture-permeable waterproof fabric without using the organic solvent as described above.

JP-A-2005-220460

However, in the case of using a water-based polyurethane resin such as a polyurethane emulsion or a water-soluble polyurethane resin, both A-1 method (calcium chloride method) and B-1 method (potassium acetate method) described in JIS L1099-1993 are used. None of them had excellent performance. Moreover, the texture of the moisture-permeable waterproof fabric obtained is hard and improvement is desired.
The object of the present invention is that the load on the working environment sanitary surface and the exhaust treatment surface is small, and the obtained moisture-permeable waterproof fabric has excellent moisture permeability in both the calcium chloride method and the potassium acetate method, An object of the present invention is to provide a moisture-permeable waterproof fabric having a soft texture.

(1) It has a urethane resin film containing a water-based urethane resin on at least one surface of the fiber fabric, the urethane resin film is porous, and the thickness of the urethane resin film is 0.5 μm to 10 μm. A moisture-permeable waterproof fabric characterized by
(2) Moisture permeability measured according to JIS L1099-1993 A-1 method is 5,000 to 13000 g / m ² · 24 hours, moisture permeability measured according to JIS L1099-1993 B-1 method is 10,000 to 50,000 g / m ^{2. The} moisture-permeable waterproof fabric according to (1) above, wherein the water pressure resistance is 700 to 6000 mm or more for ² · 24 hours.
(3) The moisture-permeable waterproof fabric according to any one of (1) and (2), wherein an average pore diameter of the porous urethane resin membrane is 0.1 to 5.0 μm.

The moisture-permeable waterproof fabric of the present invention has waterproofness and excellent moisture permeability in the calcium chloride method and the potassium acetate method, while using a water-based urethane resin with a small load on the work environment hygiene and exhaust treatment. A moisture-permeable waterproof fabric with a soft texture can be provided.
When the moisture-permeable waterproof fabric of the present invention is used for a windbreaker, a feather, a coat, a jacket, ski wear, snowboard wear, a jacket, a tent, gloves, shoes, a sleeping bag, etc. While suppressing the stickiness of the stuffiness and urethane resin film, it can provide a comfortable in-garment environment. In addition, since clothes such as windbreakers obtained using the moisture-permeable waterproof fabric of the present invention have a soft texture, it is possible to provide an excellent fiber product from the viewpoint of texture and appearance design. it can.

Preferred embodiments of the present invention will be described below, but it should be understood that the present invention is not limited only to these embodiments, and that many modifications can be made within the spirit and scope of the present invention. .

[Breathable waterproof fabric]
The moisture-permeable waterproof fabric of the present invention has a urethane resin film containing a water-based urethane resin on at least one surface of a fiber fabric, the urethane resin film is porous, and the thickness of the urethane resin film is 0.00. 5 μm to 10 μm.
The fiber fabric and the urethane resin film may be directly laminated or may be laminated via an adhesive.

The fiber fabric of the present invention may be any material such as polyester, nylon, polyurethane, acrylic, rayon, acetate, polylactic acid, soy protein, silk, wool, cotton, hemp and other chemical fibers, natural fibers, and the like. Of course, these fibers may be mixed, mixed, woven, knitted, or the like.
The form of the fiber fabric may be any form such as a woven fabric, a knitted fabric, or a non-woven fabric.
Also, textile fabrics can be dyed, printed, water-repellent, antistatic, water-absorbing, SR processed, antibacterial and deodorant, antibacterial, deodorant, ultraviolet shielding, flameproof, and calendered You may give it.

  Examples of the water-based urethane resin of the present invention include water-soluble urethane resins and self-emulsifying urethane resins. As a method for producing these resins, a method using a water-soluble raw material, a self-emulsification method, a method of chain extension in an emulsified state, a method of using a blocked isocyanate, a method of forcibly emulsifying a urethane resin in an aqueous emulsifier solution Etc.

  More specifically, those described in JP-A-2005-220460 and trade names such as resamine D-1000 (ether type), resamine D-2000 (ether type), resamine D-2060 (ether type), resamine D- 4000 (ether / carbonate), resamine D-6000 (polycarbonate), resamine D-9000 (X) (modified type), resamine W-100 (ether), resamine W-600 (carbonate), resamine W- 200 (above, manufactured by Dainichi Seika Kogyo Co., Ltd.), Parazole PNA-120 (carbonate), Parasol PNA-184 (carbonate), Paramillion AF-36 (above, Ohara Paradium Chemical Co., Ltd.), Permarin UA- 50 (ether type), Permarin UA-150 (ether type), Marine UA-300 (carbonate-based), PERMARIN UA310 (carbonate-based), PERMARIN UC-20 (ether) (all, manufactured by Sanyo Chemical Industries, Ltd.) and the like.

Moreover, what contains alkylene oxides, such as ethylene oxide and a propylene oxide, is preferably used for a water-based urethane resin from a moisture-permeable viewpoint.
In particular, it is preferable from the viewpoint of moisture permeability to mix and use a water-absorbing resin and a highly hydrophobic resin.

The urethane resin film containing the water-based urethane resin of the present invention has a water-based urethane resin as a main component. In addition to the water-based urethane resin, the urethane resin film has organic particles such as pigments for coloring, silk powder for imparting moisture absorption, gelatin powder, eggshell membrane powder, moisture permeability and waterproofness. Inorganic particles such as silicon oxide, aluminum oxide and calcium carbonate for improvement, porous particles such as porous silica for countermeasures against contamination of the resin film with disperse dyes, silver zeolite and pyridine for imparting antibacterial properties In addition, antibacterial agents such as deodorants, antistatic agents, ultraviolet absorbers, antioxidants, flame retardants, and the like may be added.
It is also preferable that a water repellent is included from the viewpoint of water repellency and waterproofness.

Moreover, that the said urethane resin film is porous has a hole on the surface of at least one surface of the said urethane resin film, and what has an average hole diameter of 0.1-5 micrometers is preferable. More preferably, at least a surface of the urethane resin film has no holes in contact with the fiber fabric.

In the moisture-permeable waterproof fabric, the urethane resin film surface that is not in contact with the fiber fabric may directly come into contact with moisture, water droplets, or skin, but the surface of the urethane resin film on this surface becomes porous. If it is porous, the water-soluble compound present in the vicinity of the urethane resin film surface is removed in the subsequent water washing step, and the urethane resin film surface (surface not in contact with the fiber fabric) is almost Since these substances do not exist, even when the urethane resin film absorbs water or absorbs moisture, it is possible to suppress stickiness of the urethane resin film surface.

The term “having a hole on at least one surface of the urethane resin film” in the present invention does not mean that a plurality of resin films are laminated, but a hole in at least one surface of one urethane resin film.

If the pore diameter is less than 0.1 μm, moisture permeability (particularly moisture permeability by the calcium chloride method) may be insufficient, and if it exceeds 5 μm, the waterproof property may be lowered. The hole diameter is the diameter of the hole. When the hole has an ellipse or an irregular shape, the longest diameter among the holes is defined as the hole diameter.
In addition, the shape of the hole is preferably a shape having a smooth hole corner from the viewpoint of texture and touch. Confirmation of the size and shape of the holes is performed by magnifying the magnification to 5000 times using an electron microscope and observing the surface and cross section of the urethane resin film.

The holes do not necessarily need to communicate from the front surface to the back surface in the thickness direction of the urethane resin film. From the viewpoint of moisture permeability, it is preferable to communicate from the front surface to the back surface of the urethane resin film.
Moreover, it is preferable that it is not connected from the surface of a urethane resin film to the back surface from a viewpoint of water pressure resistance. In this case, since the urethane resin film has holes on the surface of the urethane resin film, the urethane resin film in the part having the holes becomes thin, the resistance to moisture transmission is reduced, and while maintaining excellent moisture permeability, Since it does not communicate from the front surface to the back surface, it has excellent waterproof properties.

Moreover, the thickness of the urethane resin film of the present invention is 0.5 μm to 10 μm. More preferably, 0.5-5 micrometers is preferable. More preferably, the thickness is 1 to 3 μm.
If the thickness is less than 0.5 μm, the waterproof property may be lowered, and if it is 10 μm or more, the texture may become hard.

  The thickness of the urethane resin film is observed by enlarging the cross section of the urethane resin film to a magnification of about 3000 to 5000 times using an electron microscope, and the urethane resin film and the fiber constituting the fiber fabric are in contact with the urethane. The thickness up to the opposite surface of the resin film. In addition, the thickness is partially reduced by the holes (including through holes and communication holes), the thickness of the entangled portion of the warp and weft constituting the fabric, etc., and the urethane resin is added to the fiber fabric. The impregnated portion is not the thickness of the urethane resin film. Therefore, the thickness of the urethane resin film at the entanglement point between the warp and the weft constituting the woven fabric or the like may be 10 μm or more. Moreover, the thickness of the location which has a hole and the location which has the through-hole penetrated from the surface to the back surface of a urethane resin film may be 0.5 micrometer or less.

The moisture-permeable waterproof fabric of the present invention preferably has a moisture permeability (calcium chloride method) measured according to JIS L1099-1993 A-1 method of 5000 to 13000 g / m ² · 24 hours. If it is less than 5000 g / m ² · 24 hours, it may be stuffy when clothes or the like obtained from a moisture-permeable waterproof fabric are worn. Further, if it exceeds 13000 g / m ² · 24 hours or more, sufficient waterproofness may not be obtained.

The moisture-permeable waterproof fabric of the present invention preferably has a moisture permeability measured according to JIS L1099-1993 B-1 method (potassium acetate method) of 10,000 to 50,000 g / m ² · 24 hours. If it is less than 10000 g / m ² · 24 hours, it may be stuffy when clothes or the like obtained from a moisture-permeable waterproof fabric are worn. Further, if it exceeds 50000 g / m ² · 24 hours or more, sufficient waterproofness may not be obtained.

The moisture-permeable waterproof fabric of the present invention has a water pressure measured in accordance with JIS L1092-1998 water resistance test (hydrostatic pressure) A method (low water pressure method) or B method (high water pressure method) of 700 to 6000 mm or more. Preferably there is.
If the water pressure is less than 700 mm, clothes or the like obtained from a moisture-permeable waterproof fabric are worn, and when wet with rain or the like, the water may enter, and if it is 6000 mm or more, the moisture permeability is insufficient. there is a possibility.
The water pressure measured by the high water pressure method was converted to the same unit as the low water pressure method so that it could be easily compared with the low water pressure method.

  In addition, for the purpose of improving water pressure resistance, touch improvement, design to improve design, and functionality, the entire surface of one side of the urethane resin film, or partially pigmented or organic, such as dotted or linear Other urethane resin films or acrylic resin films containing particles, inorganic particles, antibacterial agents, heat storage agents, flame retardants, and the like may be attached without departing from the scope of the present invention.

〔Production method〕
Hereinafter, the present invention will be described in more detail with one preferable manufacturing method, but the present invention is not limited to these manufacturing methods.

<First manufacturing method>
The moisture-permeable waterproof fabric of the present invention can be produced by applying a urethane resin solution containing a water-based urethane resin to a fiber fabric, drying, washing with water, and drying.

  As the fiber fabric, the above-described fiber fabric described for the moisture-permeable waterproof fabric can be used. When textile fabrics are dyed, printed, water-repellent, antistatic, water-absorbing, SR processed, antibacterial and deodorant, antibacterial, deodorant, UV shielding, flameproof, and calendered Processing may be performed by a known method.

As a method for applying the urethane resin solution to the fiber fabric, a knife coater, a knife over roll coater, a pipe coater, a comma coater, a reverse coater, a gravure coater or the like can be used.
In particular, when a urethane resin film having a thickness of 5 μm or less is manufactured, a floating method using a knife coater is preferably used.

  As the urethane resin solution used at this time, the urethane resin described above for the moisture-permeable waterproof fabric can be used. Further, it is preferable to add a water-soluble compound to the urethane resin solution from the viewpoint of moisture permeability (calcium chloride method, potassium acetate method). By adding a water-soluble compound, the water-soluble compound can be eluted by washing with water after applying and drying the urethane resin solution to form a porous structure. In addition, the water-soluble compound can be formed in the urethane resin film. Even when some remains, moisture permeability can be prevented from lowering.

Specifically, examples of the water-soluble compound include organic compounds such as water-soluble urethane resins, water-soluble polyesters, gelatin, carboxymethyl cellulose, and polyacrylic acid, and inorganic compounds such as neutral anhydrous sodium sulfate and calcium carbonate.
The urethane resin solution is particularly preferably a water-insoluble self-emulsifying urethane resin as the urethane resin and a water-soluble urethane resin as the water-soluble compound. When a water-soluble urethane resin is used as the water-soluble compound, holes having a small pore diameter of 5 μm or less can be easily formed. Moreover, it is easy to adjust the removal ratio of the water-soluble urethane resin in the process of removing the water-soluble compound in the subsequent water washing step and manufacturing the pores, and to adjust the formation of the pores in the urethane resin, This is preferable from the viewpoint of adjustment of moisture permeability and waterproofness.

The compounding ratio of the urethane resin and the water-soluble compound is preferably 10 to 200 parts by mass of the water-soluble compound with respect to 100 parts by mass of the urethane resin.
If the blending amount of the water-soluble compound is less than 10 parts by mass, the moisture permeability may be insufficient, and if it exceeds 200 parts by mass, the waterproof property may be insufficient.

  A crosslinking agent may be added to the urethane resin solution. Examples of the crosslinking agent include an isocyanate crosslinking agent, a carbodiimide crosslinking agent, an epoxy crosslinking agent, an ethyleneimine crosslinking agent, and an oxazoline crosslinking agent.

The addition amount of the crosslinking agent added to the urethane resin solution is preferably 0.5 to 10 parts by mass with respect to 100 parts of the urethane resin.
If the amount is less than 0.5 parts by mass, the film strength and the peel strength between the fiber fabric and the urethane resin film may not be sufficient. If the amount exceeds 10 parts by mass, the texture may become hard.

  As a solvent used in the urethane resin solution of the present invention, water is used, but dimethylformamide (DMF), toluene (TOL), methyl ethyl ketone (MEK), dimethyl sulfoxide (DMSO), isopropyl alcohol (IPA), etc. An organic solvent may be included in the urethane resin solution. Preferably, 7% or less, more preferably those not containing these organic solvents.

In addition, pigments for coloring in urethane resin solutions, silk particles for imparting hygroscopicity, organic particles such as gelatin powder and egg shell membrane powder, silicon oxide for improving moisture permeability and waterproofing, oxidation Inorganic particles such as aluminum and calcium carbonate, porous particles such as porous silica to prevent contamination of resin films with disperse dyes, antibacterial agents such as silver zeolite and pyridine to impart antibacterial properties, An odorant, an antistatic agent, an ultraviolet absorber, an antioxidant and the like may be added. When adding a particulate material, since the thickness of the urethane resin film is as thin as 10 μm or less, use of particles of 1 μm or less, particularly preferably 0.5 μm or less is preferable from the viewpoint of suppressing the occurrence of coating stripes and the like. .
It is also preferable to add a water repellent from the viewpoint of water repellency.

After applying a urethane resin solution containing an aqueous urethane resin to the fiber fabric, drying is performed to form a urethane resin film. What is necessary is just to perform drying conditions for about 10 to 300 seconds at 60-130 degreeC.
After drying, heat treatment at 130 to 180 ° C. for 5 seconds to 180 seconds may be performed as necessary, such as one with a crosslinking agent added.

Dry and heat-treat as necessary, then rinse with water. By washing with water, the water-soluble compound is eluted from the urethane resin film to form a porous urethane resin film on at least one surface of the fiber fabric.
In addition, a cleaning agent such as caustic soda, soda ash, sodium tripolyphosphate or a surfactant may be added to the water at the time of washing with water.
Washing conditions are preferably performed at 20 to 120 ° C. for 1 to 30 minutes. For washing with water, a processing machine used in scouring such as a woven fabric or a knitted fabric, such as a liquid dyeing machine, wins, jet wins, or a continuous cloth-type washing machine can be used.
After washing with water and drying, if necessary, heat treatment such as finishing set is performed at 120 to 190 ° C. for about 10 to 60 seconds to obtain a moisture-permeable waterproof fabric.

  In addition, on the urethane resin film surface of the obtained moisture-permeable waterproof fabric, for the purpose of imparting water pressure, improving touch, providing a pattern for improving design, and imparting functionality, Other urethane resins or acrylic resin films containing pigments, organic particles, inorganic particles, antibacterial agents, heat storage agents, flame retardants, etc., partially or entirely, such as in the form of dots or lines, can be obtained using a gravure coater or screen printing machine. You may make it adhere in the range which does not deviate from the main point.

  In addition, after obtaining a moisture-permeable waterproof fabric, padding using a solution containing a water repellent, an antibacterial agent, a flame retardant, an SR agent, a deodorant, an antistatic agent, a water absorbing agent, an ultraviolet absorber, etc. as necessary You may give to a moisture-permeable waterproof fabric by a method, a spray method, a gravure method, etc.

<Second production method>
In the second production method for producing the moisture-permeable waterproof fabric of the present invention, a urethane resin solution containing a water-based urethane resin is applied to a releasable sheet, dried to form a urethane resin film, and then formed on the urethane resin film. An adhesive is applied, the fiber fabric and the urethane resin film are laminated via the adhesive, the release sheet is peeled off, washed with water and dried.

The release sheet of the present invention includes, for example, a release fiber fabric (woven fabric, knitted fabric, non-woven fabric, etc.) treated with a fluorine-based resin, a silicone-based resin, or the like, a release paper laminated with a silicone resin, a polypropylene resin, or the like. In addition, a resin film made of polyester or polypropylene having releasability may be used.
Since the thickness of the urethane resin film of the present invention is as very thin as 10 μm, the release paper used should be as flat as possible.

  The urethane resin solution used in the second production method can be the same as the urethane resin solution used in the first production method.

As a method for applying the urethane resin solution to the releasable sheet, a knife coater, a knife over roll coater, a pipe coater, a comma coater, a reverse coater, a gravure coater or the like can be used.
The drying conditions can be the same as in the first manufacturing method.

A urethane resin solution containing a water-based urethane resin is applied to the release sheet and dried to form a urethane resin film, and then an adhesive is applied on the urethane resin film.
As the adhesive, urethane, epoxy, melamine, nylon, and other adhesives can be used. The adhesive may be either a one-component type or a two-component type, or may be a hot-melt type urethane resin including a moisture curable type.

  Examples of these adhesives include a method in which a solution dissolved in a solvent or a solution heated and melted is applied using, for example, a gravure coater. In that case, it may be applied to the entire surface of one side of the urethane resin film without any gaps, or may be applied in the form of dots or lines. However, a dot shape is preferable from the viewpoint of moisture permeability.

After applying the adhesive on the urethane resin film, the fiber fabric is laminated on the surface of the urethane resin film to which the adhesive has been applied, after drying the urethane adhesive or before drying.
After laminating, it may be subjected to a pressure-bonding treatment as necessary. Examples of the pressure bonding method include a method using a nip roll. As pressure bonding conditions, pressure (linear pressure) of 1 to 250 kg / cm and temperature of about 80 to 130 ° C. are preferable.
After laminating the urethane resin film and the fiber fabric, aging may be performed at about 40 ° C. to 80 ° C. for about 2 to 100 hours.

  Next, after releasing the release sheet from the urethane resin film, it is washed with water and dried. Washing and drying conditions can be performed under the same conditions as in the first production method to obtain a moisture-permeable waterproof fabric.

In addition, as in the first manufacturing method, on the urethane resin film surface of the obtained moisture-permeable waterproof fabric, improvement of water pressure resistance, improvement of touch, addition of a pattern for improvement of design, addition of functionality. Gravure other urethane resins and acrylic resin films containing pigments, organic particles, inorganic particles, antibacterial agents, heat storage agents, flame retardants, etc. partially on the entire surface of one side of the urethane resin film or partially in the form of dots or lines. You may make it adhere in the range which does not deviate from the main point of this invention using a coater and a screen textile printing machine.

  In addition, after obtaining a moisture-permeable waterproof fabric, padding using a solution containing a water repellent, an antibacterial agent, a flame retardant, an SR agent, a deodorant, an antistatic agent, a water absorbing agent, an ultraviolet absorber, etc. as necessary You may give to a moisture-permeable waterproof fabric by a method, a spray method, a gravure method, etc.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited at all by these Examples. In the examples, “parts” means parts by mass.
Measurement and evaluation in the following examples were performed by the following methods.

A Thickness of urethane resin film and porous pore diameter Using a scanning electron microscope (SEMEDX Type H type: Hitachi Science Systems, Ltd.), observe and measure the cross section and surface of the moisture-permeable waterproof sheet at a magnification of 5000 times. It was.
B Measured by moisture permeability calcium chloride method JIS L1099-1993A-1.
Potassium acetate method Measured by JIS L1099-1993B-1 method.
The calcium chloride method and the calcium acetate method were both converted to moisture permeation per 24 hours.

C Water resistance Measured by a method according to JIS L1092-1998 water resistance test (hydrostatic pressure method) A method (low water pressure method) and B method (high water pressure method). The unit is described in terms of the unit of the low water pressure method so that it can be easily compared with the low water pressure method and the high water pressure method.
In addition, when the test piece is stretched by applying water pressure, a nylon taffeta (a total of about 210 warp and weft densities per 2.54 cm) is stacked on the test piece and attached to the testing machine. And measured.
D Judged by touching hands.

Example 1
Polyester taffeta (83 decitex / 72 filaments for both warp and weft yarns, density warp 180 / 2.54 cm, width 90 / 2.54 cm) is dyed red with a disperse dye, and the fluorine-based water repellent Asahi Guard AG710 ( Water repellent processing was performed using a 5% aqueous solution of Asahi Glass Co., Ltd. What was calendered at 170 ° C. after the water repellent finish was used as the fiber fabric.
Next, a urethane resin solution containing the following water-based urethane resin was applied to the fiber fabric by a floating method using a knife coater and subsequently dried at 120 ° C. for 2 minutes to obtain a urethane resin film.

Urethane resin solution Permarin UA-310 50 parts (Water-based urethane resin, carbonate-based, self-emulsifying type, solid content 39%, manufactured by Sanyo Chemical Industries, Ltd.)
60 parts of Parapylion AF-36 (aqueous urethane resin, water-soluble, solid content 34%, manufactured by Ohara Palladium Chemical Co., Ltd.)
Paracat PG-9 4 parts (Block isocyanate cross-linking agent, manufactured by Ohara Palladium Chemical Co., Ltd.)

Next, after heat-treating at 160 ° C. for 1 minute, it was washed with water at 60 ° C. for 15 minutes using a liquid dyeing machine to remove the water-soluble urethane resin from the urethane resin film.
After washing with water, drying was performed at 120 ° C. for 60 seconds, water-repellent treatment was again performed using a 5% aqueous solution of AG710, and finishing set was performed at 160 ° C. for 30 seconds to obtain a moisture-permeable waterproof fabric.
Various physical properties of the obtained moisture-permeable waterproof fabric were as follows.

Urethane resin film thickness: 1-2 μm
The state of the hole: The hole diameter is 0.1 to 2.0 μm, and the corner of the hole is smooth.
As for the distribution of the holes, the surface of the surface not in contact with the fiber fabric has a large number of holes in the vicinity of the surface, and the vicinity of the opposite surface (the surface side in contact with the fiber fabric) also has a slight number of holes. It was.
(Since the urethane resin film is thin, the center is included near both surfaces.)
Moisture permeability Calcium chloride method: 10000 g / m ² · 24 hours
Potassium acetate method: 30000g ^{/ m} 2 · 24 h Water pressure: 1500 mm
Kaze: Very soft.

Example 2
Nylon twill (warp yarn 77 decitex / 34 filament, both horizontal yarn 92 decitex / 74 filament, density warp 124 / 2.54cm, width 65 / 2.54cm) dyed red with acid dye, fluorine water repellent Water repellent processing was performed using a 5% aqueous solution of the agent Asahi Guard AG710 (Asahi Glass Co., Ltd.). What was calendered at 170 ° C. after the water repellent finish was used as the fiber fabric.
Next, a urethane resin solution containing the following water-based urethane resin was applied to a fiber fabric using a knife over roll coater and subsequently dried at 120 ° C. for 2 minutes to obtain a urethane resin film.

Urethane resin solution, 50 parts of PARAZOL PNA-120 (water-based urethane resin, carbonate-based, self-emulsifying type, solid content 30%, manufactured by Ohara Palladium Co., Ltd.)
60 parts of Parapylion AF-36 (aqueous urethane resin, water-soluble, solid content 34%, manufactured by Ohara Palladium Chemical Co., Ltd.)
Paracat PG-9 4 parts (Block isocyanate cross-linking agent, manufactured by Ohara Palladium Chemical Co., Ltd.)

Next, after heat-treating at 160 ° C. for 1 minute, it was washed with water at 60 ° C. for 15 minutes using a liquid dyeing machine to remove the water-soluble urethane resin from the urethane resin film.
After washing with water, drying was performed at 120 ° C. for 60 seconds, water-repellent treatment was again performed using a 5% aqueous solution of AG710, and finishing set was performed at 160 ° C. for 30 seconds to obtain a moisture-permeable waterproof fabric.
Various physical properties of the obtained moisture-permeable waterproof fabric were as follows.

Urethane resin film thickness: 8μm
The state of the hole: The hole diameter is 0.1 to 2.0 μm, and the corner of the hole is smooth. The surface of the urethane resin film not in contact with the fiber fabric and a large number of holes in the vicinity of the surface, and the vicinity of the opposite surface (the surface side in contact with the fiber fabric) and the central portion also had slight holes. .
Moisture permeability Calcium chloride method: 6000g ^{/ m} 2 · 24 hours
Potassium acetate method: 15000g ^{/ m} 2 · 24 h Water pressure: 2400 mm
Kaze: Soft.

(Comparative Example 1)
A moisture-permeable waterproof fabric was obtained in the same manner as in Example 2 except that the gap of the knife over roll coater was adjusted so that the thickness of the urethane resin film was 50 μm.
Various physical properties of the obtained moisture-permeable waterproof fabric were as follows.

Urethane resin film thickness: 50 μm
The state of the hole: The hole diameter is 0.1 to 2.0 μm, and the corner of the hole is smooth. However, the surface of the urethane resin film that is not in contact with the fiber fabric has a large number of holes and has holes from both surfaces to a thickness of several μm. Had no holes.
Moisture permeability Calcium chloride method: 800 g / m ² · 24 hours
Potassium acetate method: 7000g ^{/ m} 2 · 24 h Water pressure: 7500 mm
Feel: Hard.

(Example 3)
Except having changed the urethane resin solution into the following, it carried out similarly to Example 1, and obtained the moisture-permeable waterproof fabric.

Urethane resin solution Rezamin D-4000 50 parts (Aqueous urethane resin, ether / carbonate, self-emulsifying type, manufactured by Dainichi Seika Kogyo Co., Ltd.)
60 parts of Parapylion AF-36 (aqueous urethane resin, water-soluble, solid content 34%, manufactured by Ohara Palladium Chemical Co., Ltd.)
Cakenate WD725 4 parts (isocyanate-based crosslinking agent, manufactured by Mitsui Takeda Chemical Co., Ltd.)
10 parts of Paraguard EC400
(Fluorine-based water repellent, manufactured by Ohara Palladium Chemical Co., Ltd.)

  Various physical properties of the obtained moisture-permeable waterproof fabric were as follows.

Urethane resin film thickness: 1-2 μm
The state of the hole: The hole diameter is 0.1 to 2.0 μm, and the corner of the hole is smooth.
As for the distribution of the holes, there are a large number of holes on the surface of the surface not in contact with the fiber fabric and in the vicinity of the surface, and slightly on the opposite surface (the surface in contact with the fiber fabric). Was.
(Since the urethane resin film is thin, the center is included near both surfaces.)
Moisture permeability Calcium chloride method: 11000g ^{/ m} 2 · 24 hours
Potassium acetate method: 29000g ^{/ m} 2 · 24 h Water pressure: 1800 mm
Kaze: Soft.

Example 4
Nylon twill (warp yarn 77 dtex / 34 filament, horizontal yarn 92 dtex / 74 filament, density warp 124 / 2.54 cm, width 65 / 2.54 cm) dyed red with acid dye at 170 ° C What was calendered was used as a fiber fabric.
Next, on the release paper, a urethane resin solution containing the following water-based urethane resin was applied to a fiber fabric using a knife over roll coater and subsequently dried at 120 ° C. for 2 minutes to obtain a urethane resin film.

Urethane resin solution, 50 parts of PARAZOL PNA-120 (water-based urethane resin, carbonate-based, self-emulsifying type, solid content 30%, manufactured by Ohara Palladium Co., Ltd.)
60 parts of Parapylion AF-36 (aqueous urethane resin, water-soluble, solid content 34%, manufactured by Ohara Palladium Chemical Co., Ltd.)
Paracat PG-9 4 parts (Block isocyanate cross-linking agent, manufactured by Ohara Palladium Chemical Co., Ltd.)

  Next, a moisture-curing hot-melt urethane resin tie hose NH300 (manufactured by Dainippon Ink & Chemicals, Inc.) is heated to 100 ° C. and melted on the obtained urethane resin film, and is formed into dots using a gravure coater. Granted.

The urethane resin film coated with the adhesive solution and the fiber fabric were superposed and pressure-bonded at 100 ° C. A laminate of fiber fabric, adhesive, urethane resin film and release paper was aged at 70 ° C. for 100 hours, and then the release paper was peeled off.
Next, the fiber fabric having a urethane resin film was washed with water at 50 ° C. for 30 minutes with a spread water washer to remove the water-soluble urethane resin from the urethane resin film. After drying at 120 ° C., a water repellent treatment was performed using a 5% aqueous solution of a fluorine-based water repellent Asahi Guard AG710 (manufactured by Asahi Glass Co., Ltd.). After the water-repellent processing, finishing set was performed at 150 ° C. for 30 seconds.
Various physical properties of the obtained moisture-permeable waterproof fabric were as follows.

Urethane resin film thickness: 8μm
The state of the hole: The hole diameter is 0.1 to 2.0 μm, and the corner of the hole is smooth. The surface of the urethane resin film not in contact with the fiber fabric and the vicinity of the surface had a large number of holes, and the surface in contact with the adhesive had slight holes in the center.
Moisture permeability Calcium chloride method: 5200 g / m ² · 24 hours
Potassium acetate method: 11000g ^{/ m} 2 · 24 h Water pressure: 4200 mm
Kaze: Soft.

  The moisture-permeable waterproof fabrics of Examples 1, 2, 3, and 4 were moisture-permeable waterproof fabrics having waterproof properties and excellent moisture permeability in both calcium chloride and potassium acetate and having a soft texture. In contrast, the moisture-permeable waterproof fabric of Comparative Example 1 was a moisture-permeable waterproof fabric having poor moisture permeability, particularly poor moisture permeability due to calcium chloride, and having a hard texture.

Claims (3)

On at least one surface of the fiber fabric having a urethane resin film containing an aqueous urethane resin, said an urethane resin film is porous, and the thickness of the urethane resin film, Ri 0.5~10μm der, JIS L1099 -1993 The moisture permeability measured according to the A-1 method is 5000 to 13000 g / m ² · 24 hours, and the moisture permeability measured according to the JIS L1099-1993 B-1 method is 10,000 to 50000 g / m ² · 24. the time, moisture-permeable waterproof fabric water pressure resistance is characterized 700~6000mm der Rukoto. 2. The moisture-permeable waterproof fabric according to claim 1, wherein an average pore diameter of the porous pores of the urethane resin film is 0.1 to 5.0 μm. The hole of the urethane resin film is not only on the surface of the surface not in contact with the fiber cloth and the vicinity thereof, but also on the surface in contact with the fiber cloth on the opposite side and in the vicinity thereof and in the central portion in the thickness direction. The moisture-permeable waterproof fabric according to claim 1 or 2, wherein the moisture-permeable waterproof fabric is present.