JPH11227143A - Manufacture of soft and moisture-permeable waterproof cloth - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a moisture-permeable waterproof cloth which is highly waterproof and also moisture-permeable with soft feeling. SOLUTION: A porous resin layer containing 1 wt.% or more of fine powder of anhydrous silicon dioxide which is poreless and has an average particle dia. of 0.1 μm or less, is formed on a mesh cloth with mold parting properties using a wet-type process. Further, a polyurethane adhesive layer is uniformly applied on the non-entire surface of the resin layer, and a fiber cloth is laminated on the adhesive layer. After that, the mesh cloth is peeled. Thus it is possible to obtain he cloth with a water-pressure resistance of 1.0-3.0 kgf/cm<2> and a moisture permeability of 5000-11000 g/m<2> .24 hrs.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a moisture-permeable waterproof fabric used for various types of clothing such as raincoats, outer garments, mountain climbing garments, and the like.

[0002]

2. Description of the Related Art A moisture-permeable and waterproof fabric having both moisture permeability and waterproofness has a function of discharging water vapor caused by sweating from the body out of clothes and a function of preventing rain from entering into clothes. As a method for imparting these functions to a high degree, a method of coating a fiber cloth with a polyurethane resin, a polyamino acid resin, a polyester resin, a polyamide resin, a polytetrafluoroethylene resin, or the like, Methods of forming a film and laminating it with a fiber cloth are well known, and these are used for sports clothing and winter clothing, and are indispensable materials in the fields of skiing, athletic, and mountain climbing. The coating method is a method in which a resin layer is formed by directly applying a resin liquid onto a fiber cloth, and there are known resin layers having a hole and a hole having no holes. Perforated resin layers are generally easy to obtain excellent moisture permeability, but have a water resistance of only 0.2 to 0.3 kgf / cm ² water resistance, while those with non-porous resin layers Is easy to obtain excellent waterproofness, but has little or no permeability.
Only about 000 g / m ² · 24 hrs was obtained.

[0003] In order to compensate for such a drawback, a method of first forming a perforated highly moisture-permeable resin layer on a fiber fabric and then forming a thin non-porous resin layer thereon has been attempted. Although excellent waterproofness can be obtained, moisture permeability of at most 3000 to 5000 g / m ² · 24 hrs is obtained. Then, the present inventors disclosed in Japanese Patent Laid-Open No.
No. 8984 proposes a method of processing a coated fabric for forming a polyurethane resin layer containing 1% by weight or more of anhydrous silicon dioxide fine powder having an average particle size of 0.1 μm or less, and has a moisture permeability of 7000 g / m ^2. 24hrs or more, water pressure resistant
It succeeded in obtaining a moisture-permeable and waterproof fabric of 0.6 kgf / cm ² or more. However, according to this method, since the resin liquid is applied directly to the fiber cloth, the hand becomes hard due to the resin permeation into the inside of the fiber cloth, and a moisture-permeable waterproof cloth having a soft feeling cannot be obtained. Was.

[0004]

On the other hand, the laminating method is a method obtained by bonding a resin film having moisture permeability and waterproof property to a fiber cloth via an adhesive, and the amount of the adhesive at the bonded portion is reduced. It is also known to obtain a moisture-permeable and waterproof fabric having a soft feel by reducing the bonding area. In this case, however, a moisture-permeable and waterproof resin film is applied to the surface of release paper or a release film by a dry method. Due to the formation, a good waterproof material can be obtained, but a good moisture-permeable material cannot be obtained. In order to satisfy both performances, a resin film may be formed on release paper by a wet method.
During wet processing, the resin film will peel off from the release paper.
Practically, it is not possible to manufacture a moisture-permeable waterproof fabric that satisfies moisture permeability and waterproofness with such a method. SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and has as its object to obtain a moisture-permeable waterproof fabric having a high degree of moisture permeability and waterproofness and a soft feeling by using a lamination method. It is assumed that.

[0005]

The present invention attains the above object and has the following constitution. That is, the present invention relates to a "synthesis of a polyurethane resin-based synthetic material containing 1% by weight or more of substantially non-porous anhydrous silicon dioxide fine powder having an average particle size of 0.1 μm or less on a releasable mesh cloth. First step of applying a polymer solution and performing wet film formation, second step of uniformly applying a polyurethane-based adhesive solution over the entire surface of the resin layer, and laminating a fiber cloth thereto, and removing the mesh cloth A water pressure resistance of 1.0 to 3.0 kgf / cm ² and a 5,000 to 110
And a method for producing a soft, moisture-permeable waterproof fabric having a moisture permeability of 00 g / m ² · 24 hrs.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, first, a moisture-permeable waterproof resin film is formed on a mesh cloth having releasability.
The mesh cloth referred to here is, for example, a coarse cloth used for general industrial materials woven from filaments such as nylon, polyester, polyethylene, polypropylene, and polyvinylidene fluoride and monofilaments. Wire diameter 50-500 μm, 15-
Use a 200 mesh. Using a known processing agent such as a paraffin-based water repellent, a fluorine-based water-repellent, a polysiloxane-based water-repellent, or a release agent, the mesh cloth is subjected to strong water repellency or water repellency by a known method such as padding or spraying. By imparting releasability, a mesh cloth having releasability used in the present invention is obtained. Further, in the present invention, a mesh cloth made of polytetrafluoroethylene, polytetrafluoroethylene perfluoroalkyl vinyl ether copolymer or the like which is originally excellent in releasability may be used as it is as a mesh cloth having releasability. Although it is good, in view of cost, heat resistance, dimensional stability, and the like, a polyester mesh having releasability is preferably used.

In the present invention, as a first step, 1% by weight of a substantially non-porous anhydrous silicon dioxide fine powder having an average particle diameter of 0.1 μm or less is placed on the above-mentioned releasable mesh cloth. The synthetic polymer solution containing the above-mentioned polyurethane resin as a main component is applied to form a wet film. The synthetic polymer mainly composed of polyurethane resin used here has a polyurethane component of 50 to 1
A polymer containing 00% by weight. Other synthetic polymers include polyacrylic acid, polyvinyl chloride, polystyrene, polybutadiene, polyamino acids, etc., and copolymers thereof in a range of less than 50% by weight. Of course, a polymer modified with fluorine, silicon or the like can be used in the present invention. The polyurethane resin itself is a copolymer obtained by reacting an isocyanate and a polyol. An aromatic diisocyanate, an aliphatic diisocyanate or an alicyclic diisocyanate alone or a mixture thereof is used as an isocyanate component.
-Diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexane diisocyanate, 1,4-
Cyclohexane diisocyanate or the like may be used as a main component, and if necessary, trifunctional or higher functional isocyanate may be used. As the polyol component, a polyether polyol or a polyester polyol is used. As the polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or the like is used. As the polyester polyol, for example, ethylene glycol or propylene glycol is used. And a ring-opening polymer such as caprolactone, or a reaction product of a diol such as adipic acid and a dibasic acid such as sebacic acid.

In the present invention, a porous resin layer having high water pressure resistance and high moisture permeability is formed by using the above-mentioned synthetic polymer mainly composed of a polyurethane resin. Then, an anhydrous silicon dioxide fine powder having an average particle size of 0.1 μm or less is used in combination, and a synthetic polymer solution mainly composed of a polyurethane resin is formed using a polar organic solvent such as N, N-dimethylformamide. As the substantially non-porous anhydrous silicon dioxide fine powder, silicon dioxide fine powder obtained by a dry method such as a gas phase oxidation method of silicon halide, a combustion hydrolysis method or an electric arc method can be used. The fine powder obtained in (1) has no pores inside, is substantially nonporous, has a particle size of 0.1 μm or less, and has a very large amount of N, N-
It has a dimethylformamide adsorption amount and, like general silicon dioxide fine powder, has a large number of silanol groups on the particle surface, and is therefore a hydrophilic substance. In the present invention, silicon dioxide fine powder having many silanol groups on the particle surface has a sufficient effect, but this hydrophilic silicon dioxide fine powder is uniformly dispersed in a synthetic polymer solution mainly composed of polyurethane resin. In addition, the viscosity of the resin solution tends to be strong thixotropic and moisture is easily adsorbed, so care must be taken in the coating operation. Also, the obtained resin film is hydrophilic, so it may be slightly affected from the viewpoint of water leakage. Disadvantages.

In order to make up for these drawbacks, silicon dioxide fine powder is used as the fine powder, which is made to react with a silanol group with a substance such as trimethylchlorosilane, dimethyldichlorosilane, ethyl alcohol or isopropyl alcohol to make the fine particle surface hydrophobic. It is effective to use this hydrophobic fine powder, because it is not so thixotropic and the amount of adsorbed water is small, so that the stability of the substance itself is excellent and the operation is advantageous. The above-mentioned adsorption amount of N, N-dimethylformamide means that 5 g of inorganic fine powder is placed on a glass plate, and each time one drop of N, N-dimethylformamide is dropped, kneading is performed using a stainless steel spatula. It means the volume (unit: milliliter) of N, N-dimethylformamide required until immediately before softening rapidly with one drop of N, N-dimethylformamide,
N, N- instead of oil in JIS K-5101
It uses dimethylformamide.

The fine powder used in the present invention may be mainly anhydrous silicon dioxide fine powder, and may further contain aluminum oxide, magnesium oxide or the like, or a general filler, pigment, etc. as impurities or as a mixture. There is no problem even if you do. The anhydrous silicon dioxide fine powder used in the present invention is one containing at least 60% as a silicon dioxide component. The size of the fine powder used must be such that the average particle size is 0.1 μm or less.
When the thickness is equal to or smaller than 05 μm, it is more preferable in view of the effect.
If it is larger than 0.1 μm, the pore size of the fine pores of the moisture-permeable membrane of the obtained coated fabric becomes too large, and the waterproof performance is undesirably reduced. The anhydrous silicon dioxide fine powder must be uniformly contained in an amount of 1% by weight or more, preferably 3% by weight or more, based on a resin layer composed of a synthetic polymer mainly composed of a polyurethane resin. If it is less than 1% by weight, the number of micropores in the moisture-permeable film of the obtained coated fabric will be small, and high moisture-permeable performance cannot be obtained.

In the present invention, a polyurethane resin containing anhydrous silicon dioxide fine powder may be used in combination with a polyurethane resin having a different coagulation value (including a polyamino acid urethane resin). The coagulation value is defined as a value obtained by synthesizing a synthetic polymer mainly composed of polyurethane resin with a solvent (N, N-dimethylformamide)
Water, which is a coagulating liquid, is added little by little to 100 g of the resin solution diluted 4 times with stirring, and means the volume of water required immediately before the start of gelation. By mixing and using, the number of pores in the microcavities increases and the moisture permeability improves, but if there is too little difference in the coagulation value, the factors that the water pressure decreases as the moisture permeability improves Therefore, care must be taken. The difference in the coagulation value is preferably such that the coagulation value ratio (high coagulation value / low coagulation value) is 1.5 or less. When applying the above-mentioned synthetic polymer solution mainly composed of a polyurethane resin containing the fine powder of anhydrous silicon dioxide to a mesh cloth having releasability, a knife coater, a comma coater,
Coating may be appropriately performed using a reverse coater or the like, and the coating amount is 10 g / m ² or more, preferably 15 g / m ² or more in order to obtain a water pressure of 1 kgf / cm ² or more. The coating amount is adjusted as described above.
After coating, the film is immersed in a water bath at 5 to 60 ° C. for about 0.5 to 15 minutes to elute the solvent in the coating solution to form a wet film.

In the present invention, a second step of uniformly applying an adhesive solution mainly composed of a polyurethane-based resin to the entire surface of the wet-formed resin layer, drying the resultant, and laminating a fiber cloth thereon is provided. Do. As the polyurethane-based resin used for the adhesive, a resin having a urethane bond obtained from an isocyanate group and a hydroxyl group in the same molecule as described above or a resin derived from the above-described isocyanate compound may be used. The following low-molecular polyols, for example, a method of directly combining a polyol component such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol with an isocyanate compound, or a method of combining a polyol component or an isocyanate compound with the aforementioned polyether diol , Polyester diol, polycaprolactone diol and other polymer polyols and tolylene 2,4-diisocyanate, 4,4 '
-A copolymer obtained by a method of combining a urethane prepolymer modified at both terminal isocyanate groups or at both terminal hydroxyl groups by reacting with an isocyanate compound such as diphenylmethane diisocyanate has a tag property of a resin, and a polyamide fiber cloth described later. It is preferably used because it has excellent adhesion and the like. When the terminal group of the obtained resin is a hydroxyl group, the above-mentioned isocyanate compound may be used in combination with the resin.

As the isocyanate compound, tolylene
2,4-diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, or trimethyldiisocyanate, or trimethyldiisocyanate, is obtained by the addition reaction of 3 moles of these diisocyanates with 1 mole of a compound containing active hydrogen (eg, trimethylolpropane, glycerin, etc.). Isocyanates can be used. The above-mentioned isocyanates may be a compound in which isocyanate groups are released, or may be a form in which an addition block is formed with phenol, lactam, methyl ketone, or the like and dissociated by heat treatment. It may be appropriately used depending on the use or the like.

The amount of the isocyanate compound used is preferably 0.1 to 10% by weight based on the mixed solution of the polyurethane resin-based synthetic polymer, and the amount used is 0.1. When the amount is less than 10% by weight, the adhesive strength of the resin layer to the fabric is not so improved, and when the amount is more than 10% by weight, the hand tends to be hardened, which is not preferable. Further, for the purpose of accelerating the curing speed of the resin, a tin catalyst such as tin octylate and dibutyltin dioctoate, and an amine catalyst such as triethylamine and triethylenediamine may be used in combination. When both ends of the obtained resin are isocyanate groups, the resin may be used alone, or may be used in combination with the above-mentioned compounds having active hydrogen such as polyol, epoxy resin, and neoprene.

In the present invention, the above-mentioned polyurethane-based adhesive solution is uniformly applied to the entire non-surface and dried. When applying the solution, a known gravure coater, rotary screen, flat screen, or the like is used to form a dot-like or line-like image. It is applied uniformly over the entire surface in a desired shape such as a checkerboard pattern, a checkerboard pattern, and a turtle pattern, and then dried at a temperature of 50 to 100 ° C. for 0.5 to 5 minutes, and then laminated with a fiber cloth. On the surface to which the adhesive solution is applied, the adhesive is applied so that the ratio of the occupied area of the adhesive to the entire area of the applied surface is 20 to 60%, preferably 25 to 50%. If the occupied area ratio of the adhesive is less than 20%, the peeling resistance between the resin layer and the laminating cloth is poor, and if it is 60% or more, the moisture permeability is undesirably reduced.

The fiber cloth used for lamination includes polyamide synthetic fibers such as nylon 6 and nylon 66, polyester synthetic fibers such as polyethylene terephthalate, polyacrylonitrile synthetic fibers, and polyvinyl alcohol synthetic fibers. Woven fabrics, knitted fabrics, nonwoven fabrics, etc. comprising semi-synthetic fibers such as triacetate and triacetate or mixed fibers such as nylon 6 / cotton and polyethylene terephthalate / cotton. In laminating, a known method such as ordinary pressure bonding or thermocompression bonding may be employed.

Thereafter, in the present invention, as a third step, the mesh cloth is peeled off. After the peeling, if necessary, the obtained laminated fabric may be subjected to a water-repellent treatment for the purpose of improving the water pressure resistance. As the water repellent in this case, a known water repellent such as a paraffin water repellent, a polysiloxane water repellent, or a fluorine water repellent may be used. A known method such as a spray method may be used. When a particularly good water repellency is required, a fluorine-based water repellent is used.
0 (Fluorine-based water repellent emulsion manufactured by Asahi Glass Co., Ltd.)
Is padded with a 5% aqueous dispersion (a squeezing ratio of 35%), and then heat-treated at 160 ° C. for 1 minute.

[0018]

[Action] When a synthetic polymer solution mainly composed of a polyurethane resin in which anhydrous silicon dioxide fine powder is uniformly dispersed is coated on a mesh cloth having releasability and wet coagulation is performed,
Water, which is a coagulating liquid, and N, N-dimethylformamide, which is a resin solvent, are mixed, and coagulation of the resin starts when the solvent is rapidly released from the resin liquid. At this time, the average particle size is 0.1 μm. When the silicon dioxide fine powder having an extremely large amount of adsorbed N, N-dimethylformamide is uniformly dispersed in the resin solution, the surface of the silicon dioxide fine powder is more dispersed in the resin solution than other parts. The concentration of N, N-dimethylformamide is high, in other words, the concentration of N, N-dimethylformamide of a synthetic polymer mainly composed of polyurethane resin is in a low state. First, it is replaced with N, N-dimethylformamide on the surface of the silicon dioxide fine powder, and solidification starts quickly around the silicon dioxide fine powder, and the honeycomb characteristic of polyurethane resin. 1μm in addition to the camskin core structure
It is a very porous form having the following micropores countless. When a polyurethane resin having a different coagulation value is used in combination with a synthetic polymer mainly composed of polyurethane resin, solidification starts first around the silicon dioxide fine powder, then coagulation of the resin with a lower coagulation value starts, and finally Since the solidification of the resin with a high coagulation value begins, the cavity of the honeycomb skin core structure peculiar to polyurethane resin increases and the 1μ
A very porous form having countless micropores of m or less is obtained. It is presumed that because of the above-mentioned form, the waterproofness is high while having sufficient moisture permeability.

Further, when a wet film is formed using a mesh cloth having releasability as in the present invention, the resin enters into the openings of the mesh cloth, and therefore, the release film or the release cloth Since the peeling phenomenon of the resin film layer in the wet process, which tends to occur when using the method, is not caused, the wet film formation, which has been impossible in the past, can be stably performed. In the present invention, after the wet film formation on the mesh cloth, the adhesive layer is uniformly laminated on the resin layer over the entire non-surface with the fiber cloth, so that the laminated cloth has a soft feeling. Furthermore, since the mesh cloth is peeled off at the end of the cloth, the peeled resin layer surface has a matte feeling and can enjoy a dry touch feeling.

[0020]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. The measurement and evaluation of the performance of the fabric in the examples were performed by the following methods. (1) Water pressure resistance JIS L-1092 (high water pressure method) (2) Moisture permeability JIS L-1099 (A-1 method)

(3) Hand The hand was relatively evaluated by handling in the following four grades. ◎: very flexible ○: soft Δ: slightly hard ×: hard (4) Formability of resin film The formability of a moisture-permeable waterproof resin film by wet solidification in the first step was evaluated on the following three levels. : Good without peeling △: slight peeling ×: peeling

Example 1 A mesh cloth TB70 (N) woven in a plain weave with a polyester monofilament having a wire diameter of 125 μm and 70 mesh
BC Industrial Co., Ltd.) is prepared and padded (squeezing rate 25%) with a 15% solid mineral water repellent KS734 (manufactured by Shin-Etsu Chemical Co., Ltd.), and dried. And a heat treatment at 160 ° C. for 1 minute to obtain a releasable mesh cloth. Next, rack skin 1740-29B (ester type polyurethane resin manufactured by Seiko Chemical Co., Ltd.) 100
And 40 parts of Aerosil R-972 (manufactured by Nippon Aerosil Co., Ltd., hydrophobic silicon dioxide fine powder having an average particle diameter of 0.016 μm and an adsorption amount of N, N-dimethylformamide of 350 ml / 100 g) and N, N-dimethylformamide After uniformly dispersing 50 parts with a three-roll machine, 900 parts of the above-mentioned rack skin 1740-29B and 200 parts of N, N-dimethylformamide were mixed uniformly,
A polyurethane resin containing an inorganic fine powder having a viscosity of 19000 mPa · s (25 ° C.) and a solidification value of 9.8 cc (hereinafter referred to as S-
It is called PU resin. ) Got.

Subsequently, a fluorine-modified polyurethane resin (hereinafter referred to as F-PU resin) was produced by the following method. Polytetramethylene glycol (OH value 56.9) 1970
g, and 504 g of 1,6-hexamethylene diisocyanate were reacted at 90 ° C. for 5 hours to obtain a urethane prepolymer having a terminal isocyanate group. 21 g of this urethane prepolymer and 21 g of a vinyl fluoride polymer having a hydroxyl group introduced into a terminal are dissolved in 415 g of a mixed solvent of N, N-dimethylformamide / dioxane (weight ratio = 7/3), and 47 g of a 2% dimethylamine solution is stirred while stirring. And reacted at 30 ° C. for 5 hours to give a viscosity of 39000 m
A pale yellow-brown F-PU resin having a coagulation value of 7.5 cc and good flowability at Pa · s (25 ° C.) was obtained.

Here, a solid content of 2 having the composition shown in the following formulation 1
Using a knife over roll coater, apply a 5% polyurethane resin solution onto the above-mentioned mesh cloth in an amount of 8%.
Immediately after application at 0 g / m ² ,
The resin was solidified by immersion for 2 seconds, followed by washing in warm water at 50 ° C. for 10 minutes, followed by drying to form a resin layer. During the wet solidification of the resin, the resin layer could be formed stably without the resin layer peeling off the mesh cloth. Formulation 1 100 parts of S-PU resin (polyurethane resin containing fine powder of silicon dioxide) 1 part of Rezamine X-100 (isocyanate compound, manufactured by Dainichi Seika Kogyo Co., Ltd.) Next, both the warp and the weft have nylon high multifilament 70 denier / A 68-filament plain weave having a warp density of 110 yarns / inch and a weft density of 90 yarns / inch is woven and scoured and dyed by a usual method (Kayanol Navy Blue R 3% owf, manufactured by Nippon Kayaku Co., Ltd.). ) To obtain a fiber fabric for lamination.

Here, a gravure roll of 46 mesh, 180 μm depth, circular dot shape (dot width 0.3 mm, dot interval 0.25 mm, adhesive occupied area about 25%) was formed on the resin layer by the following method. A polyurethane adhesive solution having a composition shown in FIG. 2 and having a solid content of 37% was applied at a coating amount of 40 g / m ² , dried at 100 ° C. for 2 minutes, and then 3 kgf / m ²
It was laminated with the above fiber fabric at a pressure of cm ² . Formulation 2 UD-108 100 parts (Seiko Chemical Co., Ltd., ester type polyurethane adhesive) Coronate HL 7 parts (Nippon Polyurethane Industry Co., Ltd., isocyanate compound) UY-5 0.5 part (Seiko Chemical Co., Ltd. Organotin accelerator) Methyl ethyl ketone 20 parts

Thereafter, aging was performed by leaving the room at room temperature for 3 days, and then the mesh cloth was peeled off. Hereinafter, Asahi Guard LS-
317 (Asahi Glass Co., Ltd., fluorinated water repellent emulsion) padded with 5% aqueous dispersion (squeezing ratio 40%)
After drying at 110 ° C. for 1 minute, heat treatment was performed at 170 ° C. for 30 seconds to obtain a moisture-permeable waterproof fabric of the present invention.

Comparative Example 1 For comparison with the present invention, a commercially available release paper SJA70 (a product of San-A Chemical Industry Co., Ltd.) was used in place of the releasable mesh cloth used in Example 1. 1
We tried to produce a moisture-permeable and waterproof fabric in exactly the same way as in the above, but the resin film peeled off during the wet solidification of the coating resin layer in the first step, making it impossible to proceed to the next step. The fabric could not be obtained.

Comparative Example 2 For the purpose of comparison with the present invention, the same procedure as in Example 1 was carried out except that, in place of Formula 1 of Example 1, the following Formula 3, which corresponds to a formula in which silicon dioxide fine powder was omitted from Formula 1, was used. By the same method, a comparative moisture-permeable waterproof fabric was obtained. Formulation 3 Lac Skin 1740-29B 100 parts N, N-dimethylformamide 25 parts Resamine X-100 1 part

Comparative Example 3 For comparison with the present invention, when applying the adhesive solution in Example 1, the adhesive solution of Formulation 2 was applied as thinly as possible over the entire surface of the resin layer. A moisture-permeable waterproof cloth for comparison was obtained in exactly the same manner as described above.

The performances of the present invention and the comparative work cloth were measured and evaluated, and the results are shown in Table 1.

[0031]

[Table 1]

As is clear from Table 1, according to the method of the present invention, the resin film does not peel off during wet film formation, has high waterproofness and moisture permeability, and has a soft feel and moisture permeability. Fabrics can be manufactured.

Example 2 In order to obtain better moisture permeability, the following formulation 4 (coagulation value ratio 1.3) was used instead of formulation 1 in Example 1 except that a polyurethane resin having a different coagulation value was used in combination. A moisture-permeable waterproof fabric of the present invention was produced in exactly the same manner as in Example 1. Formulation 4 S-PU resin (coagulation number 9.8 cc) 85 parts F-PU resin (coagulation number 7.5 cc) 15 parts Resamine X-100 1 part

Comparative Example 4 In order to see the effect of the presence or absence of anhydrous silicon dioxide fine powder in the resin layer, rack skin 1740-29 was used in Formula 4 of Example 2 instead of S-PU resin (containing fine powder).
A moisture-permeable waterproof cloth for comparison was obtained in exactly the same manner as in Example 2 except that 85 parts of B (not containing the same fine powder) were used.

Comparative Example 5 In order to see the difference in the effect due to the difference in the coagulation number ratio between the main S-PU resin and the resin used in combination therewith, the examples were prepared so that the coagulation number ratio was 1.7. In Formula 4 of 2, F-
A transparent resin for comparison was prepared in exactly the same manner as in Example 2 except that 15 parts of rack skin 1740-29A (manufactured by Seiko Chemical Co., Ltd., polyamino acid urethane copolymer resin, coagulation value 5.8 cc) was used instead of the PU resin. A wet waterproof fabric was obtained.

The performances of the present invention and the comparative work cloth were measured and evaluated, and the results are shown in Table 2.

[0037]

[Table 2]

As is apparent from Table 2, according to the method of the present invention, the resin film does not peel off during wet film formation, has high waterproofness and moisture permeability, and has a soft feel and moisture permeability. Fabrics can be manufactured.

Example 3 A plain fabric having a warp density of 80 yarns / inch and a weft density of 60 yarns / inch was prepared by using cationically dyeable polyester filaments of 150 denier / 96 filaments for both the warp and the weft. Scouring and dyeing (Kayacryl
Blue GSL-ED 1.5% owf) to obtain a fiber fabric for lamination. Further, when applying the adhesive solution of the prescription 2, the gravure roll shape was changed to 25 mesh, depth 180
μm, circular dot shape (dot width 0.7 mm, dot interval 0.3
Example 1 except that the thickness was 5 mm and the area occupied by the adhesive was about 40%).
The moisture-permeable waterproof fabric of the present invention was obtained in exactly the same manner as described above.

Comparative Example 6 For comparison with the present invention, a comparative moisture-permeable waterproof fabric by a coating method was produced by the following usual method. Asahigard LS-317 was used as the dyed fiber fabric used in this example.
Padding (40% squeezing rate) with 5% aqueous dispersion of
After drying at 0 ° C. for 1 minute, a heat treatment is performed at 170 ° C. for 30 seconds. Then, using a calendering machine having a mirror-finished roll, the temperature is 180 ° C., the pressure is 30 kgf / cm ² , and the speed is 30 m / min.
For 1 minute, and then the polyurethane resin solution of Formulation 1 was applied to the calendered surface in Example 1.
Wet film formation was performed in exactly the same manner as in Example 1 to obtain a moisture-permeable waterproof coating fabric for comparison (referred to as Comparative Example 6).

The performances of the present invention and the comparative fabric were measured and evaluated, and the results are shown in Table 3.

[0042]

[Table 3]

As is clear from Table 3, the moisture-permeable and waterproof fabric of the present invention has a high balance of water pressure resistance and moisture permeability, has unprecedented good performance and soft feeling, and has a resin texture. It can be seen that it is also suitable for a low-density woven fabric that easily leaks.

[0044]

According to the present invention, it is possible to manufacture a moisture-permeable waterproof fabric having high waterproofness and moisture permeability and having a soft feeling. Further, in the present invention, since the laminating method is employed, a moisture-permeable waterproof fabric can be manufactured using a fabric having a large air permeability or a surface unevenness or a highly stretchable fabric as a base fabric.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 7/14 B32B 7/14 27/12 27/12

Claims (2)

[Claims] 1. A synthetic weight mainly composed of a polyurethane resin containing 1% by weight or more of a substantially non-porous anhydrous silicon dioxide fine powder having an average particle size of 0.1 μm or less on a releasable mesh cloth. The first step of applying the coalescing solution and forming a wet film
A second step of uniformly applying a polyurethane adhesive solution over the entire surface of the resin layer and laminating a fiber cloth thereon;
A water-proof pressure of 1.0 to 3.0 kgf / cm ^{2 and} a water resistance of 5000 to 11 comprising a third step of peeling the mesh cloth.
A method for producing a soft, moisture-permeable, waterproof fabric having a moisture permeability of 000 g / m ² · 24 hrs. 2. A wet-process method comprising applying a polyurethane resin having a coagulation value lower than that of the resin and a coagulation value ratio of 1.5 or less to a synthetic polymer solution mainly composed of a polyurethane resin used in the first step. The method for producing a soft moisture-permeable waterproof fabric according to claim 1, wherein the fabric is formed into a film.